表面改性及原位还原法制备聚酰亚胺/镍纳米复合薄膜

通过对均苯四甲酸二酐-4,4’-二胺基二苯醚(PMDA-4,4’-ODA)型聚酰亚胺(PI)成品薄膜的表层水解处理、并在硫酸镍水溶液中实施离子交换以及随后的乙二醇热还原的方法,制备了聚酰亚胺/镍纳米复合薄膜。通过X射线衍射仪(XRD)、傅立叶变换红外光谱仪(FT-IR),透射电子显微镜(TEM)等方法研究了复合薄膜结构的变化,结果表明,经乙二醇热还原后,水解后的聚酰亚胺表层又重新形成亚胺环结构,并在其内部形成了均匀分散的具有面心立方晶型(FCC)的金属镍粒子,直径约为100 nm~200 nm。     

具有更佳尺寸稳定性的含噁唑基团的聚酰亚胺薄膜材料

采用4,4’-二氨基二苯醚(4,4’-ODA)与2-(4-氨基苯基)-5-氨基苯并噁唑(DAPBO)作为二胺单体,通过改变二者的摩尔比,与3,3’,4,4’-联苯四甲酸二酐(s-BPDA)聚合,制备得到了一系列含有噁唑基团结构的聚酰亚胺薄膜。系统地对薄膜样品进行了红外光谱、差示扫描量热分析、热失重分析、动态力学热分析、热机械分析等表征。研究发现,随着二胺中DAPBO占比的增加,聚酰亚胺薄膜的热稳定性及玻璃化转变温度升高、热膨胀系数减小;当ODA与DAPBO的摩尔比为4:6时,聚酰亚胺薄膜的热膨胀系数与铜最接近,有望应用于柔性印刷线路板领域。     

含咪唑基团的聚酰亚胺薄膜的制备及性能

为了探究适用于柔性印刷线路板的高热稳定性、低热膨胀系数聚酰亚胺薄膜,将3,3’,4,4’-联苯四甲酸二酐(3,3’,4,4’-BPDA)与4,4’-二氨基二苯醚(4,4’-ODA)和2-(4-氨基苯基)-5-氨基苯并咪唑(DAPBI)单体进行聚合,通过改变2种二胺的用量制备了一系列不同二胺比例的聚酰亚胺薄膜。采用红外、紫外、热重分析、差示扫描量热、动态力学热分析、热机械分析多种测试方法对不同比例薄膜样品的热性能、热稳定性、动态力学性能和光透过性进行了研究。研究结果表明,随着刚性DAPBI组分的增加,所制备薄膜的玻璃化转变温度逐渐升高,耐热性能变好,储能模量从3.5 GPa逐渐增加到5.9 GPa;薄膜的热膨胀系数(CTE)明显减小。当二胺ODA与DAPBI的摩尔比为4:6或5:5时,共聚薄膜的CTE值最接近18×10^-6K^-1。     

含有氢键的聚酰亚胺薄膜的制备和性能表征

以对硝基苯甲酸为原料,通过酰氯化、酰化、还原反应成功合成了4,4’-二氨基苯酰替苯胺(DBN),DBN分别和3,3’,4,4’-联苯四酸二酐(BPDA)、均苯四甲酸二酐(PMDA)通过两步法缩聚制备出聚酰亚胺薄膜,用红外(FT-IR),差示扫描量热仪(DSC)和热重分析(TGA),拉伸测试表征其结构和性能,结果表明,成功合成了含有酰胺键的聚酰亚胺薄膜,并且酰胺键的N-H分别和酰亚胺环中的C-N和C=O形成了氢键。将其与4,4’-二氨基二苯醚(ODA)聚酰亚胺薄膜相比,对应二酐(BPDA和PMDA)分别和DBN制备的聚酰亚胺薄膜表现出了优异的热性能和耐溶剂性,尤其是拉伸强度有了显著的提高。     

