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I I I !

w
Polyimide iesins
Daniel A. Scola, University of Connecticut
__ ___________7_________7_7 7________ __ ____ _ 77_____ 7 W7 __7_7_,_7 ___7__T_ _ 7
7""' ' "' 77'7 W"'7?"""7'7' '1I lI alu"W""I lium ' "7""""'7" '7 777*""W"I "ll"7T 'I l "' ' "' "' 7
POLYI MI DE MATERI ALS can be catego-
rized by their temperature capabilities into those
with an upper limit of 230 C (450 F ) - for ex-
tended time periods, and those capable of ex-
tended use up to 315 C,(60(} F ) . Bismaleimides,
phenylethynyl-containing polyirnides, and some
condensation polyimides such as Avimid-K3 be-
long in the former category, While those mate-
rials such as PMR-15, LARC-TPI , Avimid-N
and BPDA/TF MB belong in the latter. I n_terms
of chemistry, there are two general types of com-
mercial polyimides: thermoplastic polyimides,
derived from a condensation reaction between
anhydrides or anhydride derivatives and diam-
ines, and cross-linkedpolyimides, derived from
an addition reaction between unsaturated groups
of a preformed imide monomer or oligomer. The
imide monomers or oligorners are also derived
from the typical condensation reaction to form
the imide group, but polymer formation stems
from the addition reaction. F or completeness, the
chemistry of both types and process conditions
to fabricate articles are describedin this article.
Bismaleimides are notreviewed in this article.
(See the article Bismaleimide Resinsin this
Volume.)
Properties and Applications
The specic advantages and disadvantages of
two types of polyimides are summarized in Table
1. These are generalized conclusions regarding
each type, because there are exceptions, which
depend on chemical structure.
The condensation polyimides, which are lin-
ear long-chain thermoplastic polymers, have
high melt viscosity, thereby requiring high pres-
sures and temperatures for neat resin molding or
composite processing. However, the highly aro-
matic nature of these systems coupled with ex-
ible groups, such as ether, hexouorosopropyli-
dene, or methylene Within the backbone
structure, yields materials with good toughness,
excellent thermal and thermooxidative stability,
and moderate to high glass transition tempera-
tures (Tg) .
The addition-type polyimides, derived from
preformed oligomers, undergo thermal cross
linking or chain extension to form a thermoset.
The oligomer molecularweight controls the pro-
cessability, the degree of cross linking or chain
extension, and the Tg. However, because no vol-
atiles are released during processing, and the
oligomers have a melt or softening region Where
the viscosity is relatively low near the tempera-
ture region where the addition reaction occurs,
moderate to lowpressure is required during pro-
cessing to consolidate the part being fabricated.
Polyimides are nding wide applications be-
cause of their unusual properties. The polyun-
ides derived from aromatic dianhydrides and ar-
omatic diarnines containing stable exible units
in the backbone exhibit:
0 High thermal and thermo-oxidative stability
up to 400 C (750 F )
0 Excellent mechanical properties, both at room
temperature and elevated temperatures
0 F ilm- and ber-forming ability
0 Excellent adhesive properties, both at room
temperature and elevated temperature
Nonamrnabilitywill not support combus-
U011
F luorine-containing polyimides exhibit the
properties listed previously, as well as low di-
electric constant. Polyimides containing func-
Table 2 Applications of polyimides by
industry
I as-?2 t! r--._-_ .-___- _. evrlisatiaes
Electronics F lexible circuits
F lexible connectors
Chip carriers
Tape automated bonding
High-density interconnect applications
Photosensitive polyimides
Wire insulation
Motor windings
Electrical switches
Structural adhesives
Structural composites
F oam insulation
Bushings
i Bafes
F langed bearings
~ Thrust washers
Thrust discs
Seal rings '
Electrical switches
Pacemakers
Eye lens implants
Abrasive cutting wheels
Membranes
Rockets
Spacecraft (composite, adhesives,
. coatings) p
Military applications Composites, adhesives, coatings
Manufacturing Discs in compressor valve systems
Aircraft
Automobile
Medical
Machining
Gas purication
Aerospace i
Table 3 Applications of high-temperature
polyimide composites in aircraft engines
Sector Applications
Military engines Stator vanes
Shrouds (fan section)
External nozzle aps
Bushings
Bearings A _
Table 1 General attributes of condensation (thermoplastic) and addition-type (cross- immediate cases
linked) polyimides guslglsmer ducts
- K WK - r r - an 'L1Ci.'S K
Polyhnitieltyrpewlw if Jwwli pwppndvantages W WW p Disadvantages ~ Nose cones
W C A if L *; * C Commercial engines Core cowls (nacelles)
Condensation (thermoplastic) Thermoplastic (reprocessability) Poor processabihty Union n S (Variabk vane actuaen
Moderate to high glass transition temperatures (Tg) Volatiles released in processing System? =
Toughness S I -liglipressure rerljuired in processing Q Stator Vans (1OW_presS,_m_,
Excellent thermal and thermo-oxidative stability Compressor)
Addition-type (cross-linked) Processability ' Limited reprocessability EXtgma1S_ge$ box housing and
CTOSS l.l.I 1kCl Supyeft 511-ugturgs
Hi h T Poor thermal and thermo-oxidative stability Washers
g s
No volatiles in processing 7 Bushings
Bearin s Low pressure required in processing ' g
lint ,.
.,,
Z
2
l
ll '.
gr
l
1
ll

KM El;
I I I ! w
Polyimide iesins
Daniel A. Scola, University of Connecticut
__ ___________7_________7_7 7________ __ ____ _ 77_____ 7 W7 __7_7_,_7 ___7__T_ _ 7
7""' ' "' 77'7 W"'7?"""7'7' '1I lI alu"W""I lium ' "7""""'7" '7 777*""W"I "ll"7T 'I l "' ' "' "' 7
POLYI MI DE MATERI ALS can be catego-
rized by their temperature capabilities into those
with an upper limit of 230 C (450 F ) - for ex-
tended time periods, and those capable of ex-
tended use up to 315 C,(60(} F ) . Bismaleimides,
phenylethynyl-containing polyirnides, and some
condensation polyimides such as Avimid-K3 be-
long in the former category, While those mate-
rials such as PMR-15, LARC-TPI , Avimid-N
and BPDA/TF MB belong in the latter. I n_terms
of chemistry, there are two general types of com-
mercial polyimides: thermoplastic polyimides,
derived from a condensation reaction between
anhydrides or anhydride derivatives and diam-
ines, and cross-linkedpolyimides, derived from
an addition reaction between unsaturated groups
of a preformed imide monomer or oligomer. The
imide monomers or oligorners are also derived
from the typical condensation reaction to form
the imide group, but polymer formation stems
from the addition reaction. F or completeness, the
chemistry of both types and process conditions
to fabricate articles are describedin this article.
Bismaleimides are notreviewed in this article.
(See the article Bismaleimide Resinsin this
Volume.)
Properties and Applications
The specic advantages and disadvantages of
two types of polyimides are summarized in Table
1. These are generalized conclusions regarding
each type, because there are exceptions, which
depend on chemical structure.
The condensation polyimides, which are lin-
ear long-chain thermoplastic polymers, have
high melt viscosity, thereby requiring high pres-
sures and temperatures for neat resin molding or
composite processing. However, the highly aro-
matic nature of these systems coupled with ex-
ible groups, such as ether, hexouorosopropyli-
dene, or methylene Within the backbone
structure, yields materials with good toughness,
excellent thermal and thermooxidative stability,
and moderate to high glass transition tempera-
tures (Tg) .
The addition-type polyimides, derived from
preformed oligomers, undergo thermal cross
linking or chain extension to form a thermoset.
The oligomer molecularweight controls the pro-
cessability, the degree of cross linking or chain
extension, and the Tg. However, because no vol-
atiles are released during processing, and the
oligomers have a melt or softening region Where
the viscosity is relatively low near the tempera-
ture region where the addition reaction occurs,
moderate to lowpressure is required during pro-
cessing to consolidate the part being fabricated.
Polyimides are nding wide applications be-
cause of their unusual properties. The polyun-
ides derived from aromatic dianhydrides and ar-
omatic diarnines containing stable exible units
in the backbone exhibit:
0 High thermal and thermo-oxidative stability
up to 400 C (750 F )
0 Excellent mechanical properties, both at room
temperature and elevated temperatures
0 F ilm- and ber-forming ability
0 Excellent adhesive properties, both at room
temperature and elevated temperature
Nonamrnabilitywill not support combus-
U011
F luorine-containing polyimides exhibit the
properties listed previously, as well as low di-
electric constant. Polyimides containing func-
Table 2 Applications of polyimides by
industry
I as-?2 t! r--._-_ .-___- _. evrlisatiaes
Electronics F lexible circuits
F lexible connectors
Chip carriers
Tape automated bonding
High-density interconnect applications
Photosensitive polyimides
Wire insulation
Motor windings
Electrical switches
Structural adhesives
Structural composites
F oam insulation
Bushings
i Bafes
F langed bearings
~ Thrust washers
Thrust discs
Seal rings '
Electrical switches
Pacemakers
Eye lens implants
Abrasive cutting wheels
Membranes
Rockets
Spacecraft (composite, adhesives,
. coatings) p
Military applications Composites, adhesives, coatings
Manufacturing Discs in compressor valve systems
Aircraft
Automobile
Medical
Machining
Gas purication
Aerospace i
Table 3 Applications of high-temperature
polyimide composites in aircraft engines
Sector Applications
Military engines Stator vanes
Shrouds (fan section)
External nozzle aps
Bushings
Bearings A _
Table 1 General attributes of condensation (thermoplastic) and addition-type (cross- immediate cases
linked) polyimides guslglsmer ducts
- K WK - r r - an 'L1Ci.'S K
Polyhnitieltyrpewlw if Jwwli pwppndvantages W WW p Disadvantages ~ Nose cones
W C A if L *; * C Commercial engines Core cowls (nacelles)
Condensation (thermoplastic) Thermoplastic (reprocessability) Poor processabihty Union n S (Variabk vane actuaen
Moderate to high glass transition temperatures (Tg) Volatiles released in processing System? =
Toughness S I -liglipressure rerljuired in processing Q Stator Vans (1OW_presS,_m_,
Excellent thermal and thermo-oxidative stability Compressor)
Addition-type (cross-linked) Processability ' Limited reprocessability EXtgma1S_ge$ box housing and
CTOSS l.l.I 1kCl Supyeft 511-ugturgs
Hi h T Poor thermal and thermo-oxidative stability Washers
g s
No volatiles in processing 7 Bushings
Bearin s Low pressure required in processing ' g
lint ,.
.,,
Z
2
l
ll '.
gr
l
1
ll

KM El;
I I I ! w
Polyimide iesins
Daniel A. Scola, University of Connecticut
__ ___________7_________7_7 7________ __ ____ _ 77_____ 7 W7 __7_7_,_7 ___7__T_ _ 7
7""' ' "' 77'7 W"'7?"""7'7' '1I lI alu"W""I lium ' "7""""'7" '7 777*""W"I "ll"7T 'I l "' ' "' "' 7
POLYI MI DE MATERI ALS can be catego-
rized by their temperature capabilities into those
with an upper limit of 230 C (450 F ) - for ex-
tended time periods, and those capable of ex-
tended use up to 315 C,(60(} F ) . Bismaleimides,
phenylethynyl-containing polyirnides, and some
condensation polyimides such as Avimid-K3 be-
long in the former category, While those mate-
rials such as PMR-15, LARC-TPI , Avimid-N
and BPDA/TF MB belong in the latter. I n_terms
of chemistry, there are two general types of com-
mercial polyimides: thermoplastic polyimides,
derived from a condensation reaction between
anhydrides or anhydride derivatives and diam-
ines, and cross-linkedpolyimides, derived from
an addition reaction between unsaturated groups
of a preformed imide monomer or oligomer. The
imide monomers or oligorners are also derived
from the typical condensation reaction to form
the imide group, but polymer formation stems
from the addition reaction. F or completeness, the
chemistry of both types and process conditions
to fabricate articles are describedin this article.
Bismaleimides are notreviewed in this article.
(See the article Bismaleimide Resinsin this
Volume.)
Properties and Applications
The specic advantages and disadvantages of
two types of polyimides are summarized in Table
1. These are generalized conclusions regarding
each type, because there are exceptions, which
depend on chemical structure.
The condensation polyimides, which are lin-
ear long-chain thermoplastic polymers, have
high melt viscosity, thereby requiring high pres-
sures and temperatures for neat resin molding or
composite processing. However, the highly aro-
matic nature of these systems coupled with ex-
ible groups, such as ether, hexouorosopropyli-
dene, or methylene Within the backbone
structure, yields materials with good toughness,
excellent thermal and thermooxidative stability,
and moderate to high glass transition tempera-
tures (Tg) .
The addition-type polyimides, derived from
preformed oligomers, undergo thermal cross
linking or chain extension to form a thermoset.
The oligomer molecularweight controls the pro-
cessability, the degree of cross linking or chain
extension, and the Tg. However, because no vol-
atiles are released during processing, and the
oligomers have a melt or softening region Where
the viscosity is relatively low near the tempera-
ture region where the addition reaction occurs,
moderate to lowpressure is required during pro-
cessing to consolidate the part being fabricated.
Polyimides are nding wide applications be-
cause of their unusual properties. The polyun-
ides derived from aromatic dianhydrides and ar-
omatic diarnines containing stable exible units
in the backbone exhibit:
0 High thermal and thermo-oxidative stability
up to 400 C (750 F )
0 Excellent mechanical properties, both at room
temperature and elevated temperatures
0 F ilm- and ber-forming ability
0 Excellent adhesive properties, both at room
temperature and elevated temperature
Nonamrnabilitywill not support combus-
U011
F luorine-containing polyimides exhibit the
properties listed previously, as well as low di-
electric constant. Polyimides containing func-
Table 2 Applications of polyimides by
industry
I as-?2 t! r--._-_ .-___- _. evrlisatiaes
Electronics F lexible circuits
F lexible connectors
Chip carriers
Tape automated bonding
High-density interconnect applications
Photosensitive polyimides
Wire insulation
Motor windings
Electrical switches
Structural adhesives
Structural composites
F oam insulation
Bushings
i Bafes
F langed bearings
~ Thrust washers
Thrust discs
Seal rings '
Electrical switches
Pacemakers
Eye lens implants
Abrasive cutting wheels
Membranes
Rockets
Spacecraft (composite, adhesives,
. coatings) p
Military applications Composites, adhesives, coatings
Manufacturing Discs in compressor valve systems
Aircraft
Automobile
Medical
Machining
Gas purication
Aerospace i
Table 3 Applications of high-temperature
polyimide composites in aircraft engines
Sector Applications
Military engines Stator vanes
Shrouds (fan section)
External nozzle aps
Bushings
Bearings A _
Table 1 General attributes of condensation (thermoplastic) and addition-type (cross- immediate cases
linked) polyimides guslglsmer ducts
- K WK - r r - an 'L1Ci.'S K
Polyhnitieltyrpewlw if Jwwli pwppndvantages W WW p Disadvantages ~ Nose cones
W C A if L *; * C Commercial engines Core cowls (nacelles)
Condensation (thermoplastic) Thermoplastic (reprocessability) Poor processabihty Union n S (Variabk vane actuaen
Moderate to high glass transition temperatures (Tg) Volatiles released in processing System? =
Toughness S I -liglipressure rerljuired in processing Q Stator Vans (1OW_presS,_m_,
Excellent thermal and thermo-oxidative stability Compressor)
Addition-type (cross-linked) Processability ' Limited reprocessability EXtgma1S_ge$ box housing and
CTOSS l.l.I 1kCl Supyeft 511-ugturgs
Hi h T Poor thermal and thermo-oxidative stability Washers
g s
No volatiles in processing 7 Bushings
Bearin s Low pressure required in processing ' g
lint ,.
.,,
Z
2
l
ll '.
gr
l
1
ll

KM El;
https://polycomp.mse.iastate.edu/files/2012/01/7-Polyimide-Resins.pdf
From: ASM Handbook Volume 21, Composites (ASM International)
Published: 2001
Pages: 105 - 119 (15)
http://www.asminternational.org/about/foundation/news/-/journal_content/56/10192/ASMHBA0003365/BOOK-ARTICLE
106 / Constituent Materials
tional or pendant groups in the backbone of the Since the mid-1980s, the application areas for
' ' ' r ' ' ' ' ' tut ol imides have continually aromatic dranhydnde or/and diarrnne Xl'1llJ1lI high-tempera e p y
some of the properties listed previously, as well grown. This 1S because of the ability to vary the
. . . . . V I Q ;
as selective gas permeability. polymer structure, thereby lI 2l1lOI 1I lg the p op
*3
) () .(
HZ AI JNHZ RTE0
:21A /0= H~ < .>
C-"" "-AI "
1-1,0 or ROI -I
+ 150C HO OH &Solvent
ii i
0 0 n
RO--i.:l> < E--OR Poly (anc acid)
OH
> \
Holl t50c - saoac
Q 0
o
) 1A
N NW(N-'-Ar +
Y solvent
0 o n
Polykrde
1 General reaction for condensation polyimides. Solvents can be NMP, DMF , or m-cresol diglyme.
Table 4 Commercial polyimide materials
Developer/source
p ll/I aterial p i i p p pSnpplie1fp
DuPont
DuPont Tribon '
DuPont Electronics/Hitachi Chemical
DuPont/Cytec F iberite
BF Goodrich Aerospace
Monsanto/I ST(Japan)
Monsanto/I ST(Japan) /Cytec F iberite
Mitsui Chemical
BP Amoco
General Electric
TRW/U.S. Air F orce
TRWlU.S. Air F orce/Cytec F iberite
National Aeronautics and Space
Administration (NASA) Glenn
Resemch Center
NASA Langley Research Center!
Cytec F iberite
NASA Langley Research Center
lrnitec, I nc.
Kapton lm
Vespel parts
Vespel composites
Pyralin series (solution)
Avirnid-N (prepreg, powder)
Avirnid-K3 (prepreg, powder)
Avimid-K3B (prepreg, powder)
Avirnid-R (prepreg, powder)
Avnnid-RB (prepreg, powder)
Avimid-K3A (prepreg, powder)
Superimide 800 (solution)
Skybond 700 series
Skybond 700 series (prepreg)
Aurum (all forms)
Ultradel (solution)
Torlon (pellets)
Ultem (pellets)
AF R 700B (solution, powder)
AF R 700B (prepreg)
PMR-15 (solution, powder)
PMR-15 (prepreg)
PMRJI -50 (solution, powder)
PMR-11-50 (prepreg)
Modied PMR-15 (solution, powder)
PETI -5 (solution, powder)
PETI -5 (prepreg)
LARC RP-46 (prepreg)
LARC RP-46 (solution, powder)
LARC-SI (solution, powder)
lmitec 7'72 (solution, powder)
lmitec 927(solution, powder)
DuPont
DuPont
DuPont Tribon Composites
HD Microsystems _
Cytec F iberite
Cytec F iberite
Cytec F iber-lte -
Cytec F iberite
Cytec F iberite
Cytec F iberite
Goodrich Aerospace
I ST
Cytec F iberite, Hexcel, YLA, I nc.
Mitsui Chemical
BP Amoco
BP Amoco 1
General Electric
I rnite .I nc., Eikos, lnc., Daychern C,
Labs, I nc., SP Systems, Hy Comp,
I nc.
Cytec F iberite, SP Systems
I mitec, I nc., Eikos, I nc., Daychem
Labs, lnc., Hy Comp, inc.
Cytec F iberite, YLA, I nc.
I mitec, I r1c., Eikos, lnc., Daychem
Labs, I nc., Hy Comp, I nc.
Cytec F iberite, YLA, I nc.
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, lnc.
lmitec, I nc.
Cytec F iberite
Cytec F iberite, YLA, I nc.
lmitec, I nc., Eikos, lnc., Daychern
Labs, I nc, Hy Comp, I nc.
I mitec, lI nc., Eikos, I nc.
lmitec, I nc.
I mitec, I nc.
-
ties for specic applications. Polyirnide products
are used in a variety of applications, such as
coatings, adhesives, composite matrices, bers,
lms, foams, moldings, membrane, liquid crys
talline displays, and insulation. A list of general
application areas by industry is given in Table 2. ~
Specic applications of high-temperature poly-
irnides for aircraft are listed in Table 3. Clearly,
Table 5 Developmental high-temperature
polyimide resins
Designation, Monomer components pp Ref
BPDA/TF l\/B BPDA/TF MB
3P-Pl 3F DAjAI NH2 -
36F -Pl 6F DA]3F DA/AI NHQ -
8F -PI 8F DAlAI NH2
Ar~ 3F D AI DA/3F DAM 10-12
PTPEI PEPA/BPDA/3,4-ODAI 13, 14
APB/DPEB
PPEI PA/BPDA/3,4-ODA/ 13, 14
APB/DPEB
PE Ultem 3000 BPADA/mPDAlPEPA 15
2,2',3,3-BPDA/ BPDA/AI NHQ 16
AI NH2
BTDA/TPER BTDA/TPER 17
BPDA/TPER B?DA/TPER 18
ARDA/DABTF AI DA/3.5-DABTF 19
PMMDA/AI NH2 PDMDA/AI NHQ 20
PMR-15 replacement BTDA/3,3DDS/NE 21
BTDA/BAPP/NE 22
BTDA/BAXI NE 23, 24
BTDA/DMBZ I NE 25, 26
BTDA/BABN/NE 23, 2'7
BTDA/BPAP/NE 23, 2'7
BTDA/BI SP/NE 28
BTDA/1,2,4- 29
GBABTF /NE
BTDA/3,5-DABTF /NE 29
BTDA/MCs/NE 29
BTDA/TAB/NE 30, 31
BTDA/APB/NE 31 /
BNDA/AI NH2/NE
PBDA/AI NH2/NE
AI DA/TMBZ /NE 23, 31, 33
3F DA/AI NH2/NE 34, 35
PTPEI , pendant, terminal phenylethynyl imide ollgomer; PPEI , pendant
phenylethynyl imide oligomer; 3F DA, 4,4-(2,2,2-t1"iuoro-1-phenyle-
thylidene) diphthalic anhydride or dimethyl ester; PEPA, 4~ phenylethy-
nylphthalic anhydride; BPDA, 3,3',-4,4-bipheny'l-tetracarboxylic diari-
hydride or dimethyl ester; 3,4-ODA, 3,4-oxydianiline; DPEB,
3,5-diarnino-4-phenylethynyl benzophenone; p-PDA, para-phenylene~
diamine; 6F DA, 4,4-(l,1,1,3,3,3-hexaoroisopropylidene) diphthalic
anhydride or dimethyl ester; 8F DA, 4,4-(2,2,2~ triiluoro-l-pentauoro-
phenylethylidene) dipthalic anhydride; BTDA, 3,3-4,4-benzophenone
tetracarboxylic acid dianhydride or dimethyl ester; TF MI B, 2,2'-trifluo-
romethyl biphenylene diarnine or 2,2-bis(triuoromethyl) benzidene;
BisP, 1,3-bis (4-aminophenylisopropylidene) benzene; BAX, 1,4-bis (4'-
arnino benzyl) benzene; DMBZ , 2,2~ dimethylbenzidine; BNDA, 4,4-bis
(l,l-binapthyl-2-oxy, 1,1-binepthyl2,2-oxy) dipthalic anhydride or di-
rnethyl ester; BAPP, 2,2bis (4-aminophenoxyphenyl) propane; ArDA,
aromatic dianhydrides; 3F DAM, 4,4-(2,2,2,-triuoro-1-phcnylethyli
dene) diphenyl diarnine; NE, dirnethyl ester of 5-norbomene 1,2-dicar~
boxylic acid; PBDA, 4,4-( 1,1-biphenyl-2-oxy) diphthalic anhydride or
diniethyl ester; APB, 1,3~ (4,4'~ aminopbenoxy) benzene; AI NHZ , aro-
matic diamines; TAB, l,3,5-tris (4-aminophenoxy) benzene; BPADA,
2,2' bis(pheno> ty isopropylidene) 4,4-diphthalic anydride or Bisphenol
A-4,4-diphthalic aniiydride; TPER, 1,3-bis (4a1nir1ophenoxy) benzene;
ll/iCs, l,3 and 1,4 bis (aminobenzyl and aminobenzoyl) benzenes; 1,2,4
OBABTF , 4,4-oxybis (3-triuoromet.hy1) benzamine; 3,5,-DABTF , 3,5-
diarninobenzotriflnoride; PDMDA, 3,3-bis (3,4-dicarboxyphenoxy) di
phenylmethane dianhydride; 'll\/Q BZ , 2,2',6,6'-tetramethylbenzidiue;
2,2,-B-PDA, 2,2,3,3,-biphenyltetracarboxylic dianhyclride or dimethy-
lester; PE, plienylethynyl end-capped; PPQ , polyphenylquinoxaline (so-
lution sample from H. I -lergemtother, NASA Langley Research Center) ;
I P-600, ethynyl end-capped irnide oligomer (no longer commercially
available) ; L~ 2{) , BTDAI 4-BDAF 4,4-(p aminophenoxyphenyl~ hexaf-
luoroisopropylidene) ; L-36, BTDA/4-BDAF 4,4-(p-aminophenoxy
phenyl~ hexauoroisopropylidene) ; Sixef~ 1-14, 6F DA/6F DAM, 2,2-(4~
arninophenyl) -hexauoroisopropylidene) ; ?BI , polybenzirnidazole
\OU1U1_:-~
OQ OOJQ
.5
-l= -
27, 30, 32
27, 30, 32
wtwemrnwlnt
uulv-Mina: n.ul~ .o..w:,..
t. m._m1.b.c< .,.> ..u,
.4 Y 1'-\ > v4n~ 4\ l\ '\ > * 4\ uW-irn _ vv-v/-v
106 / Constituent Materials
tional or pendant groups in the backbone of the Since the mid-1980s, the application areas for
aromatic dianhydride or/and diamine exhibit high-temperature polyirnides have continually
some of the properties listed previously, as well grown. This is because of the ability to vary the
as selective gas permeability. polymer structure, thereby tailoring the proper~
YYO
+HZ AI NHZ RTt0
R0--ll ll) -"OR Pol (amic acid)
(> 4 Y .
OH
Q ,-to
C-_h~ Ar'
H20 or ROH
&Solvent
153C Ho____. if-Q H
0 9 n
"' ll 150C - some
Q O
O
lk +H20
NYAYTN solvlpent
O O n
Polyimide
F ig. 1 General reaction for condensation polyimides. Solvents can be NMP, DMF , or m-cresol diglyme.
Table 4 Commercial polyimide materials
Developer/source Material i p p (Supplier i
DuPont
DuPont'Tribon ' 3 '5
DuPont Electronics/Hitachi Chemical
DuPont/Cytec F iberite
BF Goodrich Aerospace
Monsanto/I ST(Japan)
Monsanto/I ST(Japan) /Cytec F iberite
Mitsui Chemical
BP Amoco
General Electric
TRW/U.S. Air F orce
TRW/U.S. Air F orce/Cytec F iberite
National. Aeronautics and Space
Administration (NASA) Glenn
Research Center
NASA Langley Research Centerl
Cytec F iberite
NASA Langley Research Center
I mitec, I nc.
Kapton lm
Vespel parts
Vespel composites
Pyralin series (solution)
Avimid-N (prepreg, powder)
Avirnid-K3 (prepreg, powder)
Avirnid-K3B (prepreg, powder)
Avimid-R (prepreg, powder)
Avimid-RB (prepreg, powder)
Avimid~ K3A (prepreg, powder)
Superimide 800 (solution)
Skybond 700 series
Skybond 700 series (prepreg)
Aurum (all forms)
Ultradel (solution)
Torlon (pellets)
Ultem (pellets)
AF R 700B (solution, powder)
AF R 700B (prepreg)
PMR-15 (solution, powder)
PMR- 15 (prepreg)
PMR-I I -50 (solution, powder)
PMR-I I -50 (prepreg)
Modied PMR-15 (solution, powder)
PET! -5 (solution, powder)
PETI ~ 5 (prepreg)
LARC RP-46 (prepreg)
LARC RP-46 (solution, powder)
LARC~ SI (solution, powder)
lmitec 772 (solution, powder)
lmitec 927(solution, powder)
DuPont
DuPont
DuPont Tribon Composites
HD Microsystems
Cytec F iberite
Cytec F iberite
Cytec F iberite t
Cytec F iberite
Cytec F iberite
Cytec F iberite
Goodrich Aerospace
I ST
Cytec F iberite, Hexcel, YLA, I nc.
Mitsui Chemical
BP Amoco
BP Amoco ~
General Electric
I mitec, I nc., Eilcos, I nc., Daychem
Labs, I nc., SP Systems, Hy Comp,
I nc.
Cytec F iberite, SP Systems
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
Cytec F iberite, YLA, lnc.
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
Cytec F iberite, YLA, I nc.
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
I mitec, I nc.
Cytec F iberite
Cytec F iberite, YLA, I nc.
lmitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
I mitec, I nc., Bikos, I nc.
I mitec, I nc.
I mitec, I nc.
ties for specic applications. Polyimide products
are used in a variety of applications, such as
coatings, adhesives, composite matrices, bers,
lms, foams, moldings, membrane, liquid crys-
talline displays, and insulation. A list of general
application areas by industry is given in Table 2.
Specic applications of high-temperature poly-
imides for aircraft are listed in Table 3. Clearly,
Table 5 Developmental high-temperature
polyimide resins
Designation Monomer components p p Ref
BPDA/TF l\ /I B BPDA/TF MB
3F -PI 3F DA/AI NH2 -
36F -Pl 6F DA/3F DA/ArNH2 -
8F -PI 8F DA/AI NH2
Ar~ 3F D AI DA/3F DAM 10-12
PTPEI PEPA/BPDA13,4-ODA/ 13, 14
APB/DPEB
PPEI PA/BPDA/3,4'-ODA/ 13, 14
APB/DPEB
PE Ultem 3000 BPADA/mPDA/PEPA 15
2,2',3,3'~ BPDA/ BPDA/AI NH2 16
AI NI -I 2
BTDA/TPER BTDA/TPER 17
BPDAI TPER BPDA/TPER 18
ARDA/DABTF ArDA/3.5~ DABTF 19
PMMDA./MNH2 PDMDA/AI NHQ 20
PMR-15 replacement BTDA/3,3DDS/NE 21
BTDA/BAPP/NE 22
BTDA/BAX/NE 23, 24
BTDA/DMBZ /NE 25, 26
BTDA/BABN/NE 23, 27
BTDA/BPAP/NE 23, 2'7
BTDA/BI SP/NE 28
BTDA/l,2,4- 29
OBABTF /NE
BTDA/3,5-DABTF /NE 29
BTDA/MCs/NE H 29
BTDA/TAB/NE 30, 31
BTDA/APB/NE 31 /
BNDA/AI NH2/NE 27, 30, 32
PBDA/AI NH2/NE 27, 30, 32
ArDA/TMBZ /NE 23, 31, 33
3F DA/AI NH2/NB 34, 35
PTPEI , pendant, terminal phenylethynyl imide oligomer; PPEI , pendant
phenylethynyl imide oligomer; 3F DA, 4,4-(2,2,2-triuoro-1-phenyle-
thylidene) cliphthalic anhydride or dimethyl ester; PEPA, 4- phenylethy-
nylphthalic anhydride; BPDA, 3,3',4,4-biphenyl-tetracarboxylic diari-
hydride or dimethyl ester; 3,4-ODA, 3,4-oxydianiline; DPEB,
3,5-diamino4-phenylethynyl benzophenone; p-PDA, para-phenylene
diamine; 6F DA, 4,4-( 1,1,1,3,3,3-hexailoroisopropylidene) diphthalic
anhydride or dimethyl ester; 8F DA, 4,4'-(2,2,2-triuoro-l-pentauoro-
phenylethylidene) dipthalic anhydride; BTDA, 3,3-4,4-benzophenone
tetracarboxylic acid dianhydride or dimethyl ester; TF MB, 2,2-triuo-
romethyl biphenylene diamine or 2,2'-bis(triuoromethy1) benzidene;
BisP, 1,3-bis (4'-aminophenylisopropylidene) benzene; BAX, 1,4-bis (4'-
amino benzyl) benzene; DMBZ , 2,2~ dimethylbenzidine; BNDA, 4,4-bis
( 1,1-binapthyi-2-oxy, 1,1-binepthy1 2,2-oxy) dipthalic anhydride or di-
methyl ester; BAPP, 2,2~ bis (4-aminophenoxyphenyl) propane; ArDA,
aromatic dianhydrides; 31-DAM, 4,4'-(2,2,2,-triuoro-1-phenylethyli-
dene) diphenyl diarnine; NE, dimethyl ester of 5-norbornene 1,2-dicar~
boxylic acid; PBDA, 4,4-( 1,1-biphenyl-2-oxy) diphthalic anhydride or
dimethyl ester; APB, 1,3(4,4'~ aminophenoxy) benzene; AI NHZ , aro-
matic diamines; TAB, l,3,5~ tris (4-arninophenoxy) benzene; BPADA,
2,2-bis(phenoxy isopropylidene) 4,4-diphthalic anydride or Bisphenol
A-4,4-diphthalic anhydride; TPER, 1,3-bis (4-aroinophenoxy) benzene;
MCs, 1,3 and 1,4 bis (aminobenzyl and aminobenzoyl) benzenes; 1,2,4-
OBABTF , 4,4-oxybis (3-triuoromethyl) benzamine; 3,5,-DABTE 3,5-
diaminobenzotriuoride; PDMDA, 3,3-bis (3,4-dicarboxyphenoxy) di-
phenylmethaue dianhydrlde; TMBZ , 2,2,6,6-tetramethylbenzidine;
2,2,-BPDA, 2,2,3,3',-biphenyltetracarboxylic dianhydride or dimethy-
lester; PE, phenylethynyl end-capped; PPQ , polyphenylquinoxaline (so-
lution sample from H. Hergemrother, NASA Langley Research Center) ;
I P-600, ethynyl end-capped irnide oligomer (no longer connznercially
available) ; L~ 20, BTDAI 4-BDAF 4,4~ (p~ aminophenoxyphenyl~ hexaf-
luoroisopropylidene) ; L-30, BTDA/4 BDAF 4,4-(p-aminophenoxy
phenyl-hexauoroisoprcpylidene) ; Sixef-44, 6F DA/6F DAM, 2,2-(4~
aminophenyl) -hexauoroisopropylidene) ; PBI , polybenzimidazole
\ OU1U1r-A
OOOOEJ
P J5-

