Macromol. Chem. Phys.

197, 1171-1183 (1996) 1171

Synthesis and characterization of poly(amide-imide)s

containing 1,6-diamantane moieties in the main chain
Yaw-Terng Chern: Wan-Ho Chung

Institute of Chemical Engineering, National Taiwan Institute of Technology, Taipei, 106,

Taiwan

(Received: August 10, 1995; revised manuscript of September 8, 1995)

SUMMARY
A series of new poly(amide-imide)s were synthesized by direct polycondensation of the
1,6-bis(trimellitimido)diamantane (1) with various aromatic diamines in N-methyl-2-pyrro-
lidone (NMP) containing lithium chloride. The poly(amide4mide)s had inherent viscosities
of 0.33- 1.55 dL/g. The new polycyclic monomer 1 was synthesized from 1,6-diaminodi-
amantane with trimellitic anhydride. Dynamic mechanical analysis revealed polymers 3a - c
to have main transitions at 385 "C, 385 "C, and 330 "C, respectively. Moreover, these poly-
mers were stable at high temperatures and maintained good mechanical properties
( G = lo8 Pa) up to temperatures close to the main transition well above 350 "C. Their 5 %
weight loss temperatures ranged from 421 to 448 "C in nitrogen, and from 417 to 426°C in
air. A glass transition of poly(amide-imide)s 3 was not observed. Poly(amide-imide)s 3
(except 3e) were soluble in NMP, pyridine, and o-chlorophenol. Some of the polymers
(3 a-c) could be cast into flexible films. Their cast films had tensile strengths ranging from
35.5 to 46.9 MPa, elongations at break from 5.8 to 7.5%, and initial moduli from 1.8 to
2.1 GPa.

Introduction
Poly(amide-imide)s were developed from high-performance polymers which
combine the advantages of high temperature stability and processability. Much
research has been done on the methods for synthesizing poly(amide-imide)s ' - I 3 ) . The
conventional method for synthesis of poly(amide-imide)s is solution polycondensation
of the acid chloride of trimellitic anhydride and diamines '1. Furthermore, the direct
polycondensation of trimellitic anhydride (TMA) and diisocyanates has been
reported 1' . Poly(amide-imide)s also have been made from the dicarboxylic acyl
chloride of bisimide derived from TMA and diamines 3 - 6 ) , dicarboxylic acid of
bisimide derived from TMA with diisocyanates *) and the dicarboxylic acid of
79

bisimide derived from TMA with diamines'-"). Recently, high molecular weight
poly(amide-imide)s were synthesized by the palladium-mediated carbonylation and
condensation reactions of dihalogenated imide monomers and aomatic
diamines 12, 1 3 ) .
Diamantane is a cycloaliphatic-cage hydrocarbon containing an "extended-cage''
'*
adamantane structure Is). Although diamantane has been investigated for many
years16-19), only a few examples of polymers based on diamantane are known20'2').
Recently, we reported that incorporation of 1,6-diamantane units into polyamides and
polyesters afforded good thermal stability and good mechanical properties u p to tem-
peratures well above 350 " C ,relatively low dielectric constant, and high glass transition
Macromol. Chem. Phys. 197, No. 4, April 1996
0 1996, Hiithig & Wepf Verlag, Zug CCC 1022-1352/96/$10.00
1172 Y.-T. Chern, W.-H. Chung

temperatures 22-24). From these results, we can conclude that introduction of diaman-
tane units into the polymers backbone may result in polymers with high thermal
stability and good mechanical properties. In this work, we describe the synthesis of new
poly(amide-imide)s involving 1,6-bis(trimellitimido)diamantane(1) by direct polycon-
densation with aromatic diamines (2) by using triphenyl phospite and pyridine as
condensing agents, as shown in Scheme 2. The obtained poly(amide4mide)s contain
alternating (amide-amide)-(imide-imide) links in the polymer backbone. The solubility,
dynamic mechanical properties, and thermal properties of polymers were also
investigated.

