10 High-Performance Polyimides and High Temperature

Resistant Polymers
Kreisler S.Y. Lau
Chemco Systems, Inc., Redwood City, California, USA

O U T L I N E

Historical Perspective 297 Applicability of Thermoset Isoimides/Imides

to Resin Transfer Molding Processing 382
Polyimides from Condensation Reactions 299
Galvanic Corrosion Resistance of Polyimide
Thermoplastic Polyimides 314
Composites 385
Addition-Curable Polyimides and Other
High-Performance Polymers for Lightning
Polymers 335
Strike Protection 387
Nadimide-Terminated Thermosetting
Ultrahigh Temperature Resistant Polymers 388
Polyimides 336
Chemical Structures Suitable for Ultrahigh
Maleimide-Terminated Thermosetting
Temperature Use 389
Polyimides 344
Novel Cross
Linking Mechanisms for Stability
Cyanate-Terminated Thermosetting Polymers 351
at Ultrahigh Temperatures 396
High-Temperature Thermosetting Resins Based
Thermosets as Dielectric Interlayers in
on Phthalonitrile 356
Integrated Circuit (IC) Fabrication 396
Acetylene-Terminated Thermosetting
Polymer-Ceramic Materials 409
Polymers 361
Acknowledgments 413
Propargyl-Terminated Oligomers 374
References 413
Phenylethynyl-Terminated Thermosetting
Polymers 374

Historical Perspective successful materials were those that could overcome

After World War II, rapid expansion of the aero-
space industry created a need for new materials for
the new high technology that it generated. Many of
these requirements could not be achieved with
metallic and existing plastic materials. There was a
need for newer materials that would be lightweight,
oxidatively and thermally stable, have good
mechanical properties and could operate in space
environments. During the next half-century many
new polymers were discovered which had unusual
mechanical properties at high temperatures. Relatively
few achieved commercial success, however. The
the challenges of manufacturing cost and the inherent
difficulties to be fabricated into useful forms.
One class of polymers, the polyimides, was suc-
cessfully introduced as commercial materials in the
early nineteen-sixties by E. I. Du Pont de Nemours
and Company [1,2]. The continued success of these
polymers as commercial materials was due to the
availability of inexpensive starting material and
the ability to tailor these polymers to a variety of end
uses.
The polyimides are characterized by the presence
of repeating imide structural units (I) in the poly-
mer backbone. This structure contributes to the

Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00010-5

© 2014 Elsevier Inc. All rights reserved. 297
298
O O
R
N R' N X
O O
n X = OH or OR
O O
N N
O O
n N
II
Figure 10.1 Aromatic characteristics in polyimides
contribute to their thermo-oxidative stability.
exceptional thermal and oxidative stability of polyi-
mides. Polyimides have been prepared from a vari-
ety of dianhydride and diamine monomers. High
thermo-oxidative stability has been achieved using
aromatic structures for R and R0 (II) (Figure 10.1).
Evidently it is necessary to have the imide struc-
ture along with the aromatic moieties because wholly
aromatic polymers such as polyphenylenes are not as
thermo-oxidatively resistant as polyimides. The com-
bination of the aromatic structure and the imide struc-
ture results in a polymer with a high glass transition
temperature (Tg) and high thermo-oxidative stability.
These aromatic polyimides can be processed either as
thermosetting or as thermoplastic resins depending
on the polymer resin’s processing characteristics or
the process required to transform the prepolymer
resin into the final form or shape. These polymers are
thereby broken down conveniently into three catego-
ries depending upon their processing characteristics.
One of these categories includes thermoplastic polyi-
mides. Since their high glass transition temperatures
overlap the glass transition temperatures of some of
the thermosetting polyimides, they will be discussed
in conjunction with the thermosetting polyimides,
which represent an important commercial advance-
ment in polyimide technology.
The polyimides in the first category are processed
via precursors that undergo condensation reactions
to form the final imide structures. The precursors are
usually the amic acid or the amic ester intermediate.
They are tractable, soluble in common organic sol-
vents, and generally are applied as lacquers. Upon
conversion to the imide through curing, the polymer
HANDBOOK OF THERMOSET PLASTICS
O O O
NH R1 NH R2 NH R1
X X
O O O
– H2O or ROH
O O O
R1 N R2 N R1
O O O
Figure 10.2 Conversion of polyamic acid to
polyimide via the condensation-type thermal curing
reaction.
is rendered insoluble and intractable. Figure 10.2
illustrates the thermal cure reaction:
The cyclodehydration step requires temperatures
greater than 140°C (284°F). Generally temperatures
up to 300°C (572°F) are used to ensure complete
cyclization. It is also possible to effect cyclization
by chemical dehydration with reagents such as ali-
phatic acid anhydrides, ketenes, and strong Lewis
acids such as phosphorus trichloride. During the
transformation from the amic acid to the imide by
these reagents, the intermediacy of the relatively
thermally unstable isoimide (vide infra, “Isoimide
Modification of Polyimides”) is suggested. When
N,N-dicyclohexylcarbodiimide (DCC) is used as
the dehydrating agent, the polyamic acid is trans-
formed to polyisoimide in greater than 80% conver-
sion. Trifluoroacetic anhydride generally converts
polyamic acid to a mixture of isoimide and imide,
the isoimide content ranging from 50
70%. As
will be discussed later, the commercial isoimide
oligomer product, Thermid® IP-600, has been suc-
cessfully produced via DCC dehydration at
National Starch and Chemical Corporation (vide
infra). The isoimide form of polyimide becomes a
convenient pre-form that is more easily processible
and thermally transforms into the polyimide struc-
ture WITHOUT evolution of volatile byproducts.
The polyimides in the second category owe their
processibility to their thermoplasticity above their
glass transition temperature. They are processed
much the same way as other thermoplastics except
at much higher temperatures. Thermoplasticity of
polyimides is attained through modification of the
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 299

O O

N CH2 N

O O

III
H
C
O O O O O O O O C

N N N N

C O O O O
C
H n

IV

Figure 10.3 Illustrative examples of thermoset polyimides with reactive end-groups.

polymer backbone or by the attachment of pendent
side chains. In some cases, these polyimides have
sufficient solubility in select solvents to permit the
formulation of lacquers so they can be used as coat-
ings or laminating resins.
The third category of polyimides owes its pro-
cessibility to the use of low-molecular-weight,
soluble and fusible short-chain oligomers, which
have homopolymerizable end-groups. This permits
the polymer chain to grow by addition-type chemi-
cal reactions that do not generate volatile by-
products. The most successful reactive prepoly-
mers of this category are based on bismaleimides
(III) and acetylene-terminated polyimides (IV)
(Figure 10.3).
These prepolymers undergo homopolymeriza-
tion on heating. In order to obtain a processible
prepolymer it is necessary that they do not homo-
polymerize below their melting point and that
they have reasonable solubility in a number of
solvents that can be used as a lacquer for pre-
pregs. Thus, cross-linked polyimides have been
made by thermal polymerization of bismaleimides,
preferably by heating them above their melting
points in the presence of free-radical catalysts
such as dicumyl peroxide and also from
acetylene-terminated polyimides by thermal poly-
merization. In more recent years, phenylethyny-
lated imide prepolymers have also been studied
(referred to a later section).
Polyimides from Condensation
Reactions
The most important polyimides of this first
group are based on the monomer pyromellitic dia-
nhydride (PMDA) (V). This monomer is manufac-
tured by Du Pont Company and obtained by the
vapor-phase oxidation of durene (1,2,4,5-tetra-
methylbenzene), using a supported vanadium oxide
catalyst. The reaction of PMDA with certain aro-
matic amines, for example, m-phenylendiamine
(MPDA) (VI), benzidine, and bis(4-aminophenyl)
ether (4,40 -ODA) (VII), gives polymers having a
high degree of oxidative and thermal stability.
Figure 10.4 depicts some important commodity
monomers for polyimide commercialization.

O O
H2N NH2 O
O O

O O H2N NH2

V VI VII

Figure 10.4 Some important monomers for polyimide production.

300 HANDBOOK OF THERMOSET PLASTICS

The synthesis is carried out generally as a two- special Kapton® film designed to withstand oxygen
stage process [3], which involves the preparation of plasma etching. This special Kapton® film was pre-
the intermediate polyamic acid prepolymer and the pared by applying a low earth orbit (LEO), atomic
conversion of the prepolymer to polyimide under a oxygen resistant (AOR) thin film to DuPont’s Type
specific cure cycle. The imidization process has H Kapton® film.
been studied using infrared spectroscopy. In the
temperature range of 220°
250°C (428°
482°F),
complete imidization takes place. Higher tempera-
tures appear to cause cross-linking by the formation
of an interchain network. Russian workers have
reported that at the higher temperatures the struc-
turization depends on reversible cleavage of -CO-
N- bonds [4] and their recombination. The Du Pont
Company has marketed a number of polyimide pro-
ducts based on PMDA (V) and the aromatic amine
4,40 -ODA (VII) namely Kapton®(supplied as a
film), Vespel® (supplied as sintered parts), and
Pyre-M.L.® supplied as a lacquer of the polyamic
acid prepolymer.
The Kapton® film is supplied in several forms:
Type H is the uncoated polyimide film.
Figures 10.5 and 10.6 show two major applications
of this film. Type V is similar to type H but with a
Figure 10.5 Kapton® cover on solar panel in the
superior dimensional stability. Type F is a Type H
spaceship Discovery. (Courtesy: E.I. Du Pont de
film coated on one or both sides with a Teflont
Nemours and Company).
fluorinated ethylene propylene (FEP) resin to pro-
vide a moisture barrier and to enhance chemical
resistance. Some typical properties of these films
are shown in Tables 10.1 through 10.6 [5]. Vespel®
is supplied as sintered parts and formulated with
various fillers. A description of the various Vespel®
compositions commercially available is shown in
Table 10.7[6]. Some of the typical properties from
these compositions are shown in Tables 10.8
through 10.12 [6]. These property data are for refer-
ence only. Since service conditions may differ from
laboratory test conditions, users of Vespel® parts
and shapes should independently evaluate the suit-
ability of these parts using their own test proce-
dures. The properties of Pyralin® are shown in
Tables 10.13 and 10.14 [5].
In recent years, Sheldahl, Inc. has been involved
in manufacturing a coated material for the photo-
voltaic solar cell array assembly of NASA’s Space Figure 10.6 Kapton® Printed Circuit in Disk Drive.
Station Freedom [7]. The material selected was a (Courtesy: E.I. du Pont de Nemours and Company).
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 301

Table 10.1 Kapton® Type H Film Physical Properties [5] (1 mil)

(Reprinted by permission from Du Pont Company)

302 HANDBOOK OF THERMOSET PLASTICS

Table 10.2 Kapton® Type V Film—Typical Properties [5]

(Reprinted by permission from Du Pont Company)

Table 10.3 Kapton ® Type H Film—Typical Electrical Properties [5]

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 303

Table 10.3 (Continued)

(Reprinted by permission from Du Pont Company)

Table 10.4 Kapton® Type F Film—Typical Electrical Properties [5]


Film engineering:
120F616: 1.2 mil nominal thickness; 0.1 mil Teflont FEP; 1 mil Kapton® Type H, 0.1 mil Teflont FEP
150F019: 1.5 mils nominal thickness, 0.0 mil Teflont FEP; 1 mil Kapton® Type H, 0.5 mil Teflont FEP
250F029: 25 mils nominal thickness, 0.0 mil Teflont FEP; 2 mil Kapton® Type H; 0.5 mil Teflont FEP
(Reprinted by permission from Du Pont Company)
304 HANDBOOK OF THERMOSET PLASTICS

Table 10.5 Kapton® Type F Film-Mechanical Properties [5]


Film engineering:
120F616: 1.2 mil nominal thickness; 0.1 mil Teflont FEP; 1 mil Kapton® Type H, 0.1 mil Teflont FEP
150F019: 1.5 mils nominal thickness, 0.0 mil Teflont FEP; 1 mil Kapton® Type H, 0.5 mil Teflont FEP
250F029: 25 mils nominal thickness, 0.0 mil Teflont FEP; 2 mil Kapton® Type H; 0.5 mil Teflont FEP
(Reprinted by permission from Du Pont Company)
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 305

Table 10.6 Gas Permeability of Kapton® Type H Film [5]

(Reprinted by permission from Du Pont Company)

Table 10.7 Vespel® Polyimide Composition [6]

(Reprinted by permission from Du Pont Company)

306 HANDBOOK OF THERMOSET PLASTICS

Table 10.8 Mechanical Properties of Vespel® SP Polyimide Resins [6]


Properties are non-directional.
(Reprinted by permission from Du Pont Company)
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 307

Table 10.9 Wear and Friction Properties of Vespel® SP Polyimide Resins [6]


Properties are non-directional.

Steady state, unlubricated in air.
(Reprinted by permission from Du Pont Company)

Table 10.10 Electrical Properties at 23°C of Vespel® SP Polyimide Resins [6]

(Reprinted by permission from Du Pont Company)

308 HANDBOOK OF THERMOSET PLASTICS

Table 10.11 Thermal and Electrical Properties of Vespel® SP Polyimide Resins [6]

(Reprinted by permission from Du Pont Company)

Table 10.12 Other Select Properties of Vespel® SP Polyimide Resins [6]

(Reprinted by permission from Du Pont Company)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 309

Table 10.13 Pyralin® Coatings, Lacquer Typical Properties [5]


Typical properties; not to be used for specification purposes.
(Reprinted by permission from Du Pont Company)

Table 10.14 Pyralin® Polyimide Film Properties [5]

(Continued )
310 HANDBOOK OF THERMOSET PLASTICS

Table 10.14 (Continued)

(Reprinted by permission from Du Pont Company)

Polyimides based on the dianhydride, 3,30 ,4,40 -ben- O O O

zophenonetetracarboxylic dianhydride (BTDA) (VIII) H2N NH2
O O
and meta-phenylenediamine (MPDA) (VI) have been
marketed by Monsanto Company as the Skybond 700 O O
series [8] and by American Cyanamid Company (see VIII VI
Footnote)1 as FM-34 lacquers (Figure 10.7).
The Skybond® 700 lacquer consists of a solution Figure 10.7 Precursor monomers to commercial
of monomer reactants of the diester, diacid and skybond and FM-34 polyimides.
diamine. Solvents such as ethanol, butanol, ethyl-
ene glycol and N-methylpyrrolidinone (NMP) are
used as solvents for these monomers.

1
The readers are referred to Wikipedia entries for more details. American Cyanamid merged with American Home Products in 1994.
American Home Products (AHP) eventually changed its name to Wyeth Corporation (one of its subsidiaries). In 2009 Wyeth merged
with Pfizer. After the original AHP acquisition of American Cyanamid, the Pigments division was sold to National Lead Company.
Consumer products were sold to Procter and Gamble. In 2000, the $1.7 billion agricultural business was acquired by BASF.
Most of the chemical businesses of American Cyanamid more closely relevant to thermoset plastics are now operated by a spun-off
successor Cytec.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 311

Skybond® 700 is specifically designed for struc-
tural, electrical, and specialty applications where
extended exposure to temperatures to 371°C (700°
F) is required. These resins are useful for preparing
prepregs for laminates that can be molded by either
hot-press or vacuum bag techniques. Mechanical
properties of Skybond® 700 are shown in
Table 10.15 [8]. The properties were obtained after
a sixteen-hour postcure cycle which included a
final postcure for four hours at 371°C (700°F) for
developing adequate initial hot strength at 371°C
(700°F). Table 10.16 tabulates the electrical proper-
ties of Skybond® laminates [8]. These properties
were measured on laminates that were hot-press
molded to keep the void content low.
FM®-36 is a modified polyimide supplied as a sup-
ported film with a lightweight glass cloth [9]. It is
suitable for bonding metal to metal, composites and
various sandwich structures; and it serviceable over a
temperature range of 255°C (2 67°F) to 288°C
(550°F). Typical tensile shear properties of FM®-36
adhesive are shown in Table 10.17 [9]. FM®-34-18

Table 10.15 Mechanical Properties of Laminate Utilizing Skybond® 700 Polyimide [8]


1/8-inch thick laminates made using 181 glass cloth with A-1100 soft finish.
(Reprinted by permission from Monsanto Company); (Skybond® is a registered trademark of Monsanto Company)
312 HANDBOOK OF THERMOSET PLASTICS

Table 10.15A 600°F Long-Term Aging Study (High Temperature
High Pressure Laminates)

(Reprinted by permission from Monsanto Company); (Skybond® is a registered trademark of Monsanto Company)

Table 10.15B 550°F Long-Term Aging Data (High Temperature-High Pressure Laminates)

(Reprinted by permission from Monsanto Company); (Skybond® is a registered trademark of Monsanto Company)

Table 10.16 Electrical Properties of Laminates Using Skybond® 700 s(High Temperature
High Pressure
Laminates) [8]

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 313

Table 10.16 (Continued)

(Reprinted by permission from Monsanto Company)

Table 10.17 Typical Average Tensile Shear Properties of FM®36 Adhesive Tested with BR®36 Primer [9]


Cured two hours at 550°F.
(Reprinted by permission from American Cyanamid Company)
314
Table 10.18 Mechanical Properties of FM® 34B-18 Adhesive Film with BR® 34B-18 Adhesive Primer[10]
Metal 0.050 inch, Type 301, half-hardened stainless steel.
Cleaning Process: Prebond 700-acid pickle-acid etch.
(Reprinted by permission from American Cyanamid Company)
H2N CH2 NH2
IX
CH3 CH3
H2N CH2 CH2 CH2 Si O Si CH2 CH2 CH2 NH2
CH3 CH3
X polymer designations and the corresponding
Figure 10.8 Diamine monomers for the SiPI
polymer system. (Courtesy: General Electric
Company).
adhesives are arsenic-free versions of FM®-34 polyi-
mide adhesive film. This adhesive is available as a
supportive and unsupportive film and as a paste.
These adhesives are noted for strength retention after
long-term exposure to temperatures of 255°C
(2 67°F) to 371°C (700°F) in both metal and com-
posite constructions. The mechanical properties of
this adhesive are shown in Table 10.18 [10].
General Electric Company introduced a polyi-
mide [11] that also has the silicon-oxygen linkage
in the polymer backbone. These are known as sili-
cone polyimides (SiPI) and show promise for use
as passivation coating and as interlayer dielectrics
for electronic applications. Unlike conventional
polyimides, the SiPI possess excellent inherent
adhesive properties that eliminate the necessity of
primers. The adhesive properties seem to be insen-
sitive to moisture. SiPI is a block copolymer pre-
pared from BTDA (VIII), methylenedianiline
(MDA) (IX), and 1,3-bis(γ-aminopropyl)-tetra-
methyl disiloxane(GAP) (X) (Figure 10.8) [11].
The polyamic acid is prepared by first adding
MDA to BTDA followed by the addition of GAP.
HANDBOOK OF THERMOSET PLASTICS
The scheme for the preparation of the 70/30 MDA/
GAP block copolymer SiPI is shown in
Figure 10.9.
The electrical properties of SiPI are shown in
Table 10.19 [12] and the adhesion of SiPI and
Pyralin® on various wafer surfaces are compared in
Table 10.20 [12]. Table 10.21 lists the various
manufacturer.
Thermoplastic Polyimides
Although polyimides are generally classified as
thermoset resins because of the way they are pro-
cessed and because of the very high melt tempera-
tures, there is one class of polyimides that are
thermoplastic. They are included in this discussion
because they are very important materials and can-
not be easily separated from the other polyimides.
The thermoplastic polyimides can theoretically be
processed through the polyamic acid precursor, but
are not generally processed in that manner. The
processible polyimides were specifically developed
so that they can be processed by methods analogous
to the thermoplastics. Rather than being applied as
an amic acid precursor, they are processed in the
imidized form. This allows well-formed moldings
and compositions with a very low void content, as
no volatiles are produced during the processing.
The thermoplastic polyimides are not crosslinked
and they may have some degrees of solubility in
select solvents. To make the polyimides thermo-
plastic it is necessary to modify the polyimide
backbone. This is accomplished in a number of
ways. One technique is to introduce pendent side
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 315

O O O

O O + H2N CH2 NH2

O O

70% MPDA

1. NMP

2. 30% GAP

CH3 CH3
H2N CH2 CH2 CH2 Si O Si CH2 CH2 CH2 NH2
CH3 CH3

HO O
O
NH CH2

O
O OH
O CH3 CH3
m
NH Si O Si
NH
CH3 CH3
O O
O OH

n
NH
O
O OH

O O O CH3 CH3 O O O
Si O Si
N N N N CH2
CH3 CH3
O O O O

m
n

Figure 10.9 Synthesis of the SiPI block copolymer.

316 HANDBOOK OF THERMOSET PLASTICS

Table 10.19 Electrical Properties of SiPI Polyimide Resins (General

Electric) [12]

(Reprinted by permission from General Electric Company)

Table 10.20 Adhesion of SiPI Polyimide Resin (General Electric) and Pyralin® (Du Pont) on Various Wafer
Surfaces [12]


P
passed tape pull test; F
failed tape pull test.

AP
Adhesion promoter.
(Reprinted by permission from General Electric Company)
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 317

Table 10.21 Commercial Polyimides and their Manufacturers

1
Amoco Corporation, originally Standard Oil Company of Indiana, founded by J.D. Rockefeller in 1889, was a global chemical and oil
company. Amoco merged with British Petroleum (BP) in December 1998 forming BP Amoco, later renamed to BP. (Source: Personal
notes and abstracted Wikipedia information).
2
Originally, Ciba was a chemical company based in Basel, Switzerland, “Chemische Industrie Basel,” and merged to become Ciba-
Geigy since 1970. One of its latest successors, Ciba Specialty Chemicals sold the epoxy business, which has become Huntsman
Advanced Materials in 1997. In 2008, Ciba was acquired and integrated into BASF, and was renamed to BASF Schweiz AG in March
2010. Relevant to thermoset plastics, the vintage name Araldite (circa 1946), is now a registered trademark of Huntsman Advanced
Materials, referring to their range of engineering and structural epoxy, acrylic, and polyurethane adhesives. (Source: Personal notes
and abstracted Wkipedia information).
3
Rhône-Poulenc was founded in 1928 as the merger of Société des Usines Chimiques du Rhône (Lyon, France) and Établissements
Poulenc Frères, a Parisian apothecary enterprise founded by Étienne Poulenc in 1860 and renamed as EPF in 1900. In January 1999,
Rhône-Poulenc merged with Hoechst AG to form Aventis. Later in 2004, Aventis merged with Sanofi-Synthélabo to form Sanofi-
Aventis, and the name eventually simplified to Sanofi. In 1997, the chemicals division of Rhône-Poulenc was spun off as Rhodia. The
agricultural chemicals division of Rhône-Poulenc, after the merger with Hoechst, was sold to Bayer in 2002.
Poulenc family trivia: Étienne Poulenc’s oldest sons, Gaston and Emile, were key contributors to the apothecary business. The
youngest son Camille (1864-1942) was a pharmacist and docteur des sciences, credited as the founder of French pharmaceutical
industry. He had collaborated with Pierre and Marie Curie. Emile was the father of French composer Francis Poulenc (1899-1963), a
member of the famed Les Six in 20th Century French classical music, which also included Georges Auric, Louis Durey, Arthur
Honegger, Darius Milhaud, and Germaine Tailleferre.
(Source: Encyclopedia Britannica, Arbre Généalogique Christophe Becker, Société d’Histoire de la Pharmacie).
318
chains such as phenyl groups. Soluble and fusible
polyimides have been prepared by the introduction
of flexible linking units into the main polyimide
chain. Thus, siloxane and phosphorus-modified
homo- and copolymers have been developed. These
systems contain aliphatic chains to bring about
increase in processibility, but their thermo-
oxidative stability is greatly compromised. This
limitation was solved by incorporating fluoroalky-
lene in lieu of aliphatic groups in the polymer
chain [13].
DuPont NR-150 Polyimides
Aromatic polyimides containing the hexafluoroi-
sopropylidene (6F) group have been marketed by
Du Pont Company. This group enhances solubility
of polyimides in conventional solvents and also
yields polyimides with relatively low glass transition
temperature (Tg, 340°C, or 644°F). Thus, Du Pont
introduced the NR-150 polymer prepared from the
perfluoroisopropylidene containing acid dianhydride
(6FDA) (XI) (Figure 10.10) and a number of aro-
matic diamines [14]. These resins are expensive but
their high-temperature durability makes them one of
the best systems as advanced thermally resistant
composite and adhesive materials.
O O
O CF3 O
C O
O
CF3
XI
Figure 10.10 Fluorine-containing dianhydride 6
FDA.
The NR-150 series of polyimides has some of
the best long-term thermo-oxidative stability, par-
ticularly at 371°C (700°F) of any of the commer-
cially available polyimides. The excellent thermo-
oxidative stability is in part attributed to the per-
fluoroisopropylidene (6F) connecting units in the
polymer backbone. The NR-150 series of polyi-
mides is the resin family for the commercial high-
temperature prepregs Avimid N.
HANDBOOK OF THERMOSET PLASTICS
General Electric Ultem® Poly
(Ether-Imides)
General Electric Company introduced the
Ultem® polyetherimide resin (XII) system in 1982.
This resin is an amorphous, high performance engi-
neering thermoplastic. The ether linkage in the
polyetherimide provides sufficient flexibility yet
retains the aromatic imide characteristics of excel-
lent mechanical and thermal properties
(Figure 10.11).
O O
N
CH3
N
O C O
O O
CH3
n
XII
Figure 10.11 Chemical structure of the engineering
thermoplastic Ultem®. (Courtesy: General Electric
Company).
It is noteworthy that the Ultem® polyetherimide
shows a balance of properties which is typical of an
amorphous polymer and yet approaches the perfor-
mance of some crystalline and thermoset resins.
The synthesis of this class of resins is novel in that
the synthetic strategy involves the imide formation
cyclization reaction as the initial step to give an
unusual 4-nitrophthalimide-end-capped diamine
monomer, the bis-imide. Formation of the polymer
occurs as ether linkages are formed as the result of
a base-catalyzed nucleophilic aromatic displace-
ment reaction between the 4-nitrophthalimide-end-
capped diamine monomer and a bisphenoxide, typi-
cally the phenoxide of the commodity chemical
Bisphenol A, which can be purchased in a high-
purity crystalline form. This reaction scheme is
shown in Figure 10.12.
In Step I the bis-imide monomer is formed by
the reaction of 4-nitrophthalic anhydride and a
diamine. In step II, the bis-imide monomer is then
reacted with a bisphenol dianion from the reaction
of diphenol with two equivalents of base and
removal of water.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 319

STEP 1: Formation of bis-imide monomer and bisphenoxide

O O O

O2N O + H 2N R NH2 O2N N R N NO2 + 2 H2O

O O O

CH3 CH3

HO C OH + 2 OH− −O C O− + 2 H2O
CH3 CH3

STEP 2: Polymerization via nucleophilic nitro displacement

O O CH3
−O
O2N N R N NO2 + C O−

O O CH3

O O CH3

N R N O C O + 2 NO2−

O O CH3

Figure 10.12 Polymerization via nucleophilic aromatic substitution.