.4 Y 1'-\ > v4n~ 4\ l\ '\ > * 4\ uW-irn _ vv-v/-v


106 / Constituent Materials
tional or pendant groups in the backbone of the Since the mid-1980s, the application areas for
aromatic dianhydride or/and diamine exhibit high-temperature polyirnides have continually
some of the properties listed previously, as well grown. This is because of the ability to vary the
as selective gas permeability. polymer structure, thereby tailoring the proper~
YYO
+HZ AI NHZ RTt0
R0--ll ll) -"OR Pol (amic acid)
(> 4 Y .
OH
Q ,-to
C-_h~ Ar'
H20 or ROH
&Solvent
153C Ho____. if-Q H
0 9 n
"' ll 150C - some
Q O
O
lk +H20
NYAYTN solvlpent
O O n
Polyimide
F ig. 1 General reaction for condensation polyimides. Solvents can be NMP, DMF , or m-cresol diglyme.
Table 4 Commercial polyimide materials
Developer/source Material i p p (Supplier i
DuPont
DuPont'Tribon ' 3 '5
DuPont Electronics/Hitachi Chemical
DuPont/Cytec F iberite
BF Goodrich Aerospace
Monsanto/I ST(Japan)
Monsanto/I ST(Japan) /Cytec F iberite
Mitsui Chemical
BP Amoco
General Electric
TRW/U.S. Air F orce
TRW/U.S. Air F orce/Cytec F iberite
National. Aeronautics and Space
Administration (NASA) Glenn
Research Center
NASA Langley Research Centerl
Cytec F iberite
NASA Langley Research Center
I mitec, I nc.
Kapton lm
Vespel parts
Vespel composites
Pyralin series (solution)
Avimid-N (prepreg, powder)
Avirnid-K3 (prepreg, powder)
Avirnid-K3B (prepreg, powder)
Avimid-R (prepreg, powder)
Avimid-RB (prepreg, powder)
Avimid~ K3A (prepreg, powder)
Superimide 800 (solution)
Skybond 700 series
Skybond 700 series (prepreg)
Aurum (all forms)
Ultradel (solution)
Torlon (pellets)
Ultem (pellets)
AF R 700B (solution, powder)
AF R 700B (prepreg)
PMR-15 (solution, powder)
PMR- 15 (prepreg)
PMR-I I -50 (solution, powder)
PMR-I I -50 (prepreg)
Modied PMR-15 (solution, powder)
PET! -5 (solution, powder)
PETI ~ 5 (prepreg)
LARC RP-46 (prepreg)
LARC RP-46 (solution, powder)
LARC~ SI (solution, powder)
lmitec 772 (solution, powder)
lmitec 927(solution, powder)
DuPont
DuPont
DuPont Tribon Composites
HD Microsystems
Cytec F iberite
Cytec F iberite
Cytec F iberite t
Cytec F iberite
Cytec F iberite
Cytec F iberite
Goodrich Aerospace
I ST
Cytec F iberite, Hexcel, YLA, I nc.
Mitsui Chemical
BP Amoco
BP Amoco ~
General Electric
I mitec, I nc., Eilcos, I nc., Daychem
Labs, I nc., SP Systems, Hy Comp,
I nc.
Cytec F iberite, SP Systems
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
Cytec F iberite, YLA, lnc.
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
Cytec F iberite, YLA, I nc.
I mitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
I mitec, I nc.
Cytec F iberite
Cytec F iberite, YLA, I nc.
lmitec, I nc., Eikos, I nc., Daychem
Labs, I nc., Hy Comp, I nc.
I mitec, I nc., Bikos, I nc.
I mitec, I nc.
I mitec, I nc.
ties for specic applications. Polyimide products
are used in a variety of applications, such as
coatings, adhesives, composite matrices, bers,
lms, foams, moldings, membrane, liquid crys-
talline displays, and insulation. A list of general
application areas by industry is given in Table 2.
Specic applications of high-temperature poly-
imides for aircraft are listed in Table 3. Clearly,
Table 5 Developmental high-temperature
polyimide resins
Designation Monomer components p p Ref
BPDA/TF l\ /I B BPDA/TF MB
3F -PI 3F DA/AI NH2 -
36F -Pl 6F DA/3F DA/ArNH2 -
8F -PI 8F DA/AI NH2
Ar~ 3F D AI DA/3F DAM 10-12
PTPEI PEPA/BPDA13,4-ODA/ 13, 14
APB/DPEB
PPEI PA/BPDA/3,4'-ODA/ 13, 14
APB/DPEB
PE Ultem 3000 BPADA/mPDA/PEPA 15
2,2',3,3'~ BPDA/ BPDA/AI NH2 16
AI NI -I 2
BTDA/TPER BTDA/TPER 17
BPDAI TPER BPDA/TPER 18
ARDA/DABTF ArDA/3.5~ DABTF 19
PMMDA./MNH2 PDMDA/AI NHQ 20
PMR-15 replacement BTDA/3,3DDS/NE 21
BTDA/BAPP/NE 22
BTDA/BAX/NE 23, 24
BTDA/DMBZ /NE 25, 26
BTDA/BABN/NE 23, 27
BTDA/BPAP/NE 23, 2'7
BTDA/BI SP/NE 28
BTDA/l,2,4- 29
OBABTF /NE
BTDA/3,5-DABTF /NE 29
BTDA/MCs/NE H 29
BTDA/TAB/NE 30, 31
BTDA/APB/NE 31 /
BNDA/AI NH2/NE 27, 30, 32
PBDA/AI NH2/NE 27, 30, 32
ArDA/TMBZ /NE 23, 31, 33
3F DA/AI NH2/NB 34, 35
PTPEI , pendant, terminal phenylethynyl imide oligomer; PPEI , pendant
phenylethynyl imide oligomer; 3F DA, 4,4-(2,2,2-triuoro-1-phenyle-
thylidene) cliphthalic anhydride or dimethyl ester; PEPA, 4- phenylethy-
nylphthalic anhydride; BPDA, 3,3',4,4-biphenyl-tetracarboxylic diari-
hydride or dimethyl ester; 3,4-ODA, 3,4-oxydianiline; DPEB,
3,5-diamino4-phenylethynyl benzophenone; p-PDA, para-phenylene
diamine; 6F DA, 4,4-( 1,1,1,3,3,3-hexailoroisopropylidene) diphthalic
anhydride or dimethyl ester; 8F DA, 4,4'-(2,2,2-triuoro-l-pentauoro-
phenylethylidene) dipthalic anhydride; BTDA, 3,3-4,4-benzophenone
tetracarboxylic acid dianhydride or dimethyl ester; TF MB, 2,2-triuo-
romethyl biphenylene diamine or 2,2'-bis(triuoromethy1) benzidene;
BisP, 1,3-bis (4'-aminophenylisopropylidene) benzene; BAX, 1,4-bis (4'-
amino benzyl) benzene; DMBZ , 2,2~ dimethylbenzidine; BNDA, 4,4-bis
( 1,1-binapthyi-2-oxy, 1,1-binepthy1 2,2-oxy) dipthalic anhydride or di-
methyl ester; BAPP, 2,2~ bis (4-aminophenoxyphenyl) propane; ArDA,
aromatic dianhydrides; 31-DAM, 4,4'-(2,2,2,-triuoro-1-phenylethyli-
dene) diphenyl diarnine; NE, dimethyl ester of 5-norbornene 1,2-dicar~
boxylic acid; PBDA, 4,4-( 1,1-biphenyl-2-oxy) diphthalic anhydride or
dimethyl ester; APB, 1,3(4,4'~ aminophenoxy) benzene; AI NHZ , aro-
matic diamines; TAB, l,3,5~ tris (4-arninophenoxy) benzene; BPADA,
2,2-bis(phenoxy isopropylidene) 4,4-diphthalic anydride or Bisphenol
A-4,4-diphthalic anhydride; TPER, 1,3-bis (4-aroinophenoxy) benzene;
MCs, 1,3 and 1,4 bis (aminobenzyl and aminobenzoyl) benzenes; 1,2,4-
OBABTF , 4,4-oxybis (3-triuoromethyl) benzamine; 3,5,-DABTE 3,5-
diaminobenzotriuoride; PDMDA, 3,3-bis (3,4-dicarboxyphenoxy) di-
phenylmethaue dianhydrlde; TMBZ , 2,2,6,6-tetramethylbenzidine;
2,2,-BPDA, 2,2,3,3',-biphenyltetracarboxylic dianhydride or dimethy-
lester; PE, phenylethynyl end-capped; PPQ , polyphenylquinoxaline (so-
lution sample from H. Hergemrother, NASA Langley Research Center) ;
I P-600, ethynyl end-capped irnide oligomer (no longer connznercially
available) ; L~ 20, BTDAI 4-BDAF 4,4~ (p~ aminophenoxyphenyl~ hexaf-
luoroisopropylidene) ; L-30, BTDA/4 BDAF 4,4-(p-aminophenoxy
phenyl-hexauoroisoprcpylidene) ; Sixef-44, 6F DA/6F DAM, 2,2-(4~
aminophenyl) -hexauoroisopropylidene) ; PBI , polybenzimidazole
\ OU1U1r-A
OOOOEJ
P J5-

Polyimide Resins / 107


Table 6 Thermal properties of polyimides 0
K W V 0 0 W 0 K T0 W TT K K T .A}}13I 'GH1ail
Glass transition Cure
tern eratnre (T) i temperature Posteure temperature
_1__s_
Metsrif-# 1. 1 ._. C F _.
C F - C ' V Postcure time,
upper-use
temperature . Tg after postcure
C F C 4 F
6
Thermoplastic polyimides
Avimid-N (Ref 36-39) 371 700
Avimid-K (Ref 40-42) 250 480
Avirnid-K3A (Ref 40-42) 222 430
Avimid-K313 (Ref 40-42) 235 460
LARC-TPI (Ref 43) 265 510
3I @Pl(Ref58) 371 700
36F -PI (Ref 5-8) 371 700
L$0CSI (Ref44) 251 480
Uitem 1000 (Ref 45) 210 410
Skybond 700 Series (Ref 46) 330 630
Auium New TPI (Ref 4'7) 250 480
BPDA/TPMB (Ref 1-4)
F rom solution cure 290 550
Solid state cure 340 640
Kapton H (Ref 48) 360 680
Pyralin Pi 2525 (Ref 49) 320 610
Pyralin Pi 2610 (Ref 49) 400 750
Pyralin PI 2540 (Ref 49) 360 680
BP Amoco U1tradel4212 (Ref 50) 295 560
Vespel SP-I (Ref 51) 360 680
Torlon 4203 (Ref 52) 267 510
2,2,3,3-BPDA~ 4,4-ODA (Ref 16) 319 610
BTDA/TPER (Ref 17) 210 410
BPDA/TPER (Ref 18) 230 450
PDMTDA/ArNiI 2(4,4-MDA) (Ref 20) 210 410
Cross-linked polyimides
Avimid-R (Ref 53,54) 310 590
Avimid-RB (Ref 55) 348 660
PMR~ 15 (Ref 56-60) 340 640
LARC RP-46 (Ref 61, 62) 280 540
AF R 700B (Ref 63-65) 370 700
Superirnide 800 (Ref 66) 300 570
PETL-5 (Ref 13, 14) 270 520
PMR-H-30 (Ref 67-69) 350 660
VCAP-I f-50 (Ref 70) 311 590
BTDA/DMBZ /NE (Ref 25, 26) 433 810
PE Ultern 3000 (Ref 15) ' 230 450
3F DA/p-PDA/NE (Ref 35) 310 590
350 660
316 600
316 600
316 600
340 640
370 700
365 690
300 570
200 390, ... ...
330 630
300 570
I 04 10!
Q 00 --o
11 as
I 00 000
200 390
350 660
400 750
400 750
350 660
350 660
350 660
400 750
350 660
280 540
300 510
300 570
300 570
360 6807
360 680
316 600
316 600
390 730
370 700
370 700
416 780
316 600 316-400 6004750
370 700 ... ...
316 600 370 700
316 600 343 650
316 600 316 600
370 700 . . . . . .
371 700 3'70 700
416 780 8
410 770
416 780 8 405 760 316 600
407 760 316 600
225 437
225 437
225 437
300 572
0:1 000 -0-.
000 qno
0 Oil Q -
8 316 600
230 . 4-46
267 510
316 600
260 550
050 one 000
I 100
316 600
316 600
316 600
316- 600
316 600
225 0527
287 549
225 437
300 572
250 482
250 482
250 ~ 482
.. ... ... 250 " 528
... ... 250 528
395 740 316 600
395 740 300 572
455 850 316 600
385 730 316 600
... ... ... 250 482
24 390 730 316 600
126 362 680 275 527
8 420 790 275 4 527
... 250 482
20 385 730 316 600
I I ;
U) I \-3000000
the range of applications for the polyimides is a
good indication of the ability to modify molec
ular structure for specic properties. Hundreds
of research polyimide materials have been syn-
thesized over the years, but only a few we com-
mercially available at the present time. However,
many research polyimides are available from
specialty chemical houses. A partial list of avail-
able polyimides and their sources is shown in
Tables 4 and 5. i
The glass transition temperatures and upper
temperature capabilities of the two types of pol-
yimides are listed in Table 6. The thermal prop-
erties of the polyimides depend on the presence
of exible units, such -as ether, isopropylidene,
methylene, hexauoroisopropylidene, and car-
bonyl in the backbone of the polymer chain, or
bulky side groups pendant to the backbone struc-
ture. These groups can also affect solubility. Dis-
ruption of regularity by the copolymerization of
tvvo dianhydrides with two diamines also affects
solubility. I
An important consideration in the selection of
a polyimide for a composite application is resin
toughness. An interesting correlation of resin
toughness versus estimated cost is shown in Ta-
ble 7. The polyether imide (PEI ) Ultem has the
most favorable toughness/cost correlation. As
with all polyimides, this property must be bal-
anced between other properties, such as process-
ability, Tg, temperature capability, and mechan-
ical properties.
A summary of the thermo-oxidative stability
of several polyimides at 316 C (600 F ) and 371
C (700 F ) is given in Tables 8, 9, and 10. The
data clearly show that the uorinated aromatic
polyimides possess the highest thermo-oxidative
stability.
Table 7 Relationship of resin toughness to cost
A comparison of common physical and me-
chanical properties of polyimides is provided in
Table 11.
Chemistry of
Condensation-Type Polyimides
These materials, discovered in 1908 by T.M.
Bogert and R.R. Renshaw (Ref 75) and made
practical by W.M. Edwards and I .M. Robertson
W77 I nterlaminar fracture toughness
(Gk) at 23 C F ) p Approximate cost
Resin type Jfmz ft - lbffftz $/kg $/lb
Toughness
per unit cost(a)
PETI -5 4800
Avimid-K3B 1400
Avimid-N 2500
PMR 15
AF R 7002(0)
BMI 330
Ultem (PEI ) -5000 -
300 20
2500? 170?
330 230 500
100 45
1'/0 180 , 400 14
20 70
340 3
' 2
100 31
30-40 70-90 8-10
180 400 14
150 5
6 1667
(a) I nterlarninar fracture toughness (GI G) in I /1112 divided by cost in $/kg. (b) Toughness value listed with a question mark in source. Source: Ref 71
1
5
l
1
1
i.
1
Polyimide Resins / 107
Table 6 Thermal properties of polyimides .
K W V 5 5 W 5 K T5 W TT K K T .A}}13I 'GH1all
Glass transition Cure
tern erature (T) l temperature Postcure temperature
_1__s_
Me*s ie! __...- ._. C F _-
C F - C ' V Postcure time,
upper-use
temperature . Tg after postcure
C F C 4 F
6
Thermoplastic polyirnides
Avimid-N (Ref 36-39) 371 700
Avimid-K (Ref 40-42) 250 480
Avirnid-K3A (Ref 40-42) 222 430
Avimid-K313 (Ref 40-42) 235 460
LARC-TPI (Ref 43) 265 510
3f@PI (Ref58) 371 700
36F -PI (Ref 5-8) 371 700
L$0C SI (Ref44) 251 480
Ultem 1000 (Ref 45) 210 410
Skybond 700 Series (Ref 46) 330 630
Aurum New TPI (Ref 4'7) 250 480
BPDA/TPMB (Ref 1-4)
F rom solution cure 290 550
Solid state cure 340 640
Kapton H (Ref 48) 360 680
Pyralin Pl 2525 (Ref 49) 320 610
Pyralin PI 2610 (Ref 49) 400 750
Pyralin PI 2540 (Ref 49) 360 680
BP Amoco Ultradel 4212 (Ref 50) 295 560
Vespel SP-1(Ref 51) 360 680
Torlon 4203 (Ref 52) 267 510
2,2,3,3-BPDA-4,4,-ODA (Ref 16) 319 610
BTDA/TPER (Ref 17) 210 410
BPDA/TPER (Ref 18) 230 450
PDMTDA/ArNlI 2(4,4-MDA) (Ref 20) 210 410
Cross-linked polyimides
Avimid-R (Ref 53,54) 310 590
Avirnid-RB (Ref 55) 348 660
PMR-15 (Ref 56-60) 340 640
LARC RP-46 (Ref 61, 62) 280 540
AF R 700B (Ref 6365) 370 700
Superimide 800 (Ref 66) 300 570
PET1-5 (Ref 13, 14) 270 520
PMR-11-30 (Ref 67-69) 350 660
VCAP-I f-50 (Ref 70) 311 590
BTDA/DMBZ /NE (Ref 25, 26) 433 810
PE Ultern 3000 (Ref 15) ' 230 450
3F DA/p-PDA/NE (Ref 35) 310 590
350 660
316 600
316 600
316 600
340 640
370 700
365 690
300 570
200 390, ... ...
330 630
300 570
I 04 10!
Q 00 --o
at as
I 00 000
200 390
350 660
400 750
400 750
350 660
350 660
350 660
400 750
350 660
2so 540
300 510
300 570
300 570
360 6805
360 680
316 600
316 600
390 730
370 700
370 700
416 780
316 600 316-400 6004750
370 700 ... ...
316 600 370 700
316 600 343 650
316 600 316 600
370 700 . . . . . .
371 700 3'70 700
416 780 8
410 770
416 780 8 405 760 316 600
407 760 316 600
225 437
225 437
225 437
300 572
0:1 000 -0-.
000 qno
0 Oil Q -
8 316 600
230 . 4-46
267 510
316 600
260 550
050 sun 000
I 100
316 600
316 600
316 600
316- 600
316 600
225 1527
287 549
225 437
300 572
250 482
250 482
250 ~ 482
.. ... ... 250 " 528
... ... 250 528
395 740 316 600
395 740 300 572
455 850 316 600
385 730 316 600
... ... ... 250 482
24 390 730 316 600
s 126 362 680 275 527
8 420 790 275 4 527
... 250 482
20 385 730 316 600
I lu
U) I \ -3000000
the range of applications for the polyimides is a
good indication of the ability to modify molec-
ular structure for specic properties. Hundreds
of research polyimide materials have been syn-
thesized over the years, but only a few we com-
mercially available at the present time. However,
many research polyimides are available from
specialty chemical houses. A partial list of avail-
able polyimides and their sources is shown in
Tables 4 and 5. i
The glass transition temperatures and upper
temperature capabilities of the two types of pol-
yimides are listed in Table 6. The thermal prop-
erties of the polyimides depend on the presence
of exible units, such -as ether, isopropylidene,
methylene, hexafluoroisopropylidene, and car-
bonyl in the backbone of the polymer chain, or
bulky side groups pendant to the backbone struc-
ture. These groups can also affect solubility. Dis-
ruption of regularity by the copolymerization of
two dianhydrides with two diamines also affects
solubility. .
An important consideration in the selection of
a polyimide for a composite application is resin
toughness. An interesting correlation of resin
toughness versus estimated cost is shown in Ta-
ble 7. The polyether inside (PEI ) Ultem has the
most favorable toughness/cost correlation. As
with all polyirnides, this property must be bal-
anced between other properties, such as process-
ability, Tg, temperature capability, and mechan-
ical properties.
A summary of the thernao-oxidative stability
of several polyirnides at 316 C (600 F ) and 371
C (700 F ) is given in Tables 8, 9, and 10. The
data clearly show that the uorinated aromatic
polyimides possess the highest thermo-oxidative
stability.
Table 7 Relationship of resin toughness to cost
A comparison of common physical and me-
chanical properties of polyimides is provided in
Table 11.
Chemistry of
Condensation-Type Polyimides
These materials, discovered in 1908 by T.M.
Bogert and R.R. Renshaw (Ref 75) and made
practical by W.M. Edwards and I .M. Robertson
W5 5 I nterlaminar fracture toughness
(Gk) at 23 C F ) p Approximate cost
Resin type Jfmz ft - lbffftz $/kg $/lb
Toughness
per unit cost(a)
PETI -5 4800
Avimid-K3B 1400
Avimid-N 2500
PMR 15
AF R 700B(b)
BMI 330
Ultern (PEI ) -5000 ~
300 20
2500? 170?
330 230 500
too 45
1'/0 180 400 14
20 70
340 3
' 2
100 31
30-40 70-90 8-10
180 400 14
150 5
6 1667
(a) I nterlarninar fracture toughness (GI G) in I /1112 divided by cost in $/kg. (b) Toughness value listed with a question mark in source. Source: Ref 71
1
l
l
\
z
i.
l
Polyimide Resins / 107
Table 6 Thermal properties of polyimides .
K W V 5 5 W 5 K T5 W TT K K T .A}}13I 'GH1all
Glass transition Cure
tern erature (T) l temperature Postcure temperature
_1__s_
Me*s ie! __...- ._. C F _-
C F - C ' V Postcure time,
upper-use
temperature . Tg after postcure
C F C 4 F
6
Thermoplastic polyirnides
Avimid-N (Ref 36-39) 371 700
Avimid-K (Ref 40-42) 250 480
Avirnid-K3A (Ref 40-42) 222 430
Avimid-K313 (Ref 40-42) 235 460
LARC-TPI (Ref 43) 265 510
3f@PI (Ref58) 371 700
36F -PI (Ref 5-8) 371 700
L$0C SI (Ref44) 251 480
Ultem 1000 (Ref 45) 210 410
Skybond 700 Series (Ref 46) 330 630
Aurum New TPI (Ref 4'7) 250 480
BPDA/TPMB (Ref 1-4)
F rom solution cure 290 550
Solid state cure 340 640
Kapton H (Ref 48) 360 680
Pyralin Pl 2525 (Ref 49) 320 610
Pyralin PI 2610 (Ref 49) 400 750
Pyralin PI 2540 (Ref 49) 360 680
BP Amoco Ultradel 4212 (Ref 50) 295 560
Vespel SP-1(Ref 51) 360 680
Torlon 4203 (Ref 52) 267 510
2,2,3,3-BPDA-4,4,-ODA (Ref 16) 319 610
BTDA/TPER (Ref 17) 210 410
BPDA/TPER (Ref 18) 230 450
PDMTDA/ArNlI 2(4,4-MDA) (Ref 20) 210 410
Cross-linked polyimides
Avimid-R (Ref 53,54) 310 590
Avirnid-RB (Ref 55) 348 660
PMR-15 (Ref 56-60) 340 640
LARC RP-46 (Ref 61, 62) 280 540
AF R 700B (Ref 6365) 370 700
Superimide 800 (Ref 66) 300 570
PET1-5 (Ref 13, 14) 270 520
PMR-11-30 (Ref 67-69) 350 660
VCAP-I f-50 (Ref 70) 311 590
BTDA/DMBZ /NE (Ref 25, 26) 433 810
PE Ultern 3000 (Ref 15) ' 230 450
3F DA/p-PDA/NE (Ref 35) 310 590
350 660
316 600
316 600
316 600
340 640
370 700
365 690
300 570
200 390, ... ...
330 630
300 570
I 04 10!
Q 00 --o
at as
I 00 000
200 390
350 660
400 750
400 750
350 660
350 660
350 660
400 750
350 660
2so 540
300 510
300 570
300 570
360 6805
360 680
316 600
316 600
390 730
370 700
370 700
416 780
316 600 316-400 6004750
370 700 ... ...
316 600 370 700
316 600 343 650
316 600 316 600
370 700 . . . . . .
371 700 3'70 700
416 780 8
410 770
416 780 8 405 760 316 600
407 760 316 600
225 437
225 437
225 437
300 572
0:1 000 -0-.
000 qno
0 Oil Q -
8 316 600
230 . 4-46
267 510
316 600
260 550
050 sun 000
I 100
316 600
316 600
316 600
316- 600
316 600
225 1527
287 549
225 437
300 572
250 482
250 482
250 ~ 482
.. ... ... 250 " 528
... ... 250 528
395 740 316 600
395 740 300 572
455 850 316 600
385 730 316 600
... ... ... 250 482
24 390 730 316 600
s 126 362 680 275 527
8 420 790 275 4 527
... 250 482
20 385 730 316 600
I lu
U) I \ -3000000
the range of applications for the polyimides is a
good indication of the ability to modify molec-
ular structure for specic properties. Hundreds
of research polyimide materials have been syn-
thesized over the years, but only a few we com-
mercially available at the present time. However,
many research polyimides are available from
specialty chemical houses. A partial list of avail-
able polyimides and their sources is shown in
Tables 4 and 5. i
The glass transition temperatures and upper
temperature capabilities of the two types of pol-
yimides are listed in Table 6. The thermal prop-
erties of the polyimides depend on the presence
of exible units, such -as ether, isopropylidene,
methylene, hexafluoroisopropylidene, and car-
bonyl in the backbone of the polymer chain, or
bulky side groups pendant to the backbone struc-
ture. These groups can also affect solubility. Dis-
ruption of regularity by the copolymerization of
two dianhydrides with two diamines also affects
solubility. .
An important consideration in the selection of
a polyimide for a composite application is resin
toughness. An interesting correlation of resin
toughness versus estimated cost is shown in Ta-
ble 7. The polyether inside (PEI ) Ultem has the
most favorable toughness/cost correlation. As
with all polyirnides, this property must be bal-
anced between other properties, such as process-
ability, Tg, temperature capability, and mechan-
ical properties.
A summary of the thernao-oxidative stability
of several polyirnides at 316 C (600 F ) and 371
C (700 F ) is given in Tables 8, 9, and 10. The
data clearly show that the uorinated aromatic
polyimides possess the highest thermo-oxidative
stability.
Table 7 Relationship of resin toughness to cost
A comparison of common physical and me-
chanical properties of polyimides is provided in
Table 11.
Chemistry of
Condensation-Type Polyimides
These materials, discovered in 1908 by T.M.
Bogert and R.R. Renshaw (Ref 75) and made
practical by W.M. Edwards and I .M. Robertson
W5 5 I nterlaminar fracture toughness
(Gk) at 23 C F ) p Approximate cost
Resin type Jfmz ft - lbffftz $/kg $/lb
Toughness
per unit cost(a)
PETI -5 4800
Avimid-K3B 1400
Avimid-N 2500
PMR 15
AF R 700B(b)
BMI 330
Ultern (PEI ) -5000 ~
300 20
2500? 170?
330 230 500
too 45
1'/0 180 400 14
20 70
340 3
' 2
100 31
30-40 70-90 8-10
180 400 14
150 5
6 1667
(a) I nterlarninar fracture toughness (GI G) in I /1112 divided by cost in $/kg. (b) Toughness value listed with a question mark in source. Source: Ref 71
1
l
l
\
z
i.
l
108 / Constituent Materials
(Ref 76) , are derived from polyamic acids by
either chemical or thermal treatment over a tem-
perature range from room temperature to 370 C
(700 F ) . The polyamic acids are produced by a
series of step growth reactions at room tempera-
ture from a dianhydride or dianhydride deriva-
tive and a diamine. The general reaction for pol-
yimide formation is illustrated in F ig. 1. The
structures of several commercially available
thermoplastic polyimides are shown in F ig. 2.
Synthesis (General) . Thermoplastic polyun-
ides are prepared in dimethylacetamide (DMAC)
or N-methyl pyrrolidinone (NMP) by dissolving
the appropriate diamine in the solvent at room
temperature under nitrogen. The dianhydride is
added as a solid or a slurry in the solvent while
stirring over a period of one-half hour. The re-
action is allowed to continue from 6 to 24 h
while stirring under ambient conditions, depend-
ing on the relative reactivities of the diamiues
and dianhydride. The polyamide acid solution
thus produced can be sampled for determination
of intrinsic viscosity or analyzed by gel penne-
ation chromatography (GPC) for molecular
weight or analyzed by other methods as required.
The polyamide acid solution can be used to pre-
pare polyamide acid or polyimide powder, thin
lms, sup-ported adhesive tape, and to impreg-
nate unidirectional carbon ber, carbon cloth, or
other ber/cloth substrate.
Alternatively, thermoplastic polyimides can
also be prepared by dissolving the dialkyl ester
(methyl, ethyl, or isopropyl) of the dianhydride
in ethanol at room temperature, followed by the
addition of the aromatic diamine. This polyimide
precursor solution can also be used to prepare
powder, thin lms, supported adhesive tape, and
impregnated carbon ber, carbon cloth, or other
ber/cloth substrate. The polyamide acid can be
converted to the polyimide by thermal methods
or by chemical methods, described subsequently.
Processing of Polyamicle Acid Precursor
Solution to Polyimide. The polyamide acid so-
lution can be converted thermally in solution to
the polyimide by: the addition of a sufficient
quantity ' of toluene or o-xylene, followed by
azeotropic distillation of water in a Dean-Stark
trap overnight; by reuxing the polyamide acid
solution containing 1to 2 wt% isoquinoline cat-
alyst (based on solvent) for 6 h; or by the addi-
tion of ten-fold excess of acetic anhydride with
pyridine or triethylamine catalyst at a 4 to 1
weight ratio, followed by heating at 100 C (210
F ) for 3 h.
The polyamic acid solution can also be pre-
pared in m~ cresol solvent instead of1 DMAC. or
NMP at room temperature and converted to the
polyimide by reuxing at 200 C (390 F ) with
or without a catalyst (1to 2 Wt% isoquinoline
based on m-cresol) for 4 h. The polyimide pow-
der is isolated as described in the following par-
agraphs.
NMP or Dl\/LAC polyamic acid solution is
added while stirring vigorously to a methanol]
water (50:50) solution. The precipitated po-
lyarnic acid powder is ltered and washed again
in methanol and water, then dried at 125 C for
24 h in a vacuum, or at 200 C (390 F ) for 4 h
in vacuum. The polyamic acid powder is con-
verted to polyimide in an oven at 150 C (300
F ) for 1h +250 C (480 F ) for 1h +275 C
(525 F ) forl h. '
Alcohol solutions of the diester and diamine
composition are concentrated to a solvent-free
polyamic acid powder in a vacuum oven at 60
C (140 P) for 2 h. The polyamic acid powder
is converted thermally to polyimide powder at
150 C (300 F ) for 1 h +250 C (480 F ) for
2 h +275 C (525 F ) for 1h. A
Preparation of Polyimide F ilms from Ther-
moplastic Polyamic Acid Precursors. Centri-
fuged Nl\/[P or DMAC solutions of the polyamic
acids are cast on a clean glass plate and heated
Table 8 Thermo-oxidative stability of high-temperature polymers at 316 C (600 F ) (air
flow, 100 cm3/min, or 6 in.3/min)
Weight loss, %, after indiepted number ofhours iiiiW
Polymer (W A Cure and postpure 91 ppppif
"403 1019 2000 2927 4122
Aviinid-N (a) 0.8
p-PPQ (11) 0.7
PMR-15 (c) 2.3
I P-600 (d) 1.8
LARC-'1-PI (e) 6.8
L-20 (f) 1.9
L-30 (f) 1.5
(g)
(11)
PBX 0.4 11.5
1.0 2.1 . . . 5.3 . . .
2.9 7.7 14 20.9 28.0
2.4 4.3 9.0 10.8 15.0
Sixef 44 . . .
PMR-11-30 (1)
PMR-I 1-50 (1)
3F -PI (i)
36F -PI . . . 6)
AF R 700B (k) . . .
-we
btl
1.3 2.4 4.2 5.8 10.7
2.9 12.1 .. . 51.1 74.9
5 .7 13.4 3.4 55.4 84.9
8.2 19.8 68.5 89.2 one
12.1 19.9 . . . 46.5 82.2
6.6 21.3 72.8 100
5.8 20.9 86.1 100
* 40.8 . . 100 . . .
4.0 9.8 13.0 . . .
3.0 5.0 . . . . . .
30.0 . . . . . . --n
See Table 5 for abbreviations and denitions. (a) 316 C (600 F ) 1'1h -1- 340 C (645 F ) /4 h. (b) 325 C (615 F ) / 1 h +360 C (680 F ) /4 h. _(c) 316
C (600 F ) / 111 +316C (600 F ) / 16 h. (d) 316 C (600 F ) 2 h +375 C (705 F ) /4 h. (e) 316 C (600 F ) /1h +340 C (645 F ) /4 1'1. (1) 335 C/
1 h -1- 360 C (680 F ) /2 h (g) Sample obtained from Celanese Corp. as a 50 mm (2 in.) diam > < 6 mm (1/4 in.) thick disk. (h) Sample obtained
316 C (600 F ) /111 +370 C/
from 1-I oechst-Celanese (6F l3A/6F DAM) . (i) 316 C (600 F ) /1 11 +343 C (650 F ) /2 h +371C (700 F ) /26 h. (j)
24 h and 416 C (780 F ) /8 h. Source: Ref 7, 8, 60, 72
Table 9 Thermo-oxidative stability of polyimides at 370 C (700 F ) , 1 atm (air-circulating
oven)
lllleight lossiip , after indicatedinumber of hours(a) ; p
Resin system Cure and postcure
25 1-. 100 11 200 11 300 11 W 400 11
Avimid-N (b) 1.10 3.1
1.15 3.3
1.10 4.0
6F '-PDA-1,~ Avimicl-N(control) (b)
3F -PDA (3F -P1) (b)
Sixef 44 . (b)
PMR-H-30 (c) 2.5
PMR-11-50 (c)
(d) PMR-15 . . 5.7
no:
I ll
4 s so . . .
. . . . . . 7l.0(f)
5.0 8.0 10.0 . . .
5.9 18 (264 h) 8.0(e) . . .
4.5 11.0 (264 h) 5.5(e) 28.7
17.1 . . . 18.2(e) . . .
AF R700B . 1.57 6.4 ... ... . Co)
(b) 36F -PI 1 0.64
1.8 . . . . . . . . .
d C e and ostcure for Avimid-N, 6F F DA-13F -
Sec Table 5 for abbreviations and denitions. (a) Source: Ref 7, 8, 60, 72, except where note . (b) ur p ~ , p
PDA, 36F -PI , Sixef 44, and APR 700B: 316 C (600 F ) /1h -1- 371C (700 F ) l24 h +416 C (780 F ) /8 h. (c) Cure and postcure for PMR-I I -30
and PMR-11-50: 316 C (600 F ) /1h -1- 343 C (650 F ) l2 h +371C (700 F ) /26 h. (cl) Cure and postcure for PMR-15: 316 C (600 F ) /17h +
371C (700 F ) /24 h. (e) Source: Ref 73. (f) Source: Ref 74. PMR-I I -50 postcured 371C (700 F ) /18 1:1. 61-3-PDA and 3F -PDA postcured 371C
(700 F ) i8 h. Phthalic anhydride end-capped (aging conditions, not stated) . Source: Ref 7, 8, 60, 72, 73, 74
Table 10 Thermo-oxidative stability of polyimides at 371C (700 F ) , 4 atm (air flow, 100
cm?/min, or 6 in?/min)
5 5 T 9 if if Weight loss, %, after indicated number of hours
I . , l1,.8.(f) ,,__._. _.
Resin system Cure and postcure 10 11 25 h 5011
752
100 11
Avimid-N 1.61
6 F -PDA (control) , 1.12
3 F -PDA . a) 1.20
_ r\ r"\ f_\
8, E,
2.30
2.54
2.66
4.19
4.26
5.07
5.71
7.55
6.10
7.65
8.50
10.5
12.2
12.1
15.1
PMR-ll-30 (b) . . .
Pl\/H1-11-50
PMR-15
AF R 700B
36F -PDA
See Table 5 for abbreviations and denitions. (a) Cure and postcure for Aviinid-N, 6F -PDA, 3F -PDA, 36F -PDA, AF R 70013: 316 C (600 F ) f1
r\r\r""\\
(b)
C)
a)
a)
ou-
an
000
3.41 6.60 . . . . . .
6.60 1 . . . . . . 25.2
4.28 8.83 13.4 18.8
1.57 3.40 6.0 9.1
11+
370 C (700 F ) ! 24 h +416 C (780 F ) /8 h. (b) Cure and postcure for PMR-11-30 and PMR-I 1-50: 316 C (600 F ) /1h +343 C (650 F ) /2 h +
371C (700 F ) /26 11. (c) Cure and postcure for PI S/I R-15: 316 C (600 F ) il711 +371C (700 F ) 124 h. Source. Ref 8, 72
.._ 1:
*2? Kat
rd ; .> ; ,,:-*:._.32. gs) ,.1 ,1 W Hit:
111
. 1'-I . 1 . .; -1
I '.f_
'
ti I ii
= ; ii%i
-4. . 1
' I -
; '_'.il
C11
. .: .1
.~ '-fl
4 = 21-1:1
.1". Q = 1
:1
I ..,
I 55; -'1
.
.~ --.1
.-1~ .r> sY
.2 .541
' "Eli
.'F :"l'
' _'.; ; '; -l
orig
1
. :1!
T4, ! ..
.. ~ .4
J, 7-5!
"
-
'1
; = l
' 111
r ; '-< 11
.: ,.-31,
. -ill
yeti
. E,
1_I .; .\.~ ,; -8;
:_l
= .e< = '-r ,
. 13%; :
"{:21
- 1:-MI .
.
l V-F :"ia" A
.
; -gs; pp: qJ7 _ W .-if gr-,1= 1.; ....2. pip
- 1_r
~ ':~ .
F -15%
1
~ ::e:>
*1
.,-_; . ; ; l,
3.1
$3
= ~
H
) -
\\
108 / Constituent Materials
(Ref 76) , are derived from polyamic acids by
either chemical or thermal treatment over a tem-
perature range from room temperature to 370 C
(700 F ) . The polyarnic acids are produced by a
series of step growth reactions at room tempera-
ture from a dianhydride or dianhydride deriva-
tive and a diarnine. The general reaction for pol-
yimide formation is illustrated in F ig. 1. The
structures of several commercially available
thermoplastic polyimides are shown in F ig. 2.
Synthesis (General) . Thermoplastic polyun-
ides are prepared in dimethylacetamide (DMAC)
or N-methyl pyrrolidinone (NMP) by dissolving
the appropriate diarnine in the solvent at room
temperature under nitrogen. The dianhydride is
added as a solid or a slurry in the solvent while
stirring over a period of one-half hour. The re-
action is allowed to continue from 6 to 24 h
while stirring under ambient conditions, depend-
ing on the relative reactivities of the diamines
and dianhydride. The polyamide acid solution
thus produced can be sampled for determination
of intrinsic viscosity or analyzed by gel perme-
ation chromatography (GPC) for molecular
weight or analyzed by other methods as required.
The polyamide acid solution can be used to pre-
pare polyamide acid or polyimide powder, thin
lms, sup-ported adhesive tape, and to impreg-
nate unidirectional carbon ber, carbon cloth, or
other ber/cloth substrate.
Alternatively, thermoplastic polyimides can
also be prepared by dissolving the dialkyl ester
(methyl, ethyl, or isopropyl) of the dianhydride
in ethanol at room temperature, followed by the
addition of the aromatic diamine. This polyimide
precursor solution can also be used to prepare
powder, thin lms, supported adhesive tape, and
impregnated carbon ber, carbon cloth, or other
ber/cloth substrate. The polyamide acid can be
converted to the polyirnide by thermal methods
or by chemical methods, described subsequently.
Processing of Polyamide Acid Precursor
Solution to Polyimide. The polyamide acid so-
lution can be converted thermally in solution to
the polyirnide by: the addition of a sufficient
quantity ' of toluene or o-xylene, followed by
azeotropic distillation of Water in a Dean-Stark
trap overnight; by reuxing the polyanoide acid
solution containing 1to 2 wt% isoquinoline cat-
alyst (based on solvent) for 6 h; or by the addi-
tion of ten-fold excess of acetic anhydride with
pyridine or triethylarnine catalyst at a 4 to 1
weight ratio, followed by heating at 100 C (210
F ) for 3 h.
The polyarnic acid solution can also be pre-
pared in m~ cresol solvent instead of1 DMAC. or
NMP at room temperature and converted to the
polyirnide by reuxing at 200 C (390 F ) with
or without a catalyst (1to 2 wt% isoquinoline
based on n1-cresol) for 4 h. The polyimide pow~
der is isolated as described in the following par-
agraphs.
NMP or DMAC polyarnic acid solution is
added while stirring vigorously to a methanol]
water (50:50) solution. The precipitated po-
lyarnic acid powder is ltered and washed again
in methanol and Water, then dried at 125 C for
24 h in a vacuum, or at 200 C (390 F ) for 4 h
in vacuurn. The polyamic acid powder is con-
verted to polyimide in an oven at 150 C (300
F ) for 1h +250 C (480 F ) for 1h +275 C
(525 F ) forl h. '
Alcohol solutions of the diester and diamine
composition are concentrated to a solvent-free
polyarnic acid powder in a vacuum oven at 60
C (140 P) for 2 h. The polyamic acid powder
is converted thermally to polyimide powder at
150 C (300 F ) for 1 h +250 C (480 F ) for
2 h +275 C (525 F ) for 1h. 4
Preparation of Polyimide F ilms from Ther-
moplastic Polyamic Acid Precursors. Centri-
fuged N1\ /[ P or DMAC solutions of the polyarnic
acids are cast on a clean glass plate and heated
Table 8 Thermo-oxidative stability of high-temperature polymers at 316 C (600 F ) (air
flow, 100 cm3/min, or 6 in.3/min)
Weight loss, %, after indicated number offlrours gggg W
Polymer g y Cure and postcure 91 gggg if
67458 1019 2000 2927 4122
Avimid-N (a) 0.8
p-PPQ (b) 0.7
PMR-15 (c) 2.3
I P-600 (d) 1.8
LARC-'1-PI (e) 6.8
L-20 (1) 1.9
L-30 (f) 1.5
(s)
(11)
PBl 0.4 11.5
1.0 2.1 . . . 5.3 . . .
2.9 7.7 14 20.9 28.0
2.4 4.3 9.0 10.8 15.0
Sixef 44 . . .
PMR-11-30 (i)
PMR-I I -50 (i)
3F -PI (i)
36F -PI . . . ti)
AF R 700B (r) . . .
I 00
btl
1.3 2.4 4.2 5.8 10.7
2.9 12.1 .. . 51.1 74.9
5 .7 13.4 3.4 55.4 84.9
8.2 19.8 68.5 89.2 one
12.1 19.9 . . . 46.5 82.2
6.6 21.3 72.8 100
5.8 20.9 86.1 100
* 40.8 . . 100 . . .
4.0 9.8 13.0 . . .
3.0 5.0 . . . . . .
30.0 . . . . . . --n
See Table 5 for abbreviations and denitions. (a) 316 C (600 F ) 1'1h -i 340 C (645 F ) /4 h. (b) 325 C (615 F ) / 1 h +360 C (680 F ) /4 h. _(c) 316
C (600 F ) / 1h +316' C (600 F ) / 16 h. (d) 316 C (600 F ) 2 h +375 C (705 F ) /4 h. (e) 316 C (600 F ) /1h +340 C (645 F ) /4 h. (i) 335 C/
1 h +360 C (680 F ) /2 h (g) Sample obtained from Celanese Corp. as a 50 mm (2 in.) diam > < 6 mm (1/4 in.) thick disk. (h) Sample obtained
316 C (600 F ) /1h -1 370 C/
from 1-I oechst-Celanese (6F l3A/6F DAM) . (i) 316 C (600 F ) /1h +343 C (650 F ) /2 h +371C (700 F ) /26 h. (j)
24 h and 416 C (780 F ) /8 h. Source: Ref 7, 8, 60, 72
Table 9 Thermo-oxidative stability of polyimides at 370 C (700 F ) , 1 atm (air-circulating
oven)
Tlleight losslfip , after indicatedinumber of hours(a) ; g
Resin system Cure and postcure
25 1-. loo 11 zoo 11 300 n W 400 1;
Avirnid-N (b) 1.10 3.1
1.15 3.3
1.10 4.0
6F '-PDA-1, Avimicl-N(control) (b)
3F -PDA (3F -PI ) (b)
Sixef 44 . (b)
PMR-K-30 (c) 2.5
PMR-11-50 (c)
(d) PMR15 . . 5.7
no:
I ll
4 s so . . .
. . . . . . 71.0(f)
5.0 8.0 10.0 . . .
5.9 18 (264 h) 8.0(e) . . .
4.5 11.0 (264 h) 5.5(e) 28.7
17.1 . . . l8.2(e) . . .
AF R700B . 1.57 6.4 ... ... . Cb)
(la) 36F -PI 1 0.64
1.8 . . . . . . . . .
d C e and ostcure for Avimid-N, 6F F DA-13F -
See Table 5 for abbreviations and denitions. (a) Source: Ref 7, 8, 60, 72, except where note . (b) ur p ~ , g
PDA, 36F -PI , Sixef 44, and APR 700B: 316 C (600 F ) /1h +371C (700 F ) l24 h +416 C (780 F ) /8 h. (c) Cure and postcure for PMR-I I -30
and PMR-11-50: 316 C (600 F ) /1h +343 C (650 F ) l2 h +371C (700 F ) /26 h. (cl) Cure and postcure for PMR-15: 316 C (600 F ) /17h +
371C (700 F ) /24 h. (e) Source: Ref 73. (f) Source: Ref 74. PMR-I I -50 postcured 371C (700 F ) /18 h. 61-3-PDA and 3F -PDA postcured 371C
(700 F ) i8 h. Phthalic anhydride end-capped (aging conditions, not stated) . Source: Ref 7, 8, 60, 72, 73, 74
Table 10 Thermo-oxidative stability of polyimides at 371C (700 F ) , 4 atm (air flow, 100
cm?/min, or 6 in?/min)
3 3 7 1 if if Weight loss, %, after indicated nuinber of hours
I . , 11,.8.(f) :__., _.
Resin system Cure and postcurgeg 10 11 25 h 5011
752
106 i1
Avirnid-N 1.61
6 F -PDA (control) , 1.12
3 F -PDA . a) 1.20
_ r\ r"\ f_\
8, E,
2.30
2.54
2.66
4.19
4.26
5.07
5.71
7.55
6.10
7.65
8.50
10.5
12.2
12.1
15.1
PMR-H-30 [ b) . . .
Pl\ /H1-11-50
PMRl5
AF R 700B
36F -PDA
See Table 5 for abbreviations and denitions. (a) Cure and postcure for Avimid-N, 6F -PDA, 3F -PDA, 36F -PDA, AF R 70013: 316 C (600 F ) f1
r\ r\ r""\ \
Kb)
C)
a)
a)
ou-
an
000
3.41 6.60 . . . . . .
6.60 0 . . . . . . 25.2
4.28 8.83 13.4 18.8
1.57 3.40 6.0 9.1
11+
3'70 C (700 F ) ! 24 h +416 C (780 F ) /8 h. (b) Cure and postcure for PMR-H-30 and PMR-I I -50: 316 C (600 F ) /1h +343 C (650 F ) /2 h +
371C (700 F ) /26 h. (c) Cure and postcure for PI S/I R-15: 316 C (600 F ) i17h +371C (700 F ) 124 h. Source. Ref 8, 72
.._ q
*2? Kai
rd ; .> ; ,,:-*:._.32. M,.1 . ,1W Hit:
at 2
. 1'-I . : . .; -\
I '.f_
'
.- I ii
= ; ii%i
-4. . 1
' I -
; '_'.il
C11
. .: .1
.~ '-ti
V = 2; -:1
.1". Q = 1
:1
I ..,
I 55; -'1
.
.~ --.1
.-1~ .r> sY
.7 .541
' "iii
.'.7:"l'
' _'.; ; '; -1
srngg
1
1:1!
T4, ! ..
.. ~ .4
J, 7-5!
"
-
'1
; = l
' iii
r ; ' *1.\
.: ,.-Bi,
. -ill
est
. E,
t_I .; .= ~ ,; -< $.< ; *
:_l
= .e.< = '-r ,
. 13%; :
"eat
- 1:-MI _
.
l V-F :"l1s' A
.
; -git; pp: em ,5) _ W .-if W. 1.; .,..2. pip,
- 11-
~ ':~ .
F -15%
l
~ ::e:>
e.
.; _; .; . ; ; ; l,
.-I
$3
= ~
4

