Polymer 190 (2020) 122218

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Polymer
journal homepage: http://www.elsevier.com/locate/polymer

Synthesis of polyamide-imides with different monomer sequence and effect

on transparency and thermal properties
Nafeesa Mushtaq a, Qiaodi Wang a, Guofei Chen a, *, Beenish Bashir b, Haoji Lao a,
Yuanming Zhang a, Lala Rukh Sidra a, Xingzhong Fang a, *
a
Ningbo Key Laboratory of Polymer Materials, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang, 315201, PR
China
b
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, PR
China

A R T I C L E I N F O A B S T R A C T

Keywords: Two novel series of polyamide-imides (PAIs) with different monomer sequence were prepared by two synthesis
Polyamide-imides methods. First series of alternate polyamide-imides PAIs-2(a-e) were synthesized from polycondensation of
Monomer sequence diimide-diacids 1a-1c monomers with various aromatic diamines. Using the direct polycondensation of tri­
Coefficient of thermal expansion
melletic acid chloride (TMAC) with aromatic diamines, second series of polyamide-imides PAIs-3(a-c) were
Trimelletic acid chloride
prepared. The effect of monomer sequence on transparency and thermal properties of polymers is investigated.
The transmittance at 550 nm (T550) from the ultraviolet–visible (UV–vis) spectra of the PAIs was found in the
range of 74–87%, greatly affected by the monomer sequence in the polymer repeating units. PAI-3a from TMAC
exhibited high transparency of 87% and low coefficient of thermal expansion (CTE) of 25 ppm/� C. All co­
polymers demonstrated good organosolubility and mechanical properties with initial moduli of 3.4–4.9 GPa,
tensile strengths of 96–129 MPa and elongations at break of 3.0–5.2%. The glass transition temperatures (Tg) and
10% weight loss temperatures (T10%) of PAIs in nitrogen were in the range of 291–330 � C and 489–501 � C,
respectively.

1. Introduction imidization [6–9]. However, polycondensation of diacids containing

Flexible and transparent displays in electronic devices require
polymeric materials with low coefficient of thermal expansion (CTE),
high glass transition temperature (Tg), good thermal stability and high
transparency. Aromatic polyimides (PIs) exhibit very low CTE, high Tg,
good thermal stability and high mechanical strengths. However, PIs
with high rigid structure are difficult to process, have very dark color
films and insolubility in most organic solvents [1–4]. On the other hand,
polyamide-imides (PAIs) containing amide and imide groups in the
polymer main chain can improve the solubility and melt processability,
and inherit desirable characteristics like good thermal and mechanical
properties [5].
Polyamide-imides are usually prepared by three methods; (1) poly­
condensation of amide group containing dianhydrides or diamines; (2)
imide group containing diacids with diamines, (3) trimelletic anhydride
with diisocyanates or diamines. First method involves multi-step syn­
thesis of dianhydride or diamine monomers and high temperature
imide groups with aromatic diamines do not require high temperature
imidization step [10–13]. Trimellitic acid chloride (TMAC) is commer­
cially available, and has very reactive acid chloride group and moder­
ately reactive anhydride group at terminals for polymerization [14,15].
For achieving the present target properties such as low CTE without
sacrificing high transparency, good solution-processability and thermal
stability, the suitable diamine monomers are probably limited to CF3
containing diamine 2,20 -bis(trifluoromethyl)benzidine (TFDB) with a
rigid/linear structure which is an indispensable factor for low CTE
generation. The incorporation of electron-withdrawing bulky tri­
fluoromethyl (CF3) group increases the free volume in polymer chains,
reduces the inter-chain charge transfer complex and thereby improving
the transparency and organosolubility [8,12,16–18]. Hasegawa et al.
reported synthesis of soluble and highly colorless PAIs by traditional
polycondensation method using TFDB and amide type CF3-containing
dianhydride [7]. In contrast, among the non-fluorinated conventional
commercial diamines, such as p-phenylenediamine, 4,40 -oxydianiline,

* Corresponding authors.
E-mail addresses: gfchen@nimte.ac.cn (G. Chen), fxzhong@nimte.ac.cn (X. Fang).