Experimental part
Materials
4,4'-Oxydianiline (2 a), 4,4'-methylenedianiline (2b), 1,3-phenyIenediamine (2 c), 4,4'-sul-
fonyldianiline (2 d), and 1,4-~henylenediamine(2e) were purified by vacuum sublimation.
Anhydrous LiCl (Merck) was dried in a vacuum oven at 150°C for 6 h and at 180°C for
10 h. N-Methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide and pyridine yere purified
by distillation under reduced pressure over calcium hydride, and stored over 4 A molecular
sieves. Trimellitic anhydride (TMA) was purified by sublimation. The polycyclic diamine
1,6-diaminodiamantane was synthesized starting from 1,6-dibromodiamantane as in our
previous study2? the reaction of 1,6-dibromodiamantane with acetonitrile using H2S04as
catalyst afforded 1,6-diacetamidodiamantanewhich was then hydrolyzed with NaOH.

1,6-Bis(trimellitimido)diamantane(1)
A flask was charged with 22 mL of N,N-dimethylformamide (DMF), 1.004 g (4.6 mmol)
of 1,6-diaminodiamantane, and 1.768 g (9.2 mmol) of TMA. The flask was stirred at room
temperature for 6 h, and nitrogen was passed through the solution. Then 6.4 mL of acetic
anhydride, followed by 6.4 mL of pyridine, was added; the clear solution was then heated
by means of an oil bath to 150"C for 5 h. A yellowish precipitate which formed upon cooling
was filtered off, washed several times with methanol and water, and 1.64 g (60% yield) of
1 was obtained. The product was purified by recrystallization with N,N-dimethylacetamide;
m. p. 41 1 "C (by DSC).
IR (KBr): 2981,2850 (CH,, CH), 1770 (imide), 1709 ( CEO), 1356 (imide), 732 cm-'
(imide).
EIMS: m / z (070) = 566 (M + , 4).
'H NMR (300 MHz, DMSO-d,): 6 = 1.56 (4 H, m, J = 12.83 Hz, H-I 1a, 16a, 18a,
22a),1.82(4H,m,J= 12.78Hz,H-l1b,16b,18b,22b),1.94(2H,m,H-l2,17),2.03(4H,
d,H-13,21),3.60(4H,m,H-10, 15, 1 9 , 2 0 ) , 7 . 8 9 ( 2 H , d , J = 7.91 Hz, H-5,26),8.16(2H,
s, H-3, 28), 8.32 (2H, d, J = 9.01 Hz, H-6, 25) (shown in Fig. 1).
'3C NMR (75 MHz, DMSO-d,): 6 = 26.97 (C-12, 17), 32.30 (C-11, 16, 18, 22), 37.83
(C-10, 15, 19, 20), 40.94 (C-13, 21), 63.16 (C-9, 14), 122.67 (C-3, 28), 122.94 (C-5, 26),
131.79 (C-2, 29), 134,62 (C-7, 24), 135.22 (C-6, 25), 136.32 (C-4, 27), 165,86 (C-1, 8, 23,
30), 168.70 (COOH).

C,,H,,N,O, (566.55) Calc. C 67.78 H 4.59 N 4.94

Found C 67.85 H 4.76 N 4.90
Synthesis and characterization of poly(amide-imide)s . . . 1173

Polymerization
Poly(amide-imide)3a from 1 and 2a (typical example):A mixture of 0.906 g (1.6 mmol)
of 1, 0.32 g (1.6 mmol) of 2a, 1.0 g of LiCI, 0.984 g (3.2 mmol) of triphenyl phosphite,
4 mL of pyridine, and 16 mL of NMP was heated with stirring at 130°C for 12 h. The
obtained polymer solution was trickled on 500 mL of methanol, giving rise to a fibrous
yellowish precipitation which was washed thoroughly with methanol and hot water,
collected by filtration, and dried. The yield was almost quantitative. The inherent viscosity
of the polymer was 0.92 dL/g, measured at 0.5 g/dL concentration in NMP containing
dissolved 5 % w/v LiCl at 30°C. The IR spectrum exhibited absorptions at 3455 cm-'
(NH), 1770 cm-' (imide), 1706 cm-' (imide, C=O), 1663 cm-' (amide, C=O),
1 345 cm-I (imide), and 721 cm-' (imide), characteristic of imide and amide groups. The
elemental analysis values of the polymer 3 a are listed in Tab. 2.