\ \
108 / Constituent Materials
(Ref 76) , are derived from polyamic acids by
either chemical or thermal treatment over a tem-
perature range from room temperature to 370 C
(700 F ) . The polyarnic acids are produced by a
series of step growth reactions at room tempera-
ture from a dianhydride or dianhydride deriva-
tive and a diarnine. The general reaction for pol-
yimide formation is illustrated in F ig. 1. The
structures of several commercially available
thermoplastic polyimides are shown in F ig. 2.
Synthesis (General) . Thermoplastic polyun-
ides are prepared in dimethylacetamide (DMAC)
or N-methyl pyrrolidinone (NMP) by dissolving
the appropriate diarnine in the solvent at room
temperature under nitrogen. The dianhydride is
added as a solid or a slurry in the solvent while
stirring over a period of one-half hour. The re-
action is allowed to continue from 6 to 24 h
while stirring under ambient conditions, depend-
ing on the relative reactivities of the diamines
and dianhydride. The polyamide acid solution
thus produced can be sampled for determination
of intrinsic viscosity or analyzed by gel perme-
ation chromatography (GPC) for molecular
weight or analyzed by other methods as required.
The polyamide acid solution can be used to pre-
pare polyamide acid or polyimide powder, thin
lms, sup-ported adhesive tape, and to impreg-
nate unidirectional carbon ber, carbon cloth, or
other ber/cloth substrate.
Alternatively, thermoplastic polyimides can
also be prepared by dissolving the dialkyl ester
(methyl, ethyl, or isopropyl) of the dianhydride
in ethanol at room temperature, followed by the
addition of the aromatic diamine. This polyimide
precursor solution can also be used to prepare
powder, thin lms, supported adhesive tape, and
impregnated carbon ber, carbon cloth, or other
ber/cloth substrate. The polyamide acid can be
converted to the polyirnide by thermal methods
or by chemical methods, described subsequently.
Processing of Polyamide Acid Precursor
Solution to Polyimide. The polyamide acid so-
lution can be converted thermally in solution to
the polyirnide by: the addition of a sufficient
quantity ' of toluene or o-xylene, followed by
azeotropic distillation of Water in a Dean-Stark
trap overnight; by reuxing the polyanoide acid
solution containing 1to 2 wt% isoquinoline cat-
alyst (based on solvent) for 6 h; or by the addi-
tion of ten-fold excess of acetic anhydride with
pyridine or triethylarnine catalyst at a 4 to 1
weight ratio, followed by heating at 100 C (210
F ) for 3 h.
The polyarnic acid solution can also be pre-
pared in m~ cresol solvent instead of1 DMAC. or
NMP at room temperature and converted to the
polyirnide by reuxing at 200 C (390 F ) with
or without a catalyst (1to 2 wt% isoquinoline
based on n1-cresol) for 4 h. The polyimide pow~
der is isolated as described in the following par-
agraphs.
NMP or DMAC polyarnic acid solution is
added while stirring vigorously to a methanol]
water (50:50) solution. The precipitated po-
lyarnic acid powder is ltered and washed again
in methanol and Water, then dried at 125 C for
24 h in a vacuum, or at 200 C (390 F ) for 4 h
in vacuurn. The polyamic acid powder is con-
verted to polyimide in an oven at 150 C (300
F ) for 1h +250 C (480 F ) for 1h +275 C
(525 F ) forl h. '
Alcohol solutions of the diester and diamine
composition are concentrated to a solvent-free
polyarnic acid powder in a vacuum oven at 60
C (140 P) for 2 h. The polyamic acid powder
is converted thermally to polyimide powder at
150 C (300 F ) for 1 h +250 C (480 F ) for
2 h +275 C (525 F ) for 1h. 4
Preparation of Polyimide F ilms from Ther-
moplastic Polyamic Acid Precursors. Centri-
fuged N1\ /[ P or DMAC solutions of the polyarnic
acids are cast on a clean glass plate and heated
Table 8 Thermo-oxidative stability of high-temperature polymers at 316 C (600 F ) (air
flow, 100 cm3/min, or 6 in.3/min)
Weight loss, %, after indicated number offlrours gggg W
Polymer g y Cure and postcure 91 gggg if
67458 1019 2000 2927 4122
Avimid-N (a) 0.8
p-PPQ (b) 0.7
PMR-15 (c) 2.3
I P-600 (d) 1.8
LARC-'1-PI (e) 6.8
L-20 (1) 1.9
L-30 (f) 1.5
(s)
(11)
PBl 0.4 11.5
1.0 2.1 . . . 5.3 . . .
2.9 7.7 14 20.9 28.0
2.4 4.3 9.0 10.8 15.0
Sixef 44 . . .
PMR-11-30 (i)
PMR-I I -50 (i)
3F -PI (i)
36F -PI . . . ti)
AF R 700B (r) . . .
I 00
btl
1.3 2.4 4.2 5.8 10.7
2.9 12.1 .. . 51.1 74.9
5 .7 13.4 3.4 55.4 84.9
8.2 19.8 68.5 89.2 one
12.1 19.9 . . . 46.5 82.2
6.6 21.3 72.8 100
5.8 20.9 86.1 100
* 40.8 . . 100 . . .
4.0 9.8 13.0 . . .
3.0 5.0 . . . . . .
30.0 . . . . . . --n
See Table 5 for abbreviations and denitions. (a) 316 C (600 F ) 1'1h -i 340 C (645 F ) /4 h. (b) 325 C (615 F ) / 1 h +360 C (680 F ) /4 h. _(c) 316
C (600 F ) / 1h +316' C (600 F ) / 16 h. (d) 316 C (600 F ) 2 h +375 C (705 F ) /4 h. (e) 316 C (600 F ) /1h +340 C (645 F ) /4 h. (i) 335 C/
1 h +360 C (680 F ) /2 h (g) Sample obtained from Celanese Corp. as a 50 mm (2 in.) diam > < 6 mm (1/4 in.) thick disk. (h) Sample obtained
316 C (600 F ) /1h -1 370 C/
from 1-I oechst-Celanese (6F l3A/6F DAM) . (i) 316 C (600 F ) /1h +343 C (650 F ) /2 h +371C (700 F ) /26 h. (j)
24 h and 416 C (780 F ) /8 h. Source: Ref 7, 8, 60, 72
Table 9 Thermo-oxidative stability of polyimides at 370 C (700 F ) , 1 atm (air-circulating
oven)
Tlleight losslfip , after indicatedinumber of hours(a) ; g
Resin system Cure and postcure
25 1-. loo 11 zoo 11 300 n W 400 1;
Avirnid-N (b) 1.10 3.1
1.15 3.3
1.10 4.0
6F '-PDA-1, Avimicl-N(control) (b)
3F -PDA (3F -PI ) (b)
Sixef 44 . (b)
PMR-K-30 (c) 2.5
PMR-11-50 (c)
(d) PMR15 . . 5.7
no:
I ll
4 s so . . .
. . . . . . 71.0(f)
5.0 8.0 10.0 . . .
5.9 18 (264 h) 8.0(e) . . .
4.5 11.0 (264 h) 5.5(e) 28.7
17.1 . . . l8.2(e) . . .
AF R700B . 1.57 6.4 ... ... . Cb)
(la) 36F -PI 1 0.64
1.8 . . . . . . . . .
d C e and ostcure for Avimid-N, 6F F DA-13F -
See Table 5 for abbreviations and denitions. (a) Source: Ref 7, 8, 60, 72, except where note . (b) ur p ~ , g
PDA, 36F -PI , Sixef 44, and APR 700B: 316 C (600 F ) /1h +371C (700 F ) l24 h +416 C (780 F ) /8 h. (c) Cure and postcure for PMR-I I -30
and PMR-11-50: 316 C (600 F ) /1h +343 C (650 F ) l2 h +371C (700 F ) /26 h. (cl) Cure and postcure for PMR-15: 316 C (600 F ) /17h +
371C (700 F ) /24 h. (e) Source: Ref 73. (f) Source: Ref 74. PMR-I I -50 postcured 371C (700 F ) /18 h. 61-3-PDA and 3F -PDA postcured 371C
(700 F ) i8 h. Phthalic anhydride end-capped (aging conditions, not stated) . Source: Ref 7, 8, 60, 72, 73, 74
Table 10 Thermo-oxidative stability of polyimides at 371C (700 F ) , 4 atm (air flow, 100
cm?/min, or 6 in?/min)
3 3 7 1 if if Weight loss, %, after indicated nuinber of hours
I . , 11,.8.(f) :__., _.
Resin system Cure and postcurgeg 10 11 25 h 5011
752
106 i1
Avirnid-N 1.61
6 F -PDA (control) , 1.12
3 F -PDA . a) 1.20
_ r\ r"\ f_\
8, E,
2.30
2.54
2.66
4.19
4.26
5.07
5.71
7.55
6.10
7.65
8.50
10.5
12.2
12.1
15.1
PMR-H-30 [ b) . . .
Pl\ /H1-11-50
PMRl5
AF R 700B
36F -PDA
See Table 5 for abbreviations and denitions. (a) Cure and postcure for Avimid-N, 6F -PDA, 3F -PDA, 36F -PDA, AF R 70013: 316 C (600 F ) f1
r\ r\ r""\ \
Kb)
C)
a)
a)
ou-
an
000
3.41 6.60 . . . . . .
6.60 0 . . . . . . 25.2
4.28 8.83 13.4 18.8
1.57 3.40 6.0 9.1
11+
3'70 C (700 F ) ! 24 h +416 C (780 F ) /8 h. (b) Cure and postcure for PMR-H-30 and PMR-I I -50: 316 C (600 F ) /1h +343 C (650 F ) /2 h +
371C (700 F ) /26 h. (c) Cure and postcure for PI S/I R-15: 316 C (600 F ) i17h +371C (700 F ) 124 h. Source. Ref 8, 72
.._ q
*2? Kai
rd ; .> ; ,,:-*:._.32. M,.1 . ,1W Hit:
at 2
. 1'-I . : . .; -\
I '.f_
'
.- I ii
= ; ii%i
-4. . 1
' I -
; '_'.il
C11
. .: .1
.~ '-ti
V = 2; -:1
.1". Q = 1
:1
I ..,
I 55; -'1
.
.~ --.1
.-1~ .r> sY
.7 .541
' "iii
.'.7:"l'
' _'.; ; '; -1
srngg
1
1:1!
T4, ! ..
.. ~ .4
J, 7-5!
"
-
'1
; = l
' iii
r ; ' *1.\
.: ,.-Bi,
. -ill
est
. E,
t_I .; .= ~ ,; -< $.< ; *
:_l
= .e.< = '-r ,
. 13%; :
"eat
- 1:-MI _
.
l V-F :"l1s' A
.
; -git; pp: em ,5) _ W .-if W. 1.; .,..2. pip,
- 11-
~ ':~ .
F -15%
l
~ ::e:>
e.
.; _; .; . ; ; ; l,
.-I
$3
= ~
4