A number of formulations of the Ultem® resins
are marketed by General Electric Company to
meet various engineering demands. Ultem® 1000
is an unreinforced grade offering a heat deflection
temperature of 200°C (392°F) at 264 psi and a UL
94 flammability rating of V-O at 0.016 inch thick-
ness. The Ultem® 2000 series are glass reinforced
resins to provide greater stability and improved
dimensional stability while retaining excellent pro-
cessibility. The Ultem® 6000 series are a new
family of materials exhibiting even greater heat
capabilities than the 1000 and 2000 series. These
are particularly suitable for military electrical
components which must survive 200°C (392°F)
testing. All Ultem® 1000 and 2000 series are
available with two options: low-viscosity resin and
mold release agent. Either option increases the
flow length of the product by approximately
10
25% and will facilitate molding of complex
thin walled parts. Optimum flow length is obtained
by combining both options, which typically leads
to flow improvement of 20
50%. Typical proper-
ties of the Ultem® resins are shown in
Tables 10.22, 10.23, 10.24, and 10.25 [15].
Figure 10.13 shows a novel use for Ultem®, a
non-planar circuit board.
320 HANDBOOK OF THERMOSET PLASTICS

Table 10.22 Typical Mechanical Properties of Ultem® Resins[15]

(Reprinted by permission from General Electric Company)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 321

Table 10.23 Typical Thermal and Flammability Properties of Ultem® Resins [15]

(Reprinted by permission from General Electric Company)

322 HANDBOOK OF THERMOSET PLASTICS

Table 10.24 Typical Electrical and Other Properties of Ultem® Resin [15]

(Reprinted by permission from General Electric Company)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 323

Table 10.25 Typical Properties of Ultem® Resins (6000 Series High Temperature Copolymer Grade) [15]

(Continued )
324 HANDBOOK OF THERMOSET PLASTICS

Table 10.25 (Continued)


Testing in progress.

This rating is not intended to reflect hazards presented by this or any other material under actual fire conditions.

General Electric Company test data.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 325

O O

N R N N
H H
H n

R=

Polyphthalamide PPA

Figure 10.15 Torlon parts are long lasting in wear-

intensive applications. (Courtesy: Amoco Chemical
Corporation).
Figure 10.13 An Ultem® single sided MINT-PACTt
board with three-dimensional features on its
unplated side. All MINT-Pac exterior board
dimensions, through holes, and three-dimensional
features are molded in a single step eliminating a
great deal of costly machining. (Courtesy: General
Electric Company).

Amoco Torlon® Poly(Amide-

Imides)
Another route to fusible and processible polyi-
mides is to introduce the amide moiety into the
polyimide chain. These poly(amide-imide) poly-
mers are commercially available as Torlon®, from
Amoco. Chemically, Torlon® is a polymer from the
reaction of trimellitic anhydride and aromatic dia- Figure 10.16 The 2.0 liter, dual overhead cam
mines. The polymer is depicted by structure XIII plastic engine developed by Polimoter Research,
(Figure 10.14). Inc. utilizes Torlon®, an injection moldable
thermoplastic made by the Amoco Chemicals
O Corporation. Weighing in at 175 pounds and
O
developing 3118 brake horsepower at 9,500 rpm,
Ar NH
N the engine is 200 pounds lighter than its steel
counterpart. (Courtesy: Amoco Chemicals
O n Corporation).

XIII

Figure 10.14 Chemical structure of Torlon®, a poly
(amide-imide).
The polymer chain comprises amide alternating
with imide linkages that results in a thermoplastic
polymer. The versatility and processibility has
made these resins attractive materials. Figure 10.15
shows engineered parts fabricated from Torlon®
which demonstrate this material’s excellent wear
and temperature resistance. Torlon® has been used
to manufacture a molded plastic gasoline engine
(see Figure 10.16). The Torlon® polymer was cho-
sen because of its strength, toughness and high tem-
perature resistance. In 1982, with the looming oil
embargo, the Ford Motor Company entered a joint
program with privately held Polimotor Research
Inc. to develop and with the objective to manufac-
ture a plastic car engine by the late 1980’s [16].
One engine design for the project was Ford’s 2.3-
326
liter, weighing 153 lbs (69.5 kg), versus 415 lbs
(188.6 kg) for its cast iron counterpart [17]. Torlon
delivers a desirable combination of superior engi-
neering properties, including mechanical strength,
toughness and modulus, resistance to aviation fluids
(such as methyl ethyl ketone and Skydrol), and
passing FAA flammability tests. Most significant to
cost-effectiveness and production ease for the OEM
is Torlon’s injection moldability. It is ironic that
this technology has yet to be capitalized to-date.
Quoting from Martin Baumert of BASF’s
Engineering Plastics Group, “High oil prices,
increasing environmental awareness, and changing
political conditions are more and more focusing
attention on the energy efficiency of automo-
biles,” and the updated USA requirements of pas-
senger car gasoline consumption efficiency to
average 36.7 mpg by 2015 model year, it would
Table 10.26 Grades of Torlon® Commercially Available [19]
HANDBOOK OF THERMOSET PLASTICS
not be surprising if the plastic engine would
appear in passenger cars before long. The automo-
tive industry has estimated that a weight reduction
as high as 50 percent is achievable through
plastic-for metal substitution. Besides Torlon, sev-
eral competing thermoplastics are being applied
toward development of plastic engines, for exam-
ple, the direct replacement of die-cast aluminium
in mechanical water pump housings with the
semi-aromatic Amodel polyphthalamide PPA
(Solvay) [18].
Various grades of Torlon® are available for a
number of engineering applications. The grades
and their application are described in Table 10.26
[19]. The mechanical properties are shown
in Table 10.27 [19], electrical properties in
Table 10.28 [19], and thermal and general proper-
ties in Table 10.29 [19].
(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 327

Table 10.26 (Continued)

(Reprinted by permission from Amoco Chemicals Corporation)

Table 10.27 Torlon® Resin Compositions
Mechanical Properties [19]

(Continued )
328 HANDBOOK OF THERMOSET PLASTICS

Table 10.27 (Continued)

(Reprinted by permission from Amoco Chemicals Corporation)

Table 10.28 Torlon® Resin Compositions
Electrical Properties [19]

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 329

Table 10.29 Torlon® Resin Compositions
Thermal and General Properties [19]

(Reprinted by permission from Amoco Chemicals Corporation)

Ciba-Geigy Fully Imidized Indane- O O O

Based Polyimides N N
Ciba-Geigy Corporation markets the fully- O O
imidized polyimide XU 218 (XIV) as a powder n
(Figure 10.17). It has high solubility in volatile sol- XIV
vents such as methylene chloride, tetrahydrofuran,
as well as in solvents such as N-methylpyrrolidine. Figure 10.17 Chemical Structure of Ciba-Geigy’s
It is an excellent film former with a relatively high XU218 Polyimide.
glass transition temperature [Tg 5 320°C (608°F)].
Films made from this polyimide have excellent H2N
chemical resistance. Exposure in 5N sodium Y
hydroxide for 48 hours produced only surface pit- O Y
ting. Under similar conditions, Kapton® film O NH2
completely lost its integrity. Select properties are XVa: Y=CO
shown in Tables 10.30, 10.31, And 10.32 [20]. A XVb: Y=SO2
comparison of some properties of the XU218 film
with Kapton® H film is shown in Table 10.33. This Figure 10.18 Two novel diamine monomers based
polyimide may be useful for various electronic on 1,1,3-trimethyl-3-phenylindane.
applications requiring films and conformal coating.
Researchers at the Technische Universität
München have been interested in the properties of α-methylstyrene. Their recent interest in polyimides
poly(ether-ketones) based on the same 1,1,3-tri- prompted the functionalization of α-methylstyrene,
methyl-3-phenylindane structural unit as Ciba- via a sequential Friedel-Crafts acylation/sulfona-
Geigy’s XU 218 polyimides [21]. The standard tion
nucleophilic aromatic substitution procedure,
method of producing 1,1,3-trimethyl-3-phenylin- to yield the required diamine monomers XVa and
dane is the acid-catalyzed dimerization of XVb[22] (Figure 10.18).
330 HANDBOOK OF THERMOSET PLASTICS

Table 10.30 XU 218 Polyimide Resin, Thermal Stability-Aging of 1 Mil Films [20]

(Reprinted by permission from Ciba-Geigy Corporation)

Table 10.31 XU 218 Polyimides Resin-Electrical Properties [20]

(Reprinted by permission from Ciba-Geigy Corporation)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 331

Table 10.32 XU-218 Polyimide Film, Tensile Properties [20]


0.5 mil film
uniaxially stretched from 1.0 mil film oriented in machine direction.
(Reprinted by permission from Ciba-Geigy Corporation)

Table 10.33 Comparison of Select Properties of H Film (Du Pont) and XU-218 (Ciba-Geigy)
332 HANDBOOK OF THERMOSET PLASTICS

O
O O O

N N O
O
O
O O
n

XVIa

O
O O
O O S

N N O S
O
O
O O
n

XVIb

O
O F3C CF3 O

N N O
O
O
O O
n

XVIc

O
F3C CF3 O
O O S

N N O S
O
O
O O
O
n

XVId

Figure 10.19 Soluble, high-temperature stable poly(ether-imides) based on 1,1,3-trimethyl-3-phenylindane.

These diamines were allowed to react with
6FDA and BTDA to yield four high-temperature
stable poly(ether-imides), XVIa
XVId (Figure
10.19), which can be cast into flexible, transparent
films from common solvents, such as N,N-dimethy-
lacetamide. Table 10.34 summarizes the physical
characterization of these poly(ether-imides).
Soluble, Fully Imidized Fluorinated
Polyimides
Many fluorinated thermoplastic polyimides
have become available. The thermo-oxidative stability
of polyimides containing the hexafluoro-
isopropylidene (6F) group has been well known [23].
The introduction of 6F groups has been shown to
impart to polymers with enhanced processibility,
improved fracture toughness [24] and moisture resis-
tance, while maintaining excellent oxidative stability
[25]. A related flexible (12F) system [26] is potentially
applicable as connecting units for high-temperature
chemical building blocks (Figure 10.20). The 3F con-
necting group has been used to optimize cost, process-
ibility, and mechanical properties [27
30].
The presence of fluorine substituents in the poly-
mers also improve their processibility in terms of
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 333

Table 10.34 Properties of Indane-Containing Poly(Ether-Imides) [22]

e Mn and Mw determined by GPC in THF


Td from 5% wt loss in air at 10 K/min

Tg from DSC at 20 K/min
‡
Td from 5% wt loss in nitrogen at 10 K/min.

O O O O

O CF3 O O O
C C
O O O O
CF3 CF3

2,2-Bis (3,4-dicarboxyphenyl)- 1,1-Bis (3,4-dicarboxyphenyl)-1-phenyl-

hexafluoropropane dianhydride 2,2,2-trifluoroethane dianhydride
(6FDA) (3FDA)

O O
CF3 CF3
O O
C C
O O
CF3 CF3

1,3-bis-[2-(3,4-dicarboxyphenyl)-
hexafluoropropyl]benzene dianhydride
(12FDA)

Figure 10.20 Fluorinated dianhydrides based on special chemical connecting groups of 3F, 6F and 12F.

solvent solubility, melt characteristics, and other
properties such as low dielectric constant, low
moisture adsorptivity, and optical transparency.
Fluorinated polyimides are important to the micro-
electronic industry because of their unique electri-
cal properties. They are the topic of many other
reviews pertaining to their applications. It is suffi-
cient to mention here the R&D effort in this class
of polyimides originated in the unique dianhydride
monomer, 6FDA. The American Hoechst Company
has marketed 6FDA and their series of Sixef®
Polyimides during the 1980’s. The best known is
Sixef®-44, made from 6FDA and 2,2-bis(4-amino-
phenyl)hexafluoropropane. A related soluble,
fluorinated polyimide is Hughes Aircraft
Company’s 6F33. Other fluorinated diamines
include 2,2-bis[4-(4-aminophenoxy)phenyl]hexa-
fluoro-propane (BDAF) [31], 2,2-bis(4-aminophe-
nyl)-1-phenyl-2-trifluoroethane [28
30], and 2,20 -
bis(trifluoromethyl)-4,40 -diaminobiphenyl (PFMB)
(Figure 10.21) [32,33].
Table 10.35 summarizes some noted effort in the
design and application of low dielectric polyimides
that are based on 6FDA [34
37].
334 HANDBOOK OF THERMOSET PLASTICS

H2N NH2
CF3 CF3
H2N C NH2 C
CF3 CF3

2,2-Bis(4-aminophenyl)- 2,2-Bis(3-aminophenyl)-
hexafluoropropane hexafluoropropane
(6F44 diamine) (6F33 diamine)

H2N NH2

H2N C NH2 O C O
CF3 CF3

1,1-Bis (4-aminophenyl)-1-phenyl- 1,1-Bis[4-(3-aminophenoxyphenyl)]-

2,2,2-trifluoroethane 1-phenyl-2,2,2-trifluoroethane
(3F44 diamine) (3FP33 diamine)

CF3 CF3

H2N NH2 H2N O C O NH2

CF3
CF3

2,2'-Bis(trifluoromethyl)- 2,2-Bis[4-(4-aminophenoxyphenyl)]-
4,4'-diaminobiphenyl hexafluoropropane
(PFMB) (BDAF)

Figure 10.21 fluorinated diamines.

Table 10.35 Examples of 6FDA-Based Polyimide Dielectrics

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Table 10.35 (Continued)
Addition-Curable Polyimides
and Other Polymers
As discussed in earlier sections, commercialization
of a product is the culmination of many years of per-
sistent effort in developmental and application
research. After the synthetic feasibility of the process
has been established, the research resin is then evalu-
ated for its potential in engineering applications.
Optimization of reaction parameters ensues to produce
an efficient method for large-scale preparations. With
more materials that become available, more testing
and more extensive evaluation can be pursued.
Thermosetting polymers have long been in
demand in producing composites for the fabrication
of high-performance aerospace engineering structural
components. The success of epoxy resins as the most
developed and most widely used polymer matrix
materials rests in their excellent mechanical proper-
ties and processing characteristics. In fact, all classes
of matrix resins are measured against the epoxies in
335
evaluating their performance. Most epoxy resins are
not usable at temperatures beyond 177°C (350°F).
During the heydays of the aerospace industry in the
past several decades, there has been a continuous
demand of newer and better classes of high-
performance polymers as matrix resins and adhesives
that have to survive for longer and longer times at
higher and higher temperatures. Furthermore, the
microelectronics industry has a need for an adhesive
which must withstand processing temperatures of
over 400°C (752°F) for a few hours in an inert atmo-
sphere (vide infra: “Thermosets as Dielectric
Interlayers in Integrated Circuit (IC) Fabrication”).
Although the quantity requirement in the microelec-
tronic industry is generally not critical, more material
demands are foreseeable in the application of dimen-
sionally stable high-temperature polymer materials as
matrix resins and other engineering structures.
The search for thermally stable polymers in the
past few decades has led to the conclusion that
thermal stability and processibility are antithetical
336
in nature. Although many classes of high-
temperature resistant polymers are in theory capa-
ble of reaching end use temperatures of 300
400°
C (472°
752°F), they are too rigid in nature and
therefore too intractable to be useful. The research
in high-temperature resistant polymers has always
aimed at an optimal balance between processibility
and high-temperature stability.
Polyimides have been known for their high-
performance and potential as advanced structural
resins suitable for aerospace applications. As dis-
cussed in earlier sections, polyimides generally are
processed by conversion of the amic acid prepoly-
mer to the imidized structure via a condensation
reaction, which presents formidable processing pro-
blems. They are difficult to use as molding com-
pounds. For the fabrication of composite structures,
very high molding pressures and a carefully con-
trolled post-cure process are required to allow dissi-
pation of volatile by-products from the
condensation process. To alleviate these problems,
thermosetting, fusible and soluble short-chain polyi-
mide oligomers were developed that undergo ther-
mal cure to polyimides via homo-polymerization of
the reactive end-groups. Ideally, these end-groups
homo-polymerize into thermo-oxidatively resistant
structures without the evolution of volatile by-
products.
There are several classes of addition-curable
polyimides developed that undergo chain extension
and cure reactions at the reactive termini of shorter
and therefore more processible oligomers to yield
cross-linked thermoset matrix resins applicable to
advanced fiber composites. These addition-curable
polymers also remove the major processing prob-
lem associated with the evolution of volatiles.
Several classes of thermosetting polyimides have
attained various stages of commercialization.
Nadimide-Terminated
Thermosetting Polyimides
In the nineteen-sixties, TRW developed bismalei-
mide polymers marketed by Ciba-Geigy
Corporation known as P13N polyimides. They were
difficult to process and thereby developed only a
small market. They were eventually discontinued.
The P13N polyimides were based on nadimide-
terminated imide oligomers that underwent a reverse
Diels-Alder reaction at elevated temperatures of
HANDBOOK OF THERMOSET PLASTICS
O
N
O N O
O
O N O
O N O
n
Figure 10.22 Polymerization of P13N polyimide.
275°
350°C (527°
662°F) and then addition to
form polymers. The polymerization of the P13N
polyimide oligomers is depicted in Figure 10.22.
Investigations at the NASA-Lewis and NASA-
Langley Research Centers have been instrumental
in the development of other nadimide-terminated
addition-type polyimides to replace P13N. The
requirement for high-temperature polymers with
enhanced processibility has been met with novel
resins such as PMR, LARC-160 and LARC-13
[38]. The PMR (for in-situ Polymerization of
Monomer Reactants) technology has been reviewed
by its originator [39]. The development of the first
generation PMR matrix resins has culminated in
various forms of commercial applications. The key
features of success in the PMR composite technol-
ogy are the availability of monomers, the good sol-
ubility of monomer reactants in low boiling
alcohols, the processibility of the resins and ulti-
mately the excellent retention of properties at ele-
vated temperatures. The versatility of the PMR
approach can be demonstrated with the tailoring of
processing characteristics and properties by simple
variations on the chemical nature of either the dies-
ter acid or the aromatic diamine, or both, and the
stoichiometric proportion of the monomer
reactants.
In the PMR approach, the reinforcing fibers are
impregnated with a solution of a mixture of mono-
mers in low boiling alcohols. At room temperature
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
the monomers are essentially unreactive but at ele-
vated temperatures react to form a thermooxida-
tively stable polyimide resin. The solution of
monomers consists of a high solid content
(70
90%) of a dialkyl ester of an aromatic tetra-
carboxylic acid, an aromatic diamine, and a mono-
alkyl ester of 5-norbornene-2,3-dicarboxylic acid
(NE)(XVII) (Figure 10.23).
Various modifications of the PMR polyimides
were prepared. The first generation of PMR resin
was designated PMR-15 and the second generation
PMR-II. Thus, PMR used (NE), the dimethylester
of 3,30 ,4,40 -benzophenone-tetracarboxylic acid
(BTDE)(XVIII) and 4,40 -methylenedianiline
(MDA). The second generation of PMR resins used
the perfluorinated isopropylidene analogue of
BTDE known as 6FDE (XIX) and phenylenedia-
mine [40,41] (Figure 10.24).
The success of the second generation of PMR resins
depends on the supply of the precursor to 6FDE,
namely, 6FDA. A number of systems have been inves-
tigated and modifications of the reactants have shown
the ability of the PMR approach to produce “tailor-
made” resins with varying degrees of flow.
CO2CH3
COOH
Norborn-5-ene-2,3-dicarboxylic
methyl ester
(NE)
XVII
Figure 10.23 End-capping agent used in PMR
chemistry.
O O O O
CH3O
HO
O O
3,3',4,4'-Benzophenone
Tetracarboxylic dimethyl ester
(BTDE)
XVIII
Figure 10.24 First and second generation PMR use tetracarboxylic acid dimethyl esters, BTDE and 6FDE,
respectively.
337
H2N
H2N CH2 CH2 NH2
n
Jeffamine AP-22
XX
Figure 10.25 Polyaromatic amine, jaffamine AP-22,
for LARC-160.
The PMR system LARC-160, developed at
NASA-Langley Research Center uses the mono-
mers BTDE, NE, and the polyaromatic amine
Jeffamine AP-22 (XX), which has an average
molecular weight of 234 [42] (Figure 10.25). The
LARC 160 resin is readily processed and gives
excellent mechanical properties, but is a brittle sys-
tem and has marginal thermo-oxidative stability at
316°C (600°F).
The thermo-oxidative stability of the original
PMR resin was improved, although progress in
developing this 6FME-based PMR was slow due to
an earlier lack of a commercial source for the cor-
responding dianhydride, 6FDA. This development
is facilitated by the production of 6FDA at
American Hoechst and Hitachi Chemicals (Japan).
The room temperature properties of PMR-15
neat resin are shown in Table 10.36 [43]. Some typ-
ical properties for graphite PMR composites are
shown in Table 10.37 [43]. The excellent retention
on interlaminar shear strength of graphite fiber/
PMR-15 composites as a function of air aging and
testing at 600°F is shown in Table 10.38 [38].
As the requirements for high-temperature adhe-
sives coincide with those for structural matrix
O
OCH3 CH3O CF3 OCH3
O O
OH C
HO OH
CF3
2,2-Bis(3,4-dicarboxyphenyl)-
hexafluoropropane dimethyl ester
(6FDE)
XIX
338 HANDBOOK OF THERMOSET PLASTICS

Table 10.36 Room Temperature Properties of PMR-15 Neat Resin [43]

(Reprinted by permission of Van Nostrand Reinhold Company)

Table 10.37 Properties of HT-S/PMR-15 Composites [43]


Fiber Volume, 55% by volume; tested along 0° ply direction.
(Reprinted by permission from Van Nostrand Reinhold Company)
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 339

Table 10.38 Interlaminar Shear Strength of Graphite Fiber/PMR-15 Composites as a Function of Air Aging
and Testing at 600°F [38]

(Reprinted by permission from Dr. T. T. Serafini)

O O
O O
N AR N N AR N

O O O O O
n

H2N NH2

AR = CH2

XXI

Figure 10.26 Chemical structure of LARC-13 adhesive.

resins, the candidate high-temperature matrix resins
are also screened for their suitability as high-
temperature adhesives. The LARC-13 system was
developed as a high-temperature adhesive for bond-
ing large areas. Previous adhesive systems fre-
quently yielded poor results because large volumes
of volatiles are usually given off during the cure/
bonding process for large areas. The LARC-13 sys-
tem is an addition type cure that results in the evo-
lution of few volatiles. Its unique polymer chain
incorporates meta-linkages in the oligomer chains
(XXI) (Figure 10.26).
The oligomer has a relatively low softening tem-
perature and can be processed at 266°
316°C
(512°
600°F). This makes it attractive for bonding
metals. Based on a structure-property relationship
study on addition polyimides at NASA-Langley
[44], LARC-13 was shown to exhibit the highest
lap-shear among nadimide-end-capped polyimide
resins (Table 10.39) and was further developed as a
structural adhesive for specialized bonding applica-
tions [45]. Besides its high lap-shear strength,
LARC-13 also has a high degree of flow during
cure and is easily processible by conventional auto-
clave techniques. Its high cross-linking density pro-
vides dimensional stability during use at elevated
temperatures in excess of its glass transition tem-
perature of 270°C (518°F).
Figure 10.27 shows the chemistry of LARC-13
adhesive. Research at Langley on elastomer-
toughening of the inherently brittle LARC-13 has
produced some noteworthy salient features: [45]
340 HANDBOOK OF THERMOSET PLASTICS

Table 10.39 Adhesive Properties of Nadimide End-Capped Polyimide Resins

(Reprinted by permission of Reference [45])

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 341

H2N NH2 O O
O
CH2 + O + O O

O O O
O

DMF, 20°C

O O
O O
NH AR NH NH AR NH

OH HO O O O OH
O HO O
n
Amic acid prepolymer

180°C

O O
O O
N AR N N AR N

O O O O O
n

Imide prepolymer

300°C

Cross-linked polymide

Figure 10.27 Chemistry of LARC-13 adhesive.