https://doi.org/10.1016/j.polymer.2020.122218
Received 28 November 2019; Received in revised form 16 January 2020; Accepted 21 January 2020
Available online 31 January 2020
0032-3861/© 2020 Elsevier Ltd. All rights reserved.
N. Mushtaq et al.
and 4,40 -methylenedianiline, m-phenylenediamine (m-PDA) can give
less colored polymers [19]. In this study, TFDB is copolymerized with
rigid diamine m-PDA and a CF3 group containing flexible diamine bis
(4-amino-2-trifluoromethylphenyl)ether (TFODA).
Structural modifications in monomers, as well as chain-chain in­
teractions in polymer are undoubtedly important factors to vary the
properties of the final PAIs. Recently, wholly aromatic and semi-
aromatic transparent PAIs with different monomer sequence in poly­
mer main chain are reported. It was observed that the change in
monomer sequence significantly altered the transparency of the poly­
mers; however, its effect on CTE is not examined [15,19]. Hence, we
prepared two series of copolymers by altering position of diamines
structure between amide and imide groups (method A, PAI-2(a-d)) and
copolymerisation of TMAC with various diamines (method B, PAI-3
(a-b)) (Scheme 2). In this study, effect of monomer sequence in co­
polymers (PAI-2a, PAI-2b and PAI-3a) containing rigid comonomers
(TFDB and m-PDA) on CTE and transparency of PAIs is examined.
Moreover, flexible ether linkage containing diamine TFODA is also
introduced in copolymers (PAI-2c, PAI-2d and PAI-3b) to investigate the
dependence of flexible monomer sequence on CTE and transparency of
polymers.
2. Experimental
2.1. Materials
2,20 -Bis(trifluoromethyl)-[1,10 -biphenyl]-4,40 -diamine (TFDB) and
4,40 -oxybis(3-(trifluoromethyl)aniline) (TFODA) were obtained from
Changzhou Sunlight Pharmaceutical Co, Ltd. Benzene-1,3-diamine (m-
PDA), trimelletic anhydride (TMA), trimethylsilyl chloride (TMSCl),
dimethylaminopyridine (DMAP), triphenyl phosphite (TPP), calcium
chloride (CaCl2), pyridine and glacial acetic acid were purchased from
Aladdin Chemical Co. and used as received. Trimelletic acid chloride
(TMAC) was obtained from Aladdin Chemical Co. and stored in vacuum
desiccator. N,N-Dimehthlyacetamide (DMAc) and N-methyl-2-pyrroli­
done (NMP) were purified by distillation under reduced pressure over
calcium hydride before polymerization. All other commercially avail­
able reagent-grade chemicals were used without further purification.
2.2. Instrumentation
1
H NMR and 13C NMR spectra of monomers and polymers were
measured at 400 MHz on a Bruker 400 AVANCE III spectrometer, using
dimethyl sulfoxide (DMSO) as solvent. The Fourier transform infrared
spectra (FTIR) were obtained with a Thermo Nicolet 6700 FTIR spec­
trometer. Monomer and polymer samples were prepared with KBr pel­
lets and as thin films, respectively. The inherent viscosities were
measured with an Ubbelodhe viscometer at 30 � 0.1 � C in DMAc at a
concentration of 0.5 g/dL. Thermogravimetric analysis (TGA) was per­
formed on a PerkinElmer Diamond TG/DTA instrument at a heating rate
of 10 � C/min under nitrogen atmosphere (flow rate of 50 mL/min).
Differential scanning calorimetry (DSC) was carried out using Mettler
Toledo DSC at a heating rate of 20 � C/min under nitrogen atmosphere
with 50 mL/min gas flow. Mechanical measurements were taken using
five PI film samples by an Instron model 5567 at room temperature, and
the results were averaged. Dynamic mechanical analysis (DMA) was
performed on PI film samples on a TA Q800 at a heating of 3 � C/min
from 30 to 400 � C with a load frequency of 1 Hz in air atmosphere. The
wide-angle X-ray diffraction (WAXD) measurement of the polyimide
films was undertaken on a Bruker D8 Advance with Cu Kα radiation (40
kV, 40 mA) from 5 to 50� . The UV–vis spectra were recorded on a Per­
kinElmer lambda 950 spectrophotometer at room temperature in the
absorption mode. Thermomechanical analysis (TMA) was conducted
with a Shimadzu TMA-60, a fixed load of 1.0 g, heating rate of 5 � C/min
and nitrogen flow. The film size for TMA measurements was 5 mm wide
and 20 mm long. After a preliminary heating run to 200 � C and
2
Polymer 190 (2020) 122218
subsequent cooling to room temperature in the TMA chamber, data were
collected from the second heating run to eliminate the effects of absor­
bed water and residual stress.
2.3. Computational details
Various stacking structures of repeating units of PAIs with different
monomer sequence were searched using the Monte Carlo basin-hopping
(MCBH) [20,21] sampling method combined with density functional
tight-binding (DFTB) [22] calculations. For each of PAI-2a, PAI-2b,
PAI-2c, and PAI-2d 600 stacking structures were first sampled using the
MCBH method with constraints to keep stacking structures. Among them
the selected structures are further optimized via Gaussian 09 package
[23] within the framework of density functional theory (DFT) with the
ω97xd functional [24] and the 6–31g(d) basis set. The binding energy
elucidated by using the same functional and the 6–31 þ g (d, p) basis set,
together with the Boys’ basis set superposition error correction scheme
[25].
2.4. Monomers synthesis
Monomer 1a-1c were synthesized from TMA and aromatic diamines,
according to the reported method [11].
2.4.1. 2,20 -Bis(trifluoromethyl)-4,40 -bis(trimelletimide)biphenyl 1a
Compound 1a was obtained as white solid (yield, 56.1%). 1H NMR
(DMSO‑d6, 400 MHz, ppm): 13.30 (broad, COOH), 8.46 (dd, J ¼ 7.7, 1.3
Hz, 2H), 8.37 (s, 2H), 8.15 (d, J ¼ 7.9, 2H), 8.08 (d, J ¼ 1.8 Hz, 2H), 7.89
(dd, J ¼ 8.2, 1.8 Hz, 2H) and 7.71 (d, J ¼ 8.3 Hz, 2H). FTIR (KBr, cm 1):