\ \
at 80 C (175 F ) in a vacuum for 1h. The tack-
free lm is then cured at 100 C (210 F ) , 200
C (390 F ) , and 300 C (570 F ) for 1h at each
temperature. The lm is removed from the glass
surface by immersion into warm water. Alter-
natively, an alcohol solution of the polyamiacid
precursor is centrifuged, and then the solution is
cast on a clean glass plate using a doctor blade.
The lm solution is placed in a chamberu-nder
owing nitrogen at room temperature for 4 h to
become a tack-free lm, and cured according to
the schedule described previously.
Chemistry of
Addition-Type Polyimides
General structures of several types of addi-
tion-type polyirnides are shown in F ig. 3. Spe-
cic structures of the more common materials
are shown in F ig. 4. Generally, these materials
are low-molecular-weight imide oligomers con-
taining unsaturated end caps, capable of forming
an addition-type reaction. I n some cases, these
unsaturated groups can also be located as pen-
dant groups in the backbone of the oligomer unit.
Phenylethynyl-Containing
lmide Oligomers
Since 1985, considerable efforts have been
made in the area of phenylethynyl-containing
imide oligomers, where the phenylethynyl group
can be located at chain ends (Ref 77-83) , pen-
dant to the main chain (Ref 84, 85) , as well as
pendant and terminal (Ref 13, 14, 86--90) to the
main chain, shown schematically in F ig. 5. Of
the many phenylethynyl end-capped and pendant
imide oligomer structures investigated, the phen-
ylethynyl (PE) end-capped imide oligomer,
known as PETI -5 (Ref 81) and having a calcu-
lated molecular Weight of 5000 g/mol, has been
extensively characterized as an adhesive (Ref 13,
14, 91-93) and as a composite-matrix resin (Ref
13, 14, 94-96) . This material offered the best
combination of properties of the oligomers in-
vestigated.
The PE end groups are thermally and chemi-
cally stable at the conditions necessary to form
the imide oligomers. The inside oligomers un-
dergo thermal cure at 370 C (700 F ) without
volatile evolution, to provide polyimides with an
excellent combination of thermal stability, me-
chanical strength, adhesion, and toughness (Ref
13, 14, 81) . I
The basic chemistry of the PE series of imide
oligomers is illustrated by the two reaction
schemes (F ig. 5 and 6) . The PE end-capped im-
ide oligorners to produce the PETI series of pol-
yimides are shown in F ig. 6. Oligomers contain-
ing PE groups pendant to the oligomeric chain
end-capped with phthalic anhydride (labeled
PPEI ) and oligomers with pendant and terminal
PE groups (labeled PTPEI ) are shown in F ig. 7.
Preparation of Phenylethynyl-Containing
lmide Oligomers (Ref 13, 14, 81) . The PE
Polyimide Resins / 109
end-capped oligomers are prepared from the re- ODA) and 1,3-bis (3~ arninophenox.y) benzene
actants 3,3",4, 4-biphenyltetracarboxylic acid (APB) , and 4-phenylethynylphthalic anhydride
anhydiide (BPDA) , 3,4-oxydianiline (3,4- (PEPA) . 3,5-diarnino-4-phenylethynyl benzo-
Table 11 Physical and mechanical properties of polyimides
Material Density, g/cmfn pg g
Tensile strength
Kat
F lexural
Tensiie modulus strength
F lexural
modulus
. GPa 10 psi MPa ksi GPa 10ip
Avirnid-N (Ref 36-39)
Avimid-K3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimid~ R (Ref 53, 54)
Avimid-RB (Ref 55)
PMR-15 (Ref 56-59)
Skybond 701(Ref 46)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
LARC- S1(Ref 44)
LARC-TPI (lm) (Ref 43)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 49)
Pyralin lm PI 2610 (Ref 49)
Pyralin P12540 (Ref 49)
Pyralin PI 2525 (Ref 49)
Aurum (new TPI ) (Ref 47)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
1.40
1.31
1.35
1.34
> 6-
I 0!
1.32
1.35
1.27
1.38
1.37
1.40
1.42
1.34
1.40
1.42
1.45
1.33
1.41
1.41
110
102
83
93
117
86
38
69
104
186
141
166
1'73
72
352
104
113
96
94
.6
4.1
3.6
3.3
3.4
3.6
3.8
3.9
4.1
3.0
4.4
4.0
3.6
3.0
8.4
1.3
2.5
16.0
15.0
12.0
13.4
16.9
12.5
5.6
10.0
15 .2
27.0
19.6
24.0
25.0
10.5
52
15.3
13.5
13.4
411' iii
0.60
0.52
0.49
0.49
0.52
0.55
0.57
0.60
0.43
0.64
0.58
0.51
0.43
1.22
0.20
0.36
no-
-80
0.69
I 00
it/6
i415
211
-1-
000
'45
ii
nan --1 | |/
can coo ovu
004
61- ... ac:
0.50
0.46
0.66
10
40
'34
4.5
OOI
25.5
2i '
30.7
use
0.45 512 1'20
000 --- -qu
0.45 510 20.0
-an
coo .4. ---
I zod impact strength,
notched
Material J/I n ft - I bflin. Strain-to-fai1ure,*pppppppppppppp p p
Glass
temperature (Tg)
C F
transition
O
I nterlaminar fracture
toughness (Gk)
J/1112 in. - ib/in.2
Avimid-N (Ref 36-39)
Avimid-K-3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimd-R (Ref 53, 54)
Avimid-RB (Ref 55)
Skybond 701(Ref 46)
PMR-15 (Ref 53, 56-59)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 51)
Pyralin PI 2610 (Ref 49)
Pyralin PI 2540 (Ref 49)
Pyralin P12525 (Ref 49)
Aurum (new TPI ) (Ref 47)
LARC-S1(Ref 44)
LARC-TPI lm (Ref 43)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
742.7
--
no-
53.4
53.4
53.4
133.5
23
91'
1 21.4
0.8
00
...
not
6--
1.0
1.0
1.0
2.5
0.43
if/'
0.40
6.0
14
nuu
4.4
3.3
2.4
1.0
1.5
60
20
7.5
7.5
40
40
15
90
7.2
8.5
eon
--
340
250
222
237
3 10
349
330
340
210
267
360
> 360
> 400
360
320
250
248
259
388
379
644
482
432
459
590
660
626
644
426
5 12
680
> 680
> 754
680
608
482
479
498
730
698
2400 13.4
1400 9.3
1400 9.3
1400 9.3
-1- 010
on 1--
not
' 280 1.57
5900
-2000
-2000
-2000
00:
01!
21.9
~ 11.6
~ 11.6
~ 11.6
4200 26'
Table 12 Physical properties of phenylethynyl end-capped imide oligomers (PETI s) of
various molecular weights
Calculated molecular 1}inh(a
Meleg M99 I mide minimum
temperature (uncured)
L (Tm) Tg(b) Tg (ure) ()
O O OF OC OF
melt viscosity,
Pa - s, at
indicated temperature weight (Mn) g/mo! iiiidpijfgw pCw jg g
15 320 610 170 340 288 1250 . 0
2500 0.20 330 630 210 410 277
357 675 210 410 270 5000 0.27
550
530
520
500 (335 C, or 635 'F )
9000 (371C, or 700 F )
100,000 (371C, or 700 F )
(a) lnherent viscosity (in deciliters per gram) determined on 0.5% (W/v) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
le d ' a1 d aluminum sample by differential scanning calorimetry at a heating rate of 20 C./min (36 F fmiu) . (c) Determined on powdered samp cure in a se e g
pan for 1h at 371C (700 F ) . Source: Ref 13
Table 13 Properties of phenylethynyl end-capped polyimides
Unoriented tensile properties Tensile shearstrengtlawgi
F racture toughness p WWW W g at23 C (73 F ) At mom At 177cc
K; c GI G Strength i l\/fodulus Elongation temperature (350 F )
Calculatgd molecular 4
2 12 m ks GPa 10 1 bY68k,% 1vn> 4 ksi MPa an weight(M; |) gWg/mol MPa ./5 14414/E J/in rt - nan 4 gs N
1250(4) . . . 0 - 1 a-- --6 can
2500 ) 3.9 3.5 426(a) 29(a)
2500(4) 5.7 3.4 ssvs 266 151.7 22.0 3.5 A 0.51 14 1462 212 37.2
5000(4) 3.9 3.5 4295 294 129.6 1s.s 3.1 0.45 32 4s.s 1.0 37.9
6--
(a) Molding cured for 1h at 371C (700 F ) . (b) Molding cured for 1h 350 C (660 F ) . Source: Ref 13
nu- 4.6
5:4
5.5
36.6 5.3 31.7
at 80 C (175 F ) in a vacuum for 1h. The tack-
free lm is then cured at 100 C (210 F ) , 200
C (390 F ) , and 300 C (570 F ) for 1h at each
temperature. The lm is removed from the glass
surface by immersion into warm water. Alter-
natively, an alcohol solution of the polyamiacid
precursor is centrifuged, and then the solution is
cast on a clean glass plate using a doctor blade.
The lm solution is placed in a chamberu-nder
owing nitrogen at room temperature for 4 h to
become a tack-free lm, and cured according to
the schedule described previously.
Chemistry of
Addition-Type Polyimides
General structures of several types of addi-
tion-type polyirnides are shown in F ig. 3. Spe-
cic structures of the more common materials
are shown in F ig. 4. Generally, these materials
are low-molecular-weight imide oligomers con-
taining unsaturated end caps, capable of forming
an addition-type reaction. I n some cases, these
unsaturated groups can also be located as pen-
dant groups in the backbone of the oligomer unit.
Phenylethynyl-Containing
lmide Oligomers
Since 1985, considerable efforts have been
made in the area of phenylethynyl-containing
imide oligomers, where the phenylethynyl group
can be located at chain ends (Ref 77-83) , pen-
dant to the main chain (Ref 84, 85) , as well as
pendant and terminal (Ref 13, 14, 86--90) to the
main chain, shown schematically in F ig. 5. Of
the many phenylethynyl end-capped and pendant
imide oligomer structures investigated, the phen-
ylethynyl (PE) end-capped imide oligomer,
known as PETI -5 (Ref 81) and having a calcu-
lated molecular Weight of 5000 g/mol, has been
extensively characterized as an adhesive (Ref 13,
14, 91-93) and as a composite-matrix resin (Ref
13, 14, 94-96) . This material offered the best
combination of properties of the oligomers in-
vestigated.
The PE end groups are thermally and chemi-
cally stable at the conditions necessary to form
the imide oligomers. The inside oligomers un-
dergo thermal cure at 370 C (700 F ) without
volatile evolution, to provide polyimides with an
excellent combination of thermal stability, me-
chanical strength, adhesion, and toughness (Ref
13, 14, 81) . I
The basic chemistry of the PE series of imide
oligomers is illustrated by the two reaction
schemes (F ig. 5 and 6) . The PE end-capped im-
ide oligorners to produce the PETI series of pol-
yimides are shown in F ig. 6. Oligomers contain-
ing PE groups pendant to the oligomeric chain
end-capped with phthalic anhydride (labeled
PPEI ) and oligomers with pendant and terminal
PE groups (labeled PTPEI ) are shown in F ig. 7.
Preparation of Phenylethynyl-Containing
lmide Oligomers (Ref 13, 14, 81) . The PE
Polyimide Resins / 109
end-capped oligomers are prepared from the re- ODA) and 1,3-bis (3~ arninophenox.y) benzene
actants 3,3",4, 4-biphenyltetracarboxylic acid (APB) , and 4-phenylethynylphthalic anhydride
anhydiide (BPDA) , 3,4-oxydianiline (3,4- (PEPA) . 3,5-diarnino-4-phenylethynyl benzo-
Table 11 Physical and mechanical properties of polyimides
Material Density, g/cmfn pg g
Tensile strength
Kat
F lexural
Tensiie modulus strength
F lexural
modulus
. GPa 16 psi MPa ksi GPa 10ip
Avirnid-N (Ref 36-39)
Avimid-K3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimid~ R (Ref 53, 54)
Avimid-RB (Ref 55)
PMR-15 (Ref 56-59)
Skybond 701(Ref 46)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
LARC- S1(Ref 44)
LARC-TPI (lm) (Ref 43)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 49)
Pyralin lm PI 2610 (Ref 49)
Pyralin P12540 (Ref 49)
Pyralin PI 2525 (Ref 49)
Aurum (new TPI ) (Ref 47)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
1.40
1.31
1.35
1.34
> 6-
I 0!
1.32
1.35
1.27
1.38
1.37
1.40
1.42
1.34
1.40
1.42
1.45
1.33
1.41
1.41
110
102
83
93
117
86
38
69
104
186
141
166
173
72
352
104
113
96
94
.6
4.1
3.6
3.3
3.4
3.6
3.8
3.9
4.1
3.0
4.4
4.0
3.6
3.0
8.4
1.3
2.5
16.0
15.0
12.0
13.4
16.9
12.5
5.6
10.0
15 .2
27.0
19.6
24.0
25.0
10.5
52
15.3
13.5
13.4
411' iii
0.60
0.52
0.49
0.49
0.52
0.55
0.57
0.60
0.43
0.64
0.58
0.51
0.43
1.22
0.20
0.36
no-
-80
0.69
I 00
it/6
i415
211
-1-
000
'45
ii
nan --1 | |/
can coo ovu
004
61- ... ac:
6.44
6.46
0.66
18
43:5
'34
4.5
OOI
25.5
2i '
30.7
use
6.45 512 iii;
000 --- -qu
6.45 916 26.6
-an
coo .4. ---
I zod impact strength,
notched
Material J/I n ft - I bflin. Strain-to-fai1ure,*pppppppppppppp p p
Glass
temperature (Tg)
C F
transition
O
I nterlaminar fracture
toughness (Gk)
J/1112 in. - ib/in.2
Avimid-N (Ref 36-39)
Avimid-K-3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimd-R (Ref 53, 54)
Avimid-RB (Ref 55)
Skybond 701(Ref 46)
PMR-15 (Ref 53, 56-59)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 51)
Pyralin PI 2610 (Ref 49)
Pyralin PI 2540 (Ref 49)
Pyralin P12525 (Ref 49)
Aurum (new TPI ) (Ref 47)
LARC-S1(Ref 44)
LARC-TPI lm (Ref 43)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
742.7
--
no-
53.4
53.4
53.4
133.5
23
91'
1 21.4
0.8
00
...
not
6--
1.0
1.0
1.0
2.5
0.43
if/'
6.46
6.0
14
nuu
4.4
3.3
2.4
1.0
1.5
60
20
7.5
7.5
40
40
15
90
7.2
8.5
eon
--
340
250
222
237
3 10
349
330
340
210
267
360
> 360
> 400
360
320
250
248
259
388
379
644
482
432
459
590
660
626
644
426
5 12
680
> 680
> 754
680
608
482
479
498
730
698
2400 13.4
1400 9.3
1400 9.3
1400 9.3
-1- 010
on 1--
not
' 280 1.57
9960
-2000
-2000
-2000
00:
01!
21.9
~ 11.6
~ 11.6
~ 11.6
4260 26'
Table 12 Physical properties of phenylethynyl end-capped imide oligomers (PETI s) of
various molecular weights
Calculated molecular 1}inh(a
Meleg M93 I mide minimum
temperature (uncured)
L (Tm) Tg(b) Tg (ure) ()
O O OF OC OF
melt viscosity,
Pa - s, at
indicated temperature weight (Mn) g/mo! iiiidpijfgw pCw jg g
15 320 610 170 340 288 1250 . 0
2500 0.20 330 630 210 410 277
357 675 210 410 270 5000 0.27
550
530
520
500 (335 C, or 635 'F )
9000 (371C, or 700 F )
100,000 (371C, or 700 F )
(a) lnherent viscosity (in deciliters per gram) determined on 0.5% (W/v) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
le d ' a1 d aluminum sample by differential scanning calorimetry at a heating rate of 20 C./min (36 F fmiu) . (c) Determined on powdered samp cure in a se e g
pan for 1h at 371C (700 F ) . Source: Ref 13
Table 13 Properties of phenylethynyl end-capped polyimides
Unoriented tensile properties Tensile shearstrengtlawgi
F racture toughness p WWW W g at23 C (73 F ) At mom At 177cc
K; c GI G Strength i l\ /fodulus Elongation temperature (356 F )
Calculatgd molecular .
2 12 m ks GPa 10 1 bY68k,% 1vn> 4 ksi MPa an weight(M; |) gWg/mol MPa ./5 14414/E J/in rt - nan 4 gs N
1250(4) . . . 0 - 1 a-- --6 can
2500 ) 3.9 3.5 426(a) 29(a)
2500(4) 5.7 3.4 ssvs 266 151.7 22.0 3.5 A 0.51 14 1462 212 37.2
5000(4) 3.9 3.5 4295 294 129.6 1s.s 3.1 0.45 92 4s.s 1.0 37.9
6--
(a) Molding cured for 1h at 371C (700 F ) . (b) Molding cured for 1h 350 C (660 F ) . Source: Ref 13
nu- 4.6
5:4
5.5
36.6 5.3 31.7
at 80 C (175 F ) in a vacuum for 1h. The tack-
free lm is then cured at 100 C (210 F ) , 200
C (390 F ) , and 300 C (570 F ) for 1h at each
temperature. The lm is removed from the glass
surface by immersion into warm water. Alter-
natively, an alcohol solution of the polyamiacid
precursor is centrifuged, and then the solution is
cast on a clean glass plate using a doctor blade.
The lm solution is placed in a chamberu-nder
owing nitrogen at room temperature for 4 h to
become a tack-free lm, and cured according to
the schedule described previously.
Chemistry of
Addition-Type Polyimides
General structures of several types of addi-
tion-type polyirnides are shown in F ig. 3. Spe-
cic structures of the more common materials
are shown in F ig. 4. Generally, these materials
are low-molecular-weight imide oligomers con-
taining unsaturated end caps, capable of forming
an addition-type reaction. I n some cases, these
unsaturated groups can also be located as pen-
dant groups in the backbone of the oligomer unit.
Phenylethynyl-Containing
lmide Oligomers
Since 1985, considerable efforts have been
made in the area of phenylethynyl-containing
imide oligomers, where the phenylethynyl group
can be located at chain ends (Ref 77-83) , pen-
dant to the main chain (Ref 84, 85) , as well as
pendant and terminal (Ref 13, 14, 86--90) to the
main chain, shown schematically in F ig. 5. Of
the many phenylethynyl end-capped and pendant
imide oligomer structures investigated, the phen-
ylethynyl (PE) end-capped imide oligomer,
known as PETI -5 (Ref 81) and having a calcu-
lated molecular Weight of 5000 g/mol, has been
extensively characterized as an adhesive (Ref 13,
14, 91-93) and as a composite-matrix resin (Ref
13, 14, 94-96) . This material offered the best
combination of properties of the oligomers in-
vestigated.
The PE end groups are thermally and chemi-
cally stable at the conditions necessary to form
the imide oligomers. The inside oligomers un-
dergo thermal cure at 370 C (700 F ) without
volatile evolution, to provide polyimides with an
excellent combination of thermal stability, me-
chanical strength, adhesion, and toughness (Ref
13, 14, 81) . I
The basic chemistry of the PE series of imide
oligomers is illustrated by the two reaction
schemes (F ig. 5 and 6) . The PE end-capped im-
ide oligorners to produce the PETI series of pol-
yimides are shown in F ig. 6. Oligomers contain-
ing PE groups pendant to the oligomeric chain
end-capped with phthalic anhydride (labeled
PPEI ) and oligomers with pendant and terminal
PE groups (labeled PTPEI ) are shown in F ig. 7.
Preparation of Phenylethynyl-Containing
lmide Oligomers (Ref 13, 14, 81) . The PE
Polyimide Resins / 109
end-capped oligomers are prepared from the re- ODA) and 1,3-bis (3~ arninophenox.y) benzene
actants 3,3",4, 4-biphenyltetracarboxylic acid (APB) , and 4-phenylethynylphthalic anhydride
anhydiide (BPDA) , 3,4-oxydianiline (3,4- (PEPA) . 3,5-diarnino-4-phenylethynyl benzo-
Table 11 Physical and mechanical properties of polyimides
Material Density, g/cmfn pg g
Tensile strength
Kat
F lexural
Tensiie modulus strength
F lexural
modulus
. GPa 16 psi MPa ksi GPa 10ip
Avirnid-N (Ref 36-39)
Avimid-K3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimid~ R (Ref 53, 54)
Avimid-RB (Ref 55)
PMR-15 (Ref 56-59)
Skybond 701(Ref 46)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
LARC- S1(Ref 44)
LARC-TPI (lm) (Ref 43)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 49)
Pyralin lm PI 2610 (Ref 49)
Pyralin P12540 (Ref 49)
Pyralin PI 2525 (Ref 49)
Aurum (new TPI ) (Ref 47)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
1.40
1.31
1.35
1.34
> 6-
I 0!
1.32
1.35
1.27
1.38
1.37
1.40
1.42
1.34
1.40
1.42
1.45
1.33
1.41
1.41
110
102
83
93
117
86
38
69
104
186
141
166
173
72
352
104
113
96
94
.6
4.1
3.6
3.3
3.4
3.6
3.8
3.9
4.1
3.0
4.4
4.0
3.6
3.0
8.4
1.3
2.5
16.0
15.0
12.0
13.4
16.9
12.5
5.6
10.0
15 .2
27.0
19.6
24.0
25.0
10.5
52
15.3
13.5
13.4
411' iii
0.60
0.52
0.49
0.49
0.52
0.55
0.57
0.60
0.43
0.64
0.58
0.51
0.43
1.22
0.20
0.36
no-
-80
0.69
I 00
it/6
i415
211
-1-
000
'45
ii
nan --1 | |/
can coo ovu
004
61- ... ac:
6.44
6.46
0.66
18
43:5
'34
4.5
OOI
25.5
2i '
30.7
use
6.45 512 iii;
000 --- -qu
6.45 916 26.6
-an
coo .4. ---
I zod impact strength,
notched
Material J/I n ft - I bflin. Strain-to-fai1ure,*pppppppppppppp p p
Glass
temperature (Tg)
C F
transition
O
I nterlaminar fracture
toughness (Gk)
J/1112 in. - ib/in.2
Avimid-N (Ref 36-39)
Avimid-K-3 (Ref 40-42)
Avimid-K3A (Ref 40-42)
Avimid-K3B (Ref 40-42)
Avimd-R (Ref 53, 54)
Avimid-RB (Ref 55)
Skybond 701(Ref 46)
PMR-15 (Ref 53, 56-59)
Ultem 1000 (Ref 45)
Torlon 4203 (Ref 52)
Kapton H lm (Ref 48)
Vespel SP-1(Ref 51)
Pyralin PI 2610 (Ref 49)
Pyralin PI 2540 (Ref 49)
Pyralin P12525 (Ref 49)
Aurum (new TPI ) (Ref 47)
LARC-S1(Ref 44)
LARC-TPI lm (Ref 43)
Super I mide 800 (Ref 66)
AF R 700B (Ref 64, 65)
742.7
--
no-
53.4
53.4
53.4
133.5
23
91'
1 21.4
0.8
00
...
not
6--
1.0
1.0
1.0
2.5
0.43
if/'
6.46
6.0
14
nuu
4.4
3.3
2.4
1.0
1.5
60
20
7.5
7.5
40
40
15
90
7.2
8.5
eon
--
340
250
222
237
3 10
349
330
340
210
267
360
> 360
> 400
360
320
250
248
259
388
379
644
482
432
459
590
660
626
644
426
5 12
680
> 680
> 754
680
608
482
479
498
730
698
2400 13.4
1400 9.3
1400 9.3
1400 9.3
-1- 010
on 1--
not
' 280 1.57
9960
-2000
-2000
-2000
00:
01!
21.9
~ 11.6
~ 11.6
~ 11.6
4260 26'
Table 12 Physical properties of phenylethynyl end-capped imide oligomers (PETI s) of
various molecular weights
Calculated molecular 1}inh(a
Meleg M93 I mide minimum
temperature (uncured)
L (Tm) Tg(b) Tg (ure) ()
O O OF OC OF
melt viscosity,
Pa - s, at
indicated temperature weight (Mn) g/mo! iiiidpijfgw pCw jg g
15 320 610 170 340 288 1250 . 0
2500 0.20 330 630 210 410 277
357 675 210 410 270 5000 0.27
550
530
520
500 (335 C, or 635 'F )
9000 (371C, or 700 F )
100,000 (371C, or 700 F )
(a) lnherent viscosity (in deciliters per gram) determined on 0.5% (W/v) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
le d ' a1 d aluminum sample by differential scanning calorimetry at a heating rate of 20 C./min (36 F fmiu) . (c) Determined on powdered samp cure in a se e g
pan for 1h at 371C (700 F ) . Source: Ref 13
Table 13 Properties of phenylethynyl end-capped polyimides
Unoriented tensile properties Tensile shearstrengtlawgi
F racture toughness p WWW W g at23 C (73 F ) At mom At 177cc
K; c GI G Strength i l\ /fodulus Elongation temperature (356 F )
Calculatgd molecular .
2 12 m ks GPa 10 1 bY68k,% 1vn> 4 ksi MPa an weight(M; |) gWg/mol MPa ./5 14414/E J/in rt - nan 4 gs N
1250(4) . . . 0 - 1 a-- --6 can
2500 ) 3.9 3.5 426(a) 29(a)
2500(4) 5.7 3.4 ssvs 266 151.7 22.0 3.5 A 0.51 14 1462 212 37.2
5000(4) 3.9 3.5 4295 294 129.6 1s.s 3.1 0.45 92 4s.s 1.0 37.9
6--
(a) Molding cured for 1h at 371C (700 F ) . (b) Molding cured for 1h 350 C (660 F ) . Source: Ref 13
nu- 4.6
5:4
5.5
36.6 5.3 31.7
--
110 / Constituent Materials
phenone (DPEB) and phthalic anhydride (PA)
were added to place PE randomly (pendant)
along the oligomeric chain. PEPA and DPEB are
added together to form PE terminal to and along
the backbone of the oligomeric chain. .,,
The PE oligomers are prepared by dissolving
the appropriate diamines 3,4-ODA, APB, and,
in some cases, DPEB in N-methyl pyrrolidinone
or dimethylactarnide at room temperature under
nitrogen. The dianhydride (BPDA) and end-eap-
pers (PEPA or PA, as required) are added in one
portion as a slurry in NMP to the stirred diam-
ines. The solids concentration is subsequently
adjusted to 25 to 35% (W/W) with additional sol
vents. A mild exotherm is observed during the
first few minutes of the reaction. The solution is
stirred for about 24 h at room temperature under
nitrogen. Aliquots are removed to determine the
inherent viscosity and for GPC analysis to assess
molecular weight and molecular weight distri-
bution, or other properties as desired.
The polyarnic acid/NMP or DMAC solution
is used to prepare thin lms, supported adhesive
tape, and impregnated unidirectional carbon -
ber, cmbon cloth, or other ber/cloth substrate,
and cured as described subsequently for lm,
powder, or composites. The amide acid oligomer
is converted to the imide oligomer by adding suf-
ficient toluene or o-xylene to the solution, fol-
lowed by azeotropic distillation of water in a
Dean-Stark trap overnight in nitrogen. The imide
oligomers typically precipitate during this imi-
dization process. The pale yellow powder is iso-
lated by adding the reaction mixture to water,
ltering, and washing with water and then meth-
anol. I t is dried at 200 C (390 F ) in air to con-
stant Weight. This yellow imide oligomer pow-
der can be used to mold polyimide specimens.
Cross-linked Phenylethynyl-Containing
Polyimides (Ref 13, 14, 81) . F inal cure of
phenylethynyl-containing imide oligomers oc-
curs about 370 C (700 F ) over a 1to 2 h period.
The mechanism of the cure process is not com-
pletely understood, but it is believed that thema-
jor cure reaction is the ethynyl-to-ethynyl reac-
tion to form double bonds or polyene structures
(chain extension) (F ig. 8) (Ref 97-99) .
F abrication of Molded Phenylethynyl Pol -
yimide Specimens. Powdered imide oligomers
are compression molded in a stainless steel mold
under 345 l< Pa (50 psi) pressure by heating to
370 C (700 F ) for l to 2 h (Ref 13, 14) .
Preparation of Phenylethynyl-Containing
Polyimide F ilm (Ref 13, 14) . Phenylethynyl-
containing oligomeric amide acids in NMP or
DMAC (20 to 35 wt%) are centrifuged; the de-
cantate is doctored onto a clean plate glass sur-
face and dried to a tack-free surface in 80 C (175
F ) in a vacuum for 4 h or at 80 C (175 F ) in
an oven in nitrogen for 24 h. The lms on glass
are irnidized by heating at 100, 225, 300, and
370C (210, 435, 5'70, and 700 F ) for l h at
each temperature. The lm is removed by im-
mersion in warm water.
Constituent Properties of Phenylethynyl-
Containing Polyimides (Ref 13, 14) . The effect
of molecular weight of PETI oligomers and
< 1 g
cured polymer on inherent viscosity, Tg, and im- for uncured oligomer and inside minimum melt
ide minimum melt viscosity is shown in Table viscosity increase with molecular weight. The
12. AS expected, the inherent viscosities and Tgs Tgg Q f the cured oljgomer are higher for the
Table 14 Physical properties of phenylethynyl-containing imide oligomers and polyimides
Giass transiti n temperature (Tg) (b)
Melting . g . . . Q
temperature Tm I nitial Cured(c) melt viscosity
Q ligomer i H nin1r(a) , dL/g c 7 F W _ c p F i to fr p Pa -Ms, at an c (roe no
PETI -5 (d) 0.27 286 547 210 410 0 270 513 100,000
PPEI (d) 0.31 . . . . . . Z 209 408 279 534 600,000
PTPEi(d) 0.32 282 540 231 448 313 595 1,150,000
' d 'liters er am) determined on O 5% (W/V) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
(a) I nherent viscosity (in 6C1 p gr V .
sample by differential scanning calorimetry at heating igte of 20 C/min (36 F ! rnin) . (c) Determined on powdered sample cured in a sealed aluminum
5000 1. Source: Ref 14
pan for 1h at 371 C (700 F ) . (d) Molecular weight (Mn) g/mo
I mide minimum
l%ieZ ~ @r@< I > .
l@2@; i330P0i
listeiei
t; tQ l -
E) ll
lqrtbinl
UPI LEX, Type S
Pyralin LX Pl 2610
I 'l
Amoco Ultradel 4212
Monsanto Skybond 701,
contains cross linking via
amide thermoset
DuPont Avimid-N
LARC-TPI
Mitsui-Tuatso New TPI Aurum
00 -A
Vespei, Ar ; "i,4-ODA
Pyralin 2540, Ar = p-PDA
0 I
Tl
iti> @@i
lWt@-@r .
i~ t@~ 1> %i
Kapton
6F Pyralin
Pyralin Pl 2555
Ar = 4,4-ODA, p-PDA
0 o
Hscvci-13 n
LARC PDMDA series
LARC SI DA series
2 Structures of selected commercially available condensation polyirnide resins
f-fig
. v l
i '4
I i
.-,3,
.-\_,; .m,j.i1:f- ; < ; l,-1 .:,= 1 , =
l' .'ri.\< .2.1.\1\\?r i:- s.,, .1 :1
1'/; "~ '; ',,-< 11-'5 l; $,g~ _; 35-:-red $; *.n\R1 \-! ~ l-8",; ~ o1.(.\ -= ; '.\= z:.,.; .}f,_< = .'
_
xx)
'-= 1}. , rl'.A. .5-":,\,_
t 511- r~ 1 '~ :--:5 as 1-3:; srsita1.= :1:,~ .-:n."g -34 I -@..: 5,l \*\; \q':1! v > -Q 53 1*:-1) : :"e_*t%i; = < i~ ; .< "J
' 1'li1~ *; ! =
:3; : ::l
M _l '5"-3 [ LARC~ Sl
- y
x i 1'3
: F -:-??5i
l gt
~ 1.
t; 1@; ; ; ; ,= ._ ,1,. \31i'
. 1
iii
.315
.5;
it
1
3
1
1}
..-I .1
. 11:1!
.1 ':. 'e' _/p
l
i
i
1
; .{3l
":53
-..l
'-Li
' 52, ? > .> I
T
< ,.1.*'.~ it.1 1.. \
I
I
~ -> 1;
"I sl
.
*2?!
i ; il
:; 1;
. .,,
i
it
V - l
i
'!
-J5???
; . ?5l
at
5:1
::::
' > 11
:
.1.
. 1:
",:! \
. fii
> ; > '-at
-ti
i.':i*ll
:.i_+,1l
:25:
v . at
:1el
L7?
r "11
.
. :3; =
52-t
p
5 v av.)
\,\
E
-1
:l~ -s
I x? _ My
= ; > ; _ ; l
'2
11%
--
110 / Constituent Materials
phenone (DPEB) and phthalic anhydride (PA)
were added to place PE randomly (pendant)
along the oligomeric chain. PEPA and DPEB are
added together to form PE terminal to and along
the backbone of the oligomeric chain. .,,
The PE oligomers are prepared by dissolving
the appropriate diamines 3,4-ODA, APB, and,
in some cases, DPEB in N-methyl pyrrolidinone
or dimethylactarnide at room temperature under
nitrogen. The dianhydride (BPDA) and end-eap-
pers (PEPA or PA, as required) are added in one
portion as a slurry in NMP to the stirred diam-
ines. The solids concentration is subsequently
adjusted to 25 to 35% (W/W) with additional sol
vents. A mild exotherm is observed during the
first few minutes of the reaction. The solution is
stirred for about 24 h at room temperature under
nitrogen. Aliquots are removed to determine the
inherent viscosity and for GPC analysis to assess
molecular weight and molecular weight distri-
bution, or other properties as desired.
The polyarnic acid/NMP or DMAC solution
is used to prepare thin lms, supported adhesive
tape, and impregnated unidirectional carbon -
ber, cmbon cloth, or other ber/cloth substrate,
and cured as described subsequently for lm,
powder, or composites. The amide acid oligomer
is converted to the imide oligomer by adding suf-
ficient toluene or o-xylene to the solution, fol-
lowed by azeotropic distillation of water in a
Dean-Stark trap overnight in nitrogen. The imide
oligomers typically precipitate during this imi-
dization process. The pale yellow powder is iso-
lated by adding the reaction mixture to water,
ltering, and washing with water and then meth-
anol. I t is dried at 200 C (390 F ) in air to con-
stant Weight. This yellow imide oligomer pow-
der can be used to mold polyimide specimens.
Cross-linked Phenylethynyl-Containing
Polyimides (Ref 13, 14, 81) . F inal cure of
phenylethynyl-containing imide oligomers oc-
curs about 370 C (700 F ) over a 1to 2 h period.
The mechanism of the cure process is not com-
pletely understood, but it is believed that thema-
jor cure reaction is the ethynyl-to-ethynyl reac-
tion to form double bonds or polyene structures
(chain extension) (F ig. 8) (Ref 97-99) .
F abrication of Molded Phenylethynyl Pol -
yimide Specimens. Powdered imide oligomers
are compression molded in a stainless steel mold
under 345 l< Pa (50 psi) pressure by heating to
370 C (700 F ) for l to 2 h (Ref l3, 14) .
Preparation of Phenylethynyl-Containing