342
a. A compromise exists between toughness
improvement and elevated-temperature adhe-
sive strength;
b. Novel high-temperature resistant elastomers
are needed;
c. A 50
50 bimodal distribution of long- and
short-chained elastomers in LARC-13 can
contribute to a significant improvement of
adhesive properties.
A further investigation was conducted to find a
cross-linking end group that would improve the
thermo-oxidative stability of LARC-13 adhesive.
Table 10.40 shows that the acetylene-terminated
LARC-13-based material has 40% higher adhesive
lap shear strength than LARC-13 itself after aging
1,000 hours at elevated temperatures.
A NASA-sponsored study by Boeing Aerospace
Company on the effects surface treatment of tita-
nium on the lap shear strengths of titanium bonded
with LARC-13 shows a wide range of values with
the best values being obtained with chromic acid
anodized treatment [2,900 psi at room temperature
Table 10.40 Lap Shear Strengths of Titanium/Addition Polyimide Bonds
(Reprinted by permission of Reference [45])
HANDBOOK OF THERMOSET PLASTICS
and 200 psi at 450°F (232°C)] and the poorest with
Pasa-Jell 107 [850 psi at room temperature and
580 psi at 450°F (232°C)] [46].
LARC-13 and its modified versions thus repre-
sent some of the state-of-the-art polymeric materi-
als suitable for applications as both structural
matrix resins and high temperature adhesives.
Owing to the high cross-link density, they are able
to perform for short terms at temperatures up to
1,112°F (600°C) where linear systems fail thermo-
plastically. On the other hand, further improve-
ments are needed in terms of enhancing their
thermo-oxidative stability and long-term perfor-
mance at elevated temperatures. As experience
shows in the field of high-temperature resistant
polymers, successful development of polymer sys-
tems possessing both ultrahigh thermal and thermo-
oxidative stabilities while maintaining good pro-
cessibility and a high level of toughness will
represent a major technological breakthrough.
A likely answer lies in extending the systematic
resin-toughening studies carried out at NASA-
Langley to beyond the realm of organic polymers.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Modified Nadimide End-Groups
Ciba-Geigy researchers have evaluated the bene-
fits of using modified nadimide end-caps in thermo-
set polyimides (Figure 10.28). Prepolymers were
made at MW 5000 to ensure reasonable solvent sol-
ubility (i.e. 35% concentration or higher) and melt
processibility [47]. Laminate properties were
obtained from cured polyimide materials with these
modified nadimide end-caps, and compared signifi-
cantly better with polyimide materials without the
end-caps in thermomechanical properties such as
Tg and modulus retention under hot/wet condition.
Generally, polyimides with the dinadimide end-
capper cure to higher Tg matrices and are
suitable for applications in the 260
290°C range.
Data for the allylic nadimide-terminated polyimides
indicate a useful continuous operating range of
232°C
260°C (450°F
500°F).
The use of the dinadimide end-group originates
in earlier work at Boeing Aerospace Company.
STAR was initially developed as an experimental
resin for the increase of Tg of polyimides several
O AR
N C NH
O
Allylic nadimide
end-capped polymer
Figure 10.28 Modified nadimide end-groups for thermoset polyimides.
C C
C C
Figure 10.29 Intramolecular cycloaddition as a mechanism of chain rigidization of polymers.
343
hundred degrees above the cure temperature, with-
out post-curing and without increasing the cross-
link density. The approach involves endcapping the
oligomer with a dinadimide endcapping agent that
reacts in two distinct steps. The first step joins the
ends of two oligomers and the second step involves
the second nadimide in the end-group moiety, now
proximal, to form a double strand linkage that stif-
fens the chain and raises the Tg.
This chain rigidizing (reinforcing) concept by
the cross-linking of pre-positioned reactive sites is
similar to research work [48] at Hughes sponsored
by the Air Force on thermal intramolecular cycliza-
tion (IMC) curing of 2,20 -bis(phenylethynyl)biphe-
nyl-containing polymers (Figure 10.29). Chain-
rigidization to effect significant advancement of Tg
on curing has been successfully demonstrated at the
Air Force Materials Laboratory in their studies on
polyphenylquinoxaline (PPQ) containing 2,20 -bis
(phenylethynyl)biphenyl units [49
53].
In retrospect, the actual phenomenon that occurs
during thermal curing of the polymer matrix
O
N
O
O
O
N
O
Dinadimide
end-capped polymer
344
containing 2,20 -bis(phenylethynyl)biphenyl units
may not have been the IMC reaction to form phe-
nylphenanthrene since steric hindrance in the poly-
mer mass could have prevented or hindered the
necessary rotation to the correct conformation for
the IMC reaction. Chain rigidization could have
been through thermally induced cross-linking of
similar phenylethynyl units on adjacent chains.
Interest in this thermal cyclization reaction of 2,20 -
bis(phenyl-ethynyl)biphenyl to 9-phenyldibenzo[a,
c]anthracene prompted research into possible
monomers for polymerization [53].
AFR700B Development
The United States Air Force sponsored R&D of
the AFR700B resins as a continuing effort to
improve the PMR technology in processibility and
thermo-oxidative resistance. The cure chemistry of
AFR700B resembles that of PMR resins. The use
of 6FDE aims at improving thermo-oxidative resis-
tance and processibility of the resin. The stoichio-
metric offset of the various reactant monomers
affords an oligomeric molecular weight of 4,382 to
allow easy solubility in methanol solvent.
Imidization of the amic acid prepolymer occurs at
around 205
220°C (400
430°F) and the imide
prepolymer undergoes cross-linking at 343
371°C
(650
700°F) [54,55] (Figure 10.30).
The development of 371°C (700°F) polyimides
has been summarized by its originator [55].
Table 10.41 details the different polyimides based
on the PMR concept. The improvement on process-
ibility has been demonstrated by excellent ultra-
sonic C-scan results on quartz-supported AFR700A
and AFR700B. Tg values obtained for AFR700
materials are above 400°C (752°F). Isothermal
aging of quartz/AFR700B laminates showed that
they are superior to comparable laminates made
from PMR-15 and AFR700A. Retention of mechan-
ical properties after 371°C (700°F) aging in air for
100 hours is excellent [55].
Maleimide-Terminated
Thermosetting Polyimides
Another group of thermosetting polyimides cur-
able by addition reactions is the N-substituted bis-
maleimides (BMIs). By choosing the appropriate
moieties in the polymer chain, it is possible to
HANDBOOK OF THERMOSET PLASTICS
prepare very soluble and fusible oligomers. These
BMI prepolymers can be heated above their melting
point in the presence of a free radical catalyst, such
as dicumyl peroxide, to polymerize into a cross-
linked polyimide resin. Rhône-Poulenc Company
introduced the Kerimid® resins which are based on
mixtures of bismaleimide monomers and aromatic
diamines [56]. This results in linear chain extension
via a Michael addition reaction. Cross-linked poly
(bismaleimides) were formed from these bismalei-
mide oligomers. Improved high-temperature proper-
ties could be obtained from these resins if
nonstoichiometric mixtures of aromatic diamines
and bismaleimide were used. Two types of reactions
are postulated [57]. One type is the Michael addition
to form linear polymers as depicted in Figure 10.31.
The second type is free radical cure of the terminal
double bonds leading to cross-linking.
A melt processible bismaleimide copolymer
(Kerimid 353) was developed using a ternary mix-
ture of aliphatic and aromatic bismaleimides
[58
60]. Further developments of bismaleimide
technology using a combination of free radical cure
and diamine addition had yielded new types of pro-
cessible bismaleimide resins, the Kinels and
Kerimid® 601 series, which are suitable as molding
and laminating resins, respectively [61].
Copolymerization studies have demonstrated that
bismaleimide monomers or prepolymers can best
be used as cross-linking agents to yield products
with high glass transition temperatures
(Figure 10.32) [62].
Table 10.42 shows typical molding parameters
of these resins. Thus Kerimid® FE70003 coated on
graphite or glass cloth fibers can be molded using
vacuum bag techniques. Properties of the neat resin
are shown in Table 10.43. The low viscosity and
reasonable gel times are very important parameters
that make these resins easy to process.
Tables 10.44, 10.45, and 10.46 show typical ther-
mal mechanical and electrical properties for
Kerimid® 601/181E glass cloth laminates.
Since many years ago, Ciba-Geigy marketed a
two-component bismaleimide system XU292
which, when combined and cured, is suitable for
high temperature advanced composites and adhe-
sives applications. The system is based on 4,40 -bis
(maleimidophenyl)methane (III) and 3,30 -diallyl
Bisphenol A (XXII)[65] (Figure 10.33).
Compounds III and XXII are well known as the
Matrimid® 5292 system (III 5 5292A and
 O O
CH3O CF3 OCH3
O O
CO2CH3 + H2N NH2 + C
HO OH
COOH CF3

NE (1 Part) PPDA (9 Parts) 6FDE (8 Parts)

CH 3OH, 221°C

O O
O NH NH2
CF3
NH NH + 17 CH3OH
O O
C
O OH HO OH
CF3 8

Amic acid prepolymer

221°C

O O
O
N N CF3 N NH2 + 17 H2O
O O C
O
CF3 8

Imide prepolymer

371°C, 200 psi

Thermally cross-linked
AFR700B polymine

Figure 10.30 Cure chemistry of AFR700B polyimide.

Table 10.41 Formulations of AFR700B and Other PMR Polyimides [55]

(Reprinted by permission of Dr. T. T. Serafini)

346 HANDBOOK OF THERMOSET PLASTICS

O O O O
H H
N R1 N + H2N R NH2 N R1 N N R N

O O O O
n

Figure 10.31 Chain extension of bismaleimides via Michael addition.

O O

N CH2 N
Poly(Amide-imide) +

3 parts O 1 part O

2-ethylimidazole (catalyst)
Cross-linked resin
2 hr, 190°C
4 hr, 240°C Tg > 300°C

Figure 10.32 Application of bismaleimides as cross-linking agent.

Table 10.42 Kerimid® FE 70003 Modified Bismaleimides Resin [63]

(Reprinted by permission from Rhône-Poulenc, Inc.)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 347

Table 10.43 Kerimid® FE 70003 Modified Bismaleimide Resin Select Properties of Neat Resin [63]

Solubility: Solutions of 50% in weight in methylene chloride or methylethyl ketone.

Table 10.44 Kermid® 601/181E Glass Cloth Laminate—Electrical Properties as aResult of Aging [64]

(Reprinted by permission from Rhône-Poulenc Inc.)

348 HANDBOOK OF THERMOSET PLASTICS

Table 10.45 Kerimid® 601/181E Glass Cloth 18-Ply Laminate—Thermal Aging and Mechanical Properties [64]

The specimens were taken from laminates prepared in the following conditions:
Impregnation bath: Solution of Kermid® 601 at 45% in NMP; Fiberglass fabric: Continuous filament yarn, satin weave of the 181 type
with an aminosilane finish; Resin content in the prepreg: 30 to 35%; Rate of flow of the prepreg: 30 to 40%; Laminate thickness:
Stack of 18 plies; Curing conditions: (a) Under 210 psi pressure at 480°F and postcuring for 48 hours at 390°F, or (b) Curing under
210 psi at 390°F and postcuring for 24 hours at 480°F; Resin content: 22 to 24%; Specific gravity: 1.94; Barcol Hardness: ca 70.
(Reprinted by permission from Rhône-Poulenc Inc.)
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 349

Table 10.46 Selected Properties of Kerimid® 601/181E Glass Cloth Laminates [64]

(Reprinted by permission from Rhône-Poulenc Inc.)

350 HANDBOOK OF THERMOSET PLASTICS

O O

CH2 CH3
N N
HO C OH
O O CH3

III XXII

Figure 10.33 Components of Ciba-Geigy XU292 BMI resin (Matrimid® 5292).

XXII 5 5292B), complementing the polyimide
Matrimid® 5218. Upon combining the two compo-
nents with continuous stirring to 120°
150°C
(248°
302°F), a clear homogeneous solution is
obtained. The resulting liquid can be used either as
a casting resin for the preparation of prepregs or as
an adhesive. The two-component system provides
flexibility to provide the optimum formulation for
the prepregger. One formulation of the neat resin
reported by Ciba-Geigy [66] reports a room temper-
ature tensile strength of 13.6 ksi, a modulus of
564 ksi, an elongation of 3.0%, a flexural strength
of 26.8 ksi and a flexural modulus of 580 ksi. At
204°C (400°F), these values drop to 104 ksi for ten-
sile strength and 394 ksi for the modulus. The Tg
obtained from the TMA penetration method is 282°
C (540°F).
In many oil field downhole operations, service
tools are required to perform in a hot/wet
fluid environment with temperatures above 204°C
(400°F) and pressures above 70 MPa (ca. 10 KSI)
[67]. It appears that bismaleimides are well suited
for this application.
Other similar bismaleimide (BMI) systems have
also been developed as Ciba’s BMI family of high-
performance resins. A notable new BMI is RD85-
101, which was synthesized from 1,1,3-trimethyl-3-
phenylindane and maleic anhydride (Figure 10.34).
Formulated with common BMI co-curing agents such
as allyl phenols (e.g., Matrimid® 5292B) or aromatic
diamines, RD85-101 shows outstanding thermome-
chanical and hygrothermal peorformance.
Table 10.47 shows some exemplary physical
and thermomechanical data of this resin system [68].

O
O
N
N
O
O

RD85-101

Figure 10.34 RD85-101, BMI Based on 1,1,3-Trimethyl-3-phenylindane.

Table 10.47 Cured Neat Resin Thermomechanical Data of RD85-101/Matrimid 5292B Formulations [68]

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Table 10.47 (Continued)
Cure condition: 1 hr/180°C 1 2 hr/200°C 1 6 hr/250°C.
Immersion in 160°F water for 48 hours.
System I 5 1:1 molar ratio (RD85-101/Matrimid 5292B)
System II 5 1:0.87 molar ratio (RD85-101/Matrimid 5292B)
Cyanate-Terminated
Thermosetting Polymers
Cyanate esters are stable one-component resins
and are storageable in their crystalline form for over
1 year at 25°C (77°F) in sealed containers. Thermal
curing forms three-dimensional networks of oxygen-
linked triazine rings (Figure 10.35) [69]. The mono-
mers or prepolymers are cured with or without tran-
sition metal catalysts and active hydrogen co-
catalysts (,0.15% of formulation by weight). While
optimum cured-state properties for the homopolymer
based on Bisphenol A (Ciba Arocy B) are typically
achieved after 1
2 hours at 177°C (350°F) with a
351
post cure at 250°C (482°F), early work with uncata-
lyzed resin formulated with thermoplastics showed
that cures can be accomplished in 30 minutes at
250
270°C (482
518°F) [70].
Cyanate functional resins are chemically compat-
ible with epoxy resins. They co-cure via a combina-
tion of co-reaction and catalytic polyetherification
[71]. Dicyanates modified with epoxy resins repre-
sent one of the best routes to lower the cure tem-
peratures while improving the compatibility with
graphite/epoxy adherends. High conversions can be
achieved without transition metal catalysts.
Alternatively, the blending with epoxy resin can
improve wettability.
352 HANDBOOK OF THERMOSET PLASTICS

N
C
O

O
Heat N
N C O R O C N N O O C N
N
O
Dicyanate monomer

O
C
N

Prepolymer

Heat
R2
O

O
N
R2 O O N
N
O

R2
R1
O

O O
N N
N O O R1 O N
N N
O O

O O
R2

R1

O
N
R2 O O N
N
O

O
R2
Thermoset polymer
(Polycyanurate)

Figure 10.35 Cure of dicyanate via cyclotrimerization.

10: HIGH-PERFORMANCE POLYIMIDES
100
99
Specific volume, normalized
Gel
98
97
96
95
0 20 40 60
% Conversion
Figure 10.36 Specific volume change in uncatalyzed
Arocy RTX-366 during cure.
Cyanate esters also exhibit very low moisture
absorption (0.5
2.5% immersed in water at 100°C)
when compared to epoxies and other thermosets or
thermoplastics. To maintain good adhesive process-
ibility and mechanical properties requires an ability
to keep the adhesive dry, which is made easier with
a resin that has a low equilibrium moisture absorp-
tion. Polycyanurates are known to have excellent
adhesive properties [69]. Partly responsible for the
excellent adhesion is the low degree of shrinkage in
going from the uncured to cured state. Volume
change with cyclotrimerization produces the
expected shrinkage up to gelation (60
65% con-
version), but an unexpected expansion occurs with
continued curing (Figure 10.36) [72]. Low shrink-
age translates to reduced thermal stress between the
adhesive patch and the substrate.
A wide product range of cyanate ester resins is
commercially available from suppliers such as
AlliedSignal (which acquired Honeywell and
adopted the Honeywell name in 1999), Huntsman
AND HIGH TEMPERATURE RESISTANT POLYMERS 353
N N N
C C C
O O O
n=0.2
Figure 10.37 Polycyclic-containing polycyanate
resins from Dow and YLA.
CH3 CH3
80 100
N C O C C O C N
CH3 CH3
Figure 10.38 RTX 366 Dicyanate monomer.
Advanced Materials (formerly Ciba), Dow, Hoechst
and YLA, Inc. (a part of Tencate Advanced
Composites, Morgan Hill, California, since 2008)
to allow flexibility in matrix and adhesive formula-
tion. These cyanate esters range from those based
on Bisphenol A and low-molecular-weight novalacs
(Dow Chemical XU 71787 series, YLA RS-3
(Figure 10.37), to those based on Matrimid® [73],
RTX 366 (Figure 10.38), and the 6F analog of
Bisphenol A produced by Hoechst.
The Dow XU 71787 polycyanurates perform up
to 177°C (350°F) and offer zero cure shrinkage,
low moisture absorption, low dielectric constant
and low dielectric loss [74]. A comparable choice
is the YLA RS-3 toughened polycyanurate [75].
Both the Dow and YLA polycyanurate materials
are based on dicyclopentadiene. The polycyclic
structures in the cured polycyanurate matrix are
resposnsible for the material’s low moisture
absorption and low dielectric constant/loss
(Table 10.48).
354 HANDBOOK OF THERMOSET PLASTICS

