封端型低膨胀聚酰亚胺薄膜的制备及性能研究

以均苯四甲酸二酐（PMDA）、3,3’,4,4’-联苯四甲酸二酐（s-BPDA）为二酐单体,对苯二胺（p-PDA）、4,4’-二氨基二苯醚（ODA）为二胺单体,偏苯三酸酐（TMA）为封端剂,共聚制备了封端型聚酰亚胺（PI）浆料,并经热亚胺化得到封端型耐高温聚酰亚胺薄膜。利用傅里叶红外光谱对材料的化学结构进行了表征,研究了聚酰亚胺薄膜的热学性能和力学性能。结果表明,薄膜完全亚胺化,且末端羧基在升温过程中脱羧产生联苯键交联结构。此外,随着封端含量的增多,聚酰亚胺薄膜的耐热性能和力学性能得到改善。与未封端的聚酰亚胺薄膜相比,封端型耐高温聚酰亚胺薄膜的玻璃化转变温度上升8～15℃,1%热失重温度提高了10～24℃,而且热膨胀得到抑制,PI-8薄膜的线性热膨胀系数仅为4.16×10-6/℃。     

含烷基取代基柔性聚酰亚胺薄膜的制备

以柔性二胺单体1,3-双(4-氨基苯氧基)苯(134BAPB)和含支链二胺单体3,3′-二乙基-4,4′-二氨基二苯甲烷(DEMMD)与3,3′,4,4′-二苯酮四酸二酐(BTDA)进行三元共聚,制备了一系列聚酰亚胺(PI)薄膜。通过傅里叶红外光谱、差示扫描量热仪、热重分析仪、热机械分析仪及电子万能材料试验机对材料的结构、热性能和力学性能进行了表征。结果表明PI薄膜已经成功制备,热性能与力学性能良好。     

耐高温单组分环氧胶粘剂的制备

以3,3’-二氨基-4,4’-二羟基联苯（DADHBP）、2,2-双[4-（4-氨基苯氧基）苯基】丙烷（BAPOPP）、3,3’,4,4’-四羧基二苯醚二酐（ODPA）为主原料合成了合酚羟基的聚酰亚胺树脂（HPI）;以HPI为耐高温增韧剂,与N,N,N’,N’-四缩水甘油基-4,4’-二氨基二苯甲烷（TGDDM）、固化剂等配制了综合性能优异的耐高温单组分环氧胶粘剂。     

微波辐射合成聚酰胺酸和聚酰亚胺的研究

在N,N’-二甲基甲酰胺溶剂中,以均苯四甲酸酐和3,3’,4,4’-二苯酮四羧酸二酐为二酐单体,4,4’-二氨基二苯醚和4,4’-二氨基二苯甲烷为二胺单体,采用微波辐射低温溶液共缩聚,合成了聚酰胺酸(PAA)预聚体,然后亚胺化脱水、环化,生成共缩聚聚酰亚胺(PI)。通过红外光谱(FT-IR)、特性粘度[η]和热重分析(TG)等对聚合物进行了一系列的结构表征和性能测试。结果表明,微波辐射溶液聚合能够提高PAA的特性粘数及产率,微波的引入大大缩短了反应时间;FT-IR表明,在1 775 cm-1和1 724 cm-1处观察到聚酰亚胺特征峰;TG表明,PI的5%热失重温度(Td5%)为477℃,10%热失重温度(Td10%)为553℃。     

二层法双面挠性覆铜板用热塑性聚酰亚胺的合成与应用研究

选用合适的单体芳香二酐二苯甲酮四酸二酐（BTDA）、2,2’-双[4-（3,4-二羧基苯氧基）苯基]丙烷四羧酸二酐（BPADA）和芳香二胺3,3′,5,5′-四甲基-4,4′-二氨基二苯甲烷（AMD）、4,4′-二氨基二苯甲烷（MDA）、4,4′-二氨基二苯醚（ODA）,3,4＇-二氨基二苯醚（3,4＇-ODA）根据不同配比反应得到聚酰胺酸,用乙酸酐／三乙胺经化学亚胺化得到热塑性聚酰亚胺（TPI）,将其用N-甲基吡咯烷酮（NMP）溶解配成一定固含量的胶液,涂覆铜箔烘干溶剂得到二层挠性覆铜板（2L—FCCL）,然后将2L—FCCL高温压合制备双面挠性覆铜板,其剥离强度较高。     