2,5-双(4-氨基-2-三氟甲基苯氧基)叔丁基苯及其聚酰亚胺的制备和性能研究

通过两步反应制备得到2,5-双(4-氨基-2-三氟甲基苯氧基)叔丁基苯,将其分别与均苯四甲酸二酐(PM-DA)、3,3’,4,4’-四羧酸二苯醚二酐(ODPA)、3,3’,4,4’-二苯酮四酸二酐(BTDA)、3,3’,4,4’-联苯四酸二酐(BPDA)、双酚A二酐(BPADA)通过缩聚和热亚胺化制备得到5种性能优异的聚酰亚胺薄膜。结果表明薄膜的玻璃化转变温度(Tg)高于210℃,起始分解温度高于510℃;吸水率低于0.9%;介电常数介于2.90～3.15之间;杨氏模量在1.48～2.27GPa之间。     

含咪唑基磺化聚酰亚胺质子交换膜的结构与性能关系研究

将1,4,5,8-萘四羧酸二酐(NTDA)与4,4’-二(4-氨基苯氧基)联苯-3,3’二磺酸(BAPBDS)及3种共聚用二胺单体:2-(4-氨基苯基)-5-氨基-苯并咪唑(APABI)、1,3-二(4-氨基苯氧基)-5-(2-苯并咪唑基)苯(BAPBIB)及4,4’-二(4-氨基苯氧基)联苯(BAPB)在间甲酚中180℃进行无规共聚,分别制得了3种共聚物:主链含咪唑基磺化聚酰亚胺、含侧咪唑基磺化聚酰亚胺及不含咪唑基磺化聚酰亚胺。用溶液浇注法制得了具有良好机械性能的质子交换膜,测定了这些质子交换膜的离子交换容量、吸水率、质子导电率、水解稳定性和抗自由基氧化等性能,重点研究了含咪唑基二胺单体的化学结构对质子交换膜的抗自由基氧化性和水解稳定性的影响规律。     

聚酰亚胺/银复合薄膜的制备及银粒子迁移的动力学研究

以对苯甲酮四甲酸二酐(BTDA)、4,4’-二胺基二苯醚(4,4-’ODA)和1,1,1-三氟-2,4-戊二酮银(AgTFA)为主要原料,采用原位一步自金属化法制备了银含量在9%~15%之间的聚酰亚胺(PI)/银(Ag)复合薄膜,探讨了影响PI/Ag薄膜性能的各因素,得到了同时具有高导电(表面电阻在1Ω左右)、高反射率(绝对反射率76.30%)的PI/Ag薄膜,首次初步定量探讨了反射率与银含量、固化时间之间的动力学方程。     

含芴共聚聚酰亚胺胶黏剂的合成与性能研究

以3,3’,4,4’-二苯甲醚四甲酸酐(ODPA)为二酐单体,采用等摩尔分数的9,9’-二(4-氨基苯基)芴(BAFL)和3,4’-二氨基二苯醚(3,4’-ODA)、4,4’-二氨基二苯醚(4,4-’ODA)、1,3-双(4-氨基苯氧基)苯(1,3,4-APB)或1,4-二(4’-氨基苯氧基)苯(1,4,4-’APB)分别共聚制备含芴共聚聚酰亚胺(CPI)薄膜。对CPI薄膜进行FT-IR,DMTA,TGA和拉伸性能的测试。采用部分酰亚胺化的CPI薄膜与不锈钢黏结,制备单搭接黏结件,测试其室温及高温拉伸剪切强度,进而比较其黏结性能。结果表明,含芴CPI薄膜具有较好的力学性能和热性能。BAFL,3,4’-ODA与ODPA共聚所得CPI薄膜的黏结性能最好,室温拉伸剪切强度达到19.2MPa,250℃仍然可达13.4MPa。     

四甲基联苯二胺及有机可溶聚酰亚胺的合成与性能

以对二甲苯为原料,通过溴代、偶合、硝化和还原反应成功合成了2,2′,5,5′-四甲基联苯-4,4′-二胺(TMBPDA)。TMBPDA分别与4,4’-双酚A型二醚二酐(BPADA)和4,4′-双酚AF型二醚二酐(FBDA)通过高温一步法缩聚生成聚酰亚胺PI-A和PI-AF。结果表明,两种聚酰亚胺不仅在N-甲基-2-吡咯烷酮(NMP),N,N-二甲基甲酰胺(DMAc)中展示出良好的有机可溶性,同时拥有优良热性能,由差示扫描量热仪(DSC)测得玻璃化转变温度(Tg)分别为251℃和255℃。此外,两种聚酰亚胺薄膜在可见光范围内具有良好的透明性,在450 nm处的透光率均超过了88%。     