Polyimide F ilm (Ref 13, 14) . Phenylethynyl-
containing oligomeric amide acids in NMP or
DMAC (20 to 35 wt%) are centrifuged; the de-
cantate is doctored onto a clean plate glass sur-
face and dried to a tack-free surface in 80 C (175
F ) in a vacuum for 4 h or at 80 C (175 F ) in
an oven in nitrogen for 24 h. The lms on glass
are irnidized by heating at 100, 225, 300, and
370C (210, 435, 5'70, and 700 F ) for l h at
each temperature. The lm is removed by im-
mersion in warm water.
Constituent Properties of Phenylethynyl-
Containing Polyimides (Ref 13, 14) . The effect
of molecular weight of PETI oligomers and
< 1 g
cured polymer on inherent viscosity, Tg, and im- for uncured oligomer and inside minimum melt
ide minimum melt viscosity is shown in Table viscosity increase with molecular weight. The
12. AS expected, the inherent viscosities and Tgs Tgg Q f the cured oljgomer are higher for the
Table 14 Physical properties of phenylethynyl-containing imide oligomers and polyimides
Giass transiti n temperature (Tg) (b)
Melting . g . . . Q
temperature Tm I nitial Cured(c) melt viscosity
Q ligomer i H nin1r(a) , dL/g c 7 F W _ c p F i to fr p Pa -Ms, at an c (roe no
PETI -5 (d) 0.27 286 547 210 410 0 270 513 100,000
PPEI (d) 0.31 . . . . . . Z 209 408 279 534 600,000
PTPEi(d) 0.32 282 540 231 448 313 595 1,150,000
' d 'liters er am) determined on O 5% (W/V) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
(a) I nherent viscosity (in 6C1 p gr V .
sample by differential scanning calorimetry at heating igte of 20 C/min (36 F ! rnin) . (c) Determined on powdered sample cured in a sealed aluminum
5000 1. Source: Ref 14
pan for 1h at 371 C (700 F ) . (d) Molecular weight (Mn) g/mo
I mide minimum
l%ieZ ~ @r@< I > .
l@2@; i330P0i
listeiei
t; tQ l -
E) ll
lqrtbinl
UPI LEX, Type S
Pyralin LX Pl 2610
I 'l
Amoco Ultradel 4212
Monsanto Skybond 701,
contains cross linking via
amide thermoset
DuPont Avimid-N
LARC-TPI
Mitsui-Tuatso New TPI Aurum
00 -A
Vespei, Ar ; "i,4-ODA
Pyralin 2540, Ar = p-PDA
0 I
Tl
iti> @@i
lWt@-@r .
i~ t@~ 1> %i
Kapton
6F Pyralin
Pyralin Pl 2555
Ar = 4,4-ODA, p-PDA
0 o
Hscvci-13 n
LARC PDMDA series
LARC SI DA series
2 Structures of selected commercially available condensation polyirnide resins
f-fig
. v l
i '4
I i
.-,3,
.-\ _,; .m,j.i1:f- ; < ; l,-1 .:,= 1 , =
l' .'ri.\ < .2.1.\ 1\ \ ?r i:- s.,, .1 :1
1'/; "~ '; ',,-< 11-'5 l; $,g~ _; 35-:-red $; *.n\ R1 \ -! ~ l-8",; ~ o1.(.\ -= ; '.\ = z:.,.; .}f,_< = .'
_
xx)
'-= 1}. , rl'.A. .5-":,\ ,_
t 511- r~ 1 '~ :--:5 as 1-3:; srsita1.= :1:,~ .-:n."g -34 I -@..: 5,l \ *\ ; \ q':1! v > -Q 53 1*:-1) : :"e_*t%i; = < i~ ; .< "J
' 1'li1~ *; ! =
:3; : ::l
M _l '5"-3 [ LARC~ Sl
- y
x i 1'3
: F -:-??5i
l gt
~ 1.
t; 1@; ; ; ; ,= ._ ,1,. \ 31i'
. 1
iii
,; ; \
.5;
it
l
3
1
1}
..-I .1
. 11:1!
.1 ':. 'e' _/p
l
i
i
1
; .{ 3l
":53
-..l
'-Li
' 52, ? > .> I
T
< ,.1.*'.~ it.1 1.. \
I
I
~ -> 1;
"I sl
.
*2?!
i ; il
:; 1;
. .,,
i
it
V - l
i
'!
-J5???
; . ?5l
at
qgzl
::::
' > 11
:
.1.
. 1:
",:! \
. fii
> ; > '-at
-ti
i.':i*ll
:.i_+,1l
:25:
v . at
:1el
L7?
r "11
.
. :3; =
52-t
p
5 v av.)
\ ,\
E
-1
:l~ -s
I x? _ My
= ; > ; _ ; l
'2
11%
--
110 / Constituent Materials
phenone (DPEB) and phthalic anhydride (PA)
were added to place PE randomly (pendant)
along the oligomeric chain. PEPA and DPEB are
added together to form PE terminal to and along
the backbone of the oligomeric chain. .,,
The PE oligomers are prepared by dissolving
the appropriate diamines 3,4-ODA, APB, and,
in some cases, DPEB in N-methyl pyrrolidinone
or dimethylactarnide at room temperature under
nitrogen. The dianhydride (BPDA) and end-eap-
pers (PEPA or PA, as required) are added in one
portion as a slurry in NMP to the stirred diam-
ines. The solids concentration is subsequently
adjusted to 25 to 35% (W/W) with additional sol
vents. A mild exotherm is observed during the
first few minutes of the reaction. The solution is
stirred for about 24 h at room temperature under
nitrogen. Aliquots are removed to determine the
inherent viscosity and for GPC analysis to assess
molecular weight and molecular weight distri-
bution, or other properties as desired.
The polyarnic acid/NMP or DMAC solution
is used to prepare thin lms, supported adhesive
tape, and impregnated unidirectional carbon -
ber, cmbon cloth, or other ber/cloth substrate,
and cured as described subsequently for lm,
powder, or composites. The amide acid oligomer
is converted to the imide oligomer by adding suf-
ficient toluene or o-xylene to the solution, fol-
lowed by azeotropic distillation of water in a
Dean-Stark trap overnight in nitrogen. The imide
oligomers typically precipitate during this imi-
dization process. The pale yellow powder is iso-
lated by adding the reaction mixture to water,
ltering, and washing with water and then meth-
anol. I t is dried at 200 C (390 F ) in air to con-
stant Weight. This yellow imide oligomer pow-
der can be used to mold polyimide specimens.
Cross-linked Phenylethynyl-Containing
Polyimides (Ref 13, 14, 81) . F inal cure of
phenylethynyl-containing imide oligomers oc-
curs about 370 C (700 F ) over a 1to 2 h period.
The mechanism of the cure process is not com-
pletely understood, but it is believed that thema-
jor cure reaction is the ethynyl-to-ethynyl reac-
tion to form double bonds or polyene structures
(chain extension) (F ig. 8) (Ref 97-99) .
F abrication of Molded Phenylethynyl Pol -
yimide Specimens. Powdered imide oligomers
are compression molded in a stainless steel mold
under 345 l< Pa (50 psi) pressure by heating to
370 C (700 F ) for l to 2 h (Ref l3, 14) .
Preparation of Phenylethynyl-Containing
Polyimide F ilm (Ref 13, 14) . Phenylethynyl-
containing oligomeric amide acids in NMP or
DMAC (20 to 35 wt%) are centrifuged; the de-
cantate is doctored onto a clean plate glass sur-
face and dried to a tack-free surface in 80 C (175
F ) in a vacuum for 4 h or at 80 C (175 F ) in
an oven in nitrogen for 24 h. The lms on glass
are irnidized by heating at 100, 225, 300, and
370C (210, 435, 5'70, and 700 F ) for l h at
each temperature. The lm is removed by im-
mersion in warm water.
Constituent Properties of Phenylethynyl-
Containing Polyimides (Ref 13, 14) . The effect
of molecular weight of PETI oligomers and
< 1 g
cured polymer on inherent viscosity, Tg, and im- for uncured oligomer and inside minimum melt
ide minimum melt viscosity is shown in Table viscosity increase with molecular weight. The
12. AS expected, the inherent viscosities and Tgs Tgg Q f the cured oljgomer are higher for the
Table 14 Physical properties of phenylethynyl-containing imide oligomers and polyimides
Giass transiti n temperature (Tg) (b)
Melting . g . . . Q
temperature Tm I nitial Cured(c) melt viscosity
Q ligomer i H nin1r(a) , dL/g c 7 F W _ c p F i to fr p Pa -Ms, at an c (roe no
PETI -5 (d) 0.27 286 547 210 410 0 270 513 100,000
PPEI (d) 0.31 . . . . . . Z 209 408 279 534 600,000
PTPEi(d) 0.32 282 540 231 448 313 595 1,150,000
' d 'liters er am) determined on O 5% (W/V) NMP solution of the amide acid at 25 C (77F ) . (b) Determined on powdered
(a) I nherent viscosity (in 6C1 p gr V .
sample by differential scanning calorimetry at heating igte of 20 C/min (36 F ! rnin) . (c) Determined on powdered sample cured in a sealed aluminum
5000 1. Source: Ref 14
pan for 1h at 371 C (700 F ) . (d) Molecular weight (Mn) g/mo
I mide minimum
l%ieZ ~ @r@< I > .
l@2@; i330P0i
listeiei
t; tQ l -
E) ll
lqrtbinl
UPI LEX, Type S
Pyralin LX Pl 2610
I 'l
Amoco Ultradel 4212
Monsanto Skybond 701,
contains cross linking via
amide thermoset
DuPont Avimid-N
LARC-TPI
Mitsui-Tuatso New TPI Aurum
00 -A
Vespei, Ar ; "i,4-ODA
Pyralin 2540, Ar = p-PDA
0 I
Tl
iti> @@i
lWt@-@r .
i~ t@~ 1> %i
Kapton
6F Pyralin
Pyralin Pl 2555
Ar = 4,4-ODA, p-PDA
0 o
Hscvci-13 n
LARC PDMDA series
LARC SI DA series
2 Structures of selected commercially available condensation polyirnide resins
f-fig
. v l
i '4
I i
.-,3,
.-\ _,; .m,j.i1:f- ; < ; l,-1 .:,= 1 , =
l' .'ri.\ < .2.1.\ 1\ \ ?r i:- s.,, .1 :1
1'/; "~ '; ',,-< 11-'5 l; $,g~ _; 35-:-red $; *.n\ R1 \ -! ~ l-8",; ~ o1.(.\ -= ; '.\ = z:.,.; .}f,_< = .'
_
xx)
'-= 1}. , rl'.A. .5-":,\ ,_
t 511- r~ 1 '~ :--:5 as 1-3:; srsita1.= :1:,~ .-:n."g -34 I -@..: 5,l \ *\ ; \ q':1! v > -Q 53 1*:-1) : :"e_*t%i; = < i~ ; .< "J
' 1'li1~ *; ! =
:3; : ::l
M _l '5"-3 [ LARC~ Sl
- y
x i 1'3
: F -:-??5i
l gt
~ 1.
t; 1@; ; ; ; ,= ._ ,1,. \ 31i'
. 1
iii
,; ; \
.5;
it
l
3
1
1}
..-I .1
. 11:1!
.1 ':. 'e' _/p
l
i
i
1
; .{ 3l
":53
-..l
'-Li
' 52, ? > .> I
T
< ,.1.*'.~ it.1 1.. \
I
I
~ -> 1;
"I sl
.
*2?!
i ; il
:; 1;
. .,,
i
it
V - l
i
'!
-J5???
; . ?5l
at
qgzl
::::
' > 11
:
.1.
. 1:
",:! \
. fii
> ; > '-at
-ti
i.':i*ll
:.i_+,1l
:25:
v . at
:1el
L7?
r "11
.
. :3; =
52-t
p
5 v av.)
\ ,\
E
-1
:l~ -s
I x? _ My
= ; > ; _ ; l
'2
11%
lower-molecular-weight oligomer, presumably
due to higher cross-link density. The tensile
properties, neat resin fracture, and adhesive
properties of the various PETls are shown in
Table 13. The PE end-capped material with cal-
culated molecular weight 5000 g/mol, PE'TI -5,
was selected for extensive evaluation in com
posites.
The properties of cured phenylethynyl-com
taining polymers, comparing terminal (PETI -5) ,
pendant (PPEI ) , and pendant/terminal (PTPEI )
each with a calculated molecular weight of 5000
g/rnol, are shown in Tables 14 and 15. PET1-5
has the lowest cured Tg and also the lowest melt
viscosity, as expected. The best material, from
a processing view, is PETI -5. The tensile prop
erties of unoriented thin lms of these same
polymers are shown in Table 15. As expected,
the PPEI (pendant) and PTPEI (pendant/termi-
nal) polymers demonstrate the best tensile prop-
erties at 175 C (350 9F ) .
Nadir: End-Capped Polyimides
Nadic end-capped polyirnides, also called re-
verse Diels-Alder polyimides (Ref 100, 101)
and represented by PMR-15 and RP-46, not
only undergo the amidation and imidization re-
actions to form a low-molecular-weight oligo-
mer typical of condensation polyimides, but
also undergo an irreversible Diels-Alder reac-
tion leading to a high-molecular-weight cross-
linked polyimide. Processing of this resin is fur-
ther complicated by isomerization of the
endo-nadic end-capped imide oligomer to the
exo-isomer (Ref 102, 103) . These latter two re-
acdons distinguish the RDA addition-type pol-
yimides from the condensation polyimides.
The rst process step is amide formation,
which occurs between room temperature and
150 C (300 F ) (F ig. 9) . I n the second step,
imidization occurs over a temperature range of
150 to .2250 C (300 to 2.480 F ) . Simulta-
neously, in the temperature range of 175 to 260
C (350 to 500 l-7) , isomerization of the endo-
isorner to the exo-isomer occurs (F ig. 10) (Ref
102, 103) . F inally, in the fourth step, an irre-
versible Diels-Alder reaction of the endo/exo-
oligomers occurs, yielding the reactive inter-
mediates cyclopentadiene and bismaleimide
oligomers (F ig. 11) . These recombine to form a
stable cross-linked polyimide. The critical steps
in the processing of this polyimideare the re-
moval of residual by-products due to the imi-
dization reaction and the removal of low-mo-.
lecular-weight components formed during the
various process steps.
I t should be noted that the cross-linking
mechanism for PMR-15 and other related ad-
dition polyimides, such as RP-46 and PN-mod-
ied PMR polyimide, remains controversial.
There are at least three mechanisms that have
been proposed in the literature (Ref 104-109) .
The cross-linking mechanism of PMR-l5 de-
scribed in this article represents just one of
these mechanisms.
LARC RP46. LARC RP46 polyimide was de-
veloped (Ref 61) as an alternative to PMR-15,
because the diamine in PMR-l5,4,4'-methyl-
enedianiline (-4,4-MDA) is carcinogenic.
LARC RP46 substitutes 3,4-oxydianiline (3,4-
ODA) for 4,4-MDA'to form a nontoxic nadic,
end-capped PMR system, although the muta-
genic and carcinogenic effects of this material
are unknown. This material has essentially
equivalent mechanical property characteristics
to PMR-15 in graphite composites, but constit-
uent properties of the neat resin have not been
reported. The chemistry of this material is simi-
lar to that for PMR-15.
Other Addition-Type Polyimides. There are
several other nadic end-capped polyimides
similar to PMR-l5, but different in the mono-
Polyimide Resins / 111
mer composition and stoichiometry. However,
the chemistry of these materials is similar.
PMR-I sl-30 and PMR-I I -50 are examples. The
molecular structures are shown in F ig. 4. AF R
700B and Superimide 800 are end-capped with
nadic groups on one end of the oligomer chain.
These materials differ from PMR-15 in corn-
position and end-cap stoichiometry, and there-
fore the cross-linking mechanism is more com-
plex than in PMR-15. The structures of these
materials are also shown in F ig. 4. I n addition
to the nadic end-capped materials, the vinyl
end-capped PMRs are also available. The ends
of this imide oligomer are bonded to vinyl
groups. This material cross links by a simple
vinyl addition to give a saturated hydrocarbon
cross-linked structure. The structure of this ma-
terial is shown in F ig. 4.
Table 15 Tensile properties of phenylethynyl-containing polyimides
W 8 0 T (Test temperature Strength Elastic modulus
Oligomer "c r A/{Pa ksi W pp pGpl?apipWW106 psi Elongation at break, %
32 PETI -5(a) 23 73 129.6
177 350 84.1
PPEl(a) 23 73 117.2
177 350 64.1
PTPEI (a) 23 73 139.3
177 350 78.6
(a) Molecular weight (Mn ) , 5000 g/moi. Source: Ref 14
18.8 3.1
12.2 2.3 0.33 83
17.0
9.3 2.6 0.38
20.2 3.4 0.49 10
11.4 2.2
0.45
3.9 0.57 7
9
0.32 9
1
Nadic, end-capped ~ '$*YN.
Q O O n
, l
it Q
Vinyl, end-capped cm= C '%v~ ' CH= m
loo
Acetylene, end-capped H Y"@'ECH
l
- A
= O O
L. ..- fl
1 -------I Cross-tinked
O O I I Low pressure pQ I yifn]de$
Phenylethynyl, CE: Jk E (1"48 MP?
end~ capped A NY "' 1 or 260 psi)
O O n F
0
\
Superimide 800 t NH?
O 0
I 1
e .
AF R "zoos , in,
O Q 0 9 i
I 1
F ig. 3 General structures of addition-type polyimides
.-i-.
lower-molecular-weight oligomer, presumably
due to higher cross-link density. The tensile
properties, neat resin fracture, and adhesive
properties of the various PETls are shown in
Table 13. The PE end-capped material with cal-
culated molecular weight 5000 g/mol, PE'TI -5,
was selected for extensive evaluation in com
posites.
The properties of cured phenylethynyl-com
taining polymers, comparing terminal (PETI -5) ,
pendant (PPEI ) , and pendant/terminal (PTPEI )
each with a calculated molecular weight of 5000
g/rnol, are shown in Tables 14 and 15. PET1-5
has the lowest cured Tg and also the lowest melt
viscosity, as expected. The best material, from
a processing view, is PETI -5. The tensile prop
erties of unoriented thin lms of these same
polymers are shown in Table 15. As expected,
the PPEI (pendant) and PTPEI (pendant/termi-
nal) polymers demonstrate the best tensile prop-
erties at 175 C (350 9F ) .
Nadir: End-Capped Polyimides
Nadic end-capped polyirnides, also called re-
verse Diels-Alder polyimides (Ref 100, 101)
and represented by PMR-15 and RP-46, not
only undergo the amidation and imidization re-
actions to form a low-molecular-weight oligo-
mer typical of condensation polyimides, but
also undergo an irreversible Diels-Alder reac-
tion leading to a high-molecular-weight cross-
linked polyimide. Processing of this resin is fur-
ther complicated by isomerization of the
endo-nadic end-capped imide oligomer to the
exo-isomer (Ref 102, 103) . These latter two re-
acdons distinguish the RDA addition-type pol-
yimides from the condensation polyimides.
The rst process step is amide formation,
which occurs between room temperature and
150 C (300 F ) (F ig. 9) . I n the second step,
imidization occurs over a temperature range of
150 to .2250 C (300 to 2.480 F ) . Simulta-
neously, in the temperature range of 175 to 260
C (350 to 500 l-7) , isomerization of the endo-
isorner to the exo-isomer occurs (F ig. 10) (Ref
102, 103) . F inally, in the fourth step, an irre-
versible Diels-Alder reaction of the endo/exo-
oligomers occurs, yielding the reactive inter-
mediates cyclopentadiene and bismaleimide
oligomers (F ig. 11) . These recombine to form a
stable cross-linked polyimide. The critical steps
in the processing of this polyimideare the re-
moval of residual by-products due to the imi-
dization reaction and the removal of low-mo-.
lecular-weight components formed during the
various process steps.
I t should be noted that the cross-linking
mechanism for PMR-15 and other related ad-
dition polyimides, such as RP-46 and PN-mod-
ied PMR polyimide, remains controversial.
There are at least three mechanisms that have
been proposed in the literature (Ref 104-109) .
The cross-linking mechanism of PMR-l5 de-
scribed in this article represents just one of
these mechanisms.
LARC RP46. LARC RP46 polyimide was de-
veloped (Ref 61) as an alternative to PMR-15,
because the diamine in PMR-15 ,4,4'-rnethyl-
enedianiline (-4,4-MDA) is carcinogenic.
LARC RP46 substitutes 3,4-oxydianiline (3,4-
ODA) for 4,4-MDA'to form a nontoxic nadic,
end-capped PMR system, although the muta-
genic and carcinogenic effects of this material
are unknown. This material has essentially
equivalent mechanical property characteristics
to PMR-15 in graphite composites, but constit-
uent properties of the neat resin have not been
reported. The chemistry of this material is simi-
lar to that for PMR-15.
Other Addition-Type Polyimides. There are
several other nadic end-capped polyimides
similar to PMR-15, but different in the mono-
Polyimide Resins / 111
mer composition and stoichiometry. However,
the chemistry of these materials is similar.
PMR-I 1-30 and PMR-I I -50 are examples. The
molecular structures are shown in F ig. 4. AF R
700B and Superimide 800 are end-capped with
nadic groups on one end of the oligomer chain.
These materials differ from PMR-15 in corn-
position and end-cap stoichiometry, and there-
fore the cross-linking mechanism is more com-
plex than in PMR-15. The structures of these
materials are also shown in F ig. 4. I n addition
to the nadic end-capped materials, the vinyl
end-capped PMRs are also available. The ends
of this imide oligomer are bonded to vinyl
groups. This material cross links by a simple
vinyl addition to give a saturated hydrocarbon
cross-linked structure. The structure of this ma-
terial is shown in F ig. 4.
Table 15 Tensile properties of phenylethynyl-containing polyimides
W 8 9 T (Test temperature Strength Elastic modulus
Oligomer "c r A/{ Pa ksi W pp pGpl?apipWW106 psi Elongation at break, %
32 PETI -5(a) 23 73 129.6
177 350 84.1
PPEl(a) 23 73 117.2
177 350 64.1
PTPEI (a) 23 73 139.3
177 350 78.6
(a) Molecular weight (Mn ) , 5000 g/moi. Source: Ref 14
18.8 3.1
12.2 2.3 0.33 83
17.0
9.3 2.6 0.38
20.2 3.4 0.49 10
11.4 2.2
0.45
3.9 0.57 7
9
0.32 9
it
Nadic, end-capped ~ '$*YN.
Q O O n
, '1
it Q
Vinyl, end-capped cm= C '%v ~ ' CH= m
loo
Acetylene, end-capped H Y"@'ECH
1
- A
= O O
L. ..- fl
1 -------I Cross-tinked
O O I I Low pressure pQ I yifn]de$
Phenylethynyl, CE: Jk E (1"48 MP?
end~ capped A NY -9 1 or 260 psi)
O O n F
0
\
Superimide 800 1 NH?
O 0
I 1
e .
AF R "zoos , in,
O Q 0 0 i
I 1
F ig. 3 General structures of addition-type polyimides
.-i-.
lower-molecular-weight oligomer, presumably
due to higher cross-link density. The tensile
properties, neat resin fracture, and adhesive
properties of the various PETls are shown in
Table 13. The PE end-capped material with cal-
culated molecular weight 5000 g/mol, PE'TI -5,
was selected for extensive evaluation in com
posites.
The properties of cured phenylethynyl-com
taining polymers, comparing terminal (PETI -5) ,
pendant (PPEI ) , and pendant/terminal (PTPEI )
each with a calculated molecular weight of 5000
g/rnol, are shown in Tables 14 and 15. PET1-5
has the lowest cured Tg and also the lowest melt
viscosity, as expected. The best material, from
a processing view, is PETI -5. The tensile prop
erties of unoriented thin lms of these same
polymers are shown in Table 15. As expected,
the PPEI (pendant) and PTPEI (pendant/termi-
nal) polymers demonstrate the best tensile prop-
erties at 175 C (350 9F ) .
Nadir: End-Capped Polyimides
Nadic end-capped polyirnides, also called re-
verse Diels-Alder polyimides (Ref 100, 101)
and represented by PMR-15 and RP-46, not
only undergo the amidation and imidization re-
actions to form a low-molecular-weight oligo-
mer typical of condensation polyimides, but
also undergo an irreversible Diels-Alder reac-
tion leading to a high-molecular-weight cross-
linked polyimide. Processing of this resin is fur-
ther complicated by isomerization of the
endo-nadic end-capped imide oligomer to the
exo-isomer (Ref 102, 103) . These latter two re-
acdons distinguish the RDA addition-type pol-
yimides from the condensation polyimides.
The rst process step is amide formation,
which occurs between room temperature and
150 C (300 F ) (F ig. 9) . I n the second step,
imidization occurs over a temperature range of
150 to .2250 C (300 to 2.480 F ) . Simulta-
neously, in the temperature range of 175 to 260
C (350 to 500 l-7) , isomerization of the endo-
isorner to the exo-isomer occurs (F ig. 10) (Ref
102, 103) . F inally, in the fourth step, an irre-
versible Diels-Alder reaction of the endo/exo-
oligomers occurs, yielding the reactive inter-
mediates cyclopentadiene and bismaleimide
oligomers (F ig. 11) . These recombine to form a
stable cross-linked polyimide. The critical steps
in the processing of this polyimideare the re-
moval of residual by-products due to the imi-
dization reaction and the removal of low-mo-.
lecular-weight components formed during the
various process steps.
I t should be noted that the cross-linking
mechanism for PMR-15 and other related ad-
dition polyimides, such as RP-46 and PN-mod-
ied PMR polyimide, remains controversial.
There are at least three mechanisms that have
been proposed in the literature (Ref 104-109) .
The cross-linking mechanism of PMR-l5 de-
scribed in this article represents just one of
these mechanisms.
LARC RP46. LARC RP46 polyimide was de-
veloped (Ref 61) as an alternative to PMR-15,
because the diamine in PMR-15 ,4,4'-rnethyl-
enedianiline (-4,4-MDA) is carcinogenic.
LARC RP46 substitutes 3,4-oxydianiline (3,4-
ODA) for 4,4-MDA'to form a nontoxic nadic,
end-capped PMR system, although the muta-
genic and carcinogenic effects of this material
are unknown. This material has essentially
equivalent mechanical property characteristics
to PMR-15 in graphite composites, but constit-
uent properties of the neat resin have not been
reported. The chemistry of this material is simi-
lar to that for PMR-15.
Other Addition-Type Polyimides. There are
several other nadic end-capped polyimides
similar to PMR-15, but different in the mono-
Polyimide Resins / 111
mer composition and stoichiometry. However,
the chemistry of these materials is similar.
PMR-I 1-30 and PMR-I I -50 are examples. The
molecular structures are shown in F ig. 4. AF R
700B and Superimide 800 are end-capped with
nadic groups on one end of the oligomer chain.
These materials differ from PMR-15 in corn-
position and end-cap stoichiometry, and there-
fore the cross-linking mechanism is more com-
plex than in PMR-15. The structures of these
materials are also shown in F ig. 4. I n addition
to the nadic end-capped materials, the vinyl
end-capped PMRs are also available. The ends
of this imide oligomer are bonded to vinyl
groups. This material cross links by a simple
vinyl addition to give a saturated hydrocarbon
cross-linked structure. The structure of this ma-
terial is shown in F ig. 4.
Table 15 Tensile properties of phenylethynyl-containing polyimides
W 8 9 T (Test temperature Strength Elastic modulus
Oligomer "c r A/{ Pa ksi W pp pGpl?apipWW106 psi Elongation at break, %
32 PETI -5(a) 23 73 129.6
177 350 84.1
PPEl(a) 23 73 117.2
177 350 64.1
PTPEI (a) 23 73 139.3
177 350 78.6
(a) Molecular weight (Mn ) , 5000 g/moi. Source: Ref 14
18.8 3.1
12.2 2.3 0.33 83
17.0
9.3 2.6 0.38
20.2 3.4 0.49 10
11.4 2.2
0.45
3.9 0.57 7
9
0.32 9
it
Nadic, end-capped ~ '$*YN.
Q O O n
, '1
it Q
Vinyl, end-capped cm= C '%v ~ ' CH= m
loo
Acetylene, end-capped H Y"@'ECH
1
- A
= O O
L. ..- fl
1 -------I Cross-tinked
O O I I Low pressure pQ I yifn]de$
Phenylethynyl, CE: Jk E (1"48 MP?
end~ capped A NY -9 1 or 260 psi)
O O n F
0
\
Superimide 800 1 NH?
O 0
I 1
e .
AF R "zoos , in,
O Q 0 0 i
I 1
F ig. 3 General structures of addition-type polyimides
.-i-.
2
112 / Constituent Materials
Preparation of Nadic
End-Capped Amic Acid
Oligomer Resin Solutions
PMR-15 Polyimide. The prepolymer com-
position of this material consists of three mono -
mers: monomethyl ester of 5-norbornene-2, 3-
dicarboxylic acid; dimethyl ester of 3,3,
4,4-benzophenone tetracarboxylic acid, and
4,4-methylene dianiljne, in the mole ratio of
2:2.087:3.087(Ref 100, 101) . These monomers
undergo a reaction to yield PMR-15 polyirnide
(F ig. 9) .
The idealized structure of the imide oligomer
resulting from thermal treatment of this mono-
.
mer mixture (free of solvent) , as well as the mo-
lecular weight of each segment of the oligomer,
is shown in F ig. 12. The theoretical empirical
formula for this oligomer, where I 1 = 2.087, is
C93.s1Hss.s92N6.174O14.435= Yielding ii melecular
weight of 1501.56. Dirnethyl ester of 5~ norbor-
nene 1,2-dicarboxylic acid (13285 g, 0.0677
mol) is added to a methanol solution of benze-
phenone tetracarboxylic acid dimethyl ester
(BTDE) (60 wt%) (27296 g, 0.0766 mo-1) , While
stirring at room temperature. The diamine (4,4~
MDA, 20.460 g, 0.10319"rnol) is then added to
the ester solution. The solution is stirred at room
temperature until the diamine dissolves. This
resin solution can be used to impregnate glass,
carbon, or other cloth materials, as well as to
cr= , "
I
i
{< :> "PMR-ii polyimide series
ii
lT_e; [~ Cross-linked polyimide
rs
E3 .
or, Ni-E2 AF R 7008 poiyimide
I I 1
|- Cross-linked poiyimide
Heat
CF 3 cs,
O C]:
H2< ; ...C CF , N (E.-3 N CH2 \/CAP-I i polyirnide series
H
Y1
~ "Cross-linked polyimide
Heat 4 g
i .'
b 1'!
A L---> CrQ 3$-linked poiyimide g g_ _ WZ W _ Z .-
Heat c c_L iimide oiigomegrgg l-ergo
i _ Terminal PE imicie oiigomer
2 _ I , (PETI series)
H N N CH2-
E i ; E n ___] F , amide; oiigorner1_
l> Heat Cross-linked poiyimide < % -Pg}: 1%
05:0 W LARC PET! -5"
Pendant PE imide oi omer
O CO
A Ar r N ig
. (PPEE series)
i-I __; E,{-Cross-iinked poiyim-icie C C_i W _i5r5i,rgstmsi l--can | s it o
C C
ts it
N N Superimide 800 S
NH2
n Pendant and terminai PE imide oiigomer
L--Cross-linked poiyimicie (P-WE! series)
Heat
5 Schematic of phenylethynyl-containing imide
impregnate ber tows to form unidirectional -
ber/resin tape. The resin solution can be used to
form lms or resin powder.
Preparation of Resin Powder and Resin
Discs. The PMR-15 resin solution is allowed to
concentrate at room temperature to a viscous oil.
The solution is dried at 60 C (140 F ) in vacuum
for 2 h to a solid foam. The foam is ground to a
powder and thermally treated at 125 C (255 F )
for 1h and 200 C (390 F ) for 1h and 250 C
(480 F ) for 1.5 h to form an imidized oligomer.
Resin discs are fabricated by placing the irnidi~
zed powder (about 5.0 g) in a 25 mm (1in.) diam
stainless steel mold. The mold is placed in a pre~
heated press (150 C, or 300 F ) . The tempera-
ture is raised to 200 C (390 F ) at 5 C/min at
contact pressure, then a pressure of 28 MPa
(4000 psi) is applied at temperature and held for
10 minutes. The temperature is raised to 250 C
(480 F ) at 2 C (3.5 F ) /min, 4000 psi, held for
10 minutes, and then the pressure is released and
reapplied. The temperature is raised to 315 C
(600 F ) at 2 C/min, 4000 psi, and held for 1h.
The mold is cooled to 275 C (525 F ) and the
pressure is released. The resin disc is removed
and postcured at 315 C (600 F ) for 16 h in the
free state or at a higher temperature to increase
the glass transition temperature and thermo-ore
idative stability. Greater stability is generated
when the material is postcured at 370 C (700
F ) for 24 h.
Preparation of Adhesive F ilm. The PMR-15
resin solution, prepared as described previously,
is brushed onto glass scrim cloth, and the solvent
is allowed to evaporate to produce a tacky lm.
The process is repeated until sufficient resin is
deposited on the scrim cloth to give a nished
adhesive bond thickness of about 0.13 mm
(0.005 in.) .
Preparation of Adhesive Bond Specimens.
The impregnated glass scrim cloth is cut to the
4 Structures of selected addition-type polyimides (thermosets) oligomers. Source: Ref 14
-.:..".*-:; i_:~ ; ..1,