2651–3548 (COOH); 1782 (asym C– – O str), 1728 (sym, C– – O str), 1492
(aromatic C– – C), 1371 (C–CN str), 1214, 1177 and 1129 (C–F in CF3),
and 727 (imide ring deformation).
2.4.2. 1,3-Bis(trimelletimide)phenylene 1b
Yellow solid (yield, 68.5%). 1H NMR (DMSO‑d6, 400 MHz, ppm):
13.82 (broad, COOH), 8.43 (dd, J ¼ 8.0, 1.0 Hz, 2H), 8.33 (s, 2H), 8.10
(d, J ¼ 7.7 Hz, 2H), 7.95 (s, 1H), 7.73 (t, J ¼ 7.7 Hz, 1H), 7.60 (t, J ¼ 8.6
Hz, 1H). FTIR (KBr, cm 1): 2648–3446 (COOH); 1779 (asym C– – O str),
1732 (sym, C– – O str), 1497 (aromatic C– – C), 1364 (C–CN str) and 722
(imide ring deformation).
2.4.3. 2,2’-(Oxybis(3-(trifluoromethyl)-4,1-phenylene))bis(trimelletimide)
1c
White solid (yield, 71.3%). 1H NMR (DMSO‑d6, 400 MHz, ppm):
13.82 (broad, COOH), 8.43 (d, J ¼ 7.7 Hz, 2H), 8.34 (s, 2H), 8.13 (d, J ¼
7.8, 2H), 8.04 (d, J ¼ 2.2 Hz, 2H), 7.85 (dd, J ¼ 8.8, 2.1, Hz, 2H) and
7.47 (d, J ¼ 8.8 Hz, 2H). 13C NMR (DMSO‑d6): 166.5, 166.2, 152.8,
137.1, 136.0, 135.3, 134.1, 132.5, 128.5, 127.3, 126.8, 124.6, 124.4,
123.9, 121.8, 121.4, 121.1, 120.7, 120.4, 119.1. FTIR (KBr, cm 1):
2641–3440 (COOH); 1779 (asym C– – O str), 1725 (sym, C–– O str), 1495
(aromatic C– C), 1385 (C–CN str) and 727 (imide ring deformation).
–
2.5. Polymerization
2.5.1. PAI-2(a-e)
A typical synthesis procedure for PAI-2(a-e) is illustrated by example
PAI-2a. A two necked flask equipped with Dean-Stark trap and nitrogen
inlet was charged with monomer 1a (4.0107 g, 6.0 mmol), m-PDA
(0.6488 g, 6.0 mmol) and 88 mL of NMP. Calcium chloride (2.80 g, 25.2
mmol), 9.6 mL of TPP (40.3 mmol) and 9 mL of pyridine (111.7 mmol)
were added to the reaction mixture and heated at 100 � C for 8 h. The
polymer solution was poured in ethanol under rapid stirring. Polymer
precipitate were filtered and washed with boiling ethanol twice, dried at
120 � C for 8 h in vacuum oven. Yield: 98%. The inherent viscosity of PAI-
2a in DMAc was 0.63 dL/g at 30 � C, measured with concentration of 0.5
g/dL 1H NMR (DMSO‑d6, 400 MHz, ppm): 10.80 (s, 2H), 8.63 (s, 2H),
N. Mushtaq et al.
8.53 (d, J ¼ 8.2 Hz, 2H), 8.20 (d, J ¼ 7.5 Hz, 2H), 8.10 (s, 2H), 7.93 (d, J
¼ 8.4 Hz, 2H), 7.73 (d, J ¼ 8.5 Hz, 2H), 7.62 (d, J ¼ 6.6 Hz, 2H), 7.43 (s,
2H). FTIR (thin film, cm 1): 3351 (NH str), 1779 (asym C– – O str of
imide); 1716 (sym C– O str of imide); 1667 (C– O str of amide), 1366
– –
(C–CN str), 1252 and 1215 (C–F in CF3) and 725 (imide ring
deformation).
PAI-2b (Yield: 98%): 1H NMR (DMSO‑d6, 400 MHz, ppm): 11.03 (s,
2H), 8.62 (s, 2H), 8.52 (d, J ¼ 8.0 Hz, 2H), 8.39 (s, 2H), 8.19 (d, J ¼ 8.0
Hz, 4H), 7.76 (s, 1H), 7.68 (s, 1H), 7.63 (d, J ¼ 7.2 Hz, 2H), 7.45 (d, J ¼
8.0 Hz, 2H). FTIR (thin film, cm 1): 1779 (asym C– – O str of imide); 1716
(sym C– – O str of imide); 1667 (C– – O str of amide), 1359 (C–CN str),
1245 and 1198 (C–F in CF3) and 720 (imide ring deformation). PAI-2c
(Yield: 97%): 1H NMR (DMSO‑d6, 400 MHz, ppm): 10.96 (s, 2H), 8.63
(s, 2H), 8.52 (d, J ¼ 7.2 Hz, 2H), 8.38 (s, 2H), 8.26–8.13 (m, 4H), 8.11 (s,
2H), 7.92 (d, J ¼ 8.0 Hz, 2H), 7.73 (d, J ¼ 8.4 Hz, 2H), 7.21 (d, J ¼ 8.0
Hz, 2H). FTIR (thin film, cm 1): 1783 (asym C– – O str of imide); 1726
(sym C– O str of imide); 1664 (C– O str of amide), 1365 (C–CN str),
– –
1253 and 1216 (C–F in CF3) and 721 (imide ring deformation). PAI-2d
(Yield: 97%): 1H NMR (DMSO‑d6, 400 MHz, ppm): 11.04 (s, 2H), 8.63
(s, 2H), 8.52 (d, J ¼ 6.4 Hz, 2H), 8.39 (s, 2H), 8.19 (s, 4H), 8.08 (s, 2H),
7.89 (d, J ¼ 8.8 Hz, 2H), 7.50–7.44 (m, 4H). FTIR (thin film, cm 1):
1781 (asym C– – O str of imide); 1720 (sym C– – O str of imide); 1668
(C–– O str of amide), 1375 (C–CN str), 1241 and 1213 (C–F in CF3) and
721 (imide ring deformation). PAI-2e (Yield: 98%): 1H NMR (DMSO‑d6,
400 MHz, ppm): 11.06 (s, 2H), 8.66 (s, 2H), 8.54 (d, J ¼ 5.6 Hz, 2H),
8.41 (s, 2H), 8.24–8.19 (m, 4H), 8.12 (s, 2H), 7.93 (d, J ¼ 9.2 Hz, 2H),
7.73 (d, J ¼ 9.6 Hz, 2H), 7.46 (d, J ¼ 7.2 Hz, 2H). FTIR (thin film, cm 1):
1782 (asym C– – O str of imide); 1721 (sym C– – O str of imide); 1681
(C–– O str of amide), 1367 (C–CN str), 1252 and 1209 (C–F in CF3).
2.5.2. PAI-3(a-c)
TMAC was reacted with equimolar diamines TFDB, m-PDA and
TFODA to synthesize PAI-3(a-c). A typical procedure for synthesis is
illustrated here by using example PAI-3a. A three-neck flask equipped
with a mechanical stirrer, nitrogen in-let and out-let was charged with
20 mL of DMAc. TFDB (4.8036 g, 15.0 mmol) and m-PDA (1.6221 g,
15.0 mmol) were dissolved in DMAc at room temperature, and reaction
mixture was cooled to 0 � C. TMSCl (3.2592 g, 30.0 mmol), DMAP
(0.3665 g, 3.0 mmol) and pyridine (2.1357 g, 27.0 mmol) were added
slowly in the reaction mixture, and reaction mixture temperature was
raised to room temperature and stirred for 15 min to synthesize silyated
diamine. The reaction solution again cooled to 0 � C and TMAC (6.3171
g, 30.0 mmol) was added followed by 18 mL of DMAc, and stirred for 15
min at 0 � C and then at room temperature for 12 h. The chemical
imidization was accomplished by using an acetic anhydride (120
mmol)/Py (60 mmol) mixture at 80 � C for 2 h. Polymer was precipitated
in ethanol (300 mL) under continous stirring, washed with boiling
ethanol twice, and dried in vacuum oven at 120 � C for 12 h. Yield: 99%.
1
H NMR (DMSO‑d6, 400 MHz, ppm): 11.03 (d, N–H), 10.89 (d, N–H),
10.76 (d, N–H), 8.62 (t, Ar–H), 8.51 (t, Ar–H), 8.39 (s, Ar–H), 8.18 (d,
Ar–H), 8.11 (s, Ar–H), 8.08 (s, Ar–H), 8.04 (s, Ar–H), 7.93–7.89 (m,
Ar–H), 7.78–7.72 (m, Ar–H), 7.68 (s, Ar–H), 7.62 (s, Ar–H), 7.45 (d,
Ar–H), 7.30 (d, Ar–H). FTIR (thin film, cm 1): 3338 (NH str), 1779
(asym C– – O str of imide); 1716 (sym C–