基于酚酞结构共聚型高可溶性聚酰亚胺的合成与性能

以邻甲酚酞与2-氯-5-硝基三氟甲苯为起始原料,通过两步有机反应——芳香亲核取代和氧化还原反应得到芳香二胺单体——4,4"-(2,2’三氟甲基)-二氨基苯氧基-3,3"-二甲基酚酞。利用共聚改性的思路,由两种二胺单体〔4,4"-(2,2"三氟甲基)-二氨基苯氧基-3,3"-二甲基酚酞和2,6-二氨基甲苯〕与一种二酐单体3,3",4,4"-二苯醚四甲酸二酐（ODPA）通过不同投料比以一步法高温缩聚制备得到同时含酚酞、三氟甲基和烷基结构系列共聚型聚酰亚胺。该系列共聚型聚酰亚胺具有优异的溶解性,在室温下不仅可溶于常见的高沸点溶剂：N-甲基吡咯烷酮（NMP）,N,N-二甲基乙酰胺（DMAc）、N,N-二甲基甲酰胺（DMF）和二甲基亚砜（DMSO）,在低沸点溶剂氯仿（CHCl3）、二氯甲烷（CH2Cl2）和四氢呋喃（THF）中也表现出优异的溶解性,可便利地通过其溶液浇筑制备得到系列高性能聚酰亚胺膜材料。该类膜材料玻璃化转变温度在275~314 ℃,其在N2和O2氛围中热失重10%时的温度分别为477~507 ℃和477~49 0 ℃。该类膜材料具有低的介电常数和良好的力学性能：其在1 MHz下介电常数在2.69~2.92之间,拉伸强度、弹性模量和断裂伸长率分别在80~92 MPa、1.2~1.8 GPa和9.2 %~13.5%之间。     

冰浴法制备浅色透明聚酰亚胺薄膜

采用冰浴法,以二胺单体1,4-苯二甲胺(P-XDA)与二酐单体4,4'-氧双邻苯二甲酸酐(ODPA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)合成了两种聚酰亚胺(PI)薄膜.在二元聚合的基础上,引入脂环二胺4,4'-二氨基二环己基甲烷(PACM)进行三元聚合得到两种PI薄膜.通过红外光谱、紫外可见光谱、热机械...     

基于酚酞结构高可溶性聚酰亚胺的合成与性能

以百里香酚酞、对氟硝基苯为起始原料,通过芳香亲核取代和氧化还原反应得到新型芳香二胺单体5,5’-二异丙基-4,4’-二氨基苯氧基-2,2’-二甲基酚酞。该二胺单体分别与3,3’,4,4’-二苯醚四甲酸二酐、3,3’,4,4’-二苯酮四羧酸二酐和3,3’,4,4’-联苯四甲酸二酐以一步法高温缩聚制得了一系列同时含酚酞Cardo结构及异丙基和甲基侧基的高可溶性聚酰亚胺(PI-1、PI-2和PI-3)。该系列聚酰亚胺具有优异的溶解性,室温下不仅可溶于高沸点溶剂N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜,而且能溶于低沸点溶剂氯仿,二氯甲烷和四氢呋喃,可通过其溶液浇铸制得一系列高性能聚酰亚胺薄膜。所制聚酰亚胺薄膜具有较高的光学透明性,截断波长在324～365 nm之间,450 nm的透过率在56%～78%之间。该系列薄膜玻璃化转变温度在266～289℃之间,在N₂和O₂下10%热失重温度均≥432℃。其拉伸强度在77～95 MPa之间,断裂伸长率在9.1%～13.0%之间,1 MHz下介电常数为2.79～3.01 F/m,...     