*:~ '- = 1? ; = .:..ii:~ .= .~ . .~ ; , :::< ; i= tr


.~ Q !
iii,
.~ ,-
S5
.5:
:53
= = :
. > 1!
ii
v :_.'I 3
. .. .;
i
, ,,
Y5
Kr
._,
ii
> 4
.,-1
I i
3
r
2
112 / Constituent Materials
Preparation of Nadic
End-Capped Amic Acid
Oligomer Resin Solutions
PMR-15 Polyimide. The prepolymer com-
position of this material consists of three mono -
mers: monomethyl ester of 5-norbornene-2, 3-
dicarboxylic acid; dimethyl ester of 3,3,
4,4-benzophenone tetracarboxylic acid, and
4,4-methylene dianiljne, in the mole ratio of
2:2.087:3.087(Ref 100, 101) . These monomers
undergo a reaction to yield PMR-15 polyirnide
(F ig. 9) .
The idealized structure of the imide oligomer
resulting from thermal treatment of this mono-
.
mer mixture (free of solvent) , as well as the mo-
lecular weight of each segment of the oligomer,
is shown in F ig. 12. The theoretical empirical
formula for this oligomer, where I 1 = 2.087, is
C93.s1Hss.s92N6.174O14.435= Yielding ii melecular
weight of 1501.56. Dirnethyl ester of 5~ norbor-
nene 1,2-dicarboxylic acid (l3.285 g, 0.0677
mol) is added to a methanol solution of benze-
phenone tetracarboxylic acid dimethyl ester
(BTDE) (60 wt%) (27296 g, 0.0766 mo-1) , While
stirring at room temperature. The diamine (4,4~
MDA, 20.460 g, 0.10319"rnol) is then added to
the ester solution. The solution is stirred at room
temperature until the diamine dissolves. This
resin solution can be used to impregnate glass,
carbon, or other cloth materials, as well as to
cr= , "
I
i
{ < :> "PMR-ii polyimide series
ii
lT_e; [ ~ Cross-linked polyimide
rs
E3 .
or, Ni-E2 AF R 7008 poiyimide
I I 1
|- Cross-linked poiyimide
Heat
CF 3 cs,
O C]:
H2< ; ...C CF , N (E.-3 N CH2 \ /CAP-I i polyirnide series
H
Y1
~ "Cross-linked polyimide
Heat 9 g
i .'
b 1'!
A L---> CrQ 3$-linked poiyimide g g_ _ WZ W _ Z .-
Heat c c_L iimide oiigomegrgg l-ergo
i _ Terminal PE imicie oiigomer
2 _ I , (PETI series)
H N N CH2-
E i ; E n ___] F , amide; oiigorner1_
l> Heat Cross-linked poiyimide < % -Pg}: 1%
05:0 W LARC PET! -5"
Pendant PE imide oi omer
O CO
A Ar r N ig
. (PPEE series)
i-I __; E,{ -Cross-iinked poiyim-icie C C_i W _i5r5i,rgstmsi l--can | s it o
C C
ts it
N N Superimide 800 S
NH2
n Pendant and terminai PE imide oiigomer
L--Cross-linked poiyimicie (P-WE! series)
Heat
5 Schematic of phenylethynyl-containing imide
impregnate ber tows to form unidirectional -
ber/resin tape. The resin solution can be used to
form lms or resin powder.
Preparation of Resin Powder and Resin
Discs. The PMR-15 resin solution is allowed to
concentrate at room temperature to a viscous oil.
The solution is dried at 60 C (140 F ) in vacuum
for 2 h to a solid foam. The foam is ground to a
powder and thermally treated at 125 C (255 F )
for 1h and 200 C (390 F ) for 1h and 250 C
(480 F ) for 1.5 h to form an imidized oligomer.
Resin discs are fabricated by placing the irnidi~
zed powder (about 5.0 g) in a 25 mm (1in.) diam
stainless steel mold. The mold is placed in a pre~
heated press (150 C, or 300 F ) . The tempera-
ture is raised to 200 C (390 F ) at 5 C/min at
contact pressure, then a pressure of 28 MPa
(4000 psi) is applied at temperature and held for
10 minutes. The temperature is raised to 250 C
(480 F ) at 2 C (3.5 F ) /min, 4000 psi, held for
10 minutes, and then the pressure is released and
reapplied. The temperature is raised to 315 C
(600 F ) at 2 C/min, 4000 psi, and held for 1h.
The mold is cooled to 275 C (525 F ) and the
pressure is released. The resin disc is removed
and postcured at 315 C (600 F ) for 16 h in the
free state or at a higher temperature to increase
the glass transition temperature and thermo-ore
idative stability. Greater stability is generated
when the material is postcured at 370 C (700
F ) for 24 h.
Preparation of Adhesive F ilm. The PMR-15
resin solution, prepared as described previously,
is brushed onto glass scrim cloth, and the solvent
is allowed to evaporate to produce a tacky lm.
The process is repeated until sufficient resin is
deposited on the scrim cloth to give a nished
adhesive bond thickness of about 0.13 mm
(0.005 in.) .
Preparation of Adhesive Bond Specimens.
The impregnated glass scrim cloth is cut to the
4 Structures of selected addition-type polyimides (thermosets) oligomers. Source: Ref 14
-.:..".*-:; i_:~ ; ..1,

*:~ '- = 1? ; = .:..ii:~ .= .~ . .~ ; , :::< ; i= tr


.~ Q !
iii,
.~ ,-
S5
.5:
:53
= = :
. > 1!
ii
v :_.'I 3
. .. .;
i
, ,,
Y5
Kr
._,
ii
> 4
.,-1
I i
3
r
2
112 / Constituent Materials
Preparation of Nadic
End-Capped Amic Acid
Oligomer Resin Solutions
PMR-15 Polyimide. The prepolymer com-
position of this material consists of three mono -
mers: monomethyl ester of 5-norbornene-2, 3-
dicarboxylic acid; dimethyl ester of 3,3,
4,4-benzophenone tetracarboxylic acid, and
4,4-methylene dianiljne, in the mole ratio of
2:2.087:3.087(Ref 100, 101) . These monomers
undergo a reaction to yield PMR-15 polyirnide
(F ig. 9) .
The idealized structure of the imide oligomer
resulting from thermal treatment of this mono-
.
mer mixture (free of solvent) , as well as the mo-
lecular weight of each segment of the oligomer,
is shown in F ig. 12. The theoretical empirical
formula for this oligomer, where I 1 = 2.087, is
C93.s1Hss.s92N6.174O14.435= Yielding ii melecular
weight of 1501.56. Dirnethyl ester of 5~ norbor-
nene 1,2-dicarboxylic acid (l3.285 g, 0.0677
mol) is added to a methanol solution of benze-
phenone tetracarboxylic acid dimethyl ester
(BTDE) (60 wt%) (27296 g, 0.0766 mo-1) , While
stirring at room temperature. The diamine (4,4~
MDA, 20.460 g, 0.10319"rnol) is then added to
the ester solution. The solution is stirred at room
temperature until the diamine dissolves. This
resin solution can be used to impregnate glass,
carbon, or other cloth materials, as well as to
cr= , "
I
i
{ < :> "PMR-ii polyimide series
ii
lT_e; [ ~ Cross-linked polyimide
rs
E3 .
or, Ni-E2 AF R 7008 poiyimide
I I 1
|- Cross-linked poiyimide
Heat
CF 3 cs,
O C]:
H2< ; ...C CF , N (E.-3 N CH2 \ /CAP-I i polyirnide series
H
Y1
~ "Cross-linked polyimide
Heat 9 g
i .'
b 1'!
A L---> CrQ 3$-linked poiyimide g g_ _ WZ W _ Z .-
Heat c c_L iimide oiigomegrgg l-ergo
i _ Terminal PE imicie oiigomer
2 _ I , (PETI series)
H N N CH2-
E i ; E n ___] F , amide; oiigorner1_
l> Heat Cross-linked poiyimide < % -Pg}: 1%
05:0 W LARC PET! -5"
Pendant PE imide oi omer
O CO
A Ar r N ig
. (PPEE series)
i-I __; E,{ -Cross-iinked poiyim-icie C C_i W _i5r5i,rgstmsi l--can | s it o
C C
ts it
N N Superimide 800 S
NH2
n Pendant and terminai PE imide oiigomer
L--Cross-linked poiyimicie (P-WE! series)
Heat
5 Schematic of phenylethynyl-containing imide
impregnate ber tows to form unidirectional -
ber/resin tape. The resin solution can be used to
form lms or resin powder.
Preparation of Resin Powder and Resin
Discs. The PMR-15 resin solution is allowed to
concentrate at room temperature to a viscous oil.
The solution is dried at 60 C (140 F ) in vacuum
for 2 h to a solid foam. The foam is ground to a
powder and thermally treated at 125 C (255 F )
for 1h and 200 C (390 F ) for 1h and 250 C
(480 F ) for 1.5 h to form an imidized oligomer.
Resin discs are fabricated by placing the irnidi~
zed powder (about 5.0 g) in a 25 mm (1in.) diam
stainless steel mold. The mold is placed in a pre~
heated press (150 C, or 300 F ) . The tempera-
ture is raised to 200 C (390 F ) at 5 C/min at
contact pressure, then a pressure of 28 MPa
(4000 psi) is applied at temperature and held for
10 minutes. The temperature is raised to 250 C
(480 F ) at 2 C (3.5 F ) /min, 4000 psi, held for
10 minutes, and then the pressure is released and
reapplied. The temperature is raised to 315 C
(600 F ) at 2 C/min, 4000 psi, and held for 1h.
The mold is cooled to 275 C (525 F ) and the
pressure is released. The resin disc is removed
and postcured at 315 C (600 F ) for 16 h in the
free state or at a higher temperature to increase
the glass transition temperature and thermo-ore
idative stability. Greater stability is generated
when the material is postcured at 370 C (700
F ) for 24 h.
Preparation of Adhesive F ilm. The PMR-15
resin solution, prepared as described previously,
is brushed onto glass scrim cloth, and the solvent
is allowed to evaporate to produce a tacky lm.
The process is repeated until sufficient resin is
deposited on the scrim cloth to give a nished
adhesive bond thickness of about 0.13 mm
(0.005 in.) .
Preparation of Adhesive Bond Specimens.
The impregnated glass scrim cloth is cut to the
4 Structures of selected addition-type polyimides (thermosets) oligomers. Source: Ref 14
-.:..".*-:; i_:~ ; ..1,