– O str of imide); 1670 (C– – O str
of amide), 1363 (C–CN str), 1248 and 1210 (C–F in CF3) and 720 (imide
ring deformation). PAI-3b (Yield: 98%): 1H NMR (DMSO‑d6, 400 MHz,
ppm): 11.04 (d, N–H), 10.95 (d, N–H), 8.63 (t, Ar–H), 8.51 (t, Ar–H),
8.40 (t, Ar–H), 8.22–8.17 (m, Ar–H), 8.11 (s, Ar–H), 8.08 (s, Ar–H), 8.04
(d, Ar–H), 7.89 (d, Ar–H), 7.73 (d, Ar–H), 7.64 (d, Ar–H), 7.49–7.42 (m,
Ar–H), 7.25–7.19 (m, Ar–H). FTIR (thin film, cm 1): 3348 (NH str),
1782 (asym C– – O str of imide); 1720 (sym C– – O str of imide); 1671
(C–– O str of amide), 1373 (C–CN str), 1245 and 1214 (C–F in CF3) and
721 (imide ring deformation). PAI-3c (Yield: 98%): 1H NMR (DMSO‑d6,
400 MHz, ppm): 11.07 (s, 2H), 8.67 (s, 2H), 8.55 (s, 2H), 8.39 (s, 2H),
8.25–8.20 (m, 4H), 8.12 (s, 2H), 7.94 (s, 2H), 7.75 (s, 2H), 7.47 (s, 2H).
FTIR (thin film, cm 1): 3340 (NH str), 1782 (asym C– – O str of imide);
3
Polymer 190 (2020) 122218
1723 (sym C– – O str of imide); 1680 (C–
– O str of amide), 1368 (C–CN
str), 1242 and 1208 (C–F in CF3).
2.5.3. Polymer films preparation
A typical procedure for film casting was used as follows: the purified
and dried polymer (1.0 g) was completely dissolved in 10 mL of DMAc.
The polymer solution was casted on a levelled glass plate and casted film
was dried in an oven at 80 � C for 1 h, 100 � C 1 h, 150 � C 1 h, 200 � C for 1
h and finally 280 � C for 1 h. Finally, PAI films were cooled down to room
temperature slowly and stripped off after immersion in water.
3. Results and discussion
3.1. Synthesis and spectroscopic characterization
Three diimide-diacid monomers 1a-1c were prepared from tri­
melletic anhydride (TMA) and diamines TFDB, m-PDA and TFODA
(Scheme 1) and structures of monomers were confirmed by 1H NMR, 13C
NMR and FTIR spectroscopy (Figs. S1 and S2). The FTIR spectra of the
diacids showed characteristic stretching vibrations of phthalimide rings
and O–H of COOH in 1782–1725 and 3548-2641 cm 1 region, respec­
tively. Spectroscopic results clearly supported the structure of diacid
monomers [11].
First series of polyamide-imide PAI-2(a-e) was prepared from diacid
monomers polycondensation with aromatic diamines by using triphenyl
phosphite and pyridine as condensing agents [26], to synthesize target
PAIs containing alternate combination of diamine unit between amide
and imide linkages (Scheme 2, method A). Another series of isomeric
polyamid-imides PAIs-3(a-c) with different monomer sequence was
synthesized from direct polycondensation of trimelletic acid chloride
(TMAC) with various aromatic diamines using TMSCl, pyridine and
DMAP, as shown in Scheme 2, method B. PAIs synthesized without
activation of TMAC demonstrated very low molecular weight, insuffi­
cient for film formation and high thermal and mechanical properties
[27]. Previous reports have revealed that in the in-situ silylation method
by TMSCl and the presence of a base such as pyridine was effective
method to obtain sufficient high molecular weight PAIs. In addition,
TMSCl ensure the small amount of water do not destroy moisture sen­
sitive TMAC to reproduce high molecular weight PAIs [28,29]. Co­
polymers prepared by Method B exhibited relatively lower inherent
viscosity due to different reactivity of silylated diamines. The reactivity
of silylated diamines is strongly favored owing to the better ability of the
trimethylsilyl group to act as a leaving group [28].
The inherent viscosities of synthesized both series of PAIs were in the
range 0.42–0.68 dL/g in dimethylacetamide at 30 � C (Table 1). The
structures of the PAIs were characterized by 1H NMR and FTIR spec­
troscopy. Representative 1H NMR spectra of PAI-2a and PAI-2d exhibi­
ted the absence of acidic proton chemical shift at 13–14 ppm and
appearance of amide proton at 10.80 ppm. PAI-2a comprising of amide-
m-PDA-amide linkage displayed amide signal at 10.80 ppm, and PAI-2b
with amide-TFDB-amide linkage demonstrated at 11.03 ppm. However,
PAI-3a containing random structure exhibited three amide signals at
11.06, 10.92, and 10.78 ppm with integral ratio of 2/0.6/1, respectively
(Fig. 1). From integral ratio it can be presumed that copolymerisation of
TMAC with TFDB and m-PDA resulted into more amide-TFDB-amide
linkage than amide-m-PDA-amide, probably due to high chemical
reactivity of acid chloride of TMAC and good reactivity of silylated TFDB
diamine. Amide signal in PAI-3a spectrum at 10.92 can be attributed to
amide-diamine-imide sequences, which have less probability due to
higher reactivity of acid chloride group than anhydride [30].
FTIR spectra of PAI-2(a-e) and PAI-3(a-c) displayed characteristic
C–– O stretching of amide group at 1664-1668 cm 1 (Fig. 2). TFDB
diamine is introduced between two imide or amide linkages that influ­
enced the C–F stretching of CF3 group of PAIs [34]. Unlike other PAIs,
instead of two distinctive peaks PAI-2b and PAI-2d containing TFDB
moiety only between two amide linkages exhibited one broad peak at
N. Mushtaq et al.
Scheme 1. Synthesis of imide group containing diacid monomers 1a-1c.
1245 and 1241 cm 1.
3.2. Optical properties
Both series of the polyamide-imides could form transparent, flexible
and tough films by casting the polymer solution in dimethylacetamide
on a glass plate and evaporation of solvent. The photographs of PAI films
of ~30 μm thickness are shown in Fig. 3 to highlight the difference in
transparency of both series of PAIs. UV–vis spectroscopy was carried out
to investigate the optical transparency of the synthesized PAI films. The
cut-off wavelength (λ0) values and the transmittances at 500 and 550 nm