Characterization
A Bio-Rad FTS-40 FTIR spectrophotometer was used to record spectra using KBr pellets.
In a typical experiment, an average of 20 scans per sample was made. MS spectra were
obtained by using a JEOL JMS-D300 mass spectrometer. 'H and 13C NMR spectra were
recorded on a Bruker AMJOOWB Fourier transform nuclear magnetic resonance spectro-
meter using tetramethylsilane (TMS) as the internal standard. A Perkin-Elmer 240C elemen-
tal analyzer was used for elemental analysis. Inherent viscosities of all polymers were deter-
mined at 0.5 g/dL concentration in NMP containing dissolved 5% w/v LiCl at 30 "C using
an Ubbelohde viscometer. Next, qualitative solubility was determined using 0.01 g of poly-
mer in 2 mL of solvent. A Du Pont 9900 differential scanning calorimeter (DSC) and a Du
Pont 9900 thermogravimetric analyzer were then employed to study the transition data and
thermal decomposition temperatures of all the polymers. The DSC was run under a nitrogen
stream at a flow rate of 30 cm3/min and a heating rate of 20"C/min. The thermogravi-
metric analysis (TC) was performed under a nitrogen flow of 50 cm3/min with a heating
rate of 20 " C h i n . Dynamic mechanical analysis (DMA) was performed on a Du Pont 9900
thermal analyzer system. A sample 10 mm in length, 2 mm in width and approximately
0.8 mm in thickness was used. The dynamic shear modulus was measured by the resonance
mode at an amplitude of 0.2 mm. The wide-angle X-ray diffraction measurements were
performed on a Philips PM 1730-10 X-ray diffractometer using Cu K , radiation.
Tensile properties were determined from stress-strain curves with a Toyo Baldwin Instron
UTM-111-500 with a load cell of 10 kg at a drawing speed of 5 cm/min. Next, measurements
were performed at 28 "C with film specimens (about 0.1 mm thick, 1.0 cm wide and 5 cm
long), and an average of at least five individual determinations was used.

Results and discussion

Monomer synthesis

A new polycyclic monomer, 1,6-bis(trirnellitimido)diamantane (l),was synthesized

according t o the route shown in Scheme 1. It was prepared from 1,6-diaminodiaman-
tane and T M A by refluxing in DMF, using acetic anhydride and pyridine as condensing
agents, with 60% yield. On the basis of the shielding effect of carbon, the positions
of chemical shifts for carbons were readily assigned from DEFT experiment of 1, as
shown in Fig. 1(A). The 2D 'H-l3C COSY spectrum of 1 is shown in Fig. 1 (B). With
the aid of carbon spectrum assignments, the positions of chemical shifts for protons
1174 Y.T. Chern, W.-H. Chung

(A)

0 I

11.16,18,22 3230 ?,24 134.62

180 160 1LO 120 100 80 60 LO 20

6 in pprn

'0

6.0

L.0

2.0

1LO 100 60 20
6 in pprn

a t o m (HI 6 (C)
l l a 16a 18a22a 156
llb:16b:18d22b 1.82
12.17 194
13.21 2.03 Fig. 1. NMR
10,15,19,20 3 60 (DMSO-d,) spectra of
5,26 1. (A) I3C 135 O
3,28
6.25 832 DEPT and '3CNMR
), ( 1 hh (75 MHz); (B) 2D
'H-'3C COSU; (C)
1 1 1 , 1 1 1 , 1 1 1 1 1 1 1 1
'H NMR (300 MHz)
8.0 7.0 6.0 5.0 1.0 3.0 2.0 1.0
6 in pprn
Synthesis and characterization of poly(amide4mide)s 1175

Scheme I:

0
1

was readily assigned as shown in Fig. 1 (C). However, the protons for acid groups of
1 in the 'H NMR spectrum were not observed. This was probably due to the fast
exchange of these protons with a trace amount of moisture associated with the solvent.
The elemental analysis, the characteristic peaks in the NMR spectra, and the
characteristic bands in the IR spectra correlate sufficiently with the supposed structure
of 1.