Table 10.48 Typical Properties of Neat Polycyanurate Castings

Toughened with 10% elastomeric additive.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Cyanate Ester SIPNs
A semi-interpenetrating polymer network (SIPN)
is defined as a combination of one thermoplastic
polymer and one thermoset polymer in network
form, one of which is synthesized and/or cross-
linked in the immediate presence of the other.
Formulation of cyanate esters with thermoplastics
would provide the proper rheology for good wet
out and adhesion in the bonded joint.
Cyanate esters blended with thermoplastics usu-
ally develop excellent tack and drape. The aromatic
nature of the monomer backbone in RTX-366
imparts thermal stability to polymers cured at tem-
peratures as low as 121°C (250°F) and reduces
moisture absorption (0.6% at 100% saturation)
[76]. Other features of RTX 366 are its low melting
(68°C) and viscosity (8,000 cps at 25°C) of its
monomer. Thermoplastics of interest include poly-
arylsulfone (Figure 10.39).
O During the late 1980’s and 1990’s, aerospace
HO S O H research efforts including Lockheed and Rohr have
O focused on the viability of improving the thermo-
n
Figure 10.39 Polyarylsulfone.
Although unmodified cyanate esters possess
twice the fracture toughness of multifunctional
epoxies, they are still highly cross-linked materials
and are prone to embrittlement. Formation of
SIPNs with compatible thermoplastics improves
their fracture toughness. Several high-Tg
(170
220°C) thermoplastics are soluble in dicya-
nate monomers and phase separates during
cure. Thermoplastic resins with reactive hydroxyl
end-groups develop smaller co-continuous thermo-
plastic-rich domains (usually , 1 micron in diame-
ter) than similar thermoplastics terminated with
nonreactive end-groups. This permits formulation
of melt processable blends achieving dramatic
improvements in fracture toughness (G1C) as
shown in Figure 10.40 [70,77]. The free hydroxyl
groups also serve as a co-catalyst for the homopo-
lymerization. Several noteworthy commercial ther-
moplastics with hydroxyl termination are
polyarylsulfones (i.e. ICI’s Victrex 5003, Amoco’s
Radel A, and BASF’s PES) and copolyesters
(Vitel PE307).
355
5
Polyethersulfone (PES)
Fracture t oughness, G1c (in-lb/in2)
4 Copolyester (CPE)
Polysulfone (PS)
3
2
1
0
0.0 5.0 10.0 15.0 20.0
% Thermoplastic
Figure 10.40 Effect of thermoplastic resin
concentration on fracture toughness of Arocy B
castings.
Polyimide-Based Cyanate Esters
oxidative stability, mechanical strength, and dura-
bility of cyanates ester resins through the applica-
tion of acetylene- and phenylethynyl-terminated
imide/isoimide technologies, PMR resins, BMIs,
silicate-based polymer-ceramics [23,78
91], and
polyimide-based cyanate ester resins.
The general strategy for producing polyimide-
based cyanate ester resins comprises a two-step
process: endcapping of an anhydride-terminated
imide oligomer with 3- or 4-aminophenol, followed
by the standard cyanate ester formation between
the hydroxy-terminated oligomer and cyanogen
bromide [92]. Interpenetrating polymer network
(IPNs) and semi-interpenetrating polymer network
(SIPNs) can be formed from blending the thermo-
setting and thermplastic polyisoimides/polyimides
with the compatible liquid dicyanate monomer
AroCy L-10 (Figure 10.41). The dicyanate mono-
mer thermally cures to form a cross-linked network,
CH3
N C O C O C N
H
Figure 10.41 Low viscocity dicyanate monomer
Arocy L-10.
356
interpenetrating with the network formed by the
thermosetting polyimide (hence, IPN), or imbibing
the linear thermoplastic polyimide strands to give
an SIPN.
Polycyanurates for Flame
Retardancy
Cyanato phenyl substituted cyclotriphosphazenes
have been evaluated for their contribution toward
flame retardancy. They were synthesized and ther-
mally cured to phosphazene-triazine matrix network
polymers. The phosphazene-triazine polymer net-
work has been shown to possess better flame retar-
dancy and thermal resistance, in comparison to the
pure polycyanurates. The thermal stability and the
activation energy for thermal decomposition of the
matrix network polymer increases with cross-link
density and the phosphazene content.
Polycyanurates in Electronic
Applications
As mentioned earlier, cyanate ester materials
possess outstanding electrical properties, such as
low dielectric constant and high dielectric break-
down strength, in addition to their excellent ther-
momechanical properties such as high Tg, adhesion
to metals, chemical resistance, and dimensional sta-
bility. The microelectronic industry has used vari-
ous polycyanurates in printed wiring circuit
boards, thin cards, multichip modules and for
encapsulation [93].
To alleviate the brittleness and microcracking
problems of cyanate esters, semi-interpenetrating
polymer networks (SIPNs) have been found to be
useful. The IBM efforts on fluorinated hydroxy-
terminated polysulfone thermoplastics and a fluori-
nated dicyanate monomer (Figure 10.42) [94] hasve
resulted in significant improvement of fracture
toughness, as reflected by the KIC and GIC values.
High-Temperature Thermosetting
Resins Based on Phthalonitrile
The literature on high-performance polymers
contains references on phthalonitrile resins extend-
ing back more than 25 years. Related activities
focus on the feasibility study of optimizing phthalo-
nitrile resins as prepreg resins at Merlin
HANDBOOK OF THERMOSET PLASTICS
CF3
N C O C O C N
CF3
W+
CF3 O CF3
H O C O S
O
O C OH
CF3 n CF3
Cross-linked
network
Figure 10.42 A toughened fluorinated polycyanurate
network .
Technologies (San Carlos, CA), sponsored by the
Naval Research Laboratory [95].
The synthesis and evaluation of phthalonitrile
resins have been a key materials interest at the
Naval Research Laboratory, summarized in 46 pub-
lications and patents in the past 35 years [96
142].
For example, phthalocyanine polymers having high
thermal and oxidation resistance, good toughness
and low water absorptivity have been prepared
from various bisphthalonitriles, which in turn were
synthesized by nucleophilic displacement of nitro
group of nitrophthalonitrile with aromatic bisphe-
nols [96] or via metal-mediated coupling of 4-
iodophthalonitrile and iodofluoroalkanes [97].
Generally the reactants are heated at 250°C giving
a brown solid in 2 hours, which is postcured at
250°C for 6 hours and 315°C for 16 hours. The
fluorinated polyphthalocyanine materials
have , 1% water absorption under standard soak
tests.
The thermo-oxidative properties of
phthalonitrile-based polymers can be exemplified
by the aromatic diether-linked phthalonitrile resin,
4,40 -bis(3,4-dicyanophenoxy)biphenyl with 1,3-bis
(3-aminophenoxy)benzene (APB). This resin is eas-
ily processed from the melt of the monomer in a
controlled manner as a function of the amine con-
tent and processing conditions. The resulting poly-
mer shows an excellent retention of mechanical
properties following inert atmosphere post-cure to
375°C and oxidative aging at 315°C for 100 hours.
Results are reported for the effects of cure, post-
cure, and aging conditions on the tensile and frac-
ture properties of these polymers [111].
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Phthalonitrile adhesives prepared from 4,40 -bis
(3,4-dicyanophenoxy)-biphenyl and 1,3-bis(3-ami-
nophenoxy)benzene curing agent, can withstand
temperatures of 200
550°C and are useful for bond-
ing various substrates, especially metals. These
adhesives were tested with aluminium substrates
showing shear strength at room temperature and at
200°C, of 1,450 and 1,070 psi, respectively [104].
Polymerization of the phthalonitrile resin occurs
through the cyano groups via an addition mechanism
to afford heterocyclic cross-linked products with high
Tg and thermo-oxidative stability. Polymerization
can be easily controlled by the concentration of the
curative and the cure [142] in one step to gellation or
to any desired level of viscosity and quenched. Such
B-staged prepolymers can be kept indefinitely at
ambient temperatures. For composite missile compo-
nents that require outstanding compression and shear
strength properties during short-term use at tempera-
tures as high as 1500°F (816°C), phthalonitrile-based
resins are a viable option and have continued to be a
key research focus at the NRL.
Further, phthalonitrile hybrid structures with
polyimides, polyamides, and polybenzoxazines
show high thermal stability. Their high char yields
Table 10.49 Select Phthalonitrile Resins Studied at Naval Research Laboratory
357
are noteworthy. Up to 80% by weight has been
demonstrated by thermogravimetric analysis in an
inert atmosphere at 800°C, and up to 70% by
weight at 600°C (1,112°F) is achieved in air [143].
Similarly, a comparable study of phthalonitrile-
endcapped oligomers of pyromellitic-anhydride
(PMDA)-based polyimide were converted to cross-
linked polymer network using 4,40 -diaminodiphenyl
sulfone (DDS) (5.0 wt.%) as curative at elevated
temperatures. TGA analysis of the cured resins
showed superior thermal and thermo-oxidative sta-
bility. The temperature of 10% weight loss from
TGA are in the range of 498
511°C (in nitrogen)
and 448
461°C (in air). The high char yields of
41.7
50.2% (in air) and 70.6
83.1% (in nitrogen)
at 800°C (1,472°F) is remarkable [144].
The breadth of the research at the NRL is shown
by the representative references summarized in
Table 10.49:
Interest in phthalonitrile-based thermosetting
resins has continued both at NRL and internation-
ally. Current focus has been on processing flexibil-
ity to include resin transfer molding (RTM)
processes through the use of newer formulations
with oligomeric aromatic ether spacer groups
(Continued )
358 HANDBOOK OF THERMOSET PLASTICS

Table 10.49 (Continued)

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 359

Table 10.49 (Continued)

(Continued )
360 HANDBOOK OF THERMOSET PLASTICS

Table 10.49 (Continued)

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
endcapped with phthalonitrile units to create resins,
which possess melting points as low as 104°F to
122°F (40° to 60°C) [145]. Similar work on pro-
cessible phthalonitrile resins with low melting tem-
peratures for resin transfer molding (RTM)
industrial processes has been reported [146].
Acetylene-Terminated
Thermosetting Polymers
As a result of the development of novel synthetic
methods for attaching ethynyl and phenylethynyl
groups on aromatic systems, more and more mono-
mers, oligomers and prepolymers containing termi-
nal ethynyl and phenylethynyl groups are available
as basic units for a useful class of addition curable
resins. Similar to the development of nadimide-
terminated polyimides and bismaleimides, the devel-
opment of ethynyl-terminated, also called acetylene-
terminated (AT) polyimides and other heteroaro-
matic polymers has the important feature of an addi-
tion cure mechanism which provides chain
extension and cross-linking without the evolution of
volatile by-products. Many of the cured resins have
good solvent and moisture resistance, and exhibit
outstanding physical and mechanical properties. A
comprehensive review has summarized the research
activities that have been conducted on the develop-
ment of AT monomers, oligomers and polymers
[147]. The AT polyimides have been commercial
products for over a decade. It is sufficient here to
highlight some key features in the development of
this novel class of addition thermoset resins.
Attachment of ethynyl groups to aromatic and
heteroaromatic nuclei favors the application of
organometallic chemistry and, in particular, organo-
palladium chemistry (Figure 10.43). The availabil-
ity of a variety of organopalladium catalysts, the
catalytic nature of the palladium complexes for
synthetic applications, the simple experimental pro-
cedure, and the high yield of reaction product are
the favorable factors.
An aromatic halide and a terminal acetylene
compound can undergo coupling under the catalysis
Pd
X + H C C R C C R
X = Br, I
Figure 10.43 Palladium-catalyzed ethynylation.
361
of palladium[0] [148]. In principle, for the place-
ment of an ethynyl group on an aromatic structure,
a terminal acetylenic compound would be required
having the protective R group easily removable
after the palladium-catalyzed coupling reaction has
been effected.
In the synthesis of ethynylated aromatic com-
pounds two key terminal acetylenes have been
widely used (Figure 10.44). Both ethynyltrimethyl-
silane (variation A) and 2-methyl-3-butyn-2-ol (var-
iation B) undergo facile palladium-catalyzed
coupling with haloaromatics to give internal acety-
lene compounds. Removal of the trimethylsilyl
group or the acetonyl group generates the corre-
sponding terminal acetylenes.
The highly basic reaction medium required in
variation B for the removal of the acetonyl group
precludes compounds containing base-sensitive
functional groups. The removal of the trimethylsilyl
group (variation A) requires only mild conditions
[78]. Variation A, therefore, has specific application
in ethynylation reactions of base-sensitive com-
pounds. As stated earlier, the most important charac-
teristic of resins capable of addition cure is that no
volatile by-products are released. Void-free compo-
nents that can be produced with these thermoset
resins are critical to large dimensional structural use.
A variety of aromatic and heteroaromatic oligomers
having terminal ethynyl groups have been prepared
and evaluated. Some of them have the potential of
meeting all the processing criteria of epoxies but are
more thermally stable and moisture resistant.
Acetylene-terminated (AT) resins can be used in a
wide range of processing temperatures and conditions
[149]. Significant contributions to the synthesis and
evaluation of acetylene-terminated reactive oligomers
and polymers have been made by the Air Force
Materials Laboratory. While resins with flexible
backbones such as acetylene-terminated 2,2-bis(4-
phenoxyphenyl)propane (ATB) [150,151] exhibit
tack and drape characteristics, others with high
molecular weight and rigid backbones possess only a
short melt state, such as BATQ [152] (Figure 10.45).
(a) (b)
CH3 CH3
H C C Si CH3 H C C C OH
CH3 CH3
Figure 10.44 Ethynyl compounds used in palldium-
catalyzed ethynylation reactions.
362 HANDBOOK OF THERMOSET PLASTICS

CH3
H C C O C O C C H
CH3

ATB

N N
O O
N N N N
H C C O O C C H
N N

n
BATQ

H C C O N N N N O C C H
O O
N N N N

ATQ

Figure 10.45 Acetylene-terminated resins (Air Force Materials Laboroatory).

Table 10.50 ATB Neat Resin Mechanical Properties

(Reprinted by permission of References [150] and [151])

Good mechanical properties are obtainable in
cured AT systems, even those systems with more
flexible backbones, such as ATB (Table 10.50).
Acetylene-Terminated
Quinoxalines
Earlier studies with thermoplastic polyphenylqui-
noxalines showed that they were difficult to pro-
cess, requiring temperatures in excess of 316°C
(600°F). Subsequently, the AT-oligomers were
developed and they exhibited excellent potential as
moisture-resistant adhesives and matrix materials
[153
155]. The fully cured AT resin, acetylene-
terminated quinoxaline (ATQ), yielded a glass tran-
sition temperature of 321°C (610°F) [156].
Table 10.51 summarizes tensile strength data
obtained for this resin at both room temperature
and 232°C (450°F). Mechanical properties at both
temperatures are not affected by aging at 93.3°C
(200°F), 95% humidity environment.
The ATQ resin has also been evaluated as a
matrix in graphite composites. The resulting com-
posite showed good flexural strength and modulus.
It is noteworthy that the ease of processibility of
these AT-oligomers is inversely proportional to the
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 363

oligomer chain length. On the other hand, thermo-
oxidative stability and adhesive strength of the
cured ATQ resin increase with longer linear seg-
ments in the oligomer. The cured ATQ resins are
thermo-oxidatively less stable than the correspond-
ing parent linear polymer. These observations have
proven to be universal among AT polymers [157].
It has been suggested that the thermo-oxidative sta-
bility of the AT resins is related to the large per-
centage of polyene and enyne structures formed in
the resin during cure. Solid state carbon-13 NMR
[158] has demonstrated that only a small proportion
of the acetylene terminations of AT resins undergo
trimerization to yield thermal and thermo-
oxidatively stable benzene rings. Several acetylene-
terminated quinoxalines containing only phenyl and
quinoxaline units were synthesized specifically to
measure their thermo-oxidative stability under iso-
thermal aging conditions. Three systems, A, B, C,
each being an isomeric mixture, were synthesized
and cured prior to isothermal aging [159]
(Figure 10.46).
All three systems showed poor thermo-oxidative
stability at 371°C (700°F). The cured acetylene

Table 10.51 Mechanical Properties of Cured Neat Resin of ATQ

(Reprinted by permission of References [150] and [151])

N N
R1 N N
C C H N

R2 N
R1 R3
R2 R4

Structure A Structure B

1. R1 = ethynyl, R2 = H 1. R1 = R3 = ethynyl, R2 = R4 = H
2. R1 = H, R2 = ethynyl 2. R1 = R4 = ethynyl, R2 = R3 = H
3. R1 = R3 = H, R2 = R4 = ethynyl

N N
R2 R3
R1 R4
N N

Structure C

1. R1 = R3 = ethynyl, R2 = R4 = H
2. R1 = R4 = ethynyl, R2 = R3 = H
3. R1 = R4 = H, R2 = R3 = ethynyl

Figure 10.46 Acetylene-terminated quinoxalines designed for comparative thermo-oxidative stability

measurements.
364
Table 10.52 Correlation of Cured Acetylene Linkages with Thermo-oxidative Stability
(Reprinted by permission of Reference [159])
linkages apparently were the predominant site of
thermooxidative degradation. The rate of weight
loss at 371°C (700°F) was directly proportional to
the number of cured acetylene linkages
(Table 10.52). These results demonstrate that ther-
mally cured AT resins do not have long-term 371°
C (700°F) utility. A new cure mechanism must be
sought for high temperature resins in order to
achieve 371°C (700°F) durability.
Acetylene-terminated diluents such as BA-DAB-
BA, AA-BA and diethynylbisphenoxybenzene
(ATPB) were developed for the improvement of
processibility of BATQs so that they would become
more amenable to melt processing. These diluents
all plasticize the BATQs to give a significant low-
ering of the bulk viscosity. They then co-react with
the BATQ oligomers to become part of the thermo-
set network [160]. The BATQ most extensively
studied was the BATQ-H (Figure 10.47).
Acetylene-Terminated Sulfones
The acetylene-terminated sulfone (ATS) has
been studied quite extensively (Figure 10.48).
Depending on the method of synthesis, different
forms of ATS were obtained. Some low molecular
weight vinyl ether oligomers were present to the
extent of 15
21%. The oligomers are responsible
for the ATS’ appearance as a tacky resin that can
be melt impregnable. Neat resin mechanical proper-
ties have been determined for the ATS resins
(Table 10.53).
ATS has been evaluated as a matrix resin in
graphite fiber-reinforced composites. Although
judged as brittle, the resin yielded composites that
have good retention of mechanical properties at
HANDBOOK OF THERMOSET PLASTICS
177°C (350°F) before and after high humidity
exposure [161,162].
Successful experiments have been conducted
with semi-interpenetrating polymer network (SIPN)
blends. The objective is to achieve blends of resin
materials that can retain all good properties origi-
nally ascribed to each neat material and reduce the
undesirable properties at the same time. ATS has
been evaluated as a reactive diluent with thermo-
plastic polysulfones. The high cross-linking density
inherent in ATS can help improve the Tg, of the
thermoplastic polysulfone while the brittleness
associated with the high cross-linking density of
ATS can be compensated by the presence of the
thermoplastics. To this end, the polysulfone Radel®
(Union Carbide), after being modified with various
amounts of ATS, showed a significant improvement
in its processibility. After cure, the resin blend
showed a higher Tg (240°C versus 220°C for neat
Radel® resin) and enhances solvent resistance
[163]. Similar results were obtained for blends of
ATS with UDEL®) (Union Carbide). Ethynyl-
terminated sulfone oligomers other than ATS have
also been prepared and used to modify properties
of linear polysulfones such as UDEL® P-1700.
While the toughness and thermoform-ability indige-
nous to the thermoplastic are preserved, the pres-
ence of cross-linked ethynyl-terminated sulfone
oligomers improves the solvent resistance, expe-
cially when under load [147].
Acetylene-Terminated Imide
Oligomers
Acetylene-terminated imide oligomers were
developed with similar objectives for better
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 365

N N
O O
N N N N
HC C O O C C H
N N

n=1
BATQ-H

N
O C CH
N N
HC C O
N

BA-DAB-BA

N O C CH HC C O O
O C CH
HC C
N

AA-BA ATPB

Figure 10.47 Reactive diluents used for polyquinoxaline processing.

O chemists at Hughes Aircraft Company under

C C H
H C C O S O AFWAL sponsorship developed unique, fusible and
O tractible acetylene-terminated polyimides which
ATS
undergo addition-type homo-polymerization by vir-
tue of the terminal ethynyl (acetylene) groups. The
Figure 10.48 Acetylene-terminated sulfone. monomer system used for these oligomers was
designed so that the prepolymer would melt before
undergoing homopoymerization. The prepolymer
was synthesized from benzophenonetetracarboxylic
processibility as for nadimide-terminated or dianhydride (BTDA) (VIII), 3-aminophenyl-
maleimide-terminated polyimide resins. The termi- acetylene (APA) (XXIII), and 1,3-bis(3-aminophe-
nal ethynyl groups are capable of undergoing ther- noxy)benzene (APB) (XXIV) (Figure 10.49).
mally induced addition reactions yielding a The prepolymer is shown by structure (XXV)
complex cross-linked network [157]. In the late where n is generally one, two or three
nineteen-sixties and early nineteen-seventies, (Figure 10.50).
366 HANDBOOK OF THERMOSET PLASTICS

Table 10.53 ATS Neat Resin Mechanical Properties

(Reprinted by permission of Reference [147])

O
O O
* NH2
O O
*
H C C
O O

VII XXIII

H2N O O NH 2

XXV

Figure 10.49 Constituents of Thermid® resin (Formerly Hughes Aircraft Company HR600 Resin).

C N O O N N O O N C
C C
H H
O O O O

O O O O
n=1,2,3

Figure 10.50 Chemical structure of Thermid® 600 resin.

Higher values of n reduce prepolymers’ solubil-
ity in solvents such as N-methylpyrrolidinone
(NMP). Their proportionally higher melting tem-
peratures are often close to the homopolymerization
temperatures of about 220°C (428°F) to 275°C
(527°F).
A significant development in acetylene-
terminated imide oligomers was the commercializa-
tion of the Hughes HR600 resins as Thermid 600®
by Gulf Chemicals. Since 1983, various forms of
Thermid 600® are supplied by the National Starch
and Chemical Corporation. Although neat resin
properties, composite properties and adhesive prop-
erties [164,165] of the HR600 resins (Tables 10.54
and 10.55) are indicative of their suitability as high
temperature resistant matrix resins and adhesives,
their poor flow characteristics and insolubility in
common solvents make them difficult to process.
Thermid® MC-600 is a pre-imidized molding
powder, Thermid® LR-600, an amic acid form with
50% solids in NMP solvent, and Thermid® AL-
600, an amine and ester monomeric mixture with
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Table 10.54 Typical Properties of HR600
(Reprinted by permission of References [164] and [165])
Table 10.55 Properties of Unidirectional HT-S Graphite Fiber Laminates made with Thermid 600® Resin
(Reprinted by permission of Reference [147])
75% solids in ethanol. The properties of Thermid®
MC-600 neat resins are shown in Table 10.56.
Thermid® LR-600 is an excellent adhesive for
titanium. The University of Dayton Research
Institute generated data using heat cleaned 112
glass cloth as a adhesive carrier at 70% level of
impregnation. The adhesive was formulated with
5% hydroquinone plus primer of a 10% solids of
Thermid® LR-600 in methylethyl ketone. Curing
for 500 hours at 288°C (550°F) gave a lap shear
value of 2,600 psi and 500 hours at 316°C (600°F),
a value of 2,500 psi. All the specimens were heat
soaked at test temperature for 30 minutes before
testing.
367
Isoimide Modification
of Polyimides
To improve the processibility of these acetylene-
terminated oligomers, Hughes Aircraft Company
chemists synthesized acetylene-terminated isoi-
mides using the same monomers as for the imide
form [166,167]. These isoimides are isomeric to the
imides and are more soluble in common solvents
and more processible. The isoimide converts to its
imide form upon heating (Figure 10.51). In contrast
to the condensation closure of amic acid to imide,
the isomerization of isoimide to imide yields no
volatiles.
368 HANDBOOK OF THERMOSET PLASTICS

Table 10.56 Thermid® MC-600 Neat Resin Properties

(Reprinted by permission from National Starch and Chemical Corporation)

O
O N
Δ
N
NH
O
CO2H O
O

Amic acid Isoimide Imide

Figure 10.51 Chemistry of isoimide modification.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
O O O O
N N
C O
C C
H O O O
Figure 10.52 Thermid® IP-600 isoimide oligomer.
The isoimide form of Thermid® 600 can be con-
veniently synthesized via the deehydration of the
amic acid by N,N0 -dicyclohexylcarbodiimide
(DCC) [84
88]. This technology is the basis of the
National Starch Thermid IP-600 thermosetting
resin. Although other dehydrating agents such as
trifluoroacetic anhydride and ethyl chloroformate
are also workable, the DCC method is more univer-
sally applicable [48]. The DCC conversion of
polyamic acid to polyisoimide has been confirmed
by Japanese researchers [168].
The more processible Thermid® IP-600 isoimide
is supplied in the powder form. Developmental
quantities of higher molecular weight polyimides
(IP 603 to IP 650) are also available. The
Thermid® IP-600 series is characterized by lower
melting temperature, longer gel time and good solu-
bility in low boiling solvents, retention of strength
following high temperature exposure and superior
processibility in vacuum bag/autoclave composite
structure fabrication, in comparison with Thermid®.
These key attributes resolve many processing pro-
blems encountered with conventional polyimides.
The higher values for the degree of polymerization
(DP) for the Thermid® IP-600 series give resins
which have excellent film-forming capabilities,
lower glass transition temperature, and improved
strain capability, all with little change in tensile
strength (Figure 10.52).
These materials have substantially increased pro-
cessibility by virtue of drastically reduced melting
points and prolonged gel time. Soluble and
tractable isoimide oligomers have been prepared
with degrees of polymerization (DPs) up to 25. By
contrast, the Thermid 600® imide oligomers
become insoluble and intractable at DP . 3. At
elevated temperatures, the ethynyl groups undergo
the usual chain extension and cross-linking reac-
tions while the isoimide functions rearrange to the
amides. Adhesive and composite properties
obtained with cured acetylene-terminated isoimide
oligomers are compatible to those of cured HR600
369
O O
N N
O C
O H
n=1,2,3
imide oligomers [166,167]. The high DP materials
are excellent film formers and thus are useful for
coating applications. The properties of Thermid®
IP-600 neat resins are shown in Table 10.57.
Isoimide modification of acetylene-terminated
polyimide precursors offers the potential of improv-
ing processibility of otherwise difficult-to-process
high-temperature polyimides. Especially important
is the observation that the technology can be
applied without compromising the thermomechani-
cal properties of the final products. Previously, the
concept of producing thermally stable addition cur-
able polymers was severely limited by the intracta-
bility of the oligomers. With the introduction of
isoimide modification to polyimide precursors, the
processing window is significantly broadened.
Some commercially available diamines and dianhy-
dride monomers, which previously formed
intractable polyimide prepolymers, become useful
candidates for processible resin systems. In addition
to the melting point and gel time improvements,
the isoimides impart to the precursors increased sol-
ubility in common low-boiling, noninteracting sol-
vents, such as tetrahydrofuran. This is to be
contrasted with state-of-the-art polyimide precur-
sors, which generally are soluble only in strong
aprotic solvents, i.e., N-methylpyrrolidinone
(NMP). The latter class of solvents is very difficult
to remove during processing and its use often
results in void formation in cured composites. New
families of processible high-temperature resistant
polymers for long-term . 700°F (371°C) utility
could be obtained through isoimide modification,
leading to hybrid polyisoimides containing polyhe-
terocyclic structural units.
Cure Mechanism of Acetylene-
Terminated Oligomers
Acetylene-terminated oligomers have been of
continued interest in the development of more pro-
cessible high-temperature resistant composite
370
Table 10.57 Thermid® IP-600 Neat Resin Properties [167]
(Reprinted by permission from Hughes Aircraft Company)
resins. The final product properties obtained from
these cross-linked materials are directed related to
the structure of the 3-dimensional network. A better
understanding of the reaction mechanism of the
thermal cure of the terminal ethynyl units would
allow better design of the cure schedule and optimi-
zation of the final composite properties.
There has been much speculation as to the cure
mechanisms of acetylene-terminated thermosetting
oligomers. Although low molecular weight model
compounds were found to undergo some trimeriza-
tion to form aromatic ring, the homopolymerization
of the higher molecular weight acetylene-
terminated polyimides is more complicated [168].
The initial products of thermal curing of terminal
ethynyl groups are postulated to be ene-yne type
structures, i.e. Straus [169],. Glaser [170], and
Sabourin dimers [171], from the coupling of termi-
nal ethynyl functionalities. Condensed aromatic
compounds were isolated from thermal reactions of
monoethynylated compounds. The preliminary
report of this interesting work also suggested that
monofunctional (one terminal ethynyl group) model
compounds form condensed aromatic structures
(benzenes and naphthalenes) from the intial Straus
and Glaser dimer products, but difunctional com-
pounds tend to produce polyene chains in prepon-
derance, based on FTIR/NMR techniques and
thermal kinetics (Figure 10.53) [172,173].
HANDBOOK OF THERMOSET PLASTICS
An elegant solid state 13C cross-polarization
magic-angle spinning (CP-MAS) nuclear magnetic
resonance (NMR) spectrometric study has been car-
ried out at IBM Almaden Research Center (San
Jose, California) on ethynyl-terminated BTDA-APB
isoimide oligomers which have been selectively
labelled using 13C labelled precursors [174]
(Figure 10.54). The selectively labelled resin speci-
mens were cured in the identical way as the unla-
belled (control) samples and subsequently studied
by the NMR method. Differential spectra showing
only the selective label were obtained by subtract-
ing the resonances due to the natural abundance 13C
nuclei. In addition, delayed decoupling experiments
were performed to allow protonated carbon nuclei
to relax, thereby distinguishing them from unproto-
nated carbon nuclei. The results showed that the
carbonyl function on BTDA remained unchanged in
the cured product. The isoimide/imide carboxyl car-
bons underwent the isomerization reaction in the
expected manner. The solid-state cure products due
to the ethynyl termini were found to comprise aro-
matic structures, polycyclic aromatic structures,
backbone addition and bridge structures.
The aromatic structures were interpreted as tri-
merization products via intermediate Straus and
Glaser coupling products, in agreement with results
of the French group [172,173]. The polycyclic aro-
matic structures, backbone addition and bridge
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 371