from these spectra are listed in Table 2. Homopolymer PAI-3c synthe­
sized from TMAC and TFDB resulted into opaque film, while polymer
PAI-2e by method A produced a slight yellow film. At 550 nm, the
transmittance of PAI-2(a-d) and PAI-3(a-b) was in the range of 74–81%
and 86–87%, respectively (Fig. 4). The high transparency is attributed to
the presence of the bulky and electron-withdrawing CF3 groups in the
polymer main chain, which prohibits the formation of charge-transfer
complexes by sterically repelling adjacent chains, and lowers the elec­
tron density in the diamine moiety [31].
Optical transparency of PAIs is influenced by presence of A, B and C
segments in polymer main chain (Fig. 5). In contrast, optical trans­
parency of PAI-3(a-b) is higher than PAI-2(a-d). Such difference in the
result may arise due to asymmetric TMAC monomer which led to exis­
tence of all three segments (A, B and C), and resulted into random
monomer sequence and chain sequence irregularity. Among all co­
polymers, PAI-3a exhibited highest transparency with transmittance at
550 nm (T550) of 87%. However, optical transparency of alternate PAI-2
(a-d) is merely influenced by A and B segments (Fig. 5). The nature of
Ar2 in the B segment affected the coloration of PAI films more strongly
than Ar1 in the A segment. When rigid diamine m-PDA was located
between two imide groups in the PAI-2b polymer chains, transparency
decreased as compared to PAI-2a which have m-PDA between two amide
rings (Table 2) [19]. Similarly, PAI-2d containing TFDB diamine be­
tween two amide groups exhibited higher transparency than PAI-2c. In
this study, the order of electron-donating properties of diamines is as
follows m-PDA > TFODA > TFDB. It could be concluded that the weaker
the electron–donating nature of diamine in the segment A (between two
imides), higher the transparency of PAI. The reduction in charge transfer
complex (CTC) formation between a weak electron donating diamine
and dianhydride improved the optical transparency of the polyimide
film.
3.3. TMA and computation study
The coefficients of thermal expansion (CTE) were determined from
second heating scan of thermomechanical analysis (TMA) (Fig. 6,
Table 2). Rigid diamines m-PDA and TFDB based polyamide-imides PAI-
2a, PAI-2b and PAI-3a demonstrated comparable CTE of 23, 22 and 25
ppm/� C, respectively. Homopolymers PAI-2e and PAI-3a exhibited
4
Polymer 190 (2020) 122218
similar CTE behavior (20 and 21 ppm/� C), irrespective of the polymers
synthesis method. Copolymers PAI-3(a-b) displayed random monomer
sequence that’s why higher CTE than alternate PAI-2(a-d). However,
PAI-3a containing rigid diamines TFDB and m-PDA also exhibited some
extent of ordered arrangement with more amide-TFDB-amide linkage,
predicted from 1H NMR spectra of PAI-2(a-b) and PAI-3a (Fig. 1), and
could resulted into comparable CTE of PAI-3a with PAI-2(a-b). However,
symmetric PAI-2c and PAI-2d containing TFODA exhibited CTE of 24
and 32 ppm/� C, a difference of 8 ppm/� C. This may be attributed to
more restricted rotation of ether linkage in TFODA between two imide
groups than between amide groups. Moreover, asymmetric PAI-3b dis­
played highest CTE value of 35 ppm/� C.
In this study, it is explored that monomer sequence in copolymers
PAI-2(a-b) and PAI-3a containing two rigid diamines TFDB and m-PDA
greatly influenced the transparency of polymers while comparable CTE
irrespective of the sequence. One the other hand, monomer sequence in
PAI-2(c-d) and PAI-3b containing TFDB and flexible diamine TFODA
significantly controlled CTE and transparency depending upon the
monomer sequence in polymer main chain. The effect of monomer
sequence segment on CTE and transparency is greater in PAIs containing
flexible linkage than rigid diamines based PAIs.
The possible packing structures of alternate copolymers PAI-2(a-d)
were further investigated by DFT calculations. Fig. 7 shows the opti­
mized structures of the PAIs repeating units, along with binding energies
between the polymer chains, where the dianhydride and the diamine
groups of one chain are interacting with corresponding groups of
another chain [32]. Possible intermolecular hydrogen bonding between
amide and imide groups is shown in energy minimized structures. The
binding energies of PAI-2a and PAI-2c containing TFDB between imide
linkages were larger than copolymer PAI-2b and PAI-2d which have
TFDB between two amide groups. This suggests that restricted rotation
of biphenyl group between rigid imide groups kept the interactive
orientation with strong interlayer binding energy, which agrees with the
trend in CTE values of PAI-2c and PAI-2d, inferring that the binding
energy is inversely proportional of the coefficient of thermal expansion.
Biphenyl diamine TFDB moiety is present in all copolymers repeating
units of this study, and selected to observe the π-π stacking structures
distance between the phenyl rings. However, CTE did not show any
noticeable correlation with π-π stacking distance calculated by DFT
calculations. Fig. 8 shows the relationship between CTE and trans­
parency of PAIs. PAI-3a presented the best combination of low CTE
value of 25 ppm/� C and high transparency of T500 nm ¼ 85%.
3.4. Thermal properties
The thermal properties of PAIs were evaluated by thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC), and results
are tabulated in Table 2.
The glass transition temperature (Tg) is the key parameter for a
polymer while considering for the high temperature device fabrication
N. Mushtaq et al. Polymer 190 (2020) 122218