Tab. 1. Effects of reaction conditions on polymerizationa)

Part Reaction conditions Polymer Remarks d,

C)
[Monomer] b, [LiCI] temp. time yield qinh
mol/L w/vvo in "C in h in Vo dL/g
I 0.10 5 100 12 98.1 0.39 S
0.10 5 110 12 96.2 0.42 S
0.10 5 120 12 98.5 0.75 S
0.10 5 130 12 98.2 0.87 S
0.10 5 140 12 90.0 0.62 S
I1 0.05 5 130 12 96.6 0.85 S
0.08 5 130 12 99.4 0.92 S
0.10 5 130 12 98.2 0.87 S
0.12 5 130 12 99.5 0.86 S
I11 0.08 3 130 12 95.9 0.81 S
0.08 5 130 12 99.4 0.92 S
0.08 7 130 12 90.0 0.65 S
IV 0.08 5 130 9 95.0 0.83 S
0.08 5 130 12 99.4 0.92 S
0.08 5 130 15 94.2 0.80 S

a) Reaction conditions: pyridine/NMP vol. ratio = 0.25, P(OC,H,),/l mole ratio = 2.

b, [I] = [2a].
') Measured at 30°C and a concentration of 0.5 g/dL in NMP containing 5% w/v LiCl.
dl S, homogeneous solution.
1176 Y.-T.Chern, W.-H. Chung

Effects of reaction conditions on the inherent viscosity of 3a

Generally, the molecular weight of polymers obtained from the phosphorylation

reaction is highly dependent on the reactant concentration, reaction temperature, and
composition of the reaction medium. Hence, the effect of temperature was first studied
to find out the suitable temperature for the preparation of high-molecular-weight
poly(amide-imide) 3a. Part I in Tab. 1 indicates that the inherent viscosities of poly-
(amide-imide) 3 a increased markedly with an increase in reaction temperature up to
130 "C. However, a lower inherent viscosity (0.62 dL/g) was obtained when the reaction
was carried out at 140 "C. This might be caused by an adverse effect on the complex
formed from LiCl and phenol at an excessively high temperature, leading to an increase
in side reactionsz6).Part I1 in Tab. 1 reveals that the inherent viscosity of polymer 3 a
increased with an increase of the monomer concentration up to 0.08 mol/L. However,
higher concentrations of monomer led to a decrease of the inherent viscosity of poly-
mer 3 a above 0.10 mol/L. This may be attributed to the fact that the solubility of the
reaction medium was reduced when the concentration of the monomer was too high.
Part 111 in Tab. 1 shows that the most suitable quantity of LiCl to be added is 5% w/v.
LiCl can improve the solubility of poly(amide-imide)s by weakening the hydrogen
bonding between the molecules. Moreover, LiCl can form a complex with the generated
phenol, thus reducing side reactions and affording higher inherent viscosityz6).If the
quantity of LiCl to be added is excessive, however, the solubility of poly(amide-imide)s
may have an adverse effect. A subsequent decrease in the inherent viscosity of the
Scheme 2:

1 2

3
Synthesis and characterization of poly(amide4mide)s . . . 1177

formed polymer 3a would occur. This result is quite similar to that in previous litera-
ture22,26).Part IV in Tab. l shows that the inherent viscosities of polymer 3 a increased
with an increase in reaction time. However, if the reaction time is above 15 h, the
inherent viscosity of 3 a decreases, perhaps a result of growing side reactions. This result
is similar to those disclosed in previous literature22,z6).From the results discussed
above, we can conclude that the most favorable conditions for this system are a concen-
tration of monomer of 0.08 mol/L, a quantity of LiCl to be added of 5% w/v, a
reaction temperature of 130°C, and a reaction time of 12 h.