*:~ '- = 1? ; = .:..ii:~ .= .~ . .~ ; , :::< ; i= tr


.~ Q !
iii,
.~ ,-
S5
.5:
:53
= = :
. > 1!
ii
v :_.'I 3
. .. .;
i
, ,,
Y5
Kr
._,
ii
> 4
.,-1
I i
3
r
dimensions required for bonding. The cut adhe-
sive scrim cloth is placed on one of the surface-
treated specimens to be bonded. The other part
of the specimen to be bonded is placed on the
adhesive specimen. The bond specimen is placed
in a specially designed tool to maintain dimen-
sions of the bonded area. I t is placed in a vacuum
bag or autoclave, the temperature is raised to 275
C (525 F ) at 2 C/min, pressure is applied (700
l< ; Pa, or 100 psi) , and then the temperature is
raised to 315 C (600 F ) at 100 psi and held for
1h under these conditions.
Preparation of F ilms. The PMR-l5 resin so-
lution is ltered, the solution is doctored ontoa
clean plate glass surface, and dried to a tack-free
surface at 80 C (175 F ) in a vacuum. The lm
is then cured at 150 C (300 F ) for lh +200
C (390 F ) for l h +250 C (480 F ) for 1h
-1- 275 C (525 F ) for l h +316 C (600 F )
for l h. The lm is removed by immersion in
Warm water.
Constituent Properties of PMR-15
PMR-15 is extremely resistant to most organic
solvents, including aliphatic hydrocarbons,
Table 16 Constituent properties of PMR-
15 polyimide
I PMR-1300 I
Property pi polyimide
l.32(a) Density, g/cm?
Glass transition temperature (Tg) , C (F )
After 16 h at 316 C (600 F )
After 1h at 316 C (600 F )
Morphology
Tensile strength (dry) at room
temperature, MPa (ksi)
Tensile modulus (dry) at room
temperature, GPa (106 psi)
Tensile strain-to-failure, % 1.1
F lexural strength (dry) , MPa (ksi)
At room temperature
At 288 C (550 P)
At 316 C (600 F )
At 343 C (650 F )
F lexurai modulus (dry) , GPa (106 psi)
At room temperature
At 288 C (550 F )
At 316 C (600 F )
At 343 C (650 F )
F racture toughness
Kit. MPa ~ /E (ksi \/iii)
176 (2s.s) ()
73 < 10."/) (< .-)
4.0 (0.5s) ()
2.3 (0.34-) ()
1.8 (0.26) (c)
648 (590) (e)
280 (l.6) (d)
94 (0.52) (e)
53.37(1.0)
on I /mg (rt - ibf/in.2)
I zod impact strength, notched, J/m
(ft ' lbf/in.) t
Equilibrium moisture absorption(e) at 4.2
95% relative humidity and 71C
(160 F ) , wt%
Weight loss, %, at 288 C (550 F )
in owing air (100 cn13/min,
or 6 in.3/min) (f)
After 1000 h 0.3
After 2000 h 0.8
After 3000 h 2.0
Coefficient of thermal expansion(e) , 14
106 K
ether, ketones, aromatic hydrocarbons, and chlo-
rinated aliphatic and aromatic hydrocarbons. I t
is hydrolyzed in strong acids and strong bases,
including aqueous hydrazine solutions, at ele-
vated temperatures. The constituent materials
properties are listed in Table l6.
Current State of the Art
I n terms of commercial availability, the pol-
yimides listed in Table 4 dene the current tech-
nology. The polyirnide materials listed in these
tables have application as matrices for composite
adhesive coating materials, lm-forming mate-
rials, and electronic materials. The polyimide
materials used to make these components are
available as solutions, pellets, powder, adhesives
lms, impregnated unidirectional ber tape or
cloth, and as freestanding lms. Specic poly-
imides are available in solution for applications
in electronic applications. Most of these mate-
rials are identied only by speciccompany des-
ignations and not by chemical composition. The
processing characteristics for each type of pol-
yimide and their applications have been de-
scribed previously.
-
0.91 +
spoa
Polyimide Resins / 113
Outlook
I mprovement in polyimide processability is
essential for the ability to manufacture polyim-
ide parts, such as composites, at costs competi-
tive to other metal parts. I n order to improve pro-
cessability, a reduction in the melt viscosity of
the polyimide material is an absolute necessity.
F or the long-chain high-molecular-weight,
highly aromatic thermoplastic materials, such as
Avimid-N,-LARC-TPI , or BPDA/TF MB, this is
not readily possible. Low-molecular-weight end-
capped oligomers are potential candidates forthe
development of polyimide oligomers for im-
proved processability. The phenylethynyl end-
capped imide oligomers appear to hold consid-
erable promise, because low viscosity versions
of the phenylethynyl end-capped irnide oligo-
mers have already been developed and are being
tested (Ref 89, lll) . Research efforts to replace
4,4-methylene dianiline (4,4'-MDA) in PMR-
15 with a nonmutagenic and noncarcinogenic di-
amine will continue both from the health view-
point and for process improvements (Ref 112) .
NASA Glenn Research Center is the lead orga-
nization behind this research effort (Ref 23, 27,
32) . Therefore, the approach toward developing
Hal
ass
Mn,
3,4-on .
340 (662) (a)
32o (sso)
Amorphous, H214 Ni-I 2 ,._., Q
cross-linked +0,15 + 0.18 C.
one w
72 (10-4) ( ) ; _-- R 7> _. R
52 (7_6) 5(C C_C . C. HNW HN C""NH'-* .
Ho, cog-4 no,
1'9 ('27) () - Amide Acid Oligomer (isomers)
8.6 (5.6) (b)
39 (0.57) APB pEpA
30% solids
NMP .
czc
bi...
o
1110 (1010) (d) _H2O
Q -an Q -it
I mide Oligomer
Calcutated Molecular weight -5,000 gimot
where At = = 85 mole % and 15 mole %
(a) Ref 60. (b) Ref S6. (c) Ref 58. (d) Ref 59. (e) Ref 57. (f) Ref 110 , I c
- - We ... .. F ig. 6 Phenylethynyl end-capped imide oligomers. Source: Ref 13
dimensions required for bonding. The cut adhe-
sive scrim cloth is placed on one of the surface-
treated specimens to be bonded. The other part
of the specimen to be bonded is placed on the
adhesive specimen. The bond specimen is placed
in a specially designed tool to maintain dimen-
sions of the bonded area. I t is placed in a vacuum
bag or autoclave, the temperature is raised to 275
C (525 F ) at 2 C/min, pressure is applied (700
l< ; Pa, or 100 psi) , and then the temperature is
raised to 315 C (600 F ) at 100 psi and held for
1h under these conditions.
Preparation of F ilms. The PMR-l5 resin so-
lution is ltered, the solution is doctored ontoa
clean plate glass surface, and dried to a tack-free
surface at 80 C (175 F ) in a vacuum. The lm
is then cured at 150 C (300 F ) for lh +200
C (390 F ) for l h +250 C (480 F ) for 1h
-1- 275 C (525 F ) for l h +316 C (600 F )
for l h. The lm is removed by immersion in
Warm water.
Constituent Properties of PMR-15
PMR-15 is extremely resistant to most organic
solvents, including aliphatic hydrocarbons,
Table 16 Constituent properties of PMR-
15 polyimide
I PMR-1300 I
Property pi polyimide
l.32(a) Density, g/cm?
Glass transition temperature (Tg) , C (F )
After 16 h at 316 C (600 F )
After 1h at 316 C (600 F )
Morphology
Tensile strength (dry) at room
temperature, MPa (ksi)
Tensile modulus (dry) at room
temperature, GPa (106 psi)
Tensile strain-to-failure, % 1.1
F lexural strength (dry) , MPa (ksi)
At room temperature
At 288 C (550 P)
At 316 C (600 F )
At 343 C (650 F )
F lexurai modulus (dry) , GPa (106 psi)
At room temperature
At 288 C (550 F )
At 316 C (600 F )
At 343 C (650 F )
F racture toughness
Kit. MPa ~ /E (ksi \ /iii)
176 (2s.s) ()
73 < 10."/) (< .-)
4.0 (0.5s) ()
2.3 (0.34-) ()
1.8 (0.26) (c)
648 (590) (e)
280 (l.6) (d)
94 (0.52) (e)
53.37(1.0)
on I /mg (rt - ibf/in.2)
I zod impact strength, notched, J/m
(ft ' lbf/in.) t
Equilibrium moisture absorption(e) at 4.2
95% relative humidity and 71C
(160 F ) , wt%
Weight loss, %, at 288 C (550 F )
in owing air (100 cn13/min,
or 6 in.3/min) (f)
After 1000 h 0.3
After 2000 h 0.8
After 3000 h 2.0
Coefficient of thermal expansion(e) , 14
106 K
ether, ketones, aromatic hydrocarbons, and chlo-
rinated aliphatic and aromatic hydrocarbons. I t
is hydrolyzed in strong acids and strong bases,
including aqueous hydrazine solutions, at ele-
vated temperatures. The constituent materials
properties are listed in Table l6.
Current State of the Art
I n terms of commercial availability, the pol-
yimides listed in Table 4 dene the current tech-
nology. The polyirnide materials listed in these
tables have application as matrices for composite
adhesive coating materials, lm-forming mate-
rials, and electronic materials. The polyimide
materials used to make these components are
available as solutions, pellets, powder, adhesives
lms, impregnated unidirectional ber tape or
cloth, and as freestanding lms. Specic poly-
imides are available in solution for applications
in electronic applications. Most of these mate-
rials are identied only by speciccompany des-
ignations and not by chemical composition. The
processing characteristics for each type of pol-
yimide and their applications have been de-
scribed previously.
-
0.91 +
spoa
Polyimide Resins / 113
Outlook
I mprovement in polyimide processability is
essential for the ability to manufacture polyim-
ide parts, such as composites, at costs competi-
tive to other metal parts. I n order to improve pro-
cessability, a reduction in the melt viscosity of
the polyimide material is an absolute necessity.
F or the long-chain high-molecular-weight,
highly aromatic thermoplastic materials, such as
Avimid-N,-LARC-TPI , or BPDA/TF MB, this is
not readily possible. Low-molecular-weight end-
capped oligomers are potential candidates forthe
development of polyimide oligomers for im-
proved processability. The phenylethynyl end-
capped imide oligomers appear to hold consid-
erable promise, because low viscosity versions
of the phenylethynyl end-capped irnide oligo-
mers have already been developed and are being
tested (Ref 89, lll) . Research efforts to replace
4,4-methylene dianiline (4,4'-MDA) in PMR-
15 with a nonmutagenic and noncarcinogenic di-
amine will continue both from the health view-
point and for process improvements (Ref 112) .
NASA Glenn Research Center is the lead orga-
nization behind this research effort (Ref 23, 27,
32) . Therefore, the approach toward developing
Hal
ass
Mn,
3,4-on .
340 (662) (a)
32o (sso)
Amorphous, H214 Ni-I 2 ,._., Q
cross-linked +0,15 +0.18 C.
one w
72 (10-4) ( ) ; _-- R 7> _. R
52 (7_6) 5(C C_C . C. HNW HN C""NH'-* .
Ho, cog-4 no,
1'9 ('27) () - Amide Acid Oligomer (isomers)
8.6 (5.6) (b)
39 (0.57) APB pEpA
30% solids
NMP .
czc
bi...
o
1110 (1010) (d) _H2O
Q -an Q -it
I mide Oligomer
Calcutated Molecular weight -5,000 gimot
where At = = 85 mole % and 15 mole %
(a) Ref 60. (b) Ref S6. (c) Ref 58. (d) Ref 59. (e) Ref 57. (f) Ref 110 , I c
- - We ... .. F ig. 6 Phenylethynyl end-capped imide oligomers. Source: Ref 13
dimensions required for bonding. The cut adhe-
sive scrim cloth is placed on one of the surface-
treated specimens to be bonded. The other part
of the specimen to be bonded is placed on the
adhesive specimen. The bond specimen is placed
in a specially designed tool to maintain dimen-
sions of the bonded area. I t is placed in a vacuum
bag or autoclave, the temperature is raised to 275
C (525 F ) at 2 C/min, pressure is applied (700
l< ; Pa, or 100 psi) , and then the temperature is
raised to 315 C (600 F ) at 100 psi and held for
1h under these conditions.
Preparation of F ilms. The PMR-l5 resin so-
lution is ltered, the solution is doctored ontoa
clean plate glass surface, and dried to a tack-free
surface at 80 C (175 F ) in a vacuum. The lm
is then cured at 150 C (300 F ) for lh +200
C (390 F ) for l h +250 C (480 F ) for 1h
-1- 275 C (525 F ) for l h +316 C (600 F )
for l h. The lm is removed by immersion in
Warm water.
Constituent Properties of PMR-15
PMR-15 is extremely resistant to most organic
solvents, including aliphatic hydrocarbons,
Table 16 Constituent properties of PMR-
15 polyimide
I PMR-1300 I
Property pi polyimide
l.32(a) Density, g/cm?
Glass transition temperature (Tg) , C (F )
After 16 h at 316 C (600 F )
After 1h at 316 C (600 F )
Morphology
Tensile strength (dry) at room
temperature, MPa (ksi)
Tensile modulus (dry) at room
temperature, GPa (106 psi)
Tensile strain-to-failure, % 1.1
F lexural strength (dry) , MPa (ksi)
At room temperature
At 288 C (550 P)
At 316 C (600 F )
At 343 C (650 F )
F lexurai modulus (dry) , GPa (106 psi)
At room temperature
At 288 C (550 F )
At 316 C (600 F )
At 343 C (650 F )
F racture toughness
Kit. MPa ~ /E (ksi \ /iii)
176 (2s.s) ()
73 < 10."/) (< .-)
4.0 (0.5s) ()
2.3 (0.34-) ()
1.8 (0.26) (c)
648 (590) (e)
280 (l.6) (d)
94 (0.52) (e)
53.37(1.0)
on I /mg (rt - ibf/in.2)
I zod impact strength, notched, J/m
(ft ' lbf/in.) t
Equilibrium moisture absorption(e) at 4.2
95% relative humidity and 71C
(160 F ) , wt%
Weight loss, %, at 288 C (550 F )
in owing air (100 cn13/min,
or 6 in.3/min) (f)
After 1000 h 0.3
After 2000 h 0.8
After 3000 h 2.0
Coefficient of thermal expansion(e) , 14
106 K
ether, ketones, aromatic hydrocarbons, and chlo-
rinated aliphatic and aromatic hydrocarbons. I t
is hydrolyzed in strong acids and strong bases,
including aqueous hydrazine solutions, at ele-
vated temperatures. The constituent materials
properties are listed in Table l6.
Current State of the Art
I n terms of commercial availability, the pol-
yimides listed in Table 4 dene the current tech-
nology. The polyirnide materials listed in these
tables have application as matrices for composite
adhesive coating materials, lm-forming mate-
rials, and electronic materials. The polyimide
materials used to make these components are
available as solutions, pellets, powder, adhesives
lms, impregnated unidirectional ber tape or
cloth, and as freestanding lms. Specic poly-
imides are available in solution for applications
in electronic applications. Most of these mate-
rials are identied only by speciccompany des-
ignations and not by chemical composition. The
processing characteristics for each type of pol-
yimide and their applications have been de-
scribed previously.
-
0.91 +
spoa
Polyimide Resins / 113
Outlook
I mprovement in polyimide processability is
essential for the ability to manufacture polyim-
ide parts, such as composites, at costs competi-
tive to other metal parts. I n order to improve pro-
cessability, a reduction in the melt viscosity of
the polyimide material is an absolute necessity.
F or the long-chain high-molecular-weight,
highly aromatic thermoplastic materials, such as
Avimid-N,-LARC-TPI , or BPDA/TF MB, this is
not readily possible. Low-molecular-weight end-
capped oligomers are potential candidates forthe
development of polyimide oligomers for im-
proved processability. The phenylethynyl end-
capped imide oligomers appear to hold consid-
erable promise, because low viscosity versions
of the phenylethynyl end-capped irnide oligo-
mers have already been developed and are being
tested (Ref 89, lll) . Research efforts to replace
4,4-methylene dianiline (4,4'-MDA) in PMR-
15 with a nonmutagenic and noncarcinogenic di-
amine will continue both from the health view-
point and for process improvements (Ref 112) .
NASA Glenn Research Center is the lead orga-
nization behind this research effort (Ref 23, 27,
32) . Therefore, the approach toward developing
Hal
ass
Mn,
3,4-on .
340 (662) (a)
32o (sso)
Amorphous, H214 Ni-I 2 ,._., Q
cross-linked +0,15 +0.18 C.
one w
72 (10-4) ( ) ; _-- R 7> _. R
52 (7_6) 5(C C_C . C. HNW HN C""NH'-* .
Ho, cog-4 no,
1'9 ('27) () - Amide Acid Oligomer (isomers)
8.6 (5.6) (b)
39 (0.57) APB pEpA
30% solids
NMP .
czc
bi...
o
1110 (1010) (d) _H2O
Q -an Q -it
I mide Oligomer
Calcutated Molecular weight -5,000 gimot
where At = = 85 mole % and 15 mole %
(a) Ref 60. (b) Ref S6. (c) Ref 58. (d) Ref 59. (e) Ref 57. (f) Ref 110 , I c
- - We ... .. F ig. 6 Phenylethynyl end-capped imide oligomers. Source: Ref 13
4,
, 0 J imide Oiigomer }|-in-Q EC
\ +121 :
0 9 3,4-ODA
BPDA I
R L 1 ... A (1) A e V O Q
\ / M339? , , - A
+0.15 \/cW@_cEc_ + ma ~ = * -0 Reaco 7 } e
. \ ( _ 5:52:
"*2 WEB PEPA orPA - C_; -_
30% solids '
NM?
C.\= C3
G Q C
a :1 n e e
*-@**"~ " "HR (((( e
on M no C59 l I
H02 C 2 2 Poiyene structure
Amide Acid Oiigomer (isomers)
- H20
%W" "
imide Dligomer \~ _-_-;
V Calculated Moiecular weight ~ 5,00 girnol f
where R = H for PPE! and--cEc-Q for PTPEI --
Ar = as mcie %\UO\ and 15 moie %Q \@
K /
F ig, 7Phenyiethynyi terminal and pendant imide oligomers. Source: Ref13 g. p . .
st 1 H W. cu . "" '= j
ep +Hz Q NH: + Monomer
H3 I HQ --g () 3 l88Cf8'S
Step 2
N
(isomerization) 5
' n = 2.03?
lmidized prepolymer from NEI MDNBTDE. F ormuiated moiecuiar weight = 1500
Step 4
NE
2.000 moles 3.08?moies 2.087 V
er-1 ca,-{ii}-n
V O
1?~ 15
f:'_ E.
3 @\,/'~ .
O?/\
1? Q
Q
q|||jnI I |
Aromatic ring structure
(4)
I nterrnolecular
ethyny! -poiyene
lntramolecular A
ens-ene ' "-"
'\/
a
' ; '
H 8 Pro osed phenylethynyf curing process Source Ref 97
MBA BTDE
-V2
1&5 . K,
3
Room temperature - 150 ?C (380 F ) _
VI (:1-:1 Q are 1-1 1-1 ;
. i
._@ n = 2.087
Z 1
likmide-acid prepoymer 150-250 C (300-480 F ) > 3-gig:
=
5 5.; i.; l
...mv
- ' ; ":3
w . .~ J
.~ ; ; ; .= |
V
. ; _'~ '
i Pressure at258-316 c (480-sou r= )
i
4:
. .-3'
n 2 087
Thermaily cross-linked polyimide
E eth I ester of nadic anhydride;
9 General reaction scheme for PMR-15 reverse Diels-Alder polyimid-e. N , monom y -
MDA, 4,4-methylene dianiline; BTDE, diethyl ester of 3,3',4,4-benzophenone tetracarboxylic acid dianhy-
dride. Source: Ref 100, 101
4,
, 0 J imide Oiigomer }|-in-Q EC
\ +121 :
0 9 3,4-ODA
BPDA I
R L 1 ... A (1) A e V O Q
\ / M339? , , - A
+0.15 \ /cW@_cEc_ +ma ~ = * -0 Reaco 7 } e
. \ ( _ 5:52:
"*2 WEB PEPA orPA - C_; -_
30% solids '
NM?
C.\ = C3
G Q C
a :1 n e e
*-@**"~ " "HR (((( e
on M no C59 l I
H02 C 2 2 Poiyene structure
Amide Acid Oiigomer (isomers)
- H20
%W" "
imide Dligomer \ ~ _-_-;
V Calculated Moiecular weight ~ 5,00 girnol f
where R = H for PPE! and--cEc-Q for PTPEI --
Ar = as mcie %\ UO\ and 15 moie %Q \ @
K /
F ig, 7Phenyiethynyi terminal and pendant imide oligomers. Source: Ref13 g. p . .
st 1 H W. cu . "" '= j
ep +Hz Q NH: + Monomer
H3 I HQ --g () 3 l88Cf8'S
Step 2
N
(isomerization) 5
' n = 2.03?
lmidized prepolymer from NEI MDNBTDE. F ormuiated moiecuiar weight = 1500
Step 4
NE
2.000 moles 3.08?moies 2.087 V
er-1 ca,-{ ii}-n
V O
1?~ 15
f:'_ E.
3 @\ ,/'~ .
O?/\
1? Q
Q
q|||jnI I |
Aromatic ring structure
(4)
I nterrnolecular
ethyny! -poiyene
lntramolecular A
ens-ene ' "-"
'\ /
a
' ; '
H 8 Pro osed phenylethynyf curing process Source Ref 97
MBA BTDE
-V2
1&5 . K,
3
Room temperature - 150 ?C (380 F ) _
VI (:1-:1 Q are 1-1 1-1 ;
. i
._@ n = 2.087
Z 1
likmide-acid prepoymer 150-250 C (300-480 F ) > 3-gig:
=
5 5.; i.; l
...mv
- ' ; ":3
w . .~ J
.~ ; ; ; .= |
V
. ; _'~ '
i Pressure at258-316 c (480-sou r= )
i
4:
. .-3'
n 2 087
Thermaily cross-linked polyimide
E eth I ester of nadic anhydride;
9 General reaction scheme for PMR-15 reverse Diels-Alder polyimid-e. N , monom y -
MDA, 4,4-methylene dianiline; BTDE, diethyl ester of 3,3',4,4-benzophenone tetracarboxylic acid dianhy-
dride. Source: Ref 100, 101
4,
, 0 J imide Oiigomer }|-in-Q EC
\ +121 :
0 9 3,4-ODA
BPDA I
R L 1 ... A (1) A e V O Q
\ / M339? , , - A
+0.15 \ /cW@_cEc_ +ma ~ = * -0 Reaco 7 } e
. \ ( _ 5:52:
"*2 WEB PEPA orPA - C_; -_
30% solids '
NM?
C.\ = C3
G Q C
a :1 n e e
*-@**"~ " "HR (((( e
on M no C59 l I
H02 C 2 2 Poiyene structure
Amide Acid Oiigomer (isomers)
- H20
%W" "
imide Dligomer \ ~ _-_-;
V Calculated Moiecular weight ~ 5,00 girnol f
where R = H for PPE! and--cEc-Q for PTPEI --
Ar = as mcie %\ UO\ and 15 moie %Q \ @
K /
F ig, 7Phenyiethynyi terminal and pendant imide oligomers. Source: Ref13 g. p . .
st 1 H W. cu . "" '= j
ep +Hz Q NH: + Monomer
H3 I HQ --g () 3 l88Cf8'S
Step 2
N
(isomerization) 5
' n = 2.03?
lmidized prepolymer from NEI MDNBTDE. F ormuiated moiecuiar weight = 1500
Step 4
NE
2.000 moles 3.08?moies 2.087 V
er-1 ca,-{ ii}-n
V O
1?~ 15
f:'_ E.
3 @\ ,/'~ .
O?/\
1? Q
Q
q|||jnI I |
Aromatic ring structure
(4)
I nterrnolecular
ethyny! -poiyene
lntramolecular A
ens-ene ' "-"
'\ /
a
' ; '
H 8 Pro osed phenylethynyf curing process Source Ref 97
MBA BTDE
-V2
1&5 . K,
3
Room temperature - 150 ?C (380 F ) _
VI (:1-:1 Q are 1-1 1-1 ;
. i
._@ n = 2.087
Z 1
likmide-acid prepoymer 150-250 C (300-480 F ) > 3-gig:
=
5 5.; i.; l
...mv
- ' ; ":3
w . .~ J
.~ ; ; ; .= |
V
. ; _'~ '
i Pressure at258-316 c (480-sou r= )
i
4:
. .-3'
n 2 087
Thermaily cross-linked polyimide
E eth I ester of nadic anhydride;
9 General reaction scheme for PMR-15 reverse Diels-Alder polyimid-e. N , monom y -
MDA, 4,4-methylene dianiline; BTDE, diethyl ester of 3,3',4,4-benzophenone tetracarboxylic acid dianhy-
dride. Source: Ref 100, 101
/ _
H
N
CO2! -l O \A
H /
cozcr-1; , +H N--Ar--~
NE endokinetic isomer
/ H
we 260 so (s47- 500 F ) /'
O
Ar'~ M'~ *~
H
H O
Endonadimide
O
N\ H O
Endokinetic isomer Exothermodynamic isomer
F ig. 10 lsomerization during PMR-15 polymerization. Source: Ref 102, 103
/ H
H ,0.
O
Endo
/
Exo
2s0-290 c
(soc-554 F )
Q V -
~ .---.-> ' Q + l --Ar--~
rrreverszble _
N\
9 Recombination
O
N-Ar--
r?< ' '\
H O 6 p
t 0
Cross-linked polyimide
F ig. 11 Reverse Diels~ AI der reaction during cure. Source: Ref 104-109
6
Polyimide Resins / 115
polyirnides with improved processability With-
out undue sacrice of other desirable properties
can be summarized as follows: p
0 Control of molecular. weight
I Blends of low-molecular-weight, lowmelt-
ing, low-viscosity, reactive phenylethynyl
viscosity modiers with phenylethynyl end-
capped oligomers
Q Blends of star-shaped, branched, and linear
oligomers
i Design of monomers and oligomers with
structured features to increase bullciness, free
volume, and prevent interchain interactions
I Change of bonding in the aromatic rings from
para to a mixture of para and meta.
There is always the need to lower the dielec-
tric constant of polyimides for application in the
electronic and microelectronics industries. Sev-
eral important publications deal with the inu-
ence of fluorine on the dielectric constant (Ref
9, 113-117) . A novel approach for reducing the
dielectric constant of polyimides is the formation
of nanofoam polyimides (Ref 118, 119) . Basi-
cally, this approach replaces polyimide polymer
with air, which has a dielectric constant of 1.00.
I n addition to processing, research efforts will
continue to improve thermo-oxidative stability
(Ref 9, 120) , improve selectivity of gas separa-
tion membranes (Ref 121-125) , develop proton
exchange membranes (Ref 126, 127) for fuel cell
applications, improve solubility (Ref 16, 128-
131) for coatings, and improve optical properties
(Ref 132-138) such as optical anisotropy (Ref
132) for liquid crystal displays. Photosensitive
polyimides as photo resists for use in the eld of
microelectronics is of continued interest (Ref
139) . The newest areas of polyirnide research in-
volve the, development of nanostructured silica-
polyimides (Ref 140, 141) and polyirnide foam
for structural and insulation applications (Ref
142, 143) for use over a temperature range of
-250 to 250 C (-420 to 480 F ) .
REF ERENCES
1. F .W. Harris, S.L.C. Hsu, and C.C. Tso,
Synthesis and Characterization of Poly-
imides Based on 2,2Bis (Triuorome-
thyl) -4,4-Diaminobiphenyl, Polym.
Prepr., Vol 31(No. 5) , 1990, p 342
2. S.Z .D. Cheng, RE. Arnold, J'r., A. Z hang,
S.L.C. Hsu, and F .W. Harris, Organosolu-
ble, Segrnented Rigid-Rod Polyimide
F ilm: Smlcture F ormation, Macromole-
cules, Vol 24, 1991, p 5856-5862
2 . 3. M.Eashoo,D.Shen,Z .Wu,C.J.Lee,
'16
Cs He N02 C30 H16 N2 95 C22 His N02
F ig. 12 idealized PMR-15 structure
Molecular weight 162.154 Molecular weight 484.442 Molecular weight 328.364
Harris, and Z .D. Cheng, High Performance
Vol 34 (No. 15) , 1993, p 3209--3215
J.C. Coburn, P.D. Soper, and B.C. Auman,
Relaxation Behavior of Polyimides Based
on 2,2-Disubstituted Benzidines, Macro-
molecules, Vol 28, 1995, p 3253-3260
5. D.A. Scola, High-Temperature F luorinated
X r? \
i R 1 < > by 1 < > , 9 Aromatic Polyimide F ibers: Thermal Me-
) Q CH2 0 Q CH2 chanical and Dynamic Properties, Polymer
0 G O O
rr 4
/ _
H
N
CO2! -l O \ A
H /
cozcr-1; , +H N--Ar--~
NE endokinetic isomer
/ H
we 260 so (s47- 500 F ) /'
O
Ar'~ M'~ *~
H
H O
Endonadimide
O
N\ H O
Endokinetic isomer Exothermodynamic isomer
F ig. 10 lsomerization during PMR-15 polymerization. Source: Ref 102, 103
/ H
H ,0.
O
Endo
/
Exo
2s0-290 c
(soc-554 F )
Q V -
~ .---.-> ' Q +l --Ar--~
rrreverszble _
N\
9 Recombination
O
N-Ar--
r?< ' '\
H O 6 p
t 0
Cross-linked polyimide
F ig. 11 Reverse Diels~ AI der reaction during cure. Source: Ref 104-109
6
Polyimide Resins / 115
polyirnides with improved processability With-
out undue sacrice of other desirable properties
can be summarized as follows: p
0 Control of molecular. weight
I Blends of low-molecular-weight, lowmelt-
ing, low-viscosity, reactive phenylethynyl
viscosity modiers with phenylethynyl end-
capped oligomers
Q Blends of star-shaped, branched, and linear
oligomers
i Design of monomers and oligomers with
structured features to increase bullciness, free
volume, and prevent interchain interactions
I Change of bonding in the aromatic rings from
para to a mixture of para and meta.
There is always the need to lower the dielec-
tric constant of polyimides for application in the
electronic and microelectronics industries. Sev-
eral important publications deal with the inu-
ence of fluorine on the dielectric constant (Ref
9, 113-117) . A novel approach for reducing the
dielectric constant of polyimides is the formation
of nanofoam polyimides (Ref 118, 119) . Basi-
cally, this approach replaces polyimide polymer
with air, which has a dielectric constant of 1.00.
I n addition to processing, research efforts will
continue to improve thermo-oxidative stability
(Ref 9, 120) , improve selectivity of gas separa-
tion membranes (Ref 121-125) , develop proton
exchange membranes (Ref 126, 127) for fuel cell
applications, improve solubility (Ref 16, 128-
131) for coatings, and improve optical properties
(Ref 132-138) such as optical anisotropy (Ref
132) for liquid crystal displays. Photosensitive
polyimides as photo resists for use in the eld of
microelectronics is of continued interest (Ref
139) . The newest areas of polyirnide research in-
volve the, development of nanostructured silica-
polyimides (Ref 140, 141) and polyirnide foam
for structural and insulation applications (Ref
142, 143) for use over a temperature range of
-250 to 250 C (-420 to 480 F ) .
REF ERENCES
1. F .W. Harris, S.L.C. Hsu, and C.C. Tso,
Synthesis and Characterization of Poly-
imides Based on 2,2Bis (Triuorome-
thyl) -4,4-Diaminobiphenyl, Polym.
Prepr., Vol 31(No. 5) , 1990, p 342
2. S.Z .D. Cheng, RE. Arnold, J'r., A. Z hang,
S.L.C. Hsu, and F .W. Harris, Organosolu-
ble, Segrnented Rigid-Rod Polyimide
F ilm: Smlcture F ormation, Macromole-
cules, Vol 24, 1991, p 5856-5862
2 . 3. M.Eashoo,D.Shen,Z .Wu,C.J.Lee,
'16
Cs He N02 C30 H16 N2 95 C22 His N02
F ig. 12 idealized PMR-15 structure
Molecular weight 162.154 Molecular weight 484.442 Molecular weight 328.364
Harris, and Z .D. Cheng, High Performance
Vol 34 (No. 15) , 1993, p 3209--3215
J.C. Coburn, P.D. Soper, and B.C. Auman,
Relaxation Behavior of Polyimides Based
on 2,2-Disubstituted Benzidines, Macro-
molecules, Vol 28, 1995, p 3253-3260
5. D.A. Scola, High-Temperature F luorinated
X r? \
i R 1 < > by 1 < > , 9 Aromatic Polyimide F ibers: Thermal Me-
) Q CH2 0 Q CH2 chanical and Dynamic Properties, Polymer
0 G O O
rr 4
/ _
H
N
CO2! -l O \ A
H /
cozcr-1; , +H N--Ar--~
NE endokinetic isomer
/ H
we 260 so (s47- 500 F ) /'
O
Ar'~ M'~ *~
H
H O
Endonadimide
O
N\ H O
Endokinetic isomer Exothermodynamic isomer
F ig. 10 lsomerization during PMR-15 polymerization. Source: Ref 102, 103
/ H
H ,0.
O
Endo
/
Exo
2s0-290 c
(soc-554 F )
Q V -
~ .---.-> ' Q +l --Ar--~
rrreverszble _
N\
9 Recombination
O
N-Ar--
r?< ' '\
H O 6 p
t 0
Cross-linked polyimide
F ig. 11 Reverse Diels~ AI der reaction during cure. Source: Ref 104-109
6
Polyimide Resins / 115
polyirnides with improved processability With-
out undue sacrice of other desirable properties
can be summarized as follows: p
0 Control of molecular. weight
I Blends of low-molecular-weight, lowmelt-
ing, low-viscosity, reactive phenylethynyl
viscosity modiers with phenylethynyl end-
capped oligomers
Q Blends of star-shaped, branched, and linear
oligomers
i Design of monomers and oligomers with
structured features to increase bullciness, free
volume, and prevent interchain interactions
I Change of bonding in the aromatic rings from
para to a mixture of para and meta.
There is always the need to lower the dielec-
tric constant of polyimides for application in the
electronic and microelectronics industries. Sev-
eral important publications deal with the inu-
ence of fluorine on the dielectric constant (Ref
9, 113-117) . A novel approach for reducing the
dielectric constant of polyimides is the formation
of nanofoam polyimides (Ref 118, 119) . Basi-
cally, this approach replaces polyimide polymer
with air, which has a dielectric constant of 1.00.
I n addition to processing, research efforts will
continue to improve thermo-oxidative stability
(Ref 9, 120) , improve selectivity of gas separa-
tion membranes (Ref 121-125) , develop proton
exchange membranes (Ref 126, 127) for fuel cell
applications, improve solubility (Ref 16, 128-
131) for coatings, and improve optical properties
(Ref 132-138) such as optical anisotropy (Ref
132) for liquid crystal displays. Photosensitive
polyimides as photo resists for use in the eld of
microelectronics is of continued interest (Ref
139) . The newest areas of polyirnide research in-
volve the, development of nanostructured silica-
polyimides (Ref 140, 141) and polyirnide foam
for structural and insulation applications (Ref
142, 143) for use over a temperature range of
-250 to 250 C (-420 to 480 F ) .
REF ERENCES
1. F .W. Harris, S.L.C. Hsu, and C.C. Tso,
Synthesis and Characterization of Poly-
imides Based on 2,2Bis (Triuorome-
thyl) -4,4-Diaminobiphenyl, Polym.
Prepr., Vol 31(No. 5) , 1990, p 342
2. S.Z .D. Cheng, RE. Arnold, J'r., A. Z hang,
S.L.C. Hsu, and F .W. Harris, Organosolu-
ble, Segrnented Rigid-Rod Polyimide
F ilm: Smlcture F ormation, Macromole-
cules, Vol 24, 1991, p 5856-5862
2 . 3. M.Eashoo,D.Shen,Z .Wu,C.J.Lee,
'16
Cs He N02 C30 H16 N2 95 C22 His N02
F ig. 12 idealized PMR-15 structure
Molecular weight 162.154 Molecular weight 484.442 Molecular weight 328.364
Harris, and Z .D. Cheng, High Performance
Vol 34 (No. 15) , 1993, p 3209--3215
J.C. Coburn, P.D. Soper, and B.C. Auman,
Relaxation Behavior of Polyimides Based
on 2,2-Disubstituted Benzidines, Macro-
molecules, Vol 28, 1995, p 3253-3260
5. D.A. Scola, High-Temperature F luorinated
X r? \
i R 1 < > by 1 < > , 9 Aromatic Polyimide F ibers: Thermal Me-
) Q CH2 0 Q CH2 chanical and Dynamic Properties, Polymer
0 G O O
rr 4
116 / Constituent Materials
l1) $}1I I ]i(I l6S, U.S. Patent 4,742,152, 3 May
6. D.A. Scola, F luorinated Condensation Co-
polyimides, U.S. Patent 5,298,600, 29
March 1994 I e
7. Scola, Synthesis and Thermo-OXi-
dative Stability of [1,4-Phenylene-4,43
(2,2,2-Triuoro-Phenyl Ethylidene) Bis-
phthalimide] and Other F luorinated
Polyirnides, J. Polym. Sci A, Polym. Chem,
V0131, 1993, p 1997-2008 - p
8. Scola and M. Wai, The Thern1o-OX-
idative Stability of F luorinated Polyimides
and Polyimide/Graphite Composites at
371C, J. Appl. Polym. Sci., V0152, 1994,
p 421-429
9. E. Vaccaro and D.A. Scola, Novel F luori-
Hated Polyimides, Proc. High Temple
Workshop XX, 24-27Jan 2000 (San Diego,
Q A) , U.S. Department of Defense and Na-
tional Aeronautic and Space Administra-
tron
10. G.R.vHusk, P.E. Cassidy, and KL. Gebert,
Synthesis and Characterization of a Series
of Polyimides Derived from4,4(2,2,2-Tri-
fluoro-1-Triuoromethyl) Ethylidene] Bis
[1,3-I sopbenzofurandione], Macromole-
cnles, Vol 21, 1988, p 1234-1238
11. C.A. Arnold, J.D. Summers, and l.E.
McGrath, Syntheses and Physical Behav-
ior of Siloxane Modied Polyimides, Po-
lyrn. Eng. &Sci., Vol 29 (No. 20) , 1989, p
1413-1418 '
12. M.E..Rogers, H. Giubbs, A. Brennan, D.
Rogriques, G.L. Wilkes, and J.E. McGrath,
Vglv High T,, F ully Cyclized, Soluble Pol-
yirnides, Advances in Polyimide Science
and Technology, Proc. F ourth I nterna-
tional Conference on Polyimides, 30 Oct
to 1Nov 1991, (sponsored by the Society
of Plastics Engineers) , C. F eger, M.M.
Khojasteh, and N.S. Htoo, Ed., Tech-
nomic, Lancaster, PA, p 33-40
13. Hergenrother, J.W. Connell, and J.G.
Srnith, lr., Phenylethynyl Containing I m-
ide Oligorners, Polymer, Vol 41, 2000, p
5073-5081
14. J.G. Smith, Jr., .l.W. Connell, and P.M.
Hergenrother, The Effect of Phenylethynyl
Terminated I rnide Oligomer Molecular
Weight on the Properties of Composites, J.
Compos. Maren, Vol 34, (No. 7) , 2000, p
614-627
15. .l.E. McGrath, B. Tan, V. Vasuderan, G.W.
Meyer, A.C. Loos, and T. Bullions, Syn-
theses and Characterization of High Per-
formance Thermosetting Polyimides for
S1I 'l1CfL11'al Adhesives md Composite Ma-
tr1X Systems, paper presented at 28th I n-
ternational SAMPE Technical Conf., 4-7
Nov 1996, Society for the Advancement of
Material and Process Engineering, 1996, p
29-38
16~ Y- Tang, W. Huang, J. Luo, and M. Ding,
Syntheses and Properties of Aromatic Pol-
yimides Derived from 2,2,3,3-Biphenyl-
tetracarboxylic Dianhydride, J. Polym.
v
0 I 0
0 I " 0 0
G.L. i Wilkes, Crystallization and Multiple
Melting Behavior of a New Serniciystal-
line Polyimide Based on 1,3-Bis (4-Amino
Phenoxy) Benzene (TPER) and 3,3,4,4'-
Beiizophenonetetracarboxylic Dianhy-
dride (BTDA) , American Chemical Soci-
ety, Polymeric Materials Science and
Engineering (PMSE) Abstracts, Vol 81,
1999, p 303--304
S. Srinivas, F .E. Caputo, M. Graham, S.
Gardner, R.M. Davis, J.E. McGrath, and
G.L. Wilkes, Seniicrystalline Polyimides
Based on Controlled Molecular Weight
Phthalimide End-Capped, Macromole-
cules, Vol 30, 1977, p 1012-1022
M.K. Gerber, J.R. Pratt, AK. St.Clair,-and
TI L. St.Clair, Polyimides Prepared from
3,5-Diaminobenzotriuoride, Polym.
P1p?'., Vol 31(No. 1) , 1990, p 340-341
H.G. Boston, A.K. St. Clair, and J.R. Pratt,
Polymides derived from a Methylene-
Bridged Dianhydride, J. Appl. Polym. Sci.,
Vol 46, 1992, p 243-258 A
D.A. Scola, 3,3-DDS-PMR-16-5, A Non-
Toxic F orm of PMR-15, Proc. High Tem-
ple Workshop X, 29 Jan-1F eb 1990, U.S.
Department of Defense and National Aero-
nautic and Space Administration
R. Vannucci, Non-MDA PMR Polyimides,
Proc. High Temple Workshop XV, 16-19
Jan 1995, U.S. Department of Defense and
National Aeronautic and Space Adminis-
tration
M Meador, High Temperature Polymers
and Composites for Aeropropulsion, Proc
High Temple Workshop XVI I 10-13 F eb
1997, U S Department of Defense and Na-
tional Aeronautic and Space Administra-
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R Gray Resin Transfer Molding of High
Temperature Composites, Proc High Tem-
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Department of Defense and National Aero-
nautic and Space Administration
K C Chuang, JE Waters, andD H Green,
A High TThemiosetting Polyimide, paper
presented at 42nd I nternational SAMPE
Symposium and Exhibit, Society for the
Advancement of Material and Process En-
gineering, 1997, p 1283-1290
K C Chuang, I D Kinder, D L Hull, D B
McConvi1le, and WJ Joungs, Rigid-Rod
Polyimides Based on Noncoplanar 4,4-
Biphenylenediamines A Review of Poly-
mer Properties vs Conguration of D1-
amines, Macromolecules, Vol 30 (No 23)
1997, p 7183-7190
M Meador, R K Eby, C A Gariepy, B N
Nguyen, D Hubbard, and I Williams, Pro-
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Workshop XI X 1999, U S Department of
d N ti al Aeronautic and
Defense an a on
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shop XI X, 1-4 F eb 1999, U.S. Department
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R. Vannucci, P. Delvigs, and R. Gray, Non-
Toxic PMR-Type Polyimides, Proc. High
Temple Workshop XVI I I , 20-22 ]an 1998,
U.S. Department of Defense and National
Aeronautic and Space Administration
J. Sutter, A Review of NASA Advanced
High Temperature Engine Materials Tech-
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Matrix Composites, Proc. High Temple
Workshop XVI I , 10-13 F eb 1997, U.S. De-
partment of Defense and National Aero-
nautic and Space Administration
B.N. Nguyen, R.K. Eby, and M. Meador,
Development of Processable PMR-Type
Polyiinides with Star Branched Structures,
Proc. High Temple Workshop XX, 24-27
Jan 2000, U.S. Department of Defense and
National Aeronautic and Space Adminis-
tration .
C.A. Gariepy, R.K. Eby, and M.A. Meador,
An Approach to Processable Polyimides,
Proc. High Temple Workshop XX, 24-27
Jan 2000, U.S. Department of Defense and
National Aeronautic and Space Adminis-
tration
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D.A. Scola, High Temperature F luorinated
Polymers, U.S. Patent 4,801,682, 31Jan
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Al Hu JY Hao, THe, and SY Yang,
Synthesis and Characterization of High-
Temperature F luonnated-Containing PMR
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1999, p 8046-8051
F E Rogers, Polyarmde-acids and Poly-
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Bridged Diannne, U S Patent 3,356,648,
5 Dec 1967
D G Coe, DiarylF 1uoro Compounds, U S
Patent 3,310,573, 21March 1967
H H Gibbs and C V Breder, High Tem-
perature Laminating Resins Base on Melt
F usible Polyimides, Advances in Chemis-
try American Chemical Society Sympo-
sium Series 142, Copolymers Polyblends
and Composite 1975, p 442-457
Avirnid N Composite Materials, Dat
Sheet H-16044, DuPont
R C Boyce, TP, Gannett, H H Gibbs, and
H R Wedgewood, Processing, Properties
and Applications of K-Polymer Composite
Materials Based on Avimid K-111Pre-
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Process Engineering, 1987, p 169-184
A R Wedgewood, Melt Processable Pol-
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Sci , Polym Chem V0137, 1999, p 1425-
1433
V Ratta, A Ayambem, JE McGrath, and
l ' p ' . 35. .. , . . . . .
. , ' I ' '9 36. . . ' ' ,
' g ' p _ ' I 38. - . ' _ . . i '
. . _ . . H . . _ . . . 39. _ . , . . a
' ' ' : ' 40. . . . 2 . . '
I ' ' ' 8 ' 41. . . T
ail,
ill
~ {"51
-.= : 5 I L. .. 2]
1 Z 1:
.:-it,
.-._y.~ _. ,-1..-iN.= 4._; ,,., ,'.
1
('1
:4;
.75;
i
1
2
I
l
3
.1
i
F
F e
< -1
Q
-.1
3.1
. ..,.,, <
1-3?
. .313
. . - 1
'2
1
.
,1
1
-=
# 3

E
.1
i ...,
..5
I
116 / Constituent Materials
l1) $}1I I 1l(I l6S, U.S. Patent 4,742,152, 3 May
6. D.A. Scola, F luorinated Condensation Co-
polyimides, U.S. Patent 5,298,600, 29
March 1994 I e
7. Scola, Synthesis and Thermo-OXi-
dative Stability of [ 1,4-Phenylene-4,43
(2,2,2-Triuoro-Phenyl Ethylidene) Bis-
phthalimide] and Other F luorinated
Polyirnides, J. Polym. Sci A, Polym. Chem,
V0131, 1993, p 1997-2008 - p
8. Scola and M. Wai, The Thern1o-OX-
idative Stability of F luorinated Polyimides
and Polyimide/Graphite Composites at
371C, J. Appl. Polym. Sci., V0152, 1994,
p 421-429
9. E. Vaccaro and D.A. Scola, Novel F luori-
Hated Polyimides, Proc. High Temple
Workshop XX, 24-27Jan 2000 (San Diego,
Q A) , U.S. Department of Defense and Na-
tional Aeronautic and Space Administra-
tron
10. G.R.vHusk, P.E. Cassidy, and KL. Gebert,
Synthesis and Characterization of a Series
of Polyimides Derived from4,4(2,2,2-Tri-
fluoro-1-Triuoromethyl) Ethylidene] Bis
[ 1,3-I sopbenzofurandione], Macromole-
cnles, Vol 21, 1988, p 1234-1238
11. C.A. Arnold, J.D. Summers, and l.E.
McGrath, Syntheses and Physical Behav-
ior of Siloxane Modied Polyimides, Po-
lyrn. Eng. & Sci., Vol 29 (No. 20) , 1989, p
1413-1418 '
12. M.E..Rogers, H. Giubbs, A. Brennan, D.
Rogriques, G.L. Wilkes, and J.E. McGrath,
Vglv High T,, F ully Cyclized, Soluble Pol-
yirnides, Advances in Polyimide Science
and Technology, Proc. F ourth I nterna-
tional Conference on Polyimides, 30 Oct
to 1Nov 1991, (sponsored by the Society
of Plastics Engineers) , C. F eger, M.M.
Khojasteh, and N.S. Htoo, Ed., Tech-
nomic, Lancaster, PA, p 33-40
13. Hergenrother, J.W. Connell, and J.G.
Srnith, 11:, Phenylethynyl Containing I m-
ide Oligorners, Polymer, Vol 41, 2000, p
5073-5081
14. J.G. Smith, Jr., .l.W. Connell, and P.M.
Hergenrother, The Effect of Phenylethynyl
Terminated I rnide Oligomer Molecular
Weight on the Properties of Composites, J.
Compos. Maren, Vol 34, (No. 7) , 2000, p
614-627
15. .l.E. McGrath, B. Tan, V. Vasuderan, G.W.
Meyer, A.C. Loos, and T. Bullions, Syn-
theses and Characterization of High Per-
formance Thermosetting Polyimides for
S1I 'l1CfL11'al Adhesives md Composite Ma-
tr1X Systems, paper presented at 28th I n-
ternational SAMPE Technical Conf., 4-7
Nov 1996, Society for the Advancement of
Material and Process Engineering, 1996, p
29-38
16~ Y- Tang, W. Huang, J. Luo, and M. Ding,
Syntheses and Properties of Aromatic Pol-
yimides Derived from 2,2,3,3-Biphenyl-
tetracarboxylic Dianhydride, J. Polym.
v
0 I 0
0 I " 0 0
G.L. i Wilkes, Crystallization and Multiple
Melting Behavior of a New Serniciysta1-
line Polyimide Based on 1,3-Bis (4-Amino
Phenoxy) Benzene (TPER) and 3,3,4,4'-
Beiizophenonetetracarboxylic Dianhy-
dride (BTDA) , American Chemical Soci-
ety, Polymeric Materials Science and
Engineering (PMSE) Abstracts, Vol 81,
1999, p 303--304
S. Srinivas, F .E. Caputo, M. Graham, S.
Gardner, R.M. Davis, J.E. McGrath, and
G.L. Wilkes, Seniicrystalline Polyimides
Based on Controlled Molecular Weight
Phthalimide End-Capped, Macromole-
cules, Vol 30, 1977, p 1012-1022
M.K. Gerber, J.R. Pratt, AK. St.C1air,-and
TI L. St.Clair, Polyimides Prepared from
3,5-Diaminobenzotriuoride, Polym.
P1p?'., Vol 31(No. 1) , 1990, p 340-341
I -l.G. Boston, A.K. St. Clair, and J.R. Pratt,
Polymides derived from a Methylene-
Bridged Dianhydride, J. Appl. Polym. Sci.,
Vol 46, 1992, p 243-258 A
D.A. Scola, 3,3-DDS-PMR-16-5, A Non-
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Space Administration
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l ' p ' . 35. .. , . . . . .
. , ' I ' '9 36. . . ' ' ,
' g ' p _ ' I 38. - . ' _ . . i '
. . _ . . H . . _ . . . 39. _ . , . . a
' ' ' : ' 40. . . . 2 . . '
I ' ' ' 8 ' 41. . . T
ail,
ill
~ { "51
-.= : 5 I L. .. 2]
1 Z 1:
.:-it,
.-._y.~ _. ,-1..-iN.= 4._; ,,., ,'.
1
('1
:4;
.75;
i
1
2
I
l
3
.1
i
F
F e
< -1
Q
-.1
3.1
. ..,.,, <
1-3?
. .313
. . - 1
'2
1
.
,1
1
-=
#3

E
.1
i ...,
..5
I
116 / Constituent Materials
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d N ti al Aeronautic and
Defense an a on
Space Administration
R Gray E Collins, and L Livingston,
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l ' p ' . 35. .. , . . . . .
. , ' I ' '9 36. . . ' ' ,
' g ' p _ ' I 38. - . ' _ . . i '
. . _ . . H . . _ . . . 39. _ . , . . a
' ' ' : ' 40. . . . 2 . . '
I ' ' ' 8 ' 41. . . T
ail,
ill
~ { "51
-.= : 5 I L. .. 2]
1 Z 1:
.:-it,
.-._y.~ _. ,-1..-iN.= 4._; ,,., ,'.
1
('1
:4;
.75;
i
1
2
I
l
3
.1
i
F
F e
< -1
Q
-.1
3.1
. ..,.,, <
1-3?
. .313
. . - 1
'2
1
.
,1
1
-=
#3

