To provide polyimide (PI) with high heat resistance and ultra-low coefficient of thermal expansion (CTE) for use in flexible display substrates, a novel diamine with bisbenzimidazole and bisamide groups, namely N,N'-(1H,1'H-[5,5'-bibenzo[d]imidazole]-2,2'-diyl)bis(4-aminobenzamide) (BZBA), was designed and successfully synthesized. Several poly(benzimidazole-amide-imide) (PBIAI) films were prepared by thermal imidization with 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and 4,4'-(hexafluoroisopropylindene)-diphthalic anhydride (6FDA), respectively. Among them, BZBA-BPDA has a high glass transition temperatures (Tg = 345 °C) while achieving an extremely low coefficients of thermal expansion (CTE = 1.9 ppm K−1), meeting the processing requirements of polymer flexible substrates in OLED devices. The effects of different dianhydrides on the performance of PBIAIs were compared, providing a meaningful reference for further adjusting the PI molecular structure to meet specific requirements for industrial polymer films.
HeremansPTripathiAKde Jamblinne de MeuxA, et al.Mechanical and electronic properties of thin‐film transistors on plastic, and their integration in flexible electronic applications. Adv Mater2016; 28: 4266–4282.
2.
UmmartyotinSJuntaroJSainM, et al.Development of transparent bacterial cellulose nanocomposite film as substrate for flexible organic light emitting diode (OLED) display. Ind Crops Prod2012; 35: 92–97.
3.
SiqueiraGBrasJDufresneA. Cellulosic bionanocomposites: a review of preparation, properties and applications. Polymers2010; 2: 728–765.
4.
HasegawaMHoshinoYKatsuraN, et al.Superheat-resistant polymers with low coefficients of thermal expansion. Polymer2017; 111: 91–102.
5.
ChengICKattamisALongK, et al.Stress control for overlay registration in a‐Si: H TFTs on flexible organic‐polymer‐foil substrates. J Soc Inf Disp2005; 13: 563–568.
6.
NakanoSSaitoNMiuraK, et al.Highly reliable a‐IGZO TFTs on a plastic substrate for flexible AMOLED displays. J Soc Inf Disp2012; 20: 493–498.
7.
LewisJ. Material challenge for flexible organic devices. Mater Today2006; 9: 38–45.
8.
ChoiM-CKimYHaC-S. Polymers for flexible displays: from material selection to device applications. Prog Polym Sci2008; 33: 581–630.
9.
DocampoPBallJMDarwichM, et al.Efficient organometal trihalide perovskite planar-heterojunction solar cells on flexible polymer substrates. Nat Commun2013; 4: 2761.
10.
NiH-jLiuJ-gWangZ-h, et al.A review on colorless and optically transparent polyimide films: chemistry, process and engineering applications. J Ind Eng Chem2015; 28: 16–27.
11.
ParkJ-JShinS-SLeeJ-Y, et al.Effect of conductor radius of polyesterimide-polyamideimide enameled round wire on insulation breakdown voltage and insulation lifetime. Trans Electr Electron Mater2015; 16: 146–150.
12.
YuXLiangWCaoJ, et al.Mixed rigid and flexible component design for high-performance polyimide films. Polymers2017; 9: 451.
WangJWuGTianG, et al.Study on the orientation structure and thermal dimensional stability of polyimide films based on infrared dichroism method. J Polym Res2024; 31: 25.
15.
MaPDaiCWangH, et al.A review on high temperature resistant polyimide films: heterocyclic structures and nanocomposites. Compos Commun2019; 16: 84–93.
16.
ZhengHGongDPangY, et al.Synthesis and properties of poly (ester imide) copolymers from 3, 3′, 4, 4′-biphenyltetracarboxylic dianhydride, 2, 2′‐bis (trifluoromethyl) benzidine, and 4‐aminophenyl‐4′‐aminobenzoate. J Appl Polym Sci2024: e55182.
17.
JiangXChenKLiC, et al.Ultralow coefficient of thermal expansion and a high colorless transparent polyimide film realized through a reinforced hydrogen-bond network by in situ polymerization of aromatic polyamide in colorless polyimide. ACS Appl Mater Interfaces2023; 15: 41793–41805.
18.
HeZRenXWangZ, et al.Preparation and characterization of light-colored polyimide nanocomposite films derived from a fluoro-containing semi-alicyclic polyimide matrix and colloidal silica with enhanced high-temperature dimensionally stability. Polymers2023; 15: 3015.
19.
WangSZhouHDangG, et al.Synthesis and characterization of thermally stable, high‐modulus polyimides containing benzimidazole moieties. J Polym Sci, Part A: Polym Chem2009; 47: 2024–2031.
20.
LuoLYaoJWangX, et al.The evolution of macromolecular packing and sudden crystallization in rigid-rod polyimide via effect of multiple H-bonding on charge transfer (CT) interactions. Polymer2014; 55: 4258–4269.