Synthesis of poIy(amide-imide)s
Various new poly(amide-imide)s were prepared from 1 with some aromatic diamines
by using the most favorable conditions found from the reaction with 4,4'-oxydianiline
(2a) (Scheme 2).
Polycondensation results are listed in Tab. 2. All poly(amide-imide)s were obtained
in almost quantitative yield. The poly(amide4mide)s had medium to high inherent

Tab. 2. Synthesis and characterization of poly(amide-imide)s a)

Polymer Yield qinh b, Remarks') Elemental analysis 'To H,Od)
in Vo dL/p C H N
3a 99.4 0.92 S Calc. 72.32 4.69 7.67 4.0
Found 69.32 5.09 7.30
Corr.d) 72.21 4.84 7.60
3b 95.2 0.69 S Calc. 74.16 4.98 7.68 4.0
Found 71.12 5.34 7.37
Corr.d) 74.08 5.10 7.68
3c 98.5 0.57 S Calc. 71.46 4.74 8.77 4.0
Found 68.01 5.11 8.25
Corr.d) 70.84 4.86 8.59
3d 90.2 0.33 S Calc. 67.86 4.40 7.19 3.5
Found 65.35 4.83 6.89
Corr.d) 67.72 4.60 7.14
3ee) 95.5 1.55O G Calc. 71.46 4.74 8.77 4.0
Found 67.78 5.11 8.78
Corr.d) 70.60 4.86 8.52
a) [l] = [2] = 0.08 mol/L; pyridine/NMP vol. ratio = 0.25; P(OC6H,),/1 mole ratio =
2.0; LiCl = 5% w/v; temperature = 130°C; time = 12 h.
b, Measured at 30 "C and a concentration of 0.5 g/dL in NMP containing 5% w/v LiCl.
') Appearance of the polymerization system: S, homogeneous solution; G, swollen gel.
d, 'To HzO =
w - w, x 100%; W: weight of polymer sample after standing at room
wo
temperature; W,,: weight of polymer sample after drying in vacuum at 100 "C for 12 h;
corrected value = found value/(l - 070 H,O) for C and N, corrected value = (found
value - 'To Hz0/9)/(1 - 070 H,O) for H.
e, 12 mL of NMP supplemented after the reaction mixture became highly viscous.
1178 Y.-T. Chern, W.-H. Chung

viscosities (0.33 - 1.55 dL/g). Although the reaction medium of 3e finally formed a
swollen gel, the inherent viscosity of 3e was considerable. The unsatisfactory result
obtained with 4,4'-sulfonyldianiline (2d) may be explained by its lower nucleophilicity
due to the presence of the electron-withdrawing sulfonyl group. Elemental analysis
results for these poly(amide-imide)s are listed in Tab. 2. In all cases, the carbon values
were found to be lower than those calculated for the expected structures. The moisture
uptake of the polymers was in the range of 3.5-4.0 wt.-Yo at room temperature, which
could be calculated by the weight change of vacuum-dried polymer samples after
exposure to air. The values corrected for moisture content correlated well with the
proposed structures. FTIR spectra of the poly(amide-imide)s showed characteristic
bands at 3300-3455 cm-I (amide), 1660- 1670 cm-l (amide), 1765- 1770 cm-l
(imide), 1340-1 350 cm-' (imide), and 720-730 c m - ' (imide).

Characterization of polymers

The solubility of these polymers was tested in various solvents, and the results are
summarized in Eib. 3. Poly(amide-imide)s 3 (except 3 e) were soluble in NMP, pyridine,
and o-chlorophenol. Poly(amide4mide) 3 e had the worst solubility among the
poly(amide-imide)s 3. This may be due to the fact that polymer 3e contains the
relatively rigid and symmetrical p-phenylene groups.