DMFC用磺化聚酰亚胺质子交换膜的合成与性能

以一种磺化二胺单体2,2′-二磺酸基-4,4′-二苯醚二胺(S-ODA)与非磺化单体4,4′-二苯醚二胺(ODA),及二酐单体3,3′,4,4′-二苯甲酮四羧酸二酐(BTDA)为原料,采用高温一步法直接聚合,得到了一系列磺化聚酰亚胺(SPI)质子交换膜材料,并用红外光谱对聚合物进行了表征.通过改变聚合体系中磺化单体与非磺化单体的比例控制聚合物的磺化度,并研究了材料的组成对膜的电导率、吸水率等性能的影响。     

4-（3，5-二氨基苯甲酸甲酯基）三苯胺的合成及其聚酰亚胺

以三苯胺为原料,通过Vilsmeier—Haack反应、酯化和还原等反应合成了含三苯胺基团的二胺单体4-（3,5-二氨基苯甲酸甲酯基）三苯胺,然后使它和4,4’-二氨基二苯醚与2,2-双[4-（3,4-二羧酸基苯氧基）苯基]丙烷二酐在N-甲基-2-吡咯烷酮溶剂中进行共聚合反应,经热环化脱水得到含三苯胺基团的聚酰亚胺。采用FTIR、1HNMR、UV—Vis、荧光分光光度计等仪器对合成的聚酰亚胺结构和性能进行了表征。结果表明,含三苯胺基团聚酰亚胺呈现明显的荧光特性。     

Copolyimides using 3-phenyl tricyclo [6,2,2,02,7] dodeca-2,11-ene-5,6,9,10-tetracarboxylic dianhydride as a thermosetting functional group: Preparation,characterization, and thermal curing chemistry

Copolyimides were prepared by the reaction of 4,4-oxydianiline (ODA) with two dianhydrides, namely, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and 3-phenyl tricyclo [6,2,2,0^2,7] dodeca-2,11-ene-5,6,9,10-tetracarboxylic dianhydride (PTDDA). ODA and BTDA first reacted in DMAc solvent, then following the addition of PTDDA, which was used as a thermosetting functional group in the polymer's backbone. Two homopolyimides prepared from the reaction of ODA with BTDA or PTDDA were also synthesized. The properties of homopolyimides such as solubility, thermal properties, and thermal curing mechanism were compared to those of copolyimides. The results showed that the tricyclic structure of the PTDDA unit underwent a reverse Diels-Alder reaction at near 300°C and it controlled the thermal behaviors of copolyimides.     

基于异构联苯二酐的热塑性聚酰亚胺性能研究

制备了一系列基于异构联苯二酐[2,2’,3,3’-联苯四甲酸二酐(3,3’-BPDA)、2,3’,3,4’-联苯四甲酸二酐(3,4’-BPDA)和3,3’,4,4’-联苯四甲酸二酐(4,4’-BPDA)]的聚酰亚胺(PI)均聚物和共聚物,比较研究了这些聚合物的热学和力学性能。结果表明,当二胺结构相同时,基于3,3’-BPDA和3,4’-BPDA的PI均聚物或共聚物较基于4,4’-BPDA的均聚物有更高的玻璃化转变温度(Tg)和更好的热加工性;当二酐结构相同时,基于对苯二胺(PDA)的PI的Tg高于基于4,4’-二氨基二苯醚(ODA)的PI。基于3,4’-BPDA/PDA的PI具有最高的Tg,其值为382℃,由其制备的薄膜的拉伸强度为100 MPa,拉伸弹性模量为1.8 GPa,断裂伸长率为12%。基于4,4’-BPDA/PDA的PI薄膜具有最高的拉伸性能,其拉伸强度为307 MPa,拉伸弹性模量为4.1 GPa,断裂伸长率为23%。基于3,4’-BPDA/ODA和3,3’-BPDA/4,4’-BPDA(1/1)/ODA的PI模塑料均具有高于300℃的Tg和较好的力学性能,其冲击强度分别达到82.3 kJ/m2和94 kJ/m2。     

Properties of copolyimides prepared from different tetracarboxylic dianhydrides and diamines

Various copolymides were prepared from two acid dianhydrides (BPDA, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride; PMDA, pyromelitic dianhydride) and two diamines (PPD, p-phenylene diamine; ODA, 4,4′-oxydianiline). The thermal and mechanical properties of these polyimides were examined in detail. By appropriately selecting the ratios of the acid dianhydride component and the diamine component, polyimide films having desirable mechanical and thermal characteristics can be obtained. Further, it was proved that there is a correlation between the properties and the compositions of the copolyimides and that the properties could be estimated from the compositions by the use of multiple regression analysis. © 1996 John Wiley & Sons, Inc.     