含咪唑基团的聚酰亚胺薄膜的制备及性能EI北大核心CSCD

为了探究适用于柔性印刷线路板的高热稳定性、低热膨胀系数聚酰亚胺薄膜,将3,3',4,4'-联苯四甲酸二酐(3,3',4,4'-BPDA)与4,4'-二氨基二苯醚(4,4'-ODA)和2-(4-氨基苯基)-5-氨基苯并咪唑(DAPBI)单体进行聚合,通过改变2种二胺的用量制备了一系列不同二胺比例的聚酰亚胺薄膜。采用红外、紫外、热重分析、差示扫描量热、动态力学热分析、热机械分析多种测试方法对不同比例薄膜样品的热性能、热稳定性、动态力学性能和光透过性进行了研究。研究结果表明,随着刚性DAPBI组分的增加,所制备薄膜的玻璃化转变温度逐渐升高,耐热性能变好,储能模量从3.5 GPa逐渐增加到5.9 GPa;薄膜的热膨胀系数(CTE)明显减小。当二胺ODA与DAPBI的摩尔比为4:6或5:5时,共聚薄膜的CTE值最接近18×10^(-6)K^(-1)。     

Polyimide/sepiolite nanocomposite films: Preparation, morphology and properties

Polyimide/sepiolite nanocomposite films have been prepared via an in situ polymerization method. The process involves the dispersion of sepioite in N,N-dimethylacetamide, polycondensation of 2,2′-bis [4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride and 4,4′-oxydianiline in the presence of sepiolite suspension to form poly(amic acid), and the thermal imidization of poly(amic acid)/sepiolite nanocomposite. The morphology, thermal and mechanical performance, and water absorption of nanocomposite films were systematically studied with various sepiolite contents. The results indicated that sepiolite was dispersed homogeneously at a nanometer scale in polyimide matrix. Owing to such nanodispersion of sepiolite, the polyimide/sepiolite nanocomposite films exhibit dramatic improvements on the mechanical properties and the coefficient of thermal expansion while fine thermal stability and low water absorption capacity were also maintained. When the sepiolite content increased to 16% the polyimide/sepiolite nanocomposite film achieved as much as 41% and 94% increase on the tensile strength and modulus respectively, and 50% decreased in coefficient of thermal expansion.     

笼型聚倍半硅氧烷增韧3层聚酰亚胺薄膜的制备与性能

以3,3′,4,4′-联苯四酸二酐(BPDA)-对苯二胺(PDA)/4,4′-二苯醚二胺(ODA)型聚酰亚胺为芯层,将2,2′-双(4-(4-氨基苯氧基)苯基)丙烷(BAPP)-BPDA型聚酰胺酸涂覆于芯层的上、下表面并热亚胺化得到3层聚酰亚胺薄膜。为提高3层聚酰亚胺薄膜的韧性,将降冰片烯二酸酐-马来酰亚胺基七异丁基聚倍半硅氧烷交替共聚物(poly(MIPOSS-alt-NA))作为BPDA的共单体引入到上、下表层的热塑性聚酰亚胺中。结果表明,当poly(MIPOSS-alt-NA)的质量分数为6.0%时,3层聚酰亚胺薄膜的断裂伸长率从7.2%提高到14.5%,热膨胀系数则从27.0×10-6 K-1降低至23.6×10-6 K-1,与铜箔制备的柔性覆铜板剥离强度达到12.0 N/cm,针对拉伸断面电镜照片的变化对增韧机理进行了分析。     

Preparation SnO₂ nanolayer on flexible polyimide substrates via direct ion-exchange and in situ oxidation process