R C C H + R C C H

Dimerization

R
C R
H C Isomerization
C C H
H C C C
H H H C C
C C C
R C C
C
C
R R

Straus dimers Sabourin dimer R

Glaser dimer

Further bimolecular
reaction with monomers

Cyclization Further bimolecular

reaction with monomers
Further bimolecular
Cyclization reaction with monomers

R
R R

R
Further bimolecular + Polymer
R
reaction with monomers R

1,2,4-Trimer
R

1,3,5-Trimer

Figure 10.53 Elucidation of thermal cure mechanism for terminal ethynyl groups [172].
372 HANDBOOK OF THERMOSET PLASTICS

O
O structures were logical deductions from 13C spectro-
O NH2
* * metric analysis. Table 10.58 summarizes the corre-
O O * lation of 13C spectral results and expected products.
H C C
* *
Results from NASA-Langley’s study of ther-
O O mally induced addition of ethynyl-terminated imide
oligomers to bismaleimides supported findings
O
O
O
from previous mechanistic studies of thermal cure
NH2
* of ethynyl-terminated thermosetting polymers
O O * [175,176]. Such an addition reaction approach
H C C
yields high-performance thermoplastics with pro-
O O cessibility, toughness and thermo-oxidative stability
(Figure 10.55). The Diels-Alder addition mecha-
* = Carbon-13 label
nism has been substantiated by model compound
Figure 10.54 Carbon-13 labelled monomers for reactions both in solution and in the solid state. All
synthesis of acetylene-terminated BTDA-APB reaction products were identified by conventional
isoimide oligomers. analytical techniques including NMR, FTIR, UV-
visible, mass spectrometry, and HPLC.

Table 10.58 Correlation of Carbon-13 CP-MAS NMR Results with Ethynyl Cure Products

(Continued )
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 373

Table 10.58 (Continued)

374 HANDBOOK OF THERMOSET PLASTICS

R1
C CH
Δ R1
+ groups, propargyl-terminated oligomers represent
O R2
O yet another thermosetting resin family. The syn-
N R2
O
Figure 10.55 Addition-type thermoplastics
formation from an ethynyl-terminated imide and a
bismaleimide.
Solution reactions of the model compounds N-(3-
ethynylphenyl)phthalimide and N-phenylmaleimide
yielded a Diels-Alder product but no coupling pro-
ducts due to the ethynyl groups (Figure 10.56).
Another dienophile, benzoquinone, also underwent
Diels-Alder reaction with N-(3-ethynylphenyl)
phthalimide, but in a 1-to-2 ratio. In the solid state at
214°C (417°F), the reaction was complicated by the
volatility of N-phenylmaleimide and a less volatile
analog N-(4-phenoxy)phenylmaleimide was used.
The isolated reaction products were interpreted to
have been formed by Diels-Alder reaction of an
intermediate Straus coupling product of N-(3-ethy-
nylphenyl)phthalimide with the dienophile
(Figure 10.57).
Propargyl-Terminated Oligomers
O Resembling ethynyl and phenylethynyl end
thetic approach to the easily accessible propargyl-
terminated Bisphenol A (PTBA) is identical to that
for diglycidyl ether of Bisphenol A. Preliminary
results indicate that PTBA could be useful as high-
performance materials [177,178] (Figure 10.58).
The resin can be cured to a Tg of 360°C, and exhi-
bits tensile strength, modulus and elongation of
14.9 ksi, 660 msi, and 2%, respectively. Fracture
toughness, K1C is 387 (25°C), 401 (100°C), and
347 (177°C) psi.in 1/2.
Phenylethynyl-Terminated
Thermosetting Polymers
The high-performance thermoset polymers of
intense interest include various acetylene-
terminated (AT) arylene ether [179], arylene ether-
ketone, and imide/isoimide oligomers
[84,89,166,167], many of which have been
reviewed earlier [147]. Phenylethynyl-terminated
(PET) oligomers are of great interest as thermoset
precursors to high temperature resistant materials
[180
187]. Of special relevance are the results on
PET-imide oligomers [181
184,186,187].

N
O
O O
N
N
O
O

O C CH
N 1,2,4-Trichlorobenzene
24 hr, reflux
O
O
O N
O
O

O O
O
N
O

Figure 10.56 Solution reaction between N-(3-ethynylphenyl)-phthalimide and N-phenylmaleimide.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 375

O
O C CH H N
2 N C C O
C H
O O C
N
O

O
N O
O

O
O O
N N
O
O
C
O C
N
O

O
N O
O

O
O O
N N
O
O
O O
N N
O O
O

Figure 10.57 Solid state reaction illustrating the Diels-Alder reaction mechanism and the intermediacy of a
straus dimer.

CH3 synthesis of the phenylethynyl end-capping agent

HC C CH2 O C O CH2 C CH 3-(phenylethynyl)aniline (PEA), illustrating the
CH3
palladium-catalyzed phenylethynylation reaction.
An alternative method uses commercial 3-
Figure 10.58 Propargyl-Terminated Oligomer aminophenylacetylene as starting material
PTBA. [188,189].
3-(Phenylethynyl)aniline can be routinely pre-
pared for use in end-capping imide and isoimide
oligomers. PET-polyisoimides/polyimides and ther-
The phenylethynyl end-capping agent via the moplastic polyisoimides form compatible blends
palladium-catalyzed coupling reaction was briefly that thermally cure to SIPNs with Tg above 300°C,
studied at National Starch [182]. Palladium- which is desirable for advanced matrix resin and
catalyzed coupling reactions are a key feature in adhesive applications to hot areas on airframe and
acetylene chemistry. Figure 10.59 depicts the gas turbine engines.
376 HANDBOOK OF THERMOSET PLASTICS

C CH

O2N H2N
(Ph3)2PdCl2, PPh3
Cul Na2S
+ C C C C
NEt3, Δ
O2N

Br

Figure 10.59 Synthesis of 3-(phenylethynyl)aniline via palladium-catalyzed phenylethynylation of 1-bromo-3-

nitrobenzene. (Courtesy: National Starch and Chemical Corporation).

C CH

L2PdCl2
(L=PPh3)
O C C
+
Et3N
O
O

O Br 4-(Phenylethynyl)-
phthalic anhydride
O
O

Figure 10.60 Synthesis of the end-capping agent, 4-(phenyl-ethynyl)phthalic anhydride [190].

O H2N K2CO3
F C C C + OH
DMAC/Toluene

H2N O
O C C C

Figure 10.61 Phenylethynyl-end-capping agent, 4-(3- or 4-amino-phenoxy)-40 -phenylethynyl-benzophenone

(APEB).

Results in synthetic chemistry have revealed a
more cost-effective and efficient end-capping agent,
4-(phenylethynyl)phthalic anhydride (PEPA)
(Figure 10.60) [190], which logically replaces PEA.
The switch-over to the use of PEPA from PEA as
the end-capping agent for polyisoimides necessi-
tates a subtle modification in the small stoichiomet-
ric offset during synthesis, now requiring a slight
preponderance of the diamine monomer to generate
amine-terminated polymer strands to be end-capped
with PEPA.
NASA scientists have demonstrated the potential
of phenylethynyl-terminated imide materials as
high-temperature adhesives [184,186,187]. In partic-
ular, the phenylethynyl-terminated OPDA-3,40 -ODA
imide oligomer, PETI, is based on the homopolymer
poly(OPDA-3,40 -ODA)imide, known as LARCt-
IA. The end-capping agent, 4-(3- or 4-aminophe-
noxy)-40 -phenylethynyl-benzophenone (APEB),
resembles 3-(phenylethynyl)aniline but with an
additional “ether-ketone” connection between the
phenylethynyl and amino terminals (Figure 10.61).
The stoichiometric offset ratios for oligomeriza-
tion can be adjusted to yield PETI oligomers with
Mn of 3000, 6000, and 9000 g/mol (Figure 10.62).
The potential of these PET materials has been sub-
stantiated by the exceptionally high adhesive
strengths (Table 10.59).
The uncertain future availability of the crucial
dianhydride OPDA for the NASA phenylethynyl-
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 377

O O H2N
O H2N O O
+ + O C C C
O O
NH2
O O

Isoquinoline (cat.),
m-cresol, Δ

O O
C C C O O C C C

Imide ollgomer

Figure 10.62 Synthesis of the PETI oligomers.

Table 10.59 Fabrication Conditions and Adhesive Properties of Phenylethynyl-Terminated Imide Oligomers,
PETI [184]
378
terminated polyimides has prompted the search for
similar PETI oligomers with the commercially
more available dianhydrides, such as PMDA,
BTDA, and 3,30 ,4,40 -biphenyltetracarboxylic dia-
nhydride (BPDA). The optimal formulation
LARCt-PETI-4, which exhibits excellent pro-
cessibility, was chosen for scale-up and further
evaluation. PETI-4 comprises the end-capper 4-
(3-aminophenoxy)-40 -phenylethynylbenzophenone
(3-APEB), the dianhydride BPDA, and a 85:15
diamine ratio of 3,40 -ODA and APB, with an aver-
age Mn of 5000 g/Mol (Figure 10.63). It cures to a
tough material with a Tg of 251°C and has been
fabricated into composites and adhesives with
excellent mechanical properties (Table 10.60).
Lockheed and Rohr researchers [191] have dem-
onstrated previously that SIPNs can be formed with
phenylethynyl-terminated (PET) isoimide/imide oli-
gomers, in lieu of AT-isoimide/imide oligomers,
and can thermally cure to materials with high Tg
values in the 300°C range. A final Tg of over 300°
C is desirable for materials used in supersonic civil-
ian aircraft, currently being pursued under the
NASA-sponsored High Speed Civil Transport
(HSCT) program. Phenylethynyl-terminated isoi-
mide oligomers have comparable low melt viscosity
as acetylene-terminated isoimides. The synthesis of
various PET-polyisoimides based on benzophe-
none-3,30 ,4,40 -tetracarboxylic dianhydride (BTDA)
O O
O O H2N
O O
+
BPDA
H2N
+ O
3-APEB End-Capper
O O
C C C O
Figure 10.63 Formulation of PETI-4 imide oligomer.
HANDBOOK OF THERMOSET PLASTICS
and isophthaloyl bisphthalic dianhydride (IPDA)
has been demonstrated.
Figure 10.64 shows the structural difference of
the AT- and PET- oligomers of the illustrative
(IPDA-MPDA) isoimide system. PET-isoimide oli-
gomers have a low-melt viscosity comparable to
AT-isoimides (Figures 10.65 and 10.66). Model
compound studies showed that the PET-imides cure
to give higher Tg products. The AT- and PET-
isoimide oligomers have melt viscosities in the 100
to lower 101 poise range and are potentially useful
for RTM applications. Further reduction in the
monomer molecular weight could bring the melt
viscosities as low as 1021 poise that will match
current RTM-able epoxy resins.
The differential scanning calorimetric (DSC)
thermogram of PET-(IPDA-MPDA)isoimide oligo-
mer shows two distinct reaction exotherms at 233°C
and 372°C (Figure 10.67). DSC characteristics of
other PET-isoimides are similar. An example comes
from the National Starch study (Figure 10.68) [182].
The processing temperature for RTM has to be
selected judiciously to achieve low resin viscosity,
but not too high as to inflict penalties of shorter pot
life. Increasing the injection pressure can dislocate
fiber placement within the mold and increase the
cost of molds and clamping presses designed eco-
nomically for low-pressure operation. As a result,
there is an upper temperature limit to RTM
O H2N O O NH2
NH2
3,4’-ODA (85) APB (15)
O
C C C
O C C C
PETI- 4 Imide
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 379

Table 10.60 Mechanical Properties of PETI-4 Imide [186]

O O N O O N C
C N N C
C H
H
O O O O

O O O O
n

Acetylene-terminated (IPDA-MPDA) isoimide

O O O O N C
C N N N C
C
O O O O

C O O O
n

Acetylene-terminated (IPDA-MPDA) isoimide

Figure 10.64 End-capped (IPDA-MPDA) isoimide oligomers.

380 HANDBOOK OF THERMOSET PLASTICS

106

105

P2 [P] (+) 104

103

102

101

100
100 110 120 130 140 150 160 170 180 190 200
Temperature (°C)

Figure 10.65 Viscosity profile of AT-(IPDA-MPDA) isoimide oligomer.

106

105

104
P2 [P] (+)

103

102

101

100
100 110 120 130 140 150 160 170 180 190 200
Temperature (°C)

Figure 10.66 Viscosity profile of PET-(IPDA-MPDA) isoimide oligomer.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 381

Figure 10.67 DSC of phenylethynyl-terminated IPDA-MPDA isoimide.

2.4

2.0 Cure
404°C

1.6
Head flow (mw)

1.2 Inidization
253°c
124 J/G
0.8

120 J/G
0.4

0.0 372°C
216°c

−0.4
40 80 120 160 200 240 280 320 360 400 440
Temperature in °C

Figure 10.68 DSC of phenylethynyl-terminated BTDA-APB isoimide.

382 HANDBOOK OF THERMOSET PLASTICS

O
O N
N
O
O O
F3C CF
3
O O

n
Polyisoimide made from 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (BDAF)

O N O
N

O O
CF3
O O
n
Polyisoimide made from 2,2-bis(4-aminopheny1)1-pheny1-2-trifluoroethane

Figure 10.69 Other relevant polyimide precursors .

processing dictated by the resin chemistry. The
cure characteristics of these isoimides illustrates the
wide RTM processing window available with these
resins.
Candidate high-performance polyisoimides and
polyimides suitable for high-temperature compo-
sites applications include various combinations of
the readily available BTDA, 6FDA, BPDA, and
IPDA monomers and select diamines. Fluorinated
backbones impart enhanced thermo-oxidative sta-
bility and processibility to the resulting polymers.
6FDA is the most commonly used fluorine-
containing dianhydride. Some of the
notable fluorinated diamine monomers include
Ethyl’s 2,2-bis[4-(4-aminophenoxy)phenyl]-hexa-
fluoro-propane (BDAF) (see Figure 10.21), and
NASA-Lewis’ 2,2-bis(4-aminophenyl)-1-phenyl-2-
trifluoroethane (Figure 10.69). Workable candidates
for RTM process applications can be attained from
low molecular weight oligomeric versions of these
polyisoimides and polyimides, end-capped with
phenylethynyl groups.
Other potential PET-imide/isoimides can be
derived from polymer backbones based on
DuPont’s Avimid-N, K-III, and K-IIIB; NASA-
Lewis’ PMR-II-30 and newer variations (PMR-II-
50, VCAP-75, AFR-700B, and EMTL-8-T);
OPDA-based polyimides (previously Oxychem,
currently Imitec); and Upilex polyimides (Ube). As
discussed above, NASA-Langley’s current focus is
on the OPDA- and BPDA-based polyimides,
namely, the PETI resins, whose exceptionally high
lap-shear strengths have been demonstrated
[184,186].
Applicability of Thermoset
Isoimides/Imides to Resin Transfer
Molding Processing
Reduction of cost in processing and manufactur-
ing is a major directive to enhance the use of com-
posite technology in aircraft primary structures and
protective housings and cowls for the turbine
engines, as well as in hot regions of the aircraft,
such as the fairings. Expedient and effective pro-
cessing techniques shorten production cycles, sim-
plify production procedures, accommodate complex
parts fabrication, and enhance the performance of
composite structures. RTM has been recognized as
a process that provides the technical advantages
listed below: [192]
• Energy savings
• Low emissions
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
• Fast part production
• Relatively low tooling cost
• Encapsulation of ribs and inserts
• Short tooling lead times
• No air entrapment
• All sides of part smooth
• All sides can be gel-coated
• Close dimensional tolerances maintained
• Versatility
RTM was almost exclusively considered a pro-
cess specific for the highly processible polyester
resins. The ever-expanding requirements of the end
user and constant development of new resin formu-
lations to fit these requirements have seen epoxies
and even bismaleimides being designed for the
RTM process.
Similar RTM processing approaches for imide-
based composites at higher temperature (550
800°
F, or 288
427°C) are logical extensions. Advanced
composites suitable for high-temperature durable
airframe and engine applications are produced from
high-performance polymer materials with a high
level of fracture toughness, high modulus and
strength, and environmental durability. State-of-the-
art technologies indicate that high-performance
polymers meeting the high-temperature require-
ments are mostly polyimides.
Low molecular weight acetylene-terminated (AT-)
and phenylethynyl-terminated (PET-) isoimide oligo-
mers of the BTDA-APB, IPDA-MPDA, and BTDA-
DAB constituencies have melt viscosities in the 100
to the low 101 range, which approach the desired vis-
cosity range of 1021 to 100 for RTM applications.
The low viscosity exhibited by liquid cyanate
ester resins suggests that SIPNs incorporating
cyanate-terminated imide and isoimide oligomers
could achieve low-melt viscosities to allow hot-
melt prepregging and RTM applications.
Industrial Effort in RTM-able
Aerospace Resins
Resin transfer molding has been used success-
fully for manufacturing fiberglass parts for many
years. The main manufacturing advantages are the
reduction of cycle time, repeatable producibility in
high volumes, and accommodation of complex
383
parts via preform placement. Advanced resins of
higher use-temperatures which have been applied to
RTM processes to mold aerospace components are
epoxies, bismaleimides (BMIs), and polystyrylpyri-
dines (PSP) [193].
The liquid, monomeric dicyanate AroCy L-10
resin has a 25°C (77°F) viscosity of 140 MPa/s
(cps) or 1.40 poise and achieves the cured Tg of
approximately 259°C (498°F), typical of the poly-
cyanurates. It has been applied as a low-viscosity
reactive solvent for compatible high-temperature
thermoplastics such as polyimides, polysulfones,
and polyarylates [194]. In the 260
371°C
(500
700°F) service range, commercial choices
are limited to liquid crystal polymers, polybenzimi-
dazoles (PBIs) and the polyimides (inclusive of
BMIs) [195]. A proprietary BMI-based RTM-able
resin, FE-70,000, has been developed for transfer
molding of electronic parts and for encapsulation of
electronic elements by Nippon Polyimide Company
(a Mitsui Petrochemical Company and Rhône-
Poulenc S.A. joint venture) [196].
BP demonstrated their RTM-able BMI resins
with Toray T300B fibers in a complex flywheel
component [197]. Processing of Compimide® BMI
resins (Technochemie, GmbH) by RTM processing
compares favorably to other processing techniques
such as wet- and tow-preg filament winding and
low pressure autoclave molding [198]. DSM’s
Desbimid BMI resin is RTM-able and has been
successfully applied to manufacturing the rear
cowling beam of the Fokker 50 airplane [199].
Most of the attention has been given to issues of
the materials availability, processing technology,
automation, producibility [200] and economic
advantages over metals. Applications have been
successful in airframes and automobile bodies
[201]. The thermal expansion resin transfer mold-
ing technique (TERTM) combines the technologies
of epoxy RTM and rigid polyimide-based foam
core prefabrication with a selective mold heating
system, expanding the foam to varying densities in
different regions [202
204]. Beyond these efforts
little has been done to RTM polyimide resins.
Increased understanding of interfacial interaction
and improved materials processing techniques
potentially yield better interface, which leads to
better composite performance and durability.
Optimization of interfacial interactions is extremely
important towards facilitating fiber impregnation
and total wet-out during resin injection.
384
Process control and engineering methods are rel-
evant tools for optimizing the processes [205
207],
dielectric spectroscopic methods being the most
versatile approach to monitor cure.
Relevance of Polyimides to RTM
Processing
Aromatic polyimides are known to be useful
over a broad range of temperatures, even to beyond
700°F (371°C) for hundreds of hours. Isothermal
weight loss studies at 700°F in air indicated that
polyimides fare significantly better than other pro-
cessible, nitrogen-containing polyheterocyclic poly-
mers. Their well-defined chemistry and a vast
literature database allow many possibilities for
structural modification. Many such polyimide sys-
tems have demonstrated usefulness as structural
matrices, adhesives and coatings. The inherent poor
processibility of aromatic polyimides is due to their
high viscosity, volatilization (when processed in the
amic acid form) during cure and insolubility in
common low-boiling solvents. However, polyi-
mides are also amenable to isoimide modification
to enhance their melt processing latitude [84
89].
Low molecular weight aromatic polyisoimides
end-capped with reactive groups are potentially
useful as high-temperature resistant RTM-able
resins because of their qualifying attributes, includ-
ing low-melt viscosity, and eventual thermo-
oxidative stability, but most significantly, the
volatile-free cure from isoimide to imide.
Acetylene-terminated (AT)-isoimides/imides have
been widely used as high-temperature composite
matrices and structural adhesives. They impart
higher thermo-oxidative stability and toughness
than BMIs to laminates and adhesive joints
[208,209]. More development is needed to further
reduce the melt viscosity to conventional RTM
requirement of about 1 poise.
In principle, low-molecular-weight thermosetting
polyisoimides, with their low viscosity in the melt
stage, can enable effective impregnation of the fiber
filaments prior to resin advancement and cure.
These isoimides undergo isomerization to the imide
at 250°C (482°F) without liberation of volatiles.
The isoimidization process has been demon-
strated to be easily adaptable to commercial polyi-
mides to reduce viscosity and improve solubility
[84
89]. In addition, low-molecular-weight polyi-
soimides and polyimides, end-capped with reactive
HANDBOOK OF THERMOSET PLASTICS
phenylethynyl and cyanato end-groups, have been
shown to possess low melt viscosity during proces-
sing. This approach therefore has greatly expanded
the pool of candidate resins for selection as RTM-
able high-temperature resistant materials. In princi-
ple, an IPN blending approach, which involves these
isoimides and a liquid polycyanurate precursor, such
as the AroCy L-10 dicyanate (140 cps @ 25°C),
would produce RTM-able resins (see Figure 10.41).
Similar IPNs with low viscosities and low-melt
temperatures have been made from blending of
low-molecular-weight AT-isoimide oligomers with
BMIs. Lockheed and Rohr Industries’ collaborative
studies have shown that these resulting IPNs have
significantly higher toughness than BMIs, due prob-
ably to the chain-extending reaction of the AT oli-
gomers. Phenylethynyl-terminated (PET) oligomers
in place of the AT oligomers would result in IPNs
with higher glass transition temperatures (Tg’s).
Complementary studies using AT-imide oligomers
and BMIs were conducted at NASA-Langley [210].
Low-Viscosity SIPN Imide Blends
Dow Chemical’s perfluorocyclobutane (PFCB)
poly(aryl ether) (Figure 10.70) and poly(aryl etheri-
mide) are innovative in terms of the polymers’ ther-
mooxidative stability, potential long-term
durability, and low moisture adsorption. The step-
growth polymerization mechanism to allow molec-
ular weight advancement of the prepolymer to any
specified viscosity for processing would facilitate
processing. This step-growth polymerization also
produces no volatile by-products. High molecular
weight polymers, poly(biphenyl perfluoro-
cyclobutyl ether) and poly(1,1,1-triphenylethane
perfluorocyclobutyl ether), were obtained from
their corresponding aryl trifluorovinyl ether mono-
mers [211].
An optimal exploitation of this step-growth tech-
nique is to form an SIPN. The step-growth mecha-
nism advances the molecular weight from that of
the (trifluorovinyl) aryl ether or -aryl etherimide
monomer to a thermoplastic (MW-controlled).
Introduction of this step-growth concept of molecu-
lar weight build-up can potentially improve the pro-
cessing rheology of all SIPN blends.
A SIPN blend can be formulated by mixing the
(trifluorovinyl) aryl etherimide monomer with a
thermoset component, such as an AT-imide/isoi-
mide or a PET-imide/isoimide. Since the initial
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
O O
F2C CF CF
F2C CF O
CH3
C
O CF
F2C CF O
Figure 10.70 Perfluorocyclobutane poly(aryl ethers).
mixture is of low MWs, the viscosity can be main-
tained low for easy control during processing
(either prepregging or scrim impregnation). The
thermally induced cyclodimerization takes place at
140°C. The MW of the resin can be advanced to a
desired viscosity. The final curing of the prepreg or
impregnated scrim placed at the bondline during
consolidation completes the process. Figure 10.71
depicts the design of such a low-viscosity SIPN
system.
Galvanic Corrosion Resistance
of Polyimide Composites
Imide-based composites showed evidence of gal-
vanic corrosion in the form of nucleophilic attack
of alkali on the imide structures of polyimide and
bismaleimide (BMI) composites. The existence of a
galvanic corrosion cell under appropriate conditions
between carbon fibers and aluminium surfaces is
well known [212,213]. The General Dynamic
experiment consisted of a graphite/BMI specimen
in a tin can with 3.5 weight percent sodium chlo-
ride solution and JP5 jet fuel. The can was heated
to 60°C and corrosive attack of the composite
occurred within 24 hours. The greatest rate of deg-
radation occurred when the temperature and the
385
O O
CF2 F F
F F
F F
n
CH3
C F F
F F
CF2 O
O F
F
F O
F
O
F F
n
F F
amount of exposed graphite fibers were increased
[214]. Among different metals, only aluminium
exhibits cathodic control corrosion.
Mechanism of Corrosion
Carbon and aluminium become “electrodes” in
the presence of an aqueous electrolyte. An EMF of
approximately 800 mV exists between carbon and
aluminium. When the carbon fiber is coated with
an insulating polymer (such as a polyimide or bis-
maleimide), the carbon electrode is effectively inso-
lated, thus avoiding the creation of a corrosion cell.
However, most polymers are susceptible to water
adsorption and gradually behave like a “solid elec-
trolyte”, concentrating and transporting ions. If the
carbon and the aluminium touch, the circuit is
closed and electrochemical decomposition of alu-
minium occurs. Even if the carbon and the alumin-
ium do not touch initially, some of the carbon may
slough off with time, gradually forming a bridge
through the polymer to complete the corrosion cell.
Hydrogen and hydroxide ions are formed at the car-
bon electrode, and aluminium ions are produced at
the counter-electrode. Highly soluble aluminium
hydroxide is the product. The elevated pH due to
the hydroxide ion concentration causes the polymer
to degrade, exposing more of the carbon surface for
386 HANDBOOK OF THERMOSET PLASTICS