21.
ZhuangYLiuXGuY. Molecular packing and properties of poly (benzoxazole-benzimidazole-imide) copolymers. Polym Chem2012; 3: 1517–1525.
22.
LuoLDaiYYuanY, et al.Control of head/tail isomeric structure in polyimide and isomerism‐derived difference in molecular packing and properties. Macromol Rapid Commun2017; 38: 1700404.
23.
LianMLuXLuQ. Synthesis of superheat-resistant polyimides with high T g and low coefficient of thermal expansion by introduction of strong intermolecular interaction. Macromolecules2018; 51: 10127–10135.
24.
QianGChenHSongG, et al.Superheat-resistant polyimides with ultra-low coefficients of thermal expansion. Polymer2020; 196: 122482.
25.
YanXDaiFKeZ, et al.Synthesis of colorless polyimides with high Tg from asymmetric twisted benzimidazole diamines. Eur Polym J2022; 164: 110975.
26.
HasegawaMWatanabeYTsukudaS, et al.Solution‐processable colorless polyimides with ultralow coefficients of thermal expansion for optoelectronic applications. Polym Int2016; 65: 1063–1073.
27.
HasegawaMIshigamiTIshiiJ, et al.Solution-processable transparent polyimides with low coefficients of thermal expansion and self-orientation behavior induced by solution casting. Eur Polym J2013; 49: 3657–3672.
28.
QianGDaiFChenH, et al.Polyimides with low coefficient of thermal expansion derived from diamines containing benzimidazole and amide: synthesis, properties, and the N‐substitution effect. J Polym Sci2021; 59: 510–518.
29.
TomlinDFratiniAHunsakerM, et al.The role of hydrogen bonding in rigid-rod polymers: the crystal structure of a polybenzobisimidazole model compound. Polymer2000; 41: 9003–9010.
30.
ChenHDaiFHuM, et al.Heat‐resistant polyimides with low CTE and water absorption through hydrogen bonding interactions. J Polym Sci2021; 59: 1942–1951.
31.
LiuYTangATanJ, et al.Synthesis, properties, and molecular simulations of high‐barrier polyimide containing carbazole moiety and amide group in the main chain. J Polym Sci2020; 58: 3467–3479.
32.
YangZGuoHKangC, et al.Synthesis and characterization of amide-bridged colorless polyimide films with low CTE and high optical performance for flexible OLED displays. Polym Chem2021; 12: 5364–5376.
33.
MustoPKaraszFMacKnightW. Fourier transform infra-red spectroscopy on the thermo-oxidative degradation of polybenzimidazole and of a polybenzimidazole/polyetherimide blend. Polymer1993; 34: 2934–2945.
34.
QingSHuangWYanD. Synthesis and characterization of thermally stable sulfonated polybenzimidazoles obtained from 3, 3′‐disulfonyl‐4, 4′‐dicarboxyldiphenylsulfone. J Polym Sci, Part A: Polym Chem2005; 43: 4363–4372.
35.
HeZWangGWeiS, et al.A novel fluorinated acid-base sulfonated polyimide membrane with sulfoalkyl side-chain for vanadium redox flow battery. Electrochim Acta2021; 399: 139434.
36.
ChoiMYLeeSJKwacLK, et al.Effects of diamine isomers on the properties of colorless and transparent copoly (amide imide) s. RSC Adv2021; 11: 30479–30486.
37.
MustoPKaraszFMacKnightW. Hydrogen bonding in polybenzimidazole/polyimide systems: a Fourier-transform infra-red investigation using low-molecular-weight monofunctional probes. Polymer1989; 30: 1012–1021.
38.
ZhangKYuQZhuL, et al.The preparations and water vapor barrier properties of polyimide films containing amide moieties. Polymers2017; 9: 677.
39.
LuoLPangYJiangX, et al.Preparation and characterization of novel polyimide films containing amide groups. J Polym Res2012; 19: 1–7.
40.
AhnT-KKimMChoeS. Hydrogen-bonding strength in the blends of polybenzimidazole with BTDA-and DSDA-based polyimides. Macromolecules1997; 30: 3369–3374.
41.
GuerraGChoeSWilliamsDJ, et al.Fourier transform infrared spectroscopy of some miscible polybenzimidazole/polyimide blends. Macromolecules1988; 21: 231–234.
42.
SongGZhangXWangD, et al.Negative in-plane CTE of benzimidazole-based polyimide film and its thermal expansion behavior. Polymer2014; 55: 3242–3246.
43.
ZhuangYGuY. Poly (benzoxazole-amide-imide) copolymers for interlevel dielectrics: interchain hydrogen bonding, molecular arrangement and properties. J Polym Res2013; 20: 1–8.
44.