Scheme 2. Synthesis of polyamide-imides by method A (alternate sequence) and B (random sequence). Equimolar ratio (0.5/0.5) of diamines is employed in
method B.

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N. Mushtaq et al. Polymer 190 (2020) 122218

Table 1 and optical applications. Tgs of PAIs are measured from the second
Inherent viscosities, optical properties, CTE of polyamide-imides PAI-2(a-e) and heating scan of DSC (Fig. S3). PAI-2(a-d) synthesized from method A
PAI-3(a-c) films. consisting of more symmetric polymer chain packing displayed higher
PAIs ηinh (dL/ TFDB λ0 (nm)c T500 T550 CTE (ppm/ Tg values of 325–330 � C than homopolymers (PAI-2e and PAI-3c) and
g)a Ratiob (%)d (%)d �
C)e asymmetric PAI-3(a-b). The thermal degradation of PAIs in nitrogen and
PAI- 0.63 0.5 389 72 81 23 air atmosphere is examined by TGA curves (Fig. S4). Irrespective the
2a structure, all the PAIs showed similar degradation pattern, where, major
PAI- 0.52 0.5 405 64 74 22 weight loss occurred in the range of 450–650 � C. The char yields (CY) of
2b
PAIs at 800 � C in nitrogen were as high as 57%, indicating good thermal
PAI- 0.63 0.5 401 68 78 24
2c stability. The 10% weight-loss temperature T10% values of synthesized
PAI- 0.68 0.5 406 71 80 32 PAIs were observed at 452–501 � C and 322–492 � C in nitrogen and air
2d atmosphere, respectively (Table 2).
PAI- 1.48 1.0 390 75 77 20
2e
PAI- 0.42 0.5 393 85 87 25 3.5. Mechanical properties
3a
PAI- 0.49 0.5 399 83 86 35 The tensile properties of the PAIs tough and flexible films are listed in
3b
Table 2. PAIs-2(a-d) and PAI-3(a-b) demonstrated high storage moduli
PAI- 1.0 1.0 394 67 72 21
3c
of 3.9–4.9 and 3.4–3.8 GPa, respectively. m-PDA based alternate
a
polyamide-imides PAI-2(a-b) exhibited lower tensile strengths of 96–97
Inherent viscosity measured at 0.5 g/dL concentration at 30 � C in MPa than analogue PAI-3a with tensile strength of 115 MPa. On the
dimethylacetamide.
b other hand, TFODA based alternate polyamide-imides PAI-2(c-d)
Molar fraction of TFDB repeating unit in the total diamine content.
c exhibited higher tensile strengths of 109–129 MPa than PAI-3b with 97
λ0 Cut-off wavelength of PAI films.
d
Transparency of PAI films at 500 and 550 nm obtained from UV–vis spectra. MPa. PAI-2(c-d) and PAI-3b containing flexible ether linkage displayed
e
CTE values calculated from TMA second heating scan. longer elongation before break than PAI-2(a-b) containing rigid diamine
m-PDA. Dynamic mechanical analysis (DMA) is performed to examine