E
.1
i ...,
..5
I
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1-4 F eb 1999, U.S. Department of Defense
and National Aeronautic and Space Ad-
ministration
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18-21Jan 1993, American Chemical So-
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C , SAMPE Q ., _Vo1 19 (No. 1) , 1987, p
31-36
Polyimide Resins / 1'17
M.J. Turk, A.S. Ansari, W.B. Alston, G.S.
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1999, p 3942 3956 .
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imide Oligomers Terminated with Ther-
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1135
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minated I mide Oligomers and Polymers
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P.M. I -I ergenrother and J.W. Smith, Jr.,
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mer End-Capped with Phenylethyny1-
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22) , 1994, p 4857-4864
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Takekoshi, Synthesis and Characterization
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tion of Polyirnides End-Capped with Phen-
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Sci. A, Polym. Chem, Vol 33, 1995, p
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Nuokogu, Polyimides with Pendant Ethy-
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Hergenrother, Properties of I mide Oligo-
mers Containing Pendant Phenylethynyl
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Proc., Oct 1994 (Cleveland, OH) , NASA
Lewis Research Center
S. Peak, J. Pratte, and R.J. Boyce, Avirnid
RB High Temperature Non-l\ /EA Poly-
imide Composite Prepreg System, paper
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Symposium and Exhibit, Society for the
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gineering, 1999, p 96-102
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Blade, NASA CR-135113, National
Aeronautic and Space Administration, F eb
1976
PMR-15,Data Sheet F 670, Hexcel Cor-
poration, April 1986
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Composite Division (now Cytec F iberite)
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Toughness of Bismaleirnide and Other
Resins, Proc. 43rd Annual Technical Con-
ference and Exhibition, Society of Plastics
Engineers, Antec 85, Vol 31, 1986, p 399-
400
D.A. Scola and J.H. Vontell, High Tem-
perature Polyimides, Chemistry and Prop-
erties, Polyin. Cornpos, Vol 9 (No. 6) ,
1988, p 443-452
R.H. Pater, LARC-RP46, A New 700 F
Matrix Resin Having Attractive Overall
Properties, Proc. High Ternple Workshop
XI I , 27-30 Jan.l992, U.S. Department of
Defense and National Aeronautic and
Space Administration R
Y. Xiao, X.D. Sun, C.D. Simone, and D.A.
Scola, Cure and Postcure of RP-46, a
Nadic End-Capped Polyirnide and a Bis-
nadimide Model Compound, High Per-
form. Polym, to be submitted 2001
T.T. Serani, P.G. Cheng, K.K. Ueda, and
W.F . Wright, I mproved High Temperature
Resistant Matrix Resins, 22nd I nterna-
tional SAMPE Technical Conference, So-
ciety for the Advancement of Material and
Process Engineering, 1990, p 94-107
J.D. Russell, and J.L. Kardos, Crosslinking
Characterization of a Polyimide, AF R
700B, Polym. Campos, Vol 18 (No. 5) ,
1997, p 595-612
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Overview, HiTEMP Review 1993, NASA
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1993 _
S. Prybla, Super I rnide 800, Proc. High
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U.S. Department of Defense and National
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M. Dyer, BF Goodrich Aerospace, per-
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tional SAMPE Technical Conference,
Society for the Advancement of Material
and Process Engineering, 1988, p 562-575
D.A. Scola, J.H. Vontell, and J.P. Pinto, A
Comparison of the Thermo-Oxidative Sta-
bility of PMR-H Type and PMR-15 Poly-
irnides in Graphite Composites, Vol
XXXVI , Society of Plastics Engineers,
1990, p 1300-1301
K.C. Chuang, R.D. Vannucci, I . Anasari,
L.L. Cerny, and D.A. Scheiman, High
F low Addition Curing Polyimides, J. Po-
lym. Sci. A, Polyrn. Chem., Vol 32, 1994, p
1341-1350
R.J. Morgan, E.E. Shin, J. Z hou, J. Lin-
coln, and B. Rozenberg, Current Durability
I ssues on High Temperature Polymers Ma-
trix Composites for Aero-Space Applica-
tions, Proc. High Temple Workshop XI X,
1-4 F eb 1999, U.S. Department of Defense
and National Aeronautic and Space Ad-
ministration
D.A. Scola, Polyimides for 370 C Appli-
cations, Proc. F ourth I nterdisiplinary Sym-
posium on Recent Advances in Polyimides
and Other High Performance Polymers,
18-21Jan 1993, American Chemical So-
ciety
R.D. Vannucci, PMR Polyimide Compo-
sitions for I mproved Performance at 371
C , SAMPE Q ., _Vo1 19 (No. 1) , 1987, p
31-36
Polyimide Resins / 1'17
M.J. Turk, A.S. Ansari, W.B. Alston, G.S.
Gahn, A.A. Primer, and D.A. Scheiman,
Evaluation of the Thermal Oxidative Sta-
bility of Polyirnides via TGA Techniques,
J. Polym. Sci. A, Polym. Chem, Vol 37,
1999, p 3942 3956 .
T.M. Bogert and R.R. Renshaw, ACS Sym-
posinm Series 132, C.A. May, Ed., Vol 30,
American Chemical Society, 1980, p 1140
W.M. Edwards and I .M. Robertson, U.S.
Patent 2,710,853, 1955
EW. Harris, K. Sridhar, and S. Das, Poly-
imide Oligomers Terminated with Ther-
mally-Polyrnerizable Groups, Polyrn.
Prepr., Vol 25 (No. 1) , 1984, p 110-111
EW. Harris, A. Pamidimukkala, R. Gupta,
S. Das, T. Wu, and G. Mock, Syntheses
and Characterization of Reactive End-Cap-
ped Polyimide Oligomers, J. Macromol.
Sci.-Chem, A21(No. 8, 9) , 1984, p 1117-
1135
C.W. Paul, R.A. Schultz, and S.P. F enelli,
Polyimides End-Capped with Diaryl Sub-
stituted Acetylene: Composites, Molding
Material, Adhesives, Electronics, U.S. Pat-
ent 5,138,028,11Aug 1992; also C.-F eger,
M.M. Khoyastech, and M.S. Htoo, Ed.,
Advances in Polyimide Science and Tech-
nology, Technomic Publishing Co., I nc.,
1993, p 220-244 _
P.M. Hergenrother, R.G. Bryant, B.J. Jen-
sen, and S.J. Havens, Phenyl Ethynyl-Ter-
minated I mide Oligomers and Polymers
Therefrom, J. Polym. Sci. A, Polym. Chem,
Vol 32, 1994, p 3061-3067
P.M. I -I ergenrother and J.W. Smith, Jr.,
Chemistry and Properties of I rnide Oligo-
mer End-Capped with Phenylethyny1-
phthalic Anhydrides, Polymer, V0135 (No.
22) , 1994, p 4857-4864
J.A. Johnston, EM. Li, EW. Harris, and T.
Takekoshi, Synthesis and Characterization
of I mide Oligomers End-Capped with 4-
(Phenylethynyl) Phthalic Anhydrides,
Polymer, Vol 35, 1994, p 4865-4873
G.W. Meyer, T.E. Glass, H.J. Grubbs, and
J.E. McGrath, Syntheses and Characteriza-
tion of Polyirnides End-Capped with Phen-
ylethynylphthalic Anhydride, J. Polyrn.
Sci. A, Polym. Chem, Vol 33, 1995, p
2141-2149
B.J. Jensen, P.M. Hergenrother, and G.
Nuokogu, Polyimides with Pendant Ethy-
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J.W. Connell, J.G. Smith, Jr., and P.M.
Hergenrother, Properties of I mide Oligo-
mers Containing Pendant Phenylethynyl
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S.B. Ml< asl< s, R.V. Bhingarkar, M.B.
Sabne, R. Mercier, and S.P. Vernekar, Syn-
thesis and Characterization of End-Capped
Polyimides and Their Gas Permeability
Properties, J. Appl. Polym. Sci., Vol 77
(No. 3) , 2000, p 627-635
JKim, B.-J. Chang, S.-B. Lee, and S.Y.
Kim, I ncorporation of F luorinated Side
Groups into Polyimide Membranes on
Their Pervaporation Properties, J. Membr
Sci., Vol 169 (No. 2) , 2000, p 185-196
J. F ang, H. Kita, and K. Okamoto, Hyper-
branched Polyimides for Gas Separation
Applications I , Syntheses and Character-
118 / Constituent Materials
Properties of Cured I rnide Oligorners Con-
taining Pendant and Terminal Phenylethy-
nyl Groups, paper presented at 29th I nter-
national SAMPE Technical Conference,
Society for the Advancement of Material
and Process Engineering, 1997, p 317-331
J.W. Connell, J.G, Smith, Jr., and P.M.
Hergenrother, I mide Oligorners Contain-
ing Pendant and Terminal Phenylethynyl
Groups I I , High Perform. Poly:/n., Vol 10,
1998, p 273-283
J.G. Smith, Jr. and J.W. Connell, Chemis-
try and Properties of I mide Oligomers
from Phenylethynyl Containing Diamines,
High Perform. Polym., Vol 12, 2000, p
213-223
P.M. Hergenrother, R.G. Bryant, B.J. Jen-
sen, J.G. Smith, Jr., and S.F . Wilkinson,
Chemistry and Properties of Phenylethy-
nyl Terminate I mide Oligomers and their
Cured Polymers, paper presented at I nter-
national SAMPE Symposium and Exhibi-
tion, Society for the Advancement of Ma-
terial and Process Engineering, 1994, p
961-968
B.J. Jensen, R.G. Bryant, and P.M. Her-
genrother, Adhesive Properties of Cured
Phenylethynyl- Terminated Oligomers, J.
Adhes., Vol 54 (No. 1-4) , 1995, p 57-66
R.J. Cano and B.J. Jensen, Effect of Mo-
lecular Weight on Processing and Adhe-
sive Properties of the Phenylethynyl-Ter-
minated Polyimide LARCPETl-5, J.
Adhes., Vol 60, 1996, p 113-123
T. Hon, B.J. Jensen, and P.M. Hergen-
rother, Processing and Properties of lM7/
PETI Composites, J. Compos. Maren, Vol
30 (No; 1) , 1996, p 109-122
P.M. Hergenrotherland M.L. Rommel, Me-
chanical Properties of a Reactive End-Cap-5
ped Polyimide Based Composite from Po-
lyamic Acid, paper presented at 41st
I nternational SAMPE Symposium and EX-
hibition, Society for the Advancement of
Material and Process Engineering, 1996, p
1061-1072
M. Rommel, L. Konopka, and P.M. Her-
genrother, Composite Properties of Cured
Phenylethynyl Containing I mide Oligo-
mers, paper presented at 28th I nternational
SAMPE Technical Conference, Society for
the Advancement of Material and Process
Engineering, 1996, p 14-28
J.W. Connell, J.G. Smith, P.M. Hergen-
rother, and M.L. Rommel, Neat Resin, Ad-
hesive and Composite Properties of Reac-
tive Additive/PETI -5 Blends, High
Perform. P0lym., Vol 12 (No. 2) , 2000, p
323-333
X. F ang, X.-Q . Xie, C.D. Simone, M.P.
Stevens, and D.A. Scola, A Solid State BC
NMR Study of the Cure of BC-Labeled
Phenylethynyl End-Capped Polyirnides,
Macromolecules, Vol 33, 2000, p 1671-
1681
C.C. Roberts, J.M. Apple, and G.E. Wnek,
Curing Chemistry of Phenylethynyl-Ter-
I
99
100
101
102
103
104
105
106
107
108
109
110
lll
rninated I mide Oligomers: Synthesis of
BC-Labeled Oligomers and Solid-State
NMR Studies, J. Polym. Sci. A, Polym.
Chem, Vol 38, 2000, p 3486-3497, _
T.V. Holland, T.E. Glass, and J.E. Mc-
Grath, I nvestigation of the Thermal Curing
Chemistry of the Phenylethynyl Groups
Using a Model Arylether I mide, Polymer,
Vol 41, 2000, p 4965-4990
HR. Lubowitz, Polyimide Polymers,
U.S. Patent 3,528,590, 15 Sept 1970
T.T. Serani, P. Delvigs, and G.R. Light-
sey, Thermally Stable Solutions of Mono-
meric Reactants, J. Appl. Polym. Sci., Vol
16 (No. 4) , 1972, p 905-916; also U.S. Pat-
ent 3,765,149, July 1973
P.R. Young and A.C. Chang, Characteriza-
tion of Geometric I somers of Norbornene
End-Capped I mides, J. Heterocylic Chem,
Vol 20, 1983, p 177-182
D.A. Scola and -JVontell, Some Chem-
ical Characteristics of the Reverse-Diels-
Alder (RDA) Polyimide, PMR-15, Proc.
Second I nternational Conference on Poly-
imides: Chemistry, Characterization, and
Applications, Society of Plastics Engi-
neers, I nc., 1985, p 247-252 3
M.A. Meador, J.C. Johnston, and P.J. Ca-
vano, Elucidation of the Cross-Link Struc-
ture of Nadic End-Capped Polyimides Us-
ing NMR of 13C-Labeled Polymers,
Macromolecules, V0130, 1997, p 515-519
A.C. Wong and W.M. Ritchey, Nuclear
Magnetic Resonance of Study of Norber-
nene End-Capped Polyimides I , Polymer-
ization of N-Phenylnadimide, Macromol-
ecules, Vol 14, 1981, p 825-831
Y. Liu, X.D. Sun, X.-Q . Xie, and D.A.
Scola, Kinetics of the Crosslinking Reac-
tion of all Bisnadimide Model Coinpound'
in Thennal and Microwave Cure Pro-
cesses, ]. Polym. Sci. A: Polym. Chem, Vol
36, 1998, p 2653-2665
H.R. Lubowitz, New Thermosetting Res-
ins F or Composites, ACS Div.'Org. Coar-
ings Plast. Chem. Pap., Vol 31 (No.1) ,
American Chemical Society, 1971, p 560-
568
E.A. Burns, R.J. Jones, R.W. Vaughn, and
W.P. Kendrick, Nadirnide,CR-72633
12-16, NASA, 1970
T.T. Serani, P. Delvigs, and G.R. Light-
sey, Thermally Stable Solutions of Mono-
meric Reactants, J. Appl. Polym. Sci., Vol
16, 1972, p 905-915
D.A. Scola, Thermo-Oxidative Stability
and Moisture Absorption Behavior of
Glass- and Graphite F iber-Reinforced
PMR-Polyimide Composites, paper pre-
sented at 22nd National Symposium and
Exhibition, Society for the Advancement
of Material and Process Engineering,
1977, p 238-252 1
C. Simone and D.A. Scola, Novel F luor-
inated PolyimidesProc. F luoro Polymer
2000, American Chemical Society, 15-18
Oct 2000
B. Nguyen, R.K. Eby, and M.A.-Meador,
High Temperature PMR-Type Polyimides
with Branched Structure: Syntheses and
Characterization, Polym. Prepr., Vol 41
(No. 1) , 2000, p 225-226
A.E. F eiring, B.C. Auman, and E.R. Wen-
choba, Syntheses and Properties of F luor-
inated Polyimides from Novel 2,2-Bis
(F luoroalkoxy) Benzidenes, Macromole-
cules, V0126 (No. 11) , 1993, p 2779-2784
G. Hougham, G. Tesero, and J. Shaw, Syn-
theses and Properties of Highly F luori-
nated Polyimides, Macromolecules, V0127
(No. 13) , 1994, p 3642-3649
BC. Auman, F luorinated Low Thermal
Expansion Coefficient Polyimides for I n-
terlayer Dielectric Applications: Thermal
Stability, Refractive I ndex and High Tem-
perature Molecules Measurements, Mater:
Res. Soc. Proc., Vol 381, 1995, p 19
J.0. Simpson and A.K. St. Clair, F unda-
mental I nsight on Developing LowDielec-
tric Constant Polyimides,Thin Solid
F ilms, 1997, p 308-309
S. Hermciuc, E. Harnciuc, I . Sava, I . Dia-
conu, and M. Bruma, New F luorinated
Poly (I mide-Ether-Amide) s, High Per-
form. Polym., Vol 12, 2000, p 205-276
J.L. Hedrick and Y. Charlier, High Tem-
perature Polyimide Nanofoams, Polym.
Prepr., Vol 35 (No. 1) , 1994, p 245-346
J.L. Hedrick, KR. Carter, R. Ritcher, RD.
Miller, T.P. Russell, V. F lores, D. Meccer-
eyes, and P.H. Jerome, Polyimide Nano-
foams from Alphatic Polyester-Based Co-
polymers, Chem. Maren, Vol 10 (No. 1) ,
1998, p 39-49
S. Tarnai, W. Yamashita, and A. Yamaga-
chi, Thermo-Oxidatively Stable Polyim-
lides"'a7iitlilThir Chemical Structures, .11. Po-
lym. Sci. A, Polym. Chem., Vol 36, 1998, p
1717-1723
LC. Kim, J.I -I . Kim, K.H. Lee, and T.M.
Tali, Preparation of Soluble Polyimides
and Ultraltration Membrane Perfor-
mances, J. Appl. Polym. Sci., V0175, 2000,
p 1-9
G.A. Polotskaya, V.P. Sklizkova, N.D. Ko-
zhurnikova, G.K. Elyashevich, and V.V.
Kudryavtsev, F ormation and Analysis of a
Polyimide Layer in Composite Mem-
branes, J. Polym. Sci., Vol 75, 2000, p
1026-1032
S.B. Ml< asl< s, R.V. Bhingarkar, M.B.
Sabne, R. Mercier, and S.P. Vernekar, Syn-
thesis and Characterization of End-Capped
Polyimides and Their Gas Permeability
Properties, J. Appl. Polym. Sci., Vol 77
(No. 3) , 2000, p 627-635
JKim, B.-J. Chang, S.-B. Lee, and S.Y.
Kim, I ncorporation of F luorinated Side
Groups into Polyimide Membranes on
Their Pervaporation Properties, J. Membr
Sci., Vol 169 (No. 2) , 2000, p 185-196
J. F ang, H. Kita, and K. Okamoto, Hyper-
branched Polyimides for Gas Separation
Applications I , Syntheses and Character-
118 / Constituent Materials
Properties of Cured I rnide Oligorners Con-
taining Pendant and Terminal Phenylethy-
nyl Groups, paper presented at 29th I nter-
national SAMPE Technical Conference,
Society for the Advancement of Material
and Process Engineering, 1997, p 317-331
J.W. Connell, J.G, Smith, Jr., and P.M.
Hergenrother, I mide Oligorners Contain-
ing Pendant and Terminal Phenylethynyl
Groups I I , High Perform. Poly:/n., Vol 10,
1998, p 273-283
J.G. Smith, Jr. and J.W. Connell, Chemis-
try and Properties of I mide Oligomers
from Phenylethynyl Containing Diamines,
High Perform. Polym., Vol 12, 2000, p
213-223
P.M. Hergenrother, R.G. Bryant, B.J. Jen-
sen, J.G. Smith, Jr., and S.F . Wilkinson,
Chemistry and Properties of Phenylethy-
nyl Terminate I mide Oligomers and their
Cured Polymers, paper presented at I nter-
national SAMPE Symposium and Exhibi-
tion, Society for the Advancement of Ma-
terial and Process Engineering, 1994, p
961-968
B.J. Jensen, R.G. Bryant, and P.M. Her-
genrother, Adhesive Properties of Cured
Phenylethynyl- Terminated Oligomers, J.
Adhes., Vol 54 (No. 1-4) , 1995, p 57-66
R.J. Cano and B.J. Jensen, Effect of Mo-
lecular Weight on Processing and Adhe-
sive Properties of the Phenylethynyl-Ter-
minated Polyimide LARCPETl-5, J.
Adhes., Vol 60, 1996, p 113-123
T. Hon, B.J. Jensen, and P.M. Hergen-
rother, Processing and Properties of lM7/
PETI Composites, J. Compos. Maren, Vol
30 (No; 1) , 1996, p 109-122
P.M. Hergenrotherland M.L. Rommel, Me-
chanical Properties of a Reactive End-Cap-5
ped Polyimide Based Composite from Po-
lyamic Acid, paper presented at 41st
I nternational SAMPE Symposium and EX-
hibition, Society for the Advancement of
Material and Process Engineering, 1996, p
1061-1072
M. Rommel, L. Konopka, and P.M. Her-
genrother, Composite Properties of Cured
Phenylethynyl Containing I mide Oligo-
mers, paper presented at 28th I nternational
SAMPE Technical Conference, Society for
the Advancement of Material and Process
Engineering, 1996, p 14-28
J.W. Connell, J.G. Smith, P.M. Hergen-
rother, and M.L. Rommel, Neat Resin, Ad-
hesive and Composite Properties of Reac-
tive Additive/PETI -5 Blends, High
Perform. P0lym., Vol 12 (No. 2) , 2000, p
323-333
X. F ang, X.-Q . Xie, C.D. Simone, M.P.
Stevens, and D.A. Scola, A Solid State BC
NMR Study of the Cure of BC-Labeled
Phenylethynyl End-Capped Polyirnides,
Macromolecules, Vol 33, 2000, p 1671-
1681
C.C. Roberts, J.M. Apple, and G.E. Wnek,
Curing Chemistry of Phenylethynyl-Ter-
I
99
100
101
102
103
104
105
106
107
108
109
110
lll
rninated I mide Oligomers: Synthesis of
BC-Labeled Oligomers and Solid-State
NMR Studies, J. Polym. Sci. A, Polym.
Chem, Vol 38, 2000, p 3486-3497, _
T.V. Holland, T.E. Glass, and J.E. Mc-
Grath, I nvestigation of the Thermal Curing
Chemistry of the Phenylethynyl Groups
Using a Model Arylether I mide, Polymer,
Vol 41, 2000, p 4965-4990
HR. Lubowitz, Polyimide Polymers,
U.S. Patent 3,528,590, 15 Sept 1970
T.T. Serani, P. Delvigs, and G.R. Light-
sey, Thermally Stable Solutions of Mono-
meric Reactants, J. Appl. Polym. Sci., Vol
16 (No. 4) , 1972, p 905-916; also U.S. Pat-
ent 3,765,149, July 1973
P.R. Young and A.C. Chang, Characteriza-
tion of Geometric I somers of Norbornene
End-Capped I mides, J. Heterocylic Chem,
Vol 20, 1983, p 177-182
D.A. Scola and -JVontell, Some Chem-
ical Characteristics of the Reverse-Diels-
Alder (RDA) Polyimide, PMR-15, Proc.
Second I nternational Conference on Poly-
imides: Chemistry, Characterization, and
Applications, Society of Plastics Engi-
neers, I nc., 1985, p 247-252 3
M.A. Meador, J.C. Johnston, and P.J. Ca-
vano, Elucidation of the Cross-Link Struc-
ture of Nadic End-Capped Polyimides Us-
ing NMR of 13C-Labeled Polymers,
Macromolecules, V0130, 1997, p 515-519
A.C. Wong and W.M. Ritchey, Nuclear
Magnetic Resonance of Study of Norber-
nene End-Capped Polyimides I , Polymer-
ization of N-Phenylnadimide, Macromol-
ecules, Vol 14, 1981, p 825-831
Y. Liu, X.D. Sun, X.-Q . Xie, and D.A.
Scola, Kinetics of the Crosslinking Reac-
tion of all Bisnadimide Model Coinpound'
in Thennal and Microwave Cure Pro-
cesses, ]. Polym. Sci. A: Polym. Chem, Vol
36, 1998, p 2653-2665
H.R. Lubowitz, New Thermosetting Res-
ins F or Composites, ACS Div.'Org. Coar-
ings Plast. Chem. Pap., Vol 31 (No.1) ,
American Chemical Society, 1971, p 560-
568
E.A. Burns, R.J. Jones, R.W. Vaughn, and
W.P. Kendrick, Nadirnide,CR-72633
12-16, NASA, 1970
T.T. Serani, P. Delvigs, and G.R. Light-
sey, Thermally Stable Solutions of Mono-
meric Reactants, J. Appl. Polym. Sci., Vol
16, 1972, p 905-915
D.A. Scola, Thermo-Oxidative Stability
and Moisture Absorption Behavior of
Glass- and Graphite F iber-Reinforced
PMR-Polyimide Composites, paper pre-
sented at 22nd National Symposium and
Exhibition, Society for the Advancement
of Material and Process Engineering,
1977, p 238-252 1
C. Simone and D.A. Scola, Novel F luor-
inated PolyimidesProc. F luoro Polymer
2000, American Chemical Society, 15-18
Oct 2000
B. Nguyen, R.K. Eby, and M.A.-Meador,
High Temperature PMR-Type Polyimides
with Branched Structure: Syntheses and
Characterization, Polym. Prepr., Vol 41
(No. 1) , 2000, p 225-226
A.E. F eiring, B.C. Auman, and E.R. Wen-
choba, Syntheses and Properties of F luor-
inated Polyimides from Novel 2,2-Bis
(F luoroalkoxy) Benzidenes, Macromole-
cules, V0126 (No. 11) , 1993, p 2779-2784
G. Hougham, G. Tesero, and J. Shaw, Syn-
theses and Properties of Highly F luori-
nated Polyimides, Macromolecules, V0127
(No. 13) , 1994, p 3642-3649
BC. Auman, F luorinated Low Thermal
Expansion Coefficient Polyimides for I n-
terlayer Dielectric Applications: Thermal
Stability, Refractive I ndex and High Tem-
perature Molecules Measurements, Mater:
Res. Soc. Proc., Vol 381, 1995, p 19
J.0. Simpson and A.K. St. Clair, F unda-
mental I nsight on Developing LowDielec-
tric Constant Polyimides,Thin Solid
F ilms, 1997, p 308-309
S. Hermciuc, E. Harnciuc, I . Sava, I . Dia-
conu, and M. Bruma, New F luorinated
Poly (I mide-Ether-Amide) s, High Per-
form. Polym., Vol 12, 2000, p 205-276
J.L. Hedrick and Y. Charlier, High Tem-
perature Polyimide Nanofoams, Polym.
Prepr., Vol 35 (No. 1) , 1994, p 245-346
J.L. Hedrick, KR. Carter, R. Ritcher, RD.
Miller, T.P. Russell, V. F lores, D. Meccer-
eyes, and P.H. Jerome, Polyimide Nano-
foams from Alphatic Polyester-Based Co-
polymers, Chem. Maren, Vol 10 (No. 1) ,
1998, p 39-49
S. Tarnai, W. Yamashita, and A. Yamaga-
chi, Thermo-Oxidatively Stable Polyim-
lides"'a7iitlilThir Chemical Structures, .11. Po-
lym. Sci. A, Polym. Chem., Vol 36, 1998, p
1717-1723
LC. Kim, J.I -I . Kim, K.H. Lee, and T.M.
Tali, Preparation of Soluble Polyimides
and Ultraltration Membrane Perfor-
mances, J. Appl. Polym. Sci., V0175, 2000,
p 1-9
G.A. Polotskaya, V.P. Sklizkova, N.D. Ko-
zhurnikova, G.K. Elyashevich, and V.V.
Kudryavtsev, F ormation and Analysis of a
Polyimide Layer in Composite Mem-
branes, J. Polym. Sci., Vol 75, 2000, p
1026-1032
S.B. Ml< asl< s, R.V. Bhingarkar, M.B.
Sabne, R. Mercier, and S.P. Vernekar, Syn-
thesis and Characterization of End-Capped
Polyimides and Their Gas Permeability
Properties, J. Appl. Polym. Sci., Vol 77
(No. 3) , 2000, p 627-635
JKim, B.-J. Chang, S.-B. Lee, and S.Y.
Kim, I ncorporation of F luorinated Side
Groups into Polyimide Membranes on
Their Pervaporation Properties, J. Membr
Sci., Vol 169 (No. 2) , 2000, p 185-196
J. F ang, H. Kita, and K. Okamoto, Hyper-
branched Polyimides for Gas Separation
Applications I , Syntheses and Character-
ization, Macromolecules, Vol 33 (No. 13) ,
2000, p 4639466()
C.J. Wang, W.,Harrison, J. Mecharn, R.
F ormato, R. Kovan, P. Osenar, and J.E.
McGrath, Synthesis of Sulfonated Poly
(Arylene Ether Sulfones) via DirectPoly-
merization, Polym. Prepr. Vo141(No. 1) ,
2000, p 237-2381 .
Y. Z hang, M. Litt, R.F . Savinell, J.S. Wain-
right, and J. Vandraniini, Molecular De-
sign of Polyimides Toward High Proton
Conducting Meterials, Polym. Prepra, Vol
41(No. 2) , 2000, p 1651-1562
C.S. Wang and T.S. Leu, Soluble Polyim-
ides Containing Napthalene Structure, P0-
lym. Prepr. Vol 41(No. 2) , 2000, p 1205-
1206
T.L. Grubb, KL. Ulery, TJ. Smith, G.L.
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C.J. Wang, W.,Harrison, J. Mecharn, R.
F ormato, R. Kovan, P. Osenar, and J.E.
McGrath, Synthesis of Sulfonated Poly
(Arylene Ether Sulfones) via DirectPoly-
merization, Polym. Prepr. Vo141(No. 1) ,
2000, p 237-2381 .
Y. Z hang, M. Litt, R.F . Savinell, J.S. Wain-
right, and J. Vandraniini, Molecular De-
sign of Polyimides Toward High Proton
Conducting Meterials, Polym. Prepra, Vol
41(No. 2) , 2000, p 1651-1562
C.S. Wang and T.S. Leu, Soluble Polyim-
ides Containing Napthalene Structure, P0-
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Polyirnide F oams for Aerospace Vehicles,
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12
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T.L. Grubb, KL. Ulery, TJ. Smith, G.L.
Tullos, H. Yagci, L.J. Mathia, and M.
Langsam, Highly Soluble Polyimides from
Sterically Hindered Diamines, Polymer,
V0140, 1999, p 4279-4288
I .C. Kim and I .M. Tak, Synthesis and
Characterization of Soluble Random Co-
plyimides, J. Appl. Polym. Sci., Vol 74,
1999, p 272-277
C.~ P. Yang and H.-W. Yang, Preparation
and Chmacterization of Organosoluble Co-
polyimides Based on a Pair of Commercial
Aromatic Dianhydride and One Aromatic
Diamine, 1,4-Bis (4-AminophenoXy) -2-
Tera-Bntybenzene Series, J. Appl. Polym.
Sci., Vol 75 (N0. 1) , 2000, p 87 -95
132.
133
134
135
136
137.
S.Z .D. Cheng, F . Li, E.P. Savitsks, and
F .W. Harris, Molecular Design of Aro-
matic Polyimide F ilms, as Uniaxial Neg-
ative Birefrigent Optical Compensators in
Liquid Crystal Displays, TRI P, V015 (N0.
2) , F eb 1997, p 51--58 _
B. Li, T. He, and M. Ding, Correlation Be-
tween Chain Conformation and Optical
Anisotropy of Thin F ilms of an Organo-
Soluble Polyirnide, Polymer, Vol 38 (No.
26) , 1997, p 6413-6416
S. Akimoto, M. Jikei, and M.-A. Ka1< i-
rnoto, A Novel Photosensitive Polyirnide:
A Polyimide Containing the Hydroxy Tri-
phenylamine Structure with Diaz.onaphth-
oquinone, High Perform. P0lym., Vol 21
(No. 11) , 2000, p 177-184
L. Bes, A. Rosseau, B. Bouterin, R. Mer-
cier, B. Sillion, and E. Joussaere, Synthesis
and Characterization of Aromatic Poly-
imides Bearing Nonlinear Optical Chro-
mophores, High Pezform. P0lym., Vol 12
(No. 1) , 2000, p 169176
M.H. Davey, V.Y Lee, L.-M. Wu, C.R.
Moylan, W. Volksen, A. Knoesen, R.D.
Miller, and T.J. Marks, Ultra High Tem-
perature Polymers for Second-Order Non-
linear Optics, Synthesis and Properties of
Robust, Processable, ChI OI I 10pl'116-EH1-
bedded Polyimides, Chem. Mater, Vol 12
(No. 6) , 2000, p 1679-1693
H.Y. Woo, H.-K. Shim, K.-S. Lee, M.-Y.
Jeong, and T.-K. Lim, An Alternate Syn-
Polyimide Resins / 119
thetic Approach F or Soluble Non-Linear
Optical Polyirnides, Chem. Maren, Vol 11
(No. 2) , 1999, pp2182,26
K. Han, W.-H. Jang, and T.-H. Rhee, Syn-
theses of F luorinated Polyimide and Their
Application of Passive Optical Wavegui-
des, J. Appl. Polym. Sci., Vol 72 (No. 10 ) ,
2000, p 2172-2177
M. Berrada, F . Carriere, B. Coutin, P. Mon-
jol, H. Sekignchi, and R. Mercier, Novel
Negative-Type Soluble Photosensitive
Polyiniides: Synthesis and Characteriza-
tion, Chem. Mater, Vol 8 (No. 5) , 1996, p
1029-1034
Y. Chen and J.0. I roh, Synthesis and Char-
acterization of Polyimide/Silica Hybrid
Composites, Chem. Mater, Vol 11, 1999,
p 1218-1222 .
SJ. Hobsen and KJ. Shea, Bridged Bis-
imide Polysilsequioxane Xerogels: New
Hybrid Organic-I norganic Materials,
Chem. Maren, Vol 9, 1997, p 616-623
E.S. Weiser, J.F . Johnson, T.L. St. Clair, Y.
Echigo, H. Kaneshiro, and B.W. Grimsley,
Polyirnide F oams for Aerospace Vehicles,
High Pelform POZ ym., Vol 12, 2000, p 1-
12
V.E. Yudin, LU. Otaigbe, and V.N.Arten:1--
iera, Processing and Properties of a New
High Temperature Lightweight Compos-
ites Based on F oam Polyimide Binder, P0-
lym. C0mp., V0120 (No. 3) , 1999, p 337-
345