DuanGLiuSJiangS, et al.High-performance polyamide-imide films and electrospun aligned nanofibers from an amide-containing diamine. J Mater Sci2019; 54: 6719–6727.
45.
WakitaJJinSShinTJ, et al.Analysis of molecular aggregation structures of fully aromatic and semialiphatic polyimide films with synchrotron grazing incidence wide-angle X-ray scattering. Macromolecules2010; 43: 1930–1941.
46.
KimKYooTKimJ, et al.Effects of dianhydrides on the thermal behavior of linear and crosslinked polyimides. J Appl Polym Sci2014; 132.
47.
NuriogluAGAkpinarHKanikFE, et al.Further investigation of intramolecular H-bonding in benzimidazole and EDOT containing monomer. J Electroanal Chem2013; 693: 23–27.
48.
KerberSBrucknerJWozniakK, et al.The nature of hydrogen in x‐ray photoelectron spectroscopy: general patterns from hydroxides to hydrogen bonding. J Vac Sci Technol A1996; 14: 1314–1320.
49.
StevensJGainarAJayeC, et al.NEXAFS and XPS of p-Aminobenzoic acid polymorphs: the influence of local environment. Proc J Phys Conf Ser2016; 712: 012133. IOP Publishing.
50.
Bouchet-FabreBZellamaKGodetC, et al.Comparative study of the structure of a-CNx and a-CNx:H films using NEXAFS, XPS and FT-IR analysis. Thin Solid Films2005; 482: 156–166.
51.
SunZLiuMYiL, et al.High glass transition of organo-soluble copolyimides derived from a rigid diamine with tert-butyl-substituted triphenylpyridine moiety. RSC Adv2013; 3: 7271–7276.
52.
ChoiHChungISHongK, et al.Soluble polyimides from unsymmetrical diamine containing benzimidazole ring and trifluoromethyl pendent group. Polymer2008; 49: 2644–2649.
53.
ShaoLChungT-SPramodaK. The evolution of physicochemical and transport properties of 6FDA-durene toward carbon membranes; from polymer, intermediate to carbon. Micropor Mesopor Mat2005; 84: 59–68.
54.
SazanovYNFlorinskyFKotonM. Investigation of thermal and thermooxidative degradation of some polyimides containing oxyphenylene groups in the main chain. Eur Polym J1979; 15: 781–786.
55.
PramodaKChungTLiuS, et al.Characterization and thermal degradation of polyimide and polyamide liquid crystalline polymers. Polym Degrad Stabil2000; 67: 365–374.
56.
QinHSuQZhangS, et al.Thermal stability and flammability of polyamide 66/montmorillonite nanocomposites. Polymer2003; 44: 7533–7538.
57.
KeZWangMGuQ, et al.Polyimides with super‐high T g and ultra‐low coefficient of thermal expansion from N‐substituted bibenzimidazole diamines. J Polym Sci2023; 61: 174–182.
58.
PottigerMTCoburnJCEdmanJR. The effect of orientation on thermal expansion behavior in polyimide films. J Polym Sci, Part B: Polym Phys1994; 32: 825–837.
59.
JiaoLDuZDaiX, et al.Based on rigid xanthone group and hydrogen bonding to construct polyimide films with low coefficient of thermal expansion, high temperature resistance, and fluorescent property. Eur Polym J2022; 173: 111260.
60.
JouJ-HHuangP-TChenH-C, et al.Coating thickness effect on the orientation and thermal expansion coefficient of polyimide films. Polymer1992; 33: 967–974.
61.
WangZ-HChenXYangH-X, et al.The in-plane orientation and thermal mechanical properties of the chemically imidized polyimide films. Chin J Polym Sci2019; 37: 268–278.
62.
HasegawaMOkudaKHorimotoM, et al.Spontaneous molecular orientation of polyimides induced by thermal imidization. 3. Component chain orientation in binary polyimide blends. Macromolecules1997; 30: 5745–5752.
63.
HasegawaMMatanoTShindoY, et al.Spontaneous molecular orientation of polyimides induced by thermal imidization. 2. In-plane orientation. Macromolecules1996; 29: 7897–7909.
64.
HasegawaMIshigamiTIshiiJ. Optically transparent aromatic poly (ester imide) s with low coefficients of thermal expansion (1). Self-orientation behavior during solution casting process and substituent effect. Polymer2015; 74: 1–15.
65.
LuoLZhangJHuangJ, et al. The dominant factor for mechanical property of polyimide films containing heterocyclic moieties: in‐plane orientation, crystallization, or hydrogen bonding. J Appl Polym Sci2016; 133(39). DOI: 10.1002/app.44000.
66.
ChenWChenWZhangB, et al.Thermal imidization process of polyimide film: interplay between solvent evaporation and imidization. Polymer2017; 109: 205–215.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