含苯环侧基三元共聚PI的合成及其表征

以4,4’-二胺基二苯醚(ODA)、2,2’-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)和均苯四甲酸酐(PMDA)为单体,采用溶液共缩聚方法合成了一系列共聚聚酰亚胺(PI)薄膜;采用傅里叶红外光谱仪(FTIR)、差示扫描量热仪(DSC)等分析了PI薄膜的结构和性能。结果表明:随着高聚物中柔性体系含量的增加,PI薄膜的热学性能和力学性能都有一定程度降低;但其加工性能得到了改善。     

Synthesis and characterization of benzimidazole‐based low CTE block copolyimides

A series of block and random copolyimide films were synthesized from various molar ratios of two diamines, rigid 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (APBI) and flexible 4,4′‐oxydianiline (ODA) by polycondensation with dianhydride 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The contents of APBI ranged from 10 to 60 mol % in copolyimides. The copolyimide films obtained by thermal imidization of poly(amic acid) solutions, were characterized by TMA, DMA, TGA, DSC, wide‐angle X‐ray diffraction, FTIR, tensile testing, water uptake (WU), and dielectric constant measurements. Rigid heterocyclic diamine APBI with interchain hydrogen bonding capability, led to low coefficient of thermal expansion (CTE), high T_g, high thermal stability and better mechanical properties. Increasing the APBI mol % caused a gradual decrease in the CTE and increase in T_g, thermal stability and tensile strength properties of the copolyimides films. Moreover, significantly enhanced thermal and mechanical properties of the block copolyimides were also found as compared to random copolyimides. The block copolyimide with APBI content of 60 mol %, achieved excellent properties, that is, a low CTE (4.7 ppm/K), a high T_g at 377°C, 5% weight loss at 562°C and a tensile strength at 198 MPa. This can be interpreted because of comparatively higher degree of molecular orientation in block copolyimides. These copolyimides also exhibited better dielectric constant and WU. This combination of properties makes them attractive candidates for base film materials in future microelectronics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of novel borosiloxane‐containing aromatic copolyimides with excellent thermal stability and low coefficient of thermal expansion

The properties of borosiloxane‐containing copolyimides with borosiloxane in the main chain and in the side chain were studied. Two series of borosiloxane‐containing copolyimides were synthesized by the reaction of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA ) and 2,3′,3,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA ) with p ‐phenylenediamine (PDA ), 4,4′‐oxydialinine (4,4′‐ODA ) and different borosiloxane diamine monomers (BSiAs ). The synthesized borosiloxane‐containing copolyimides exhibited better solubility than borosiloxane‐free copolyimides and showed high glass transition temperatures (320–360 °C), excellent thermal stability (570–620 °C for T ₁₀), great elongation at break (10% ? 14%) and a low coefficient of thermal expansion (14–24 ppm °C^?1). More specifically, the copolyimides containing BSiA‐2 formed nano‐scale protrusions and the copolyimides containing BSiA‐1 formed micro‐scale protrusions. The contact angles of the copolyimides increased from 72° for neat copolyimide to 96° for 5% of borosiloxane in the main chain of the copolymer up to 107° for 10% of borosiloxane in the side chain of the copolymer. © 2017 Society of Chemical Industry     

Effect of monomer composition on properties of copolyimides derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐oxydianiline/1,3‐bis (4‐aminophenoxy)benzene

A series of uncontrolled molecular weight homopolyimides and copolyimides based on 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/4,4′‐oxydianiline (4,4′‐ODA)/1,3‐bis(4‐aminophenoxy)benzene (TPER) were synthesized. All the polyimides displayed excellent thermal stability and mechanical properties, as evidenced by dynamic thermogravimetric analysis and tensile properties testing. A singular glass transition temperature (T_g) was found for each composite from either differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), but the values determined from tan δ of DMA were much different from those determined from DSC and storage modulus (E′) of DMA. The Fox equation was used to estimate the random T_g values. Some composites exhibited re‐crystallization after quenching from the melt; upon heating, multi‐melting behavior was observed after isothermal crystallization at different temperatures. The equilibrium melting temperature was estimated using the Hoffman‐Weeks method. Additionally, DMA was conducted to obtain E′ and tan δ. Optical properties were strongly dependent on the monomer composition as evidenced by UV‐visible spectra. X‐ray diffraction was used to interpret the crystal structure. All the results indicated that composites with TPER composition ≥ 70% were dominated by the TPER/s‐BPDA polyimide phase, and ≤40% by the 4,4′‐ODA/s‐BPDA polyimide phase. When the ratio between the two diamines was close to 1:1, the properties of the copolyimides were very irregular, which means a complicated internal structure. Copyright © 2011 Society of Chemical Industry     