Tab. 3. Solubility of poly(amide-imide)s

Polymer Solvent a)

NMP DMAc DMF DMSO pyridine o-chlorophenol

3a + +- +- +- + +
3b ++ +- +- +- + ++
3c ++ + +- +- + +
3d ++ +- +- +- ++ ++
3e +- +- +- +- +- +-
a) Key: + +, soluble at room temperature; +, soluble on heating at 60 "C; + -, partially
soluble on heating at 60 " C . Abbreviations: DMAc, N,N-dimeihylacetamide; NMP, i-
methyl-2-pyrrolidone; DMF, N,N-dimethylformamide; DMSO, dimethyl sulfoxide.

A n approach to structural characterization has been made by X-ray method using

the "as-prepared" powders. Poly(amide-imide)s 3 had almost the same semicrystalline
patterns, exhibiting crystalline peaks (28) at around 16 O and 25 O, as shown in Fig. 2.
Additional work is required to characterize the structures more accurately.
Yellowish films of poly(amide4mide)s 3a and 3b, and colorless films of polymer 3c,
were obtained by casting from their N M P or DMAc solutions containing 3% w/v LiC1.
The mechanical properties were determined with an Instron machine. The tensile
properties of the poly(amide-imide)s are summarized in Tab. 4. The films of 3 had
Synthesis and characterization of poly(amide4mide)s . . . 1179

3 100
73
._
111
E 80

LO

20

n"
10" 20° 30° 100 200 300 LOO 500 600
70 Temperature in "C

Fig. 2. Fig. 3.

Fig. 2. Wide-angle X-ray diffraction curves of poly(amide-imide)s

Fig. 3. TG curves of poly(amide4mide)s in nitrogen atmosphere at a heating rate of

2O"C/min in nitrogen: ( A ) 3a; ( 0 )3b; ( 0 )3c; ( A ) 3d; ( x ) 3e

tensile strengths ranging from 35.5 to 46.9 MPa, elongations at break from 5.8 to 7.5%,
and initial moduli ranging from 1.8 to 2.1 GPa. Polymer 3 d could also be cast into film,
but was quite brittle. Polymer 3 a was difficult to cast into film owing to its poor
solubility.

Tab. 4. Tensile properties of polymer films

Polymer Tensile strength Elongation at break Initial modulus

in MPa in % in GPa

46.9 5.8 2.1

43.5 1.5 1.8
35.5 7.5 1.9

a) Films were cast from polymer solution in DMAc containing 3% w/v LiCI.
') Films were cast from polymer solution in NMP containing 3% w/v LiCI.

The thermal properties of these polymers were evaluated by means of TG, DSC, and
DMA, and are summarized in Tab. 5 . The TG curves for these polymers are shown in
Fig. 3. Their 5 % weight loss temperatures are ranging from 421 "C to 448°C in
nitrogen, and from 417 "C to 426 " C in air. Thus, introduction of 1,6-diamantane units
1180 Y.-T. Chern, W.-H. Chung

Tab. 5. Thermal properties of poly(amide-imide)s

Polymer T , a)
- T,/"C b,

"C
in N, in air

3a 385 421 417

3b 385 423 417
3c 330 428 426
3d -4 425 420
3e 448 426

a) The a transition temperature measured by DMA.

b, Temperature at which 5% weight loss occurred in TG at a heating rate of 20"C/min.
Not detected.

into the polymer backbone resulted in poly(amide-imide)s with high thermal stability.
Since the influence of residual water or solvent, and history of thermal annealing,
are sometimes observed in the first heating run of DSC, the first heating of the samples
was restricted to 300°C; in addition, the Tg and thermal properties were evaluated
from the DSC charts of the second heating. The DSC traces shown in Fig. 4 d o not
show any detectable glass transition up to S O O T , which is in agreement with our
previous work on polyamides with 1,6-diamantane units22). Polymers 3 a and 3 b
exhibited a featureless trace up to a temperature of around 380°C, followed by the

1.5

Jl
1.0

-
0.5

0
I
5 ~ " " " " ' " J
100 200 300 LOO 500 -100 0 100 200 300 LOO
T e m p e r a t u r e in O C T e m p e r a t u r e in OC

Fig. 4. Fig. 5.