Fig. 1. 1H NMR spectra of PAI-2a, PAI-2b and PAI-3a.

6
N. Mushtaq et al. Polymer 190 (2020) 122218

Fig. 2. FTIR spectra of PAIs films.

Fig. 3. The photographs of copolymers and homopolymers films with a thickness of around 30 μm (Turbidity of homopolymer PAI-3c film is illustrated with
black background).

Table 2
Thermal and mechanical properties of polyamide-imides PAI-2(a-e) and PAI-3(a-c) films.
PAIs Tg (� C)a T10% (� C)b CYc Initial Modulus (GPa)d Tensile Strength (MPa)d Elongation at break (%)d

DSC DMA N2 Air

PAI-2a 329 352 495 400 49 3.9 97 3.7

PAI-2b 330 354 501 438 57 4.0 96 3.0
PAI-2c 325 344 489 322 53 3.9 109 4.7
PAI-2d 328 348 452 363 52 4.9 129 4.1
PAI-2e 321 355 515 514 51 5.8 159 5.4
PAI-3a 304 ̶ 493 492 54 3.8 115 5.2
PAI-3b 291 ̶ 489 477 44 3.4 97 4.9
PAI-3c 301 340 519 534 48 4.9 116 3.8
a
Obtained from DSC at a heating rate of 20 � C/min in nitrogen.
b
T10% ¼ 10% weight loss temperature obtained by TGA at a heating rate of 10 � C/min in nitrogen and air.
c
CY char yield at 800 � C in nitrogen.
d
the mechanical properties were measured using about 30 μm thick films.

the mechanical properties of PAIs as a function of temperature (Figs. 9 relaxation process (Fig. 9b, Table S1) [33,34]. The peak temperature
and S5). in the tan δ curves is regarded as the Tg of the polymer. The Tgs of PAIs by
DMA of the films exhibited α and β transitions (observed in Tan delta DMA were between in the range of 344–354 � C, slight higher than
curve), probably corresponding to glass transition and rotation-related measured by DSC. High Tg and excellent mechanical properties may

7
N. Mushtaq et al. Polymer 190 (2020) 122218

resulted into poor intermolecular packing [31].

The mean intermolecular distances (d-spacing) of these PAIs were
calculated from the maxima of the broad diffraction peaks by Bragg’s
equation. PAIs-2(a-d) demonstrated the diffraction peak at 2Ѳ ¼
21.8–24.1� with d-spacing of 3.6–4.1 Å, whereas PAIs-3(a-b) exhibited
diffraction peak at 2Ѳ ¼ 15.3–23.7� with d-spacing of 3.8–5.8 Å. WAXD
data indicated that the d-spacing are greater for less rigid diamine
TFODA and asymmetric TMAC, which offered loose chain packing and
aggregation. It could be concluded that m-PDA based PAI-2(a-b) and
PAI-3a have relatively denser polymer chain packing than TFODA based
PAIs-2(c-d) and PAI-3b. WXRD result is consistent with other findings
from CTE, Tg, and mechanical properties.