O O pin-hole free) may not be easily achieved.

O
H2N
O F
+ O O
Alternatively, the surface of the cathode may be ren-
F F
dered inactive by the deposition of a stable oxide
O O layer that eliminates the high EMF. Aluminium, in
fact, forms an inactive oxide layer in an acidic envi-
ronment, but this layer is destabilized at high pH.
Results from Lockheed and Sandia National labora-
F F tory in conductive polymers, specifically the polya-
O O
O O F
F
O niline variety, suggest a useful and cost-effective
N N
F F approach to offset the BMI corrosion problem.
O O

Conductive Polymer Blends

O O
O O
N N
O O
Thermoplastic Component
C C
C O O C
O
N N
O O
Thermoset Component (as imide or isoimide)
Figure 10.71 Design for a low-viscosity SIPN
polymer blend.
further destruction. Such catastrophic corrosion can
be prevented by several approaches. The corrosion
cell can be rendered inactive by removal of any
one of the components needed to complete the elec-
trochemical cell.
Insulative Coatings
Isolation of the anode can be achieved by a nonin-
teractive coating on the carbon fibers. The use of
hydrophobic polymers may insulate the anode and/
or avoid the formation of a solid electrolyte.
However, such polymers are prohibitively expen-
sive, and the necessary 100% surface coverage (i.e.
Certain emeraldine salts may be blended with
polyimides to render the latter conductive [215].
Addition of protonic acids to the polyaniline free-
OF base produces emeraldine salts. The proton is
mobile. While concentrated solutions of the salts
F F
F have the green color of the protonated form (emer-
F F
aldine), the dilute solutions have the blue color of
n
polyaniline free-base. High temperature also causes
reversion of emeraldine to the free-base form.
The emeraldine salt has been shown to blend
well with the BMI or the polyimide matrix of the
composite. Its presence provides a proton source
that may shift the equilibrium potential and avoid
the production of hydroxide ions, which chemically
degrade the BMI matrix. A high hydrogen ion con-
centration may also have stabilized the inactive
oxide layer on the aluminium. Both conditions
effectively shut off the corrosion cell. The emeral-
dine salt at least extends the useful life of the
imide-based composite by neutralizing the hydrox-
ide ion, thus preventing fast decomposition of the
polymer.
To test the effectiveness of polyaniline as an anti-
corrosion agent, a carbon fabric was treated with a
BMI resin, such as Ciba Geigy’s Matrimid, and
another was treated with a blend of Matrimid and
polyaniline tosylate. Pieces of these treated fabrics
were placed in separate containers each with a 3%
aqueous sodium hydroxide solution, along with a
piece of aluminium. A conducting wire connected
these two materials. The temperature, pH, open-
circuit voltage and corrosion current were monitored
periodically. Indicators of a positive anti-corrosion
response have included the absence of an increased
pH, a decreased cell potential, and decreased cell
current over the time of the test. Ideally, the cell cur-
rent should drop to zero. Visually, very little decom-
position of the polyimide matrix was observed.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Imide Structural Analogs
Imide analogs are five-membered heterocyclic
amides that mimic the imide ring structurally, and
follow synthetic schemes similar to those for imi-
des. Structurally, they are much less susceptible to
base-catalyzed hydrolysis as the imides by having
one amide-type linkage eliminated. Polyimidines
[216
219] and polybenzodipyrrolediones [220,221]
are representative heat-resistant imide analogs
(Figure 10.72). For example, the polyimidine does
not contain adjacent amide linkages as in the case
of imides. Hydrolysis still occurs at the sole amide
linkage, but the entire polymer chain would not be
scissioned. Polyimidines can be easily made from
readily available starting materials as light-colored
polymers, soluble in common organic solvents.
A relevant research project in the 1990’s at
PolyComp Technologies (Del Mar, California),
supported by the Naval Air Warfare Center, has
included selecting some appropriate molecular-
weight-controlled thermoplastic version of these
imide analogs (based on a balance of processibility
and fracture toughness) to be blended with a low-
molecular-weight Acetylene-terminated (AT)- or
phenylethynylated (PET)-oligomer based on the
O O O
N N
A BTDA-based polyimidine
O O O
N N
A BTDA-based polybenzodipyrroledione
Figure 10.72 Heat-resistant imide analog polymers.
387
same imide analog structure to give a processible
SIPN coating system.
High-Performance Polymers
for Lightning Strike Protection
Continued development of conductive polymers
has eventually resulted in improvement of their
environmental and thermal stability, processibility,
and level of conductivity. Switching devices, EMI
shielding, and static electricity dissipation have
become possible with nonmetallic conductive poly-
mers. The electrical current capacity of lightning
attachment and the accompanying shock wave gen-
erated by the ionized air column require very rapid
dispersal of the I2R electrical heating lest severe
damage would be sustained. Epoxy composite
materials used in select aircraft and other engineer-
ing structures cannot resist the pyrolysis induced by
the undissipated I2R heating.
Lightning strike protection of composite struc-
tures involves such issues as thermal resistance,
environmental resistance, repairability, and Mil
Spec requirements. Until high-conductivity nonme-
tallic materials can be available, nonmetallic
AR
AR
388
conductive materials continue to provide protection
as sacrificial layers. While lightning strike damages
cannot be avoided, they can be reduced to a less
severe and manageable level.
High-Temperature Resistant
Coatings
A straightforward approach is the replacement of
epoxy materials with more thermal and thermo-
oxidative resistant polymers such as high-
temperature epoxies, bismaleimides (BMIs), and
high-Tg polyimide (and polyisoimide) materials
that can perform long-term (near 10,000 hours) at
204°C (400°F) or short-term (i.e., minutes) at over
650°C (1,202°F).
Polymer-ceramic materials (PCMs) (vide infra)
have been shown to offer thermo-oxidative resis-
tance much higher than available organic heat-
resistant polymers. Continued development of these
materials often must yield to economic changes and
technological focus shifts in the aerospace industry,
and achieving consistent production quantities is an
arduous task.
Conductive Paint and Adhesive
Formulations
Commercial nickel-filled polyurethane sprayable
or brush-on paints are easy to apply and repair.
Nickel will not corrode. Urethanes are not
suitable to render lightning strike protection, and
give way to BMIs and polyimides as better candi-
dates per their much higher temperature resistance.
Nickel-coated graphite fibers or Kevlar structural
fibers (for reducing Radar signals) are able to pro-
vide better approximation to an equipotential cur-
rent density across the structures, as compared with
graphite-reinforced structures [222].
Similarly, nickel-filled structural adhesives can
be developed from polyimides and/or BMIs. These
are known high-temperature resistant structural
materials for adhesives. Conductive adhesives
are important in providing electrical continuity
around the joining areas to prevent sparking and
heating.
Nonmetallic Conductive Materials
Conductive polymers based on polyaniline, poly-
thiophene, polypyrrole and others can offer
HANDBOOK OF THERMOSET PLASTICS
increased conductivities and improved processibil-
ity via better morphological control. The ultimate
goal has been to achieve the metallic level of carry-
ing high current density. They can be formulated as
polymer blends with polyimide-type materials and
used as spray coatings or paints, and as conductive
composites, serving the dual role of load-bearing
and electrical current dispersal.
Polymer layers of Carbon-Silicon Frameworks
(CSFs) are relevant engineered material systems.
They possess electrical conductivities
21 21
. 10 W cm , which compare well with metal-
6
lic conductivities. They are lightweight, noncorro-
sive, and environmentally stable [223].
Polymer layers of interconnecting carbon frame-
works and fullerene C60 and C70 molecular spher-
oids can potentially address the issues of
conductivity and current-carrying capacity, equipo-
tential current density, loadbearing ability, noncor-
rosiveness, and thermal/environmental stability.
Indeed, the recent decade’s research and develop-
ment at IBM in interconnecting carbon nano-
tube frameworks have ushered in a new era of
continued miniaturization of integrated circuitry
[224]. Catalyst-mediated chemical-vapor-deposition
growth of nanotubes has been shown to be compati-
ble with the requirements of microelectronics tech-
nology, and can be exploited for carbon nanotubes.
Semiconducting single-walled nanotubes can be
successfully operated as carbon nanotube field
effect transistors (CNTFET) [225]. Novel carbon-
based resistive memory materials for high-
density non-volatile memories have been fabricated
with carbon nanotubes, graphene-like conductive
carbon, and insulating carbon. Repetitive high-
speed switching and the potential for multi-
level programming have been successfully demon-
strated [226].
Ultrahigh Temperature Resistant
Polymers
The late 1980s, fueled by projected requirements
for next-generation high-performance jet engines
and aircraft structures for civilian and military uses
(such as NASA’s High Speed Civil Transport
(HSCT) initiative and the Air Force Advanced
Tactical Fighter (ATF) program), necessitated
extensive use of advanced composite materials and
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
high-temperature structural adhesives. These
requirements include high specific strength and
stiffness at very high temperatures, as many
advanced jet engine and select airframe compo-
nents have to withstand temperature surges to 371°
C (700°F) and above.
For advanced air-to-air tactical missiles and air-
launched stand-off missiles in military applications,
composite airframe structures capable of maintain-
ing strength for short periods (minutes) at 538°C
(1,000°F) and above will be needed. Although
extended exposure of the skin of airframe structures
at the Mach 2 range (HSCT) of cruise speed does
not require sustained performance at higher tem-
peratures than 177°C (350°F), the consideration of
long-term durability dictates the need for materials
that have thermo-oxidative stability in the
316
371°C (600
700°F) range.
Other needs for composites and adhesives capable
of performing at these high-temperatures include
structures for extended range cruise missiles, spe-
cialty materials for Stealth applications, and, poten-
tially, space-plane structures. The critical need for
an easily processible resin capable of meeting these
performance parameters has become a continual
effort to pushing the envelope of the state-of-the-art
high-temperature materials. Structurally, high-
temperature-resistant polymers capable of such per-
formance exist, but practical processing to usable
engineering structures is perennially a substantial
barrier to technological advances.
Some examples of these high temperature resistant
chemical structures include polybenzimidazoles
(PBls), polyphenylquinoxalines (PPQs), polybenzo-
thiazoles (PBTs), and polybisbenzimidazobenzophen-
anthrolines (BBBs). The persistent problem is that the
solubility, flow, gel time, and melting temperature
of such linear and branched heteroaromatic
polymer molecules are inadequate to achieve
suitable processibility. Successful development of
polymer systems possessing both ultrahigh thermal
stability and good processibility, while maintaining a
high level of toughness, represents a major technolog-
ical breakthrough.
Most of the relevant high-temperature composite
resin and adhesive systems are based on aromatic
polyimides. The multifaceted engineering applica-
tions of various forms of polyimides are well
known. High temperature resistance, in general,
results from a high degree of aromaticity and cross-
linking in the polymer structure [227]. The thermal
389
stability of the imide ring is one of the major fac-
tors which would allow the use of aromatic polyi-
mides as 371°C (700°F) resins.
An ideal connecting linkage for the aromatic
structural components in high-performance polymers
must possess high thermo-oxidative resistance and
good chemical resistance, comparable to the aro-
matics. The linkage must also facilitate processibility
by state-of-the-art techniques and have the ability to
promote high polymer formation either directly, via
efficient reactions actually taking place at the group,
or indirectly, by activation of another functional
group. The hexafluoroisopropylidene (6F) group has
been utilized to connect aromatic rings in macromo-
lecules, providing high-temperature and chemical
resistance and also enhancing processing properties.
Incorporation of the 6F groups in the polymer back-
bone has been one of the key features in the devel-
opment of 371°C (700°F) polymers that possess
good processibility.
As stated earlier, new cross-linking and chain
extension techniques are required so that the ulti-
mate structure, after thermal cross-linking, will be
able to withstand long-term exposure at 371°C
(700°F) in air. Some representative chemical cure
mechanisms have been thermal and catalyzed
biphenylene opening, and acetylene trimerization.
The potential 371°C (700°F) polymers thus have
two characteristics in common: high thermal stabil-
ity of the monomers and stability of the groups or
bonds linking the monomers in the polymers.
Advancement in ceramic technology has provided
the possibility of designing refractory materials at
low temperatures. It represents a viable entry to a
new processing technique whereby polymer-
ceramic composite materials can be made via
blending techniques to achieve lightweight, dimen-
sional stability, and environmental resistance. It is
interesting to note that the structural material
Quazite® was molded from inorganic and organic
polymer mixtures (vide infra).
Chemical Structures Suitable for
Ultrahigh Temperature Use
Heterocyclic Ladder-like
Structures
Improved thermal stability in polymers can be
achieved through the incorporation of rigid
390 HANDBOOK OF THERMOSET PLASTICS

O
O O O
X N
N N N
N
N N N
n
n
BBL (X = CH) BBB
TAP-BB (X = N)

O O O O
O O
S
N N N N
N N N
N N
N N
n n
BBL-DBS BTP

O O
AR'
AR
N N

N N
n
BBQ AR, AR' = Aryl

Figure 10.73 Fused ring structures for high temperature stability.

heterocyclic units, in particular ladder structures S N

[228], along the polymer chain. Chain scission in
ladder structures is less likely to occur by a single
bond-breaking reaction. Many of the potential 371°
C (700°F) polymers have heterocyclic and/or ladder
structures. Some well known examples are 1,4,5,8-
naphthalenetetracarboxylic dianhydride-based poly
[bis(benzimidazo-benzophen-anthrolines)], e.g.,
BTP [229], BBB [230
232], BBL [233], BBL-
DBS [234], TAP-BB [235], and bis(naphthalenedi-
carboxylic anhydride)-based poly[bis(benzimidazo-
benzoisoquinolinones)] (BBQ) [236]. An important
aspect of the BBB and BBL (ladder) polymers is
that they show weight retention of 58% and 87%,
respectively, after a 500-hour isothermal aging at
371°C (700°F) [237] (Figure 10.73).
Bisazoles
High molecular weight polybenzothiazoles have
been prepared and shown to have excellent thermal
stability via isothermal thermogravimetric (ITGA)
analyses. These polymers at 316°C (600°F) for 200
N S
n
Figure 10.74 Chemical structure of
polybenzothiazole.
hours have shown negligible weight loss [238,239]
(Figure 10.74).
Other novel polybenzobisazoles containing ben-
zothiazole pendants were possible by the reaction of
2-benzothiazole or 2,5-dibenzothiazole terephthalic
acids with the appropriate aminomercapto, aminohy-
droxy or tetraamino monomers in polyphosphoric
acid at elevated temperatures. The polymerizations
were carried out at concentrations (10
18%), which
would promote anistropic reaction mixtures.
Thermogravimetric-mass spectral analysis in vacuo
showed that the pendent benzothiazole group was the
initial product of thermal degradation, maximizing at
590°C (1,094°F). It is important to note that mixtures
from anisotropic polymerization could be wet-spun
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 391

aromatic polyimides without sacrificing thermal sta-

N
N N
N N
N analog of Hoechst’s 6F44 Diamine. The availability
n
N N
N N
N N
n polybenzimidazole was developed based on 3,30 -
Figure 10.75 PIQ polymers.
into fiber with modulus values between 25
30 MSI
and tenacity values up to 350 KSI [240,241].
Structures containing trigonal nitrogens have
been known to impart outstanding thermal stability
to polymer systems. It is noteworthy that poly(benzi-
midazoquinazolines) (PlQs) showed excellent reten-
tion of thermo-oxidative and thermomechanical
properties after 200 hours exposure to air at 371°C
(700°F) [242
244] (Figure 10.75).
As mentioned earlier, it has been recognized since
the 1980s that incorporating the hexafluoro-
isopropylidene (6F) group in the molecular structure
could improve the processing characteristics of
bility. Hughes’ Technology Support Division
attempted the synthesis of the key tetraamino mono-
mer, bis(3,4-diaminophenyl)hexafluoro-propane, as
an extension of their materials research for the meta-
of 6F-Tetramine (Figure 10.75a) would have allowed
the development of the 6F-PIQ (polybenzimidazo-
quinazolines) polymers (Figure 10.75b).
This direction was eventually not pursued at
Hughes in favor of a new direction in organic-
inorganic hybrid materials. Continued interest in 6F
Tetramine [245] has led to a revised procedure with
higher yields, which facilitated Hoechst’s pursuit of
6F-containing polybenzimidazoles (Figure 10.75c).
A structurally complementary variant of 6F-
diamino-benzidine (DAB), and 6F44 Diacid
(Figure 10.75d). Thermal resistant and mechani-
cally strong membranes were developed for fabrica-
tion into membrane electrode assemblies (MEA)
and the constructed MEA units were tested success-
fully in single cell fuel cells [246] under various
conditions, with a focus on fuel impurity tolerance
and higher (above 120°C) temperature of utility to
possibly improve over the perfluorosulfonic acid
(PFSA) membrane technology [247].
From a cost standpoint, DAB is a widely available
commercial product useful in immuno-histochemical
and blotting applications, and 6F44 Diacid would be
less costly to produce than 6F-Tetramine.
From an environmental health and safety stand-
point, it should be noted that the parent compound

H2N NH2
CF2 CF3
H2N C NH2 C

CF3 CF3

2,2-Bis(4-aminophenyl)- 2,2-Bis(3-aminophenyl)-
hexafluoropropane hexafluoropropane
(6F44 Diamine) (6F33 Diamine)

H2N NH2
CF3
H2N C NH2
CF3

2,2-Bis(3,4-diaminophenyl)-
hexafluoropropane
(6F Tetramine)

Figure 10.75a Notable 6F-containing monomers.

392 HANDBOOK OF THERMOSET PLASTICS

CF3 N

N N
CF3
N
N
N

Figure 10.75b A 6F-containing polybenzimidazoquinazoline from 6 F tetramine.

H2N NH2 CF3

CF3 C
N NH
H2N C NH2 CF3
N N
CF3
H

n
2,2-Bis(3,4-diaminophenyl)-
A 6F-containing
hexafluoropropane
Polybenzimidazole
(6F Tetramine)

Figure 10.75c A 6F-containing polybenzimidazole from 6F tetramine.