Fig. 4. DSC curves of poly(amide-imide)s in nitrogen atmosphere at a heating rate of

20 "C/ min

Fig. 5 . Dynamic mechanical analysis curves for 3 a film at a heating rate 5 " C h i n
Synthesis and characterization of poly(amide-imide)s . . . 1181

beginning of a broad endothermic peak at around 380°C, probably caused by

simultaneous melting and decomposition. Polymer 3c showed a rather featureless DSC
trace from 50°C to 410°C. At around 425 "C, a small endothermic peak started to
occur in this temperature range, probably caused by a melting process. Next, thermal
decomposition occurred above 430°C. Polymer 3d exhibited a featureless trace up to
a temperature of around 390°C, followed by endothermic peaks at around 400°C
interpreted here as arising from simultaneous melting and decomposition. Polymer 3 e
showed a rather featureless DSC trace from 50 "Cto 325 "C. At around 325 "C, a broad
exothermic process started to occur, probably caused by a recrystallization process.
Next, a broad endothermic process showed up at around 425 "C, most probably coming
again from a simultaneous melting and decomposition process.
More detailed information can be obtained from the dynamic mechanical measure-
ments taken on the films as a function of temperature. Films of about 80 pm thickness
were studied between - 100 "Cand 450 "C.The mechanical relaxation spectra of 3a are
shown in Fig. 5 . Three profound relaxations based on tan6 and G peaks are observed,
i. e., at -65 "C, at approximately 225 "C, and at 385 "C. The relaxation process can be
approached by verifying the results obtained with other related polymer^^^*^'-^^). The
low temperature of - 65 "C is a typical relaxation for polyamides. This relaxation can
be attributed to the motion (rotation) of the amide bonds together with water molecules
that are bonded to them. The second temperature, approximately at 225 "C, is very
broad in G and tans. This transition in poly(amide-imide)s is probably related to the
rotation of rigid segments of p-phenylene and amide groups around "hinges" such as
-0- and - CH,- in diamines. Such a transition was also observed in polyamides
with 1,6-diamantane units 22) and in other related polymers 28-30). With increasing
temperature from - 100 "C to 350 "C, G decreases steadily, without showing neither
abrupt changes nor a marked relaxation. The main transition, at around 385 "C, is
probably due to thermal decomposition.
The mechanical relaxation spectra of polymer 3 b are shown in Fig. 6. Three relax-
ations were observed, at - 50 "C ,200 "Cand 385 "C,based on t a n s and G peaks. nYo

-
0,

Fig. 6 . Dynamic mechani- 6

cal analysis curves for 3 b
film at a heating rate
5 "Chin 5
-100 0 100 200 300 COO
Temperature in O C
 1182 Y.-T. Chern, W.-H. Chung

lower relaxations of 3 b are similar to those of 3a. However, a shoulder peak was
observed at 200 "C in G'. Moreover, the transition at 200 "C is associated with approxi-
mately half order of magnitude decrease in G . The main transition at 385 "C in G ' is
probably due to thermal decomposition. Poly(amide4mide)s 3a and 3 b show rather
high G values (about lo8 Pa), even at temperatures higher than 350°C.
Polymer 3 c was brittle at - 100 "C, and therefore the dynamic mechanical behavior
of 3c was studied between 30°C and 350"C, as shown in Fig. 7. TWO relaxations were
observed, at 90°C and 33OoC, based on t a n s and G peaks. The low temperature
transition at 90°C is associated with a slight increase in G . The reason for this
transition still remains uncertain. We believe that such a transition can be attributed
to the enhanced film density due to evaporization of residual water. A shoulder peak
was observed at 200 "C in tans, another shoulder peak also appeared at 225 "C in G .
The main transition at 330 "C is probably due to thermal decomposition. However, this
transition was observed in t a n s and G but not in G'.