Synthesis of new sulfonated copolyimides in organic and ionic liquid media for fuel cell application

New sulfonated copolyimides containing ether, carbonyl, and bulky naphthyl group in backbone were synthesized in two reaction media: organic solvent and ionic liquid media. For this purpose a new sulfonated diamine (BANBPDS) and an unsulfonated diamine (BANBP) was prepared through reactions of 4,4′‐dichlorobenzophenone‐3,3′‐disulfonic acid, and also 4,4′‐dichlorobenzophenone with 5‐amino‐1‐sodium naphthoxide, respectively. Three series of sulfonated copolyimide with different sulfonation contents (40–80%) were prepared by reaction of the sulfonated diamine (BANBPDS) in companion with three unsulfonated diamines including BANBP, 4,4′‐oxydianiline (ODA), and 1,8‐diamino‐3,6‐dioxaoctane (DADO) with 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA). Two media were selected for preparation of copolyimides. Copolyimides synthesized in ionic liquid had higher inherent viscosity and higher molecular weight in comparison with similar copolyimides that were synthesized via common organic solvent method. Incorporation of flexible groups in polyimide structures increased solubility and processability of the copolyimides. After characterization of polymers with common methods, their water uptake, water stability, ion exchange capacity (IEC), thermal behavior and stability, crystallinity, and morphology were studied. The polymers showed suitable properties including high thermal stability and ion exchange capacity, which were the basic requirements for application as fuel cell membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of chemical structure of aromatic dianhydrides on the thermal, mechanical and electrical properties of their terpolyimides with 4,4′-oxydianiline

Aromatic terpolyimides were synthesized by the reaction of 3,3′,4,4′-oxydiphthalicdianhydride(ODPA), 3,3′,4,4′-biphenyldianhydride(BPDA) and 3,3′,4,4′-benzophenonetetracaboxylicdianhydride(BTDA) with 4,4′-oxydianiline(ODA) via thermal imidization with the view to enhance their tensile properties without compromising thermal properties compared to their homo and copolyimides. Their films were characterized by FTIR, TGA, DSC and XRD. Their FTIR spectra established formation of polyimide by the characteristic vibrations at 1375cm⁻¹(C-N stretch) and 1113 cm⁻¹(imide ring deformation). TGA results showed imidization of residual polyamide acid close to 250 °C and decomposition of polyimides at about 540 °C. XRD results showed amorphous nature for all terpolyimides. Their tensile strength and tensile modulus were higher than either homo or copolyimides. Incorporation of BPDA, without bridging groups between the aromatic rings into the backbone of ODPA/BTDA-ODA is suggested as the cause for such an enhancement. Such terpolyimide can find application as adhesives in making flexible single/multilayer polyimide metal-clad laminates in flexible printed circuits and tape automated bonding applications. In addition, the terpolyimide, BPDA/BTDA/ODPA-ODA (mole ratio 0.5:0.25:0.25:1), showed low dielectric constant (3.52) as BPDA could offer slight rigidity by which the orientation of polar groupings could be reduced.     

Preparation and characterization of aromatic polyimides and related copolymers

Copolyimides containing BTDA-3DDS and BTDA-4ODA units have been synthesized by solution imidization methods. The copolyimides have high T_g's (267–283°C) and high decomposition temperatures (540–575°C; nitrogen); both properties are dependent on composition. Those copolymides with low concentrations of BTDA-4ODA are generally soluble in organic solvents, whereas those copolyimides with higher BTDA-4ODA content are only partially soluble or insoluble. However, all the copolyimides prepared can be compression molded. It has also been found that segmental motion above T_g is heavily suppressed in the BTDA-4ODA homopolymer relative to that in the BTDA-3DDS homopolymer. This reduction in molecular motion may severely hinder the solubility and fusibility of the BTDA-4ODA homopolymer. © 1993 John Wiley & Sons, Inc.