H2N NH2
CF3
H2N NH2 + HO2C C CO2H
CF3
3,3'-Diaminobenzidine (DAB)

CF3

C
H CF3
N N

HN N
n

DAB-based 6F Polybenzimidazole

Figure 10.75d A DAB-based 6F-containing polybenzimidazole.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
benzidine is a well-known carcinogen, While 3,30 -
diaminobenzidine (DAB) has not been the subject of
in-depth carcinogenicity studies, it is a known muta-
gen. The US National Toxicology Program (NTP)
considers all benzidine derivatives carcinogens [248].
Phthalocyanine Polymers
The phthalocyanine structure is recognized as one
of the most thermally and thermo-oxidatively
stable organic structures known and has been incor-
porated in the synthesis of thermally stable hybrid oli-
gomers [249] and polymers (e.g. benzimidazoles)
[250,251]. The most relevant are phthalocyanine tet-
raamines and benzophenonetetracarboxylic dianhy-
dride (BTDA) [252] and those derived from metal
phthalocyanine tetraamines and pyromellitic dianhy-
dride (PMDA) [253]. Because of the apparent ease of
synthesis of the phthalocyanine derivatives and the
exceptional thermo-oxidative stability of the derived
polymers, these phthalocyanine polyimides can be
considered as potentially useful 371°C (700°F) resins.
Development of the relevant phthalonitrile resins has
been discussed in an earlier section (vide supra).
A parallel and apparently quite promising devel-
opment in phthalocyanine-based polymers is the
silicon-phthalocyanine polymers (Figure 10.76).
They have been readily synthesized in large quanti-
ties, dissolved in trifluoromethanesulfonic acid and
wet spun into fibers (either in pure form or as
blends with Kevlar®) [254,255]. This class of
potential ultrahigh temperature resistant polymers is
especially attractive because of its structural simi-
larities relative to high-temperature silane type cou-
pling agents (needed for adhesive bonding) and
silicate glassy networks produced by low-
temperature high-tech ceramic processing, which
will find ultrahigh temperature utility.
These stacked phthalocyanine polymers also can
be synthesized with germanium or tin as the metal-
lic center. The neat, wet-spun fibers can be doped
with iodine to conductivities of 1
2 Ω21cm21,
while the Kevlar-metal phthalo-cyanine blends
reach conductivities of 0.01
0.1 Ω21cm21.
Adamantane and Related
Structures
Ultrahigh thermal stability can be attained
through the incorporation of cage-like
393
dicarbadodecaborane (carborane) units [256].
Similarly, the incorporation of adamantane units in
polyimides [257
261] (Figure 10.77) is also
expected to enhance processibility without
compromising their thermal and thermo-oxidative
stabilities. Comparable studies, albeit less exten-
sive, have also been carried out with biadamantane-
based polymers [262,263]. An adamantane-based
polybenz-oxazole [264] has been developed as a
useful 450°C (842°F) material. It is noteworthy that
the unsubstituted equivalent apical positions of ada-
mantane are reactive sites for functionalization and
therefore are more susceptible to oxidative degrada-
tion. The ultrahigh thermally stable structural units
would contain both adamantane and phenyl units, i.
e., 1,3,5,7-tetrakis(aryl)adamantanes.
The diamondoid structure of adamantane and the
exceptional high temperature stability and mechani-
cal strength of diamonds have been a sustaining
topic for materials science research into isolation
and/or synthesis of diamondoid compounds, and
structural series from low diamondoids of ,1nm,
CVD diamonds (nm to μm size) [265
267]. The
development of adamantane derivatives as mono-
mers for the synthesis of high temperature polymers
is particularly important in polymer materials
[268]. Similar synthetic strategies are also
adaptable to diamantanes [269].
From the early 1990s to early 2000s, when spin-
on organic low k dielectric thin films [269
273]
underwent a competitive development against the
conventional equipment and infrastructure-intensive
CVD technologies, and among several aromatic
polymers. The better materials developed turned
out to be a logical combination of 1,3,5,7-tetrakis
(aryl)adamantane structures in phenylethynyl ther-
mosets (vide infra: “High Temperature Thermosets
as Dielectric Interlayers in Integrated Circuitry
Fabrication”). Tg as high as 450°C (842°F) has
been reached.
Hydrogen-Free Polyimides
Aromatic hydrogen atoms become labile at ultra-
high temperatures and participate in degradative
and cross-linking reactions, thus decreasing the
long-term thermo-oxidative stability of the polymer
(reflected by isothermal aging). The anhydride pre-
cursor pyrazine-tetracarboxylic dianhydride
(PTDA), which does not contain any hydrogen, was
shown to impart unusual thermo-oxidative stability,
394 HANDBOOK OF THERMOSET PLASTICS

O
N

N N

N M N
N N

O
N

N N

N M N
N N

OH O
N
N
N N N
N
N M N
M N
N N N
N N - H2O
N
N
OH O
N

M = Si N N

N M N
N N

N
O
N

N N

N M N
N N

N
O

Figure 10.76 Silicon-phthalocyanine polymer.

HO OH HO OH

R
HO OH
R

R = H, OH, NH2, -ethnyl, -phenylethynyl

Figure 10.77 Monomers for adamantane-based polymers.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 395

O O O O O
N N N N
O O NC CN
O O N N . 8H20 + C C
N S N
O O O O H 2N NH2
O O n
O
PTDA PTDA-DATD

Figure 10.78 Hydrogen-free heterocyclic polymer.

Acetic acid
2 hr

i.e. 25 hours at 400°C (752°F) in air, to polyimides

containing this structural moiety [274] NC CN
(Figure 10.78).
N N
A similar heterocyclic anhydride precursor, hexaa-
zatriphenylene trianhydride (HTTA) (Figure 10.79), N N
NC CN
without hydrogens in its structure, also produces N N
polyimides with high-temperature resistance up to NC CN
700°C (1,292°F) in air [275,276]. 81%
The addition of HTTA as a cross-linking agent
augments the reaction of pyromellitic dianhydride
with aminophenyl ether. Even when the amount of
HTTA added reached 30% of the total anhydride
content, films could be cast and post-cured ther- O
O
O
mally to provide polyimide films with good thermal
stabilities and a high degree of cross-linking. N N
Polymerization using HTTA as the only anhydride
N N
component followed by imidization afforded a deep O O
red polyimide film; thermogravimetric analysis in O N N O
argon revealed that 60% of this sample remained at O O
850°C [277
279].
HTTA
HTTA derives from hexaazatriphenylenehexani-
trile (HT(CN)6), which was prepared in analytically Figure 10.79 Synthesis of hexaazatriphenylene
pure form in 81% yield on a large scale from hex- trianhydride.
aoxocyclohexane octahydrate and (Z)-2,3-diamino-
but-2-en-1,4-dinitrile for 2 hours in refluxing acetic
acid [279,280]. The conversions of HT(CN)6 to the
corresponding hexaamide, hexaacid, hexaester deri-
vatives and HTTA were then accomplished The fundamental properties of the 6F-monomers
(Figure 10.79) [281]. and also of the polymers in which they are incorpo-
In summary, imide-based hybrid polymers rated have indicated improved thermo-oxidative
incorporating the various classes of high tempera- stability (c.f. DuPont’s NR-150®, which incorpo-
ture resistant structures are potential 371°C (700° rates the 6F-containing dianhydride 6FDA). The
F) resin materials if good processibility could be application of 2,2-bis[4-(4-aminophenoxy)phenyl]
achieved. The introduction of fluorine-containing hexafluoropropane (BDAF) (see Figure 10.21) in
monomers, particularly those containing the 6F polyimide coatings for 371°C (700°F) exposure is
and 3F groups, have been shown to yield poly- also illustrative [283]. The hydrophobic nature of
mers with increased processibility while maintain- the hexafluoroisopropylidene group is expected to
ing excellent thermo-oxidative stability and enhance the moisture resistance of the resin systems
improved moisture resistance [25]. Many 6F- and of which it is a part. Furthermore, the flexible
3F-containing monomers are readily available nature of the 6F-linkage is conducive to improve-
(vide supra) [23,282]. ment of fracture toughness [161].
396
Novel Cross
Linking Mechanisms
for Stability at Ultrahigh
Temperatures
The harsh environmental conditions at 371°C
(700°F) in air pose severe limitations on the choice
of a suitable cross-linking and/or chain extension
mechanism. The ultimate structure after thermal
cross-linking must be able to withstand long-term
exposure up to 371°C (700°F) in air. It has been
demonstrated that ethynyl and phenylethynyl end-
groups on polyphenylquinoxa-lines undergo ther-
mally induced chain extension and cross-linking. In
the case of ethynyl end-capped polymers, the final
cured resins have less thermo-oxidative stability
than the corresponding polymers that do not contain
the ethynyl groups [284,285]. The thermo-oxidative
instability is ascribed to the presence of non-
aromatic end products as a result of the ethynyl
groups undergoing thermally induced cross-linking.
Biphenylene
An attractive cross-linking mechanism presents
itself in the thermally induced ring opening of
biphenylene, to give dimeric and polymeric pro-
ducts via diradical intermediates [277
281]
(Figure 10.80). Such a cross-linking mechanism for
high-temperature polymers containing these biphe-
nylene units along the polymer chain provides ther-
mally stable cross-links and yields no volatile by-
products.
Figure 10.80 Cross-linking mechanism based on biphenylene ring opening and recombination.
+ C C
Figure 10.81 Thermal or catalytic cycloaddition of biphenylene to acetylene.
HANDBOOK OF THERMOSET PLASTICS
Bisbiphenylene compounds having the corre-
sponding skeletal structures to the respective imide,
quinoline, and phenylene oxide polymers were syn-
thesized. The presence of the bisbiphenylene cross-
linking agent in the polymer initially plasticizes the
polymer and, on curing, this plasticizer forms a
cross-linked network with the polymers [286]. The
addition of an organometallic reagent to catalyze
the cross-linking reaction did not seem to affect the
ultimate thermal and thermo-oxidative stability of
the resins. Although the mechanism looks promis-
ing, certain technical problems persist. For exam-
ple, the control over completeness in ring opening
reaction is lacking. Furthermore, it is not certain
that the recombination of the radical species gener-
ated necessarily produces thermally stable products.
An extension of the biphenylene recombination
cure mechanism is the application of the thermal
(or nickel-catalyzed) cycloaddition of biphenylene
to acetylene [287,288] as the cure mechanism [289]
(Figure 10.81). An excellent review on the multi-
faceted possibilities of organometal complex cataly-
sis of the cycloaddition of biphenylene and
diphenylacetylene has included this relevant discus-
sion [290].
Organometallic complex-catalyzed trimerization
[291], intramolecular cycli-zation [292,293], and
polymerization [294] of many acetylenic com-
pounds often lead to well-defined highly condensed
aromatic structures. Of particular interest are com-
plexes based on cobalt, nickel, palladium, rhodium,
and most recently, tungsten, tin, niobium, and
or Ni[0]
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Figure 10.81a Catalytic formation of 9,10.
disubstituted phenanthrenes (RQMe, Ph, CO2Me,
TMS).
Figure 10.81b Proposed mechanism for the
formation of 9,10-diphenylphenanthrenes.
tantalum. The catalyzed reactions are often facile
and proceed at relatively low temperatures.
With reference to the generally accepted cata-
lytic effect of organometallic compounds in the
reactions of aromatic acetylene compounds, the
addition of organometallic reagents is expected to
catalyze trimerization specifically and at the same
time lower the temperature required for the reac-
tion. Candidate reagents for achieving this include
rhodium[I] carbonyl, nickel[0] carbonyl, and palla-
dium[II] benzonitrile complexes. The ultimate
product after the acetylene cure would have ther-
mally stable cross-links. The inherent high-
temperature-instability in thermally cured
acetylene-terminated resins is due to the low per-
centage of stable aromatic and/or heterocyclic ring
structures (vide supra).
397
[2.2]Paracyclophane
During the 1980s and 1990s, advanced compo-
sites have been a key to the development of new
generation high-speed civil transport aircraft
engines. The driving forces for the development of
advanced engines are mission-enabling capabilities
and reduced life-cycle costs [292,293,295].
Scientists at NASA-Lewis evaluated [2.2]paracy-
clophane as a high-temperature stable cross-linking
unit for polyimide resins with a 425°C (797°F) use
potential. The objective is to develop a better end-
capping agent than the nadic group for the proces-
sing of the PMR-II-50 resin.
The CyCAP resins have been reported [293] to
have excellent thermo-oxidative stability, high glass
transition temperatures, and excellent processibility.
They form void-free consolidated disks and gener-
ate no volatiles during consolidation. The
N-CyCAP resin comprises a chloroform solution of
4-amino[2.2]-paracyclophane, the dianhydride
6FDA, and p-phenylenediamine (PPDA).
Figure 10.82 depicts the idealized polymer struc-
ture. The resin itself processes similar to PMR
polyimides [38]. Laminate testing results indicated
that N-CyCAP is comparable to PMR-II-50, both
being good performers at 343°C (650°F). However,
PMR-II-50 matrix composites are more thermo-
oxidatively stable than N-CyCAP at 371°C (700°F)
(Table 10.61). Mechanical strength measurements
at 371°C (700°F) do not indicate significant differ-
ences in performance between N-CyCAP and
PMR-II-50 composites (Table 10.62).
New addition-curing polyimides were prepared
with 4-amino [2.2]-paracyclo-phane as the endcap,
as the result of improved synthesis of 4-amino-[2.2]
para-cyclophane, in yields to 60% via a simplified
procedure. DSC and rheological analysis of end-
capped polyimide oligomers confirmed that the
onset for polymerization of the ethylene bridge was
250°C (482°F). 13C CP/MAS NMR was used to
determine the structural changes of the oligomers
after thermal treatment. Compression molding of
paracyclophane-capped polyimides successfully
formed void free neat resin specimens.
Thermomechanical analysis (TMA) demonstrated a
high Tg of 353°C (667.4°F) for postcured samples.
TGA measurements on these resins showed a high
onset of decomposition ranging from 549 to 567°C
(1,020 to 1,053°F) [296].
398 HANDBOOK OF THERMOSET PLASTICS

O
N F3C
CF3
C
O O O

N N

O O O
C
F3C
CF3 N
n
O

Figure 10.82 Idealized structure of N-CyCAP polyimide (NASA-Lewis).

Table 10.61 371°C Isothermal Weight Loss Comparison Between N-CyCAP and PMR-II-50 on T-40R and
G40-700 Fibers

Laminates (12-ply, 2.54 cm 3 10.16 cm) were tested in 1 atm flowing air.
All fibers used were unsized 12 k tow.
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Table 10.62 Preliminary Mechanical Properties of N-CyCAP and PMR-II-50 Composites
Flexural strength (ASTM D790-81): All fibers were unsized and 12k tow.
Interlaminar shear strength (ASTM D2433): Composites were post-cured at 385°C (16 hr, air).
Benzocyclobutene
Benzocyclobutene-terminated imide oligomers
have been developed as a close counterpart to
biphenylene-terminated resins, with an expected
advantage of a lower cure temperature (250°C ver-
sus 380
400°C for biphenylene materials)
[297,298]. The thermally-induced electrocyclic ring
opening of benzocyclobutene is well-referenced
[48]. The highly reactive o-quinodimethane inter-
mediate either self-react or undergoes Diels-Alder
reactions with dienophiles.
Bis(benzocyclobutene)imide monomers were
prepared from 4-aminobenzo-cyclobutene and sev-
eral dianhydrides. The cured samples from these
materials only lost 7
10% of the original weights
during isothermal ageing at 600°F for 200 hours
[297] (Figure 10.83).
A series of aromatic imide AB-monomers con-
taining both benzocyclobutene and acetylene end-
groups were prepared to evaluate the potential of a
single reactant polymerization technique
(Figure 10.84). Among the compounds evaluated,
only N-(4-benzocyclobutenyl)-4-(phenylethynyl)
phthalimide gave a clean single exotherm by differ-
ential scanning calorimetry, indicating the expected
benzocyclobutene ring opening and Diels-Alder
reaction [298].
399
The bis(benzocyclobutene) materials have been
under development at Dow Chemical Company due
to their potential as easily processible matrix resins
for high-performance advanced composites. The bis
(benzocyclobutene) diketone monomer, DK-bis-
BCB (Figure 10.85), has a Tg at 340°C (644°F)
and can be processed by resin transfer molding
(RTM) techniques. The graphite composites
obtained from it have excellent 274°C (525°F) hot/
wet properties and are potentially useful at service
temperatures of 260°C (500°F) or above [299,300].
AB-monomers having both BCB and maleimide
termini have also been studied [301
303]. Besides
the advantage of being single components for poly-
merization, the AB monomers also resolve the
observed difficulty in improving fracture toughness
of bis(benzocyclobutenes) via reaction with
bisolefin-type dienophiles. As summarized in
Table 10.63, the residual compression strength after
impact (CAI) measured for Celion® G30-500 8HS
fabric/AB-BCB was 332 MPa (48.1 ksi), which is
comparable to the typical value of 300 MPa
(43.5 ksi) for thermoplastic composites.
With the rapid progress in the semiconductor
industry, newly found applications of high-
temperature resistant polymer materials offered
great potential for use in various microelectronic
applications. For example, conductive polymers
400 HANDBOOK OF THERMOSET PLASTICS

O O
O O
R O
O
O O
N N
+
R O
O
H2N

CF3 O CF3 O O O O
R = C C S
CF3 CF3 O

Figure 10.83 Bis(benzocyclobutene)imide oligomers.

O O
N N
C
C
R C C O C6H5 O O

R = H, C6H5

C N
C O
C6H5
O

Figure 10.84 Benzocyclobutene-ethynyl-terminated AB-imides.

O O
O

N O

O
DK-bis-BCB AB-BCB

Figure 10.85 BCB monomers for RTM composites processing.

have made great entry as effective discharge layers
and conducting resists in electron beam lithogra-
phy, excellent electrostatic discharge protection for
packages and housings of electronic equipment,
and corrosion protection for metals, and may have
applications as interconnections or for electronic
devices [304]. Nano-imprinting techology could
also benefit from practical thermoset polymers as a
cost-effective alternative to imprinting stamp fabri-
cation by e-beam lithography [305,306].
Various types of high temperature resistant
organic polymers potentially offer spin-coating pro-
cessibility to make insulating dielectric layers as a
cost-effective alternative to the equipment-intensive
chemical vapor deposition of silicon dioxide thin
films as these insulation layers (vide infra).
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Table 10.63 Mechanical Properties of Benzocyclobutene Composites

8-ply [0,90]4; 24-ply [45,0,
45,90]3S.
Acenaphthylene
Acenaphthylenyl-terminated phenylquinoxaline
(PPQ) and aroylene (e.g., aryl ether-ketone, aryl ether)
oligomers have been evaluated as alternative high-
performance thermosetting resins to BMIs to over-
come the latter’s moisture sensitivity and improve
their thermo-oxidative stability [307] (Figure 10.86).
Acenaphthylenyl oligomers have been synthesized
by facile conversion of low-cost acenaphthene start-
ing material. Their ease of polymerization is compa-
rable to that of BMIs. The known chemistry of
thermal reactions of acenaphthylene to yield high-
temperature stable fused ring systems (Figure 10.87)
suggests that acenaphthylenyl-terminated oligomers
can cure to thermo-oxidatively stable materials.
Diazine
Two interesting diazine compounds [308,309],
capable of undergoing 1,3-dipolar addition
401
reactions with various dipolarophiles, also can be
considered in the context of chain extension and
thermal cure for acetylene-terminated, nadimide-
terminated, and propargyl-terminated polymers. In
particular, the tetrakis-(trifluoromethyl) derivative,
i.e. hexafluoroacetone-azine, forms a 1:1 copolymer
with norbornadiene at ambient temperature in quan-
titative yields [309] (Figure 10.88). It also reacts
similarly with diallyl resorcinol [310], diallyl
α,ω-alkylenedisilanes [311], α,ω-alkylenedienes
[312], and nadimide-terminated oligomers [313].
The reaction between hexafluoroacetone azine and
bisnadimides (mole ratio 1:1) yielded polymers
with number-average molecular weight (Mn)
1700
5700 depending on the reactants. It is inter-
esting that maleimide-terminated oligomers do not
undergo chain-extension with hexafluoroacetone-
azine [312]. A spontaneous rearrangement of
the primary product, a 1:1 adduct, to 1-H-
pyrazolines.
402 HANDBOOK OF THERMOSET PLASTICS

O O
C AR C

O
AR =
O C

Cl CF3
C
Cl CF3

N N Figure 10.87 Fused aromatic systems resulting

N N
from thermal reactions of acenaphthylene.

R = —O— , — , —CH2 — , —SO2 —

Figure 10.86 Acenaphthylenyl-terminated aroylene

and phenylquinoxaline oligomers.

R1 R1
C N N C
R2 R2 R2
R1
N
+ R3 R3
N
R2
R3 C C H R1

a. R1 = R2 = CF3
b. R1 = C6H5, R2 = H

F3C
CF3
N
N 99%
F3C CF3
C N N C F3C CF3
o
F3C CF3 3:1 t rati
tan
ac
Re
24°C
+ F3 C
24 hr CF3
N CF3
Re
ac 2:1 CF3
tan N
t ra
tio N
F3C CF3 N

F3C n
CF3

100%

Figure 10.88 Polymerization of Norbornadiene and Hexafluoroacetone-azine.