4. Conclusion

Two series of polyamide-imides were synthesized from poly­

Fig. 4. Ultraviolet–vis spectra of PAIs Films.
have caused due to the structural rigidity induced by imide groups and
biphenyl group in polymer main chain. However, TMAC based polymers
PAI-3a and PAI-3b synthesized by method B yielded at 250 and 220 � C,
respectively, revealing poor mechanical stability at high temperature.
3.6. Solubility behavior
condensation of diimide-diacid (method A) and TMAC (method B) with
aromatic diamines. PAI-2(a-d) comprised of symmetric alternate
sequence of monomers, synthesized from diimide-diacids showed higher
Tg (an increase of about 40 � C) and comparable decomposition tem­
peratures T10% with asymmetric polyamide-imides PAI-3(a-b). On the
other hand, TMAC based PAIs possibly composed of a disordered (or
random) chain sequence exhibited higher transparency �86% and lower
Tg values. The mechanical properties of TFODA based PAIs were found

The qualitative solubility of homopolymers and copolymer series

PAI-2(a-e) and PAI-3(a-c) was examined in various organic solvents, and
the results are listed in Table 3. Both series of PAIs exhibited good sol­
ubility in polar organic solvents due to bulky CF3 groups and amide
linkage. PAI-2c and PAI-2d consisting of flexible ether linkage displayed
partial solubility in less polar solvent THF. The introduction of m-PDA
between two imide rings in PAI-2b experienced steric hindrance and
slight twisted orientation (Fig. S6) which may also result into better
organosolubility than PAI-2a and PAI-3a [19,35].

3.7. Wide-angle X-ray diffraction (WAXD)

The crystallinity and chain packing of the copolymer films was

analysed by wide-angle X-ray diffraction (WAXD). Regardless of the
synthesis method and employed diamine structure, the WAXD patterns
of all the PAI films were broad without obvious peak features, indicating
the amorphous nature of PAIs (Fig. 10). The amorphous nature of these
polyamide-imides could be attributed to the bulky CF3 group containing
Fig. 6. TMA (second heating scan) results of PAIs Films.
diamines and imide groups in the polymer chain backbone, which

Fig. 5. Monomer sequence segments (A, B and C) in polymer main chains of PAI-2(a–e) and PAI-3(a–c).

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N. Mushtaq et al. Polymer 190 (2020) 122218

Fig. 7. Optimized structures of poly(amide-imide)s (A) PAI-2a, (B) PAI-2b, (C) PAI-2c and (D) PAI-2d repeating units and binding energies by DFT calculations.
Green dotted lines indicate hydrogen bonds. The π-π stacking structures between two biphenyl units along with the distances (red dotted line) between two phenyl
rings are separately shown on the right side. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

9
N. Mushtaq et al. Polymer 190 (2020) 122218

Table 3
Solubility behavior of polyamide-imides.
PAIs Solvents

m-Cresol NMP DMAc DMF DMSO THF CHCl3

PAI-2a þ þ þ þ þ – –
PAI-2b þ þ þ þ þ þ- þ-
PAI-2c þ þ þ þ þ þ- þ-
PAI-2d þ þ þ þ þ þ- þ-
PAI-2e þ þ þ þ þ þ- –
PAI-3a þ þ þ þ þ – –
PAI-3b þ þ þ þ þ – –
PAI-3c þ þ þ þ þ þ- –

þ Soluble at room temperature, þ- partially soluble, - insoluble.

Fig. 8. Relationship of transmittance (T500) and CTE in the PAIs.

higher than rigid diamine m-PDA based PAIs. PAI-3a synthesized from
direct polycondensation of TMAC with m-PDA and TFDB tailored the
excellent properties of higher transparency 87%, CTE of 25 ppm/� C and
Tg of 304 � C. It could be recognized from comparison of PAI-2(a-b) and
PAI-3a that method B using direct polycondensation of commercially
available TMAC with rigid diamines is better method than method A to
obtain transparent and low CTE polyamide-imide films.

Fig. 10. WAXD curves of PAIs with d spacing.

Declaration of competing interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

CRediT authorship contribution statement

Nafeesa Mushtaq: Conceptualization, Methodology, Writing -

original draft. Qiaodi Wang: Methodology, Data curation. Guofei
Chen: Resources. Beenish Bashir: Software, Validation. Haoji Lao:
Methodology, Data curation. Yuanming Zhang: Formal analysis,
Investigation. Lala Rukh Sidra: Investigation. Xingzhong Fang:
Supervision.

Acknowledgements

This work was financially supported by National Key R&D Program

of China (Grant No. 2018YFA0209200), research fund for international
young scientists (No. 51950410586), by National Natural Science
Foundation of China, Science and Technology Planning Project of
Guangdong Province, China (No: 2016B090906004), the program for
Ningbo Municipal Science and Technology Innovative Research Team
(No. 2016B10005 and 2015B11002) and Natural Science Foundation of
Ningbo City (No. 2015A610026).

Fig. 9. (a) Storage modulus and (b) Tan delta curves of PAIs Films as function Appendix A. Supplementary data
of temperature by DMA.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2020.122218.

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N. Mushtaq et al. Polymer 190 (2020) 122218

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