Fig. 7. Dynamic mechani-

cal analysis curves for 3c
film at a heating rate
2.5 "C/min

I) Y. Imai, N. N. Malder, M. J. Kakimoto, J. Polym. Sci., Polym. Chem. Ed. 23,2077 (1985)
2, M. Kakimoto, R. Akiyama, Y. S. Negi, Y. Imai, J. Polym. Sci., Part A: Polym. Chem.
26, 99 (1988)
3, W. Wrasidlo, J. M. Augl, J. Polym. Sci., Polym. Chem. Ed. 7, 321 (1969)
4, A. Ray, Y. V. Rao, V. K. Bhattacharya, S . Maiti, Polym. J. 15, 169 (1983)
') J. D. Abajo, J. P. Gabarda, J. Fontan, Angew. Makromol. Chem. 71, 143 (1978)
6, S. Das, S . Maiti, Makromol. Chem., Rapid Commun. 1, 403 (1980)
7, J. L. Jieto, J. G. D. Campa, J. D. Abajo, Makromol. Chem. 183, 557 (1982)
*) J. G. D. Campa, J. D. Abajo, J. L. Nieto, Makromol. Chem. 183, 571 (1982)
9, C. P. Yang, W. T. Chen, J. Polym. Sci., Part A: Polym. Chem. 32, 1101 (1994)
lo) C. P. Yang, S. H. Hsiao, J. H. Lin, .Polym. Sci., Part A: Polym. Chem. 31,2995 (1993)
I
I*) C. P. Yang, J. M. Cheng, S. H. Hsiao, Makrornol. Chem. 193, 1299 (1992)
12) R. J. Perry, S. R. Turner, R. W. Blevins, Makromolecules 27, 4058 (1994)
'3) R. J. Perry, S. R. Turner, R. W. Blevins, Macromolecules 28, 2607 (1995)
Synthesis and characterization of poly(amide4mide)s . . . 1183

14) G. A. Olah, G. K. S. Prakash, J. G. Shin, V. V. Krishnamurthy, G. D. Mateescu, G.

Liang, G. Sipos, V. Buss, T. M. Gund, P. v. R. Schleyer, J Am. Chem. SOC. 107, 2764
(1985)
'*) 0. Vogel, B. C. Anderson, D. M. Simons, Tetrahedron Lett. 415 (1966)
16) T. M. Gund, E. Osawa, V. Z. Williams, P. v. R. Schleyer, J. Org. Chem. 39, 2979 (1974)
17) T. M. Gund, P. v. R. Schleyer, G. D. Unruh, G . J. Gleicher, J. Org. Chem. 39,2995 (1974)
18) T. M. Gund, M. Nomura, P. v. R. Schleyer, J; Org. Chem. 39, 2987 (1974)
19) L. Vodicka, J. Janku, J. Burkhard, Collect, Czech. Chem. Commun. 48, 1162 (1983)
20) A. A. Malik, T. G. Archibald, K. Baum, Macromolecules 24, 5266 (1991)
21) T. D. Dang, T. G. Archibald, A. A. Malik, F. 0.Bonsu, K. Baum, L. S. Tan, F. E. Arnold,
Polym. Prep. (Am. Chem. SOC.,Div. Polym. Chem.) 32 (3), 199 (1991)
22) Y. T. Chern, W. L. Wang, Macromolecules 28, 5554 (1995)
23) Y. T. Chern, Macromolecules 28, 5561 (1995)
Y. T. Chern, J. S. Fang, S. C. Kao, J. Polym. Sci., Part A: Polym. Chem. 33,2833 (1995)
25) Y. T. Chern, J. J. Wang, Tetrahedron Lett. 36, 5805 (1995)
26) N. Yamazaki, M. Matsumoto, F. Higashi, J. Polym. Sci., Part A: Polym. Chem. 13,1373
(1 995)
27) P. A. M. Steeman, F. H. J. Maurer, Polymer 33, 4236 (1992)
28) V. Frosini, E. Butta, . IPolym. Sci., Polym. Lett. Ed. 9, 253 (1971)
29) Z. Sun, L. Dong, Y. Zhuang, L. Cao, M. Ding, Z. Feng, Polymer 33,4728 (1992)
30) D. S. Petris, V. Frosini, E. Butta, M. Baccaredda, Makromol. Chem. 109, 54 (1967)