10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
Thermosets as Dielectric
Interlayers in Integrated Circuit
(IC) Fabrication
In the early 1990s, advancement in semiconduc-
tor technology and the explosive development of
newer and faster computer microprocessors contin-
ued to demand better materials for their design and
manufacture. To increase the performance and
speed of semiconductor devices, reduction of the
linewidth and spacing of interconnects must be
realized in conjunction with transmission loss mini-
mization and reduction of the capacitative coupling
of interconnects. A productive approach to mini-
mize power consumption and reduce capacitance is
by way of utilizing low dielectric constant (low-k,
or -κ, kappa) materials as the insulating layer, i.e.
the dielectric layer that separates interconnects.
Conventional wisdom at the time has been that
low-k materials as insulators typically allow faster
signal propagation, reduce capacitance and cross-
talk between conductor lines, and lower voltages
required to drive integrated circuits. Since air has a
dielectric constant of 1.0, the ultimate goal for
dielectric material development is to reduce the
dielectric constant of insulator materials down to
the theoretical limit of 1.0.
Among the more promising approaches to mini-
mizing capacitance in the multilevel interconnect of
integrated circuits containing sub-half micron and
narrower metal spacings, two are most notable:
1. Introduction of elemental fluorine to the
equipment-intensive but high precision indus-
try standard of silicon dioxide layers formed
by chemical vapor deposition (CVD SiO2),
and
2. Development of organic polymers that exhibit
high performance in key attributes such as
thermal stability, low dielectric constant, and
low moisture absorption, coupled with high
outgassing rates of what little moisture may
be present.
Organic polymers possess lower dielectric con-
stants than inorganic oxides and nitrides, and have
been evaluated as the intermetal dielectric layers in
sub-quarter micron devices. The dimension of
microelectronic interconnect design rules undergo
progressive shrinkage to sub-quarter micron and
403
even smaller metal spacings. The use of organic
polymer dielectrics to minimize capacitance and
reduce power consumption and cross talk, while
increasing signal propagation speed have become a
necessity [314].
The organic dielectrics must possess a dielectric
constant value of no higher than 3.0, and as low as
possible toward a theoretical limit of 1.0. The prac-
tical expectation for polymer dielectrics was a
range of 2.2
3.0 for the sub-0.25-micron features,
but dielectric material development in the ensuing
decade has brought forth innovative designs of
nanoporous inorganic or organic dielectrics, which
have further reduced dielectric constant (to .2) for
applications in sub-tenth-micron IC feature designs.
The organic dielectrics must have Tg values
above 300°C (572°F) and as high as possible toward
500°C (932°F), a value determined by the thermal
stability of organic polymers. The organic dielec-
trics should also be easily processible by standard
spin-bake-cure processing techniques. The organic
dielectrics must be free from moisture and outgas-
sing problems, in addition to their expected adhe-
sive and gap-filling qualities, and their dimensional
stability towards harsh tungsten (via-fill) and hot
aluminium (metallic layer) depositions, thermal
cycling, etching, and chemical mechanical polishing
(CMP) processes.
Several classes of organic polymers have the
potential to be used as dielectric materials. To take
advantage of the low dielectric property of organic
materials the IC industry has become serious to
assess this significant shift in the paradigm. New
processing methodologies have been explored in
many areas such as the use of spin-coater with the
attending viscosity control and plumbing issues;
solvent selection for cleaning, edge-bead removal,
and back rinse; spin-bake-cure control of the film;
adhesion and gap-filling issues. The design of rele-
vant organic materials for the IC industry has fol-
lowed conventional wisdom of polymer structural
design and modification guided by structure-
property relationships. Their environmental benevo-
lence, ease in clean up, and fundamental character-
istics such as the all-important high purity, low
viscosity, wide range of practical concentrations to
yield desirable gap-fill, regional and global planar-
izability over circuitry design features, film thick-
nesses, and resistance to cracking are much desired.
A continual challenge to the chemist is one of seek-
ing out new forms of chemical structures that can
404
be conveniently synthesized and processed through
modest means and yet highly innovative and condu-
cive to evolutionary modifications and revolutionary
drop-in replacements within the industry guideline
per the Moore’s Law [315], if need be. Such have
been extremely demanding expectations.
In the early 1990s, polyimides have been the
most extensively characterized polymer thin film
dielectrics, and were in many cases suitable for the
intermetal dielectrics in multichip modules.
Unfortunately, their tendency to absorb significant
quantities of moisture, coupled with relatively slow
outgas characteristics, presumably due to water
molecules hydrogen bonded to the polar carbonyl
groups of the polyimide, significantly impede
throughput in fabrication [316,317].
The search for alternative polymers which incor-
porate the “good” characteristics of polyimides
while exhibiting improvements in electrical, mois-
ture, and processing characteristics led to the devel-
opment of thin films derived from a family of non-
imide-containing aromatic poly(arylene ethers)
[318
320], notably, fluorinated poly(arylene
ethers) (FLAREt) [318
327], in thin-film multi-
ple-chip modules [321].
As intermetal dielectrics for applications in sub-
quarter micron multilevel interconnects, several
polymer systems have been developed, which
include thermosets such as Dow Chemical’s BCB
and PFCB [272,273,328,329], both based on the
benzocyclobutene structure, Promerus’ polynorbor-
nene [330], ATT’s polyphenylene, and several vari-
eties of poly(arylene ethers), including
Schumacher’s PAE-2 [271],. Raychem’s fluorinated
poly(arylene ethers) FLAREt, and later the
AlliedSignal modifications of them. A high purity
commercializable product eventually emerged as a
non-fluorine-containing FLAREt polymer
[317
325], commercialized by Honeywell in 2000.
Whimsically, the acronym FLARE originally
denoting FLuorinated poly(ARylene Ethers), also
accommodated the improved material, as Fluorine-
Less poly(ARylene Ethers). Examples of these use-
ful high temperature resistant polymer systems as
dielectric layers are shown in Figure 10.89.
Table 10.64 summarizes representative proper-
ties of poly(arylene ether) low-k dielectric
FLAREt.
In the late 1990s and early 2000s, Dow
Chemical commercialized two key organic polymer
systems, BCB and SiLK, suitable for
HANDBOOK OF THERMOSET PLASTICS
microelectronic applications. Silicon is included in
the structural design of the Dow low-k organic
dielectrics to facilitate interfacial adhesion to the
wafer surface. BCB and SiLK have 13.4% and
6.7% silicon contents, respectively. AlliedSignal-
Honeywell’s FLAREt has a 100% organic content.
The market competition between SiLK and
FLAREt is noteworthy [273,325].
Compared to polyimides, these newer polymer
systems exhibit similar or better thermal stability.
They also have lower moisture absorption, and pos-
sess a low isotropic dielectric constant, and good
retention of storage modulus above their glass tran-
sition temperatures (Tg’s). The thermomechanical
strength and high Tg of the cured thin film must
derive from a thermosetting mechanism. Further,
good adhesion and gap-filling ability are stronger
attributes to polymer materials’ usefulness for inter-
connect dimensions smaller than 0.25 μm.
Fluorinated polymers initially thought to be
essential to achieve low dielectric constant and
moisture resistance have the drawback of insuffi-
cient thin film adhesion to the wafer surface. In
addition, scanning electron microscope (SEM)
images show corrosion of the metal line pattterns
induced by the fluorinated polymer. Although a
protective barrier layer is feasible, it would add to
the processing steps. As it becomes obvious later,
the viable spin-on dielectrics emcompass process-
ible (i.e., spin-coatable) thermoset non-fluorinated
polymers which ultimately cure to thin film struc-
tures with low-k, mechanically strong (high com-
pressive strength, high Tg, low residual stress),
thermo-oxidative stability, with strong adhesion to
the wafer surface, and low metal contamination.
As mentioned earlier (vide supra, “Adamantane
and Related Structures”), adamantane-based com-
pounds and monomers have been effectively used to
form aromatic thermoset polymers containing api-
cally arylated adamantanes and with each tetra-
arylated adamantane defining a local radial symme-
try by virtue of its inherent tetrahedral symmetry.
The compounds previously described included para-
isomer 1,3,5,7-tetrakis[4-(phenylethynyl)phenyl]
adamantane and 1,3,5,7-tetrakis[4-(4-iodopheny-
lethynyl)phenyl]adamantane (Figure 10.90)
[331
334].
It is important to point out that while apical tet-
raphenylation of 1,3,5,7-tetrabromoadamantane via
the Friedel-Crafts reaction afforded a high yield of
tetrakis(phenyl)adamantane, the reaction of
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 405

CH3 CH3

Si Si
O
H3C CH3

B-staged Cyclotene 3022 series

(DVS-BCB) from Dow Chemical

C C
C C
CH3 CH3

C C Si Si C C
O
H3C CH3

SiLK Polymer fCrom Dow Chemical

Low k Aromatic Polymers from ATT

O O
O O

n
n

PAE2 (from Schumacher) is a copolymer of these two units

Figure 10.89 High temperature resistant polymers as dielectric layer.

406 HANDBOOK OF THERMOSET PLASTICS

F F F F

O O
O
F F F F
F F F F

n F F F F m

FLARE Poly(arylene ether) copolymer from Raychem, licensed by AlliedSignal

O
O O C C O O C

n m

A Fluorine-less FLARE copolymer with improved

Tg and adhesion to SiO2 surfaces

O O
O C

C C

A second generation FLARE homopolymer designed to resolve

inherent manufacturing challenge of copolymerization

Figure 10.89 (Continued).

bromobenzene with 1,3,5,7-tetrabromoadamantane consists of an internal isomeric distribution of the

was found to be lacking regioselectivity, and to
have led to 1,3,5,7-tetrakis(3- or 4-bromophenyl)
adamantane as an internal isomeric distribution of
the bromo attachments in the meta and para-
positions (Figure 10.91 and 10.92).
Phenylethynylation of this tetrabromo compound
with phenylacetylene under palladium catalysis (the
Heck reaction) gives 1,3,5,7-tetrakis[3- or 4-(phe-
nylethynyl)phenyl]adamantane, which in turns
phenylethynyl extensions in the meta and para-
positions.
The isomeric mixture of 1,3,5,7-tetrakis[3- or 4-
(phenylethynyl)phenyl]-adamantane has been
developed at Honeywell as the GX low-k dielec-
tric spin-coatable organic polymer system. After
the thin film is cast, the thermoset polymer cures
to afford a Tg of 450°C (842°F) and a remarkable
retention of a low-k value of ,2.6 and film
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 407

Table 10.64 Exemplary Properties of Nonfluorinated FLAREt Polymers

408 HANDBOOK OF THERMOSET PLASTICS

I Br

Br2

AICI3 Br Br
Br

I
I

PhBr
I AIBr3

Figure 10.90 Radially symmetric tetrakis(aryl)

adamantanes. Br

Br

Br

Br

Pd

Figure 10.91 1,3,5,7-Tetrakis[3- or 4-

(phenylethynyl)phenyl]-adamantane as thermoset
GX polymer.

thickness after 10 hours at 450°C (842°F)

(Table 10.65).
Thus, the next generation low-k organic dielec-
trics have capitalized on the mechanical perfor-
mance of high temperature thermoset polymer
systems. Both Dow’s new SiLK and Honeywell’s
GX material are based on the chemistry of pheny-
lethynylated thermosets and have received favor-
able customer feedback during the developmental
phases. Since they are organic-based, they were
considered interchangeable and deemed extendible
to future CMOS scaling including nanoporous
materials. One small, yet noteworthy, advantage
that emerged was that the GX material after ther-
mal cure possesses 2x higher hardness value than
FLARE and SiLK (Table 10.65). The high level of
Figure 10.92 Synthetic route to GX thermoset,
1,3,5,7-tetrakis[3- or 4-(phenylethynyl)phenyl]
adamantane.
hardness (close to 1 GPa) was attributed to the
presence of the rigid framework structure of the
adamantane units in the GX polymer [335].
Honeywell and Dow Chemical have continued
the competition in the CMOS scaling arena in
ultralow-k nanoporous dielectrics, where nanopor-
osity was deemed a necessity to attain lower levels
of dielectric constant near and below 2.0. In collab-
oration with IBM on the design of nanoporous
SiO2-based thin films, where sacrificial thermally
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 409

Table 10.65 Improvement in Thermal and Mechanical Characteristics of Dielectric Films via Phenyleythynyl
Thermosets
Thermal Anneal Effect on Nonporous GX Polymer Film

Anneal Condition RI k Thickness (%)

No Anneal 1.627 2.59 100.00
400°C 10 hrs 1.621 2.57 99.0
425°C 10 hrs 1.617 2.57 98.0
450°C 10 hrs 1.620 2.59 95.8

• Film thickness shrink age at 400°C is very small

• No difference was seen for measurement conducted immediately after anneal, or one day after anneal

Glass Transition Temperature, Modulus and Hardness

Tg Modulus (GPa) Hardness (GPa)

GX Polymer 450 6.3–7.1 0.79–0.84
FLAREt 400 4.8–5.1 0.35–0.40
Film thickness shrinkage at 400°C is very small
No difference was seen for measurement conducted immediately after anneal, or one day after anneal
Modulus and hardness are measured by nano-indentation

labile polymers were incorporated as a second
phase in spin-on glass systems, and subsequently
burned off, Dow applied the same “thermally labile
second phase” approach to the SiLK polymer sys-
tem, to create a totally organic nanoporous dielec-
tric thin films [336], which inherently diminished
the needed mechanical strength the thin films must
have to be viable. This task was daunting from the
start and in the last few years has given way to the
advances in single-wall carbon nanotubes
(SWCNTs) as potential field effect transistors
(FETs) materials. SWCNTs have gained much
attention to be the new materials for still more
compact chip designs towards continued miniaturi-
zation, in the spirit of Moore’s Law.
High-k (or kappa, κ) dielectrics (κB20
30) such
as zirconium oxide (ZrO2) and hafnium oxide (HfO2)
have been actively pursued as gate insulators for sili-
con devices [337] and device integration on carbon
nanotube molecular electronics. It has been recog-
nized that these exceedingly small molecular struc-
tures could not be achieved by top-down lithography,
and are therefore essential to miniaturization. Single-
walled carbon nanotubes (SWNTs) have molecular-
scale diameters (B1 nm), and are promising for
nanotube FET development. The high carrier mobil-
ity characteristics of high purity carbon nanotube
materials combined with high-k advanced gate
dielectrics have opened a new route to advanced
miniature field effect devices (FETs). More recently,
3-dimensional design has been achieved. As this fas-
cinating technology is beyond the scope of this arti-
cle, interested readers are encouraged to follow more
authoritative reviews and reports in microelectronics
technology [338
340]
Polymer-Ceramic Materials
Reinforcing polymers with a high-modulus,
high-temperature resistant, and compatible inor-
ganic second phase results in organic-inorganic
polymer networks (OIPNs) with increased ablation
resistance, modulus, and higher level of thermal
and thermooxidative resistance. Multicomponent
systems that involve both organic and inorganic
materials are noteworthy. The inorganic compo-
nents include a multitude of silicates (zeolite, liti-
dionite, clay), aluminium phosphates, alumina,
titania, and zirconia. Although these are naturally
occurring, but many have been synthesized in a
controlled environment via solgel polymerization
techniques. Silicate-based OIPNs are generally
available from solgel polymerization of tetraalkoxy-
silanes in the presence of the organic components.
This interdisciplinary materials research explores
the synergism of polymer technology and ceramic
technology, and has been pursued at Frauenhofer
410
Institut für Silicatforschung (Würzburg, Germany),
Virginia Tech (Blacksburg, Virginia), and the
University of Arizona (Tucson, Arizona). Polymer-
ceramic materials have been shown to be applicable
as high-temperature structural matrices, adhesives,
and ablative resistant coatings. Notably significant
is that the shrinkage associated with solgel-derived
ceramics can be mitigated by the organic compo-
nents [341
343]. The proper choice of the polymer
resin and the inorganic component can lead to
materials with tailorable adhesive, optical, laser
damage resistant, and ablative resistant properties.
The conventional precursor for solgel polymeri-
zation is tetraethoxysilane. Modification of the
inorganic component of the OIPNs can be carried
out by incorporation of diarylsiloxy units during
solgel polymerization. The presence of such units
strongly contributes to the thermoplasticity and sol-
vent solubility of the OIPN materials
[342,344,345]. Careful control of reaction condi-
tions and the order of mixing during OIPN prepara-
tion are vital to the control of microstructural,
mechanical, and optical properties of the final prod-
uct. Toward this end, applications of the solgel pro-
cess to designing polymer-ceramic materials for
hot-melt adhesives and contact lens with improved
oxygen permeability have been realized [345,346].
OIPNs open the possibilities of merging organic
materials with inorganic materials. Processible
materials to service the thermal regime of 371°C
(700°F) to 1,000°C (1,832°F) can be a reality.
Silicon Alkoxide-Derived Polymer
Ceramic Materials
The low-temperature aspect in preparing and
processing silicon alkoxide-based glass materials
[347
349] allows reinforcement with polymer
fibers and preparation of polymer-ceramic compos-
ite materials based on otherwise hard-to-process
high-temperature polymers. Siloxane and inorganic
silicon chemistries afford a unique opportunity to
modify polyimides with alkali free polysilicates,
while retaining the polyimides’ processibility dur-
ing processing and cure.
Researchers at Hughes Aircraft Company have
previously established the beneficial qualities, such
as improved structural integrity (modulus and
toughness) and optical properties, of inorganic
components incorporated into organic polymer
resins [350]. Thermidt 600 polyimides, similar
HANDBOOK OF THERMOSET PLASTICS
acetylene-terminated resins and/or 6F-containing
polyimides have been used as the organic compo-
nents. Compatibility of organic and inorganic com-
ponents has been demonstrated in organosilicates
and organoaluminosilicates [81]. The ultimate resin
ultrastructure is single phase, i.e. there is no dis-
cernible boundary going from the organic compo-
nent to the inorganic.
Thin films can be formed from organic polyimides
and silicon acetates [351]. The resulting silicate-
containing polyimide film (1 to 2 micron) resisted
high temperatures ( . 530°C or 986°F) in air. Under
the same conditions, films from cured organic polyi-
mide underwent precipitous weight loss.
Researchers at Virginia Polytechnic Insitute
[352,353] have produced “creamer” materials by
incorporating poly(dimethylsiloxane) oligomers
into silicate glass network during low-temperature
solgel polymerization (Figure 10.93). The choice of
siloxane oligomers for this study was based on the
high thermal stability characteristic of these materi-
als, and that a direct silanol coupling reaction is
possible between the oligomers and tetraalkoxysi-
lane. The final ceramic obtained was thermal
stable up to 500°C (932°F). The fact that only low-
molecular-weight polydimethylsiloxane materials
(MW 5 1.7 3 103) were used suggests that even
higher level of thermal stability can be achieved
with high-molecular-weight polymeric dimethylsi-
loxanes. At the ultrahigh molecular weight range
(MW . 106), the enhanced polymer entanglement
further enhances mechanical and dimensional
stability.
Electron microscopy [354] of similar silicate-
reinforced organic materials indicated that the sili-
cious particular precipitates were not agglomerated
and had an average particle size of 200 Å.
Mechanical testing showed an increase in ultimate
tensile strength was observed with increasing
amount of the inorganic component.
An elaborate study on the interplay of several sol-
gel reactions of tetraalkoxysilane, mixed silicon alk-
oxide and titanium alkoxide, diphenyldialkoxysilane,
methylvinyldialkoxysilane, and subsequent thermal
curing has led to the development of an optimized
hot-melt sealant formulation which consisted of 5
parts of tetraethyl silicate [Si(OCH2CH3)4], 60
parts of diphenyl disilanol ((C6H5)2Si(OH)2, 5
parts of tetraethyl titanate [Ti(OCH2CH3)4], and 30
parts of methylvinyldiethoxysilane [(CH2QCH)
(CH3)Si(OCH2CH3)2][345] (Figure 10.94).
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS 411

OCH3 OCH3 OCH3

H3CO Si OCH3 + HO Si O Si OH

OCH3 OCH3 OCH3

n

O OCH3 O
H2O , H+
O Si O Si O Si O Si O

O OCH3 OCH3 O
n

Ceramer

Figure 10.93 Formation of a ceramer material.

OR OR
H2O
OR Ti OR + OR Si OR + R'nSi(OR)4-n O Ti O Si O Si O
OR OR R'

OR OH
HCl, H2O
OR Si OR + OR Si OR O Si O Si O
OR OH

cure
Si CH3 + H2C CH Si Si CH2 CH2 CH2 Si

cure
Si OH + HO Si Si O Si + H2O

cure
Si OH + RO Ti Si O Ti + H2O

Figure 10.94 Interplay of reactions in solgel chemistry.

412
Aluminium Phosphate and Silicate
Refractory Materials
The possibility of preparing refractory materials
at very low temperatures has been demonstrated,
and these materials have been shown to be
stable well beyond 371°C (700°F). For example,
aluminium phosphate-based glass material is refrac-
tory up to 1,600°C (2,912°F), at which point alu-
minium phosphate begins to decompose. The
processing is typically carried out at low tempera-
ture and heat treatment requires only temperatures
as low as 100°C [355]. Physical blending of an
inorganic (ceramic) precursor and a high-
temperature polymer has been studied in the devel-
opment of a high-temperature adhesive-sealant
composition [356]. The composition comprised a
mixture of an aluminous cement and a poly(amic
acid) precursor. A rectangular glass fiber sheet was
formed into a cylinder and the edges were joined
with the adhesive system. After drying for 3 hours
at 204°C (400°F) and heating for 3 hours at 426°C
(800°F), the joint was shown to have good cohesive
and adhesive strength.
Commercially available Quazite® is an improved
structural material molded from 95% inorganic
material [357] and 5% high-performance organic
polymers. The process, which involves controlled
mixing, molding and curing, is proprietary to
Quazite Corporation. The ultimate structure is an
intertwined cross-linked network, monolithic in
nature and having tailorable characteristics.
Quazite® possesses the formability of fiberglass,
twice the bending strength of and more abrasion
resistance than granite, excellent impermeability to
liquids and chemical resistance equal to titanium-
clad steel. It could also be fiber-reinforced,
polished, or gel-coated. A 20-foot 3 1
1/2 inch
thick Quazite® panel is able to withstand a 50,000-
amp, 10,000-volt arc. Temperatures above 1,094°C
(2,000°F) were contained. Chemically, it resisted
temperatures up to 232°C (450°F) and pressures to
500 psi in a highly concentrated, corrosive salt
solution.
Partially Stabilized Zirconia
The utilization of ceramic materials in matrix
resins and structural adhesives affords still another
beneficial feature. Chemical compounds which
undergo expansive phase transformations such as
HANDBOOK OF THERMOSET PLASTICS
the one occurring in partially stabilized zirconium
oxide (PSZ), can contribute to the toughening of
the structural adhesive matrix. The PSZ is a matrix
of cubic zirconium oxide containing 20% to 50%
of the metastable tetragonal form. As the adhesive
matrix sustains a crack, the crack tip induces the
metastable tetragonal particles to transform to the
monoclinic form, with a net volume increase. Such
a volume increase exerts a compressive stress to
the crack tip thus halting further propagation.
While PSZ is known to impart toughening to
alumina-based ceramics, other silicate-based expan-
sive toughening agents, such as calcium silicate,
can perform well in silicon-derived ceramic mat-
xices [358].
Organically Modified Litidionite
An inherently fibrous siloxane polymer having
pendent trimethylsilyl (Me3Si, MeQCH3) groups
was prepared from synthetic litidionite using a
Lentz-type extraction-substitution process [359].
The polymer was prepared from litidionite by treat-
ment with a mixture of chlorotrimethylsilane, water,
and an organic solvent for a period of days at room
temperature. The polymer had a waxy texture and
was insoluble in a wide range of organic solvents.
The IR spectra of the polymer showed trimethylsilyl
(SiMe3), silanol (SiOH), and siloxane (SiaOaSi)
bands while its Si 2p3/2 x-ray photoelectron (ESCA)
spectrum showed overlapping SiO4 and SiOC3
peaks. Spectral data showed the presence of a small
amount of potassium but no sodium or chlorine. The
polymer was further characterized by electron
microscopy, elemental analysis, differential thermal
analysis (DTA), differential scanning calorimetry
(DSC), and X-ray powder diffractometry. Many
fibers, often with diameters of 40
60 Å, were seen
in the micrographs obtained [360].
Litidionite was prepared from a Na-K-Cl silicate
glass by devitrification or from a 2:1:1:8 mole ratio
mixture of CuO, Na2CO3, K2CO3, and silica by sin-
tering at 765°C (1,409°F) for several days [361].
Clay-Polymer Nanocomposites
The mechanical and thermal properties of
sodium montmorillonite (MMT) clay-polymer
nanocomposites often are superior to the polymer
itself [362]. Intercalation of the polyimide derived
from pyromelltitic dianhydride (PMDA) and
10: HIGH-PERFORMANCE POLYIMIDES AND HIGH TEMPERATURE RESISTANT POLYMERS
4,40 oxydianiline (4,40 -ODA) in the galleries of
extended-chain monoalkyl-ammonium montmoril-
lonite indicates that the polyimide forms a mono-
layer, with the aromatic nuclei parallel to the clay
layers [363]. Polyimide films with the incorporation
of 2.0 wt.% and 5.0 wt.% of clay decrease carbon
dioxide transmission to 50% and 20%, respectively.
Tailoring of surface properties of these polyimide-
MMT clay nanocomposites in terms of wettability,
adhesion, polarity and tribological properties have
been demonstrated for applications in microelec-
tronics and biotech [364
367].
Solgel-Derived Polyimide-Silica
Nanocomposites
Based on previous work on epoxy-silica and
polyethersulfone-silica [368] and solgel polymeri-
zation techniques [341
344,369], polyimide-silica
nanocomposites have been attained from solgel
polymerization of tetraethoxysilane (TEOS) in the
presence of poly(PMDA-4,40 -ODA)amic acid in N,
N-dimethylacetamide. Macrophase separation was
observed due to early separation of phases as a con-
sequence of solubility limitation [370]. As solgel
polymerization of tetramethoxysilane (TMOS) in
the presence of poly(PMDA-4,40 -ODA)amic acid
and triethylamine in methanol was carried out, bet-
ter solubility was achieved and much different mor-
phology of the resulting nanocomposite was
observed [371]. The solgel synthesis of silica struc-
tures has resulted in the formation of intercon-
nected globular microstructures of sizes of 0.2
micron and 0.07 micron at drying temperatures of
60°C and 20°C, respectively. That the globular
microstructure was formed during drying of the sol-
gel product, and not as a consequence of the 800°C
firing of the polyimide-silica film, was demon-
strated by the observation of the same globular
structure by SEM of a polyimide-silica film etched
with hydrazine hydrate to remove the organic poly-
mer. In theory, these inorganic films of intercon-
nected silica globules of uniform size can be
stacked and compacted at moderate to high pres-
sures to yield ceramic sheets of controlled
thicknesses.
Similar polyimide films containing a homoge-
neous dispersion of silica particles were prepared
via similar solgel processes [372]. Analogous to the
earlier Hughes work, an alkoxysilane-terminated
organic monomer has been transformed via the
413
solgel process into a network polymer [373].
Application of this organic-inorganic polymer net-
work concept has led to the formation of a nonli-
nearly optically active silica-polyimide
nanocomposite. The polyamic acid used in this
research was Skybond 705, which is Monsanto’s
poly(BTDA-MDA)amic acid [374].
The interdisciplinary research in polymer-
ceramic materials has the potential of offering a
novel solution to the quest for high-temperature
( . 371°C or .700°F) processible polymer resins,
particularly thermosetting resins.
Related to the development of polmer-ceramic
materials is their potential in improving compres-
sive modulus in polymeric materials. Such an
approach of polymer hybrids permits entry into the
nanometer domain foretelling future continued
advancement. Solgel chemistry as a viable chemical
technology to achieving polymer ceramic hybrids
with remarkable properties has been reported
[375,376] and more recently reviewed [377].
Conceivably, enhancement of inherent compressive
modulus of the polymer also can be achieved
through integration of star-shaped polymers as sec-
ond components [378,379].
Acknowledgments
This chapter is dedicated to Dr. Abraham L.
Landis (1928
2009), my mentor, colleague, and
friend.
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