Tin oxide (SnO(2)) nanolayers were formed on flexible polyimide (PI) substrate via direct ion-exchange and in situ oxidation process utilizing pyromellitic dianhydride/4,4'-oxidianiline-based poly(amic acid) films as polyimide precursor. During an ion-exchange process, stannous ions were doped into the precursor by immersion in ethanolic solution of stannous chloride. Subsequent thermal treatment of the tin(II)-containing precursor at a constant heating rate not only imidized poly(amic acid) to PI but also converted stannous ions into SnO(2) clusters, which diffused and aggregated onto the surface of polymer matrix, forming continuous tin oxide layers. Inductively coupled plasma (ICP) was used to investigate the ion-exchange process. Changes in chemical structure of the poly(amic acid) film and the crystal structure of tin oxides were analyzed by attenuated total reflection-Fourier transform infrared (ATR-FTIR) and X-ray diffraction (XRD). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to study the microstructure of the PI/SnO(2) nanocomposite films. The nanocomposite film maintained essential mechanical property and thermal stability of pristine PI films.     

正交设计法研究聚酰胺酸分子量及其影响因素

采用正交试验设计方法,研究了聚酰胺酸固体含量、反应温度、加料间隔时间和反应时间对聚酰胺酸分子量的影响,采用凝胶渗透色谱仪测试了不同反应条件下合成的聚酰胺酸的分子量。正交设计试验结果表明,合成最高分子量聚酰胺酸的反应条件为:反应温度为15℃,固体含量为8%,加料间隔时间为9min,反应时间为3h。在此基础上,使用TGA测试了由不同分子量聚酰胺酸合成的聚酰亚胺薄膜的热稳定性。试验结果显示,聚酰胺酸分子量越大,薄膜的热稳定性越好。     

Preparation and properties of the polyimide/multi-walled carbon nanotubes (MWNTs) nanocomposites

The polyimide/multi-walled carbon nanotubes (MWNTs) nanocomposite films were prepared by mixing of poly(amic acid) (PAA) solution and MWNTs/DMAc suspension follow by mixture casting, evaporation and thermal imidization. To increase the chemical compatibility between polyimide matrix and MWNTs, MWNTs were modified with mixed strong acid. The results show that the dispersion of the MWNTs is improved greatly in the polyimide matrix after acid modification. The modified MWNTs are dispersed homogeneously in the polyimide matrix while the structure of the polyimide and MWNTs structures is stable in the preparation process. With the incorporation of MWNTs, the mechanical properties of the resultant nanocomposite films were greatly improved due to the strong interfacial interaction between the modified MWNTs and the polyimide matrix. The thermal stability of the nanocomposites was lower a little than pure polyimide because of the drop of thermostability of MWNTs through acid-treatment. The electrical conductivity and the dielectric constant of the nanocomposites were also having sharp increase, which is favorable for practical use in anti-static materials and embedded capacitors.     

用原位聚合法制备聚酰亚胺/滑石粉复合薄膜的聚集态结构

用原位聚合法合成一系列不同滑石粉含量的聚酰胺酸/滑石粉(PAA/talc)溶液,再将其热酰亚胺化制备出聚酰亚胺/滑石粉(PI/talc)复合薄膜.偏光显微镜(POM).广角X衍射(WXRD)和扫描电子显微镜(SEM)的观测结果表明,滑石粉的引入使PAA形成一种丝状有序结构,且随着热酰亚胺化的进行或者滑石粉含量的增加,这种结构不但得以保持且越来越明显,最终相互交错形成网状织构,红外光谱(FT-IR)给出的结果表明,滑石粉与PAA间存在氢键相互作用.丝状结构的形成,是在存在氢键的前提下滑石粉诱导被应力驱动的大分子链发生规整有序排列的结果.     

聚酰亚胺/纳米Al_2O_3三层复合薄膜的制备

将掺杂纳米Al2O3的聚酰胺酸与未掺杂聚酰胺酸在玻璃板上逐层涂膜,热亚胺化制备了3层聚酰亚胺/纳米Al2O3复合薄膜.采用扫描电镜(SEM)对该薄膜的微观形貌进行了表征,测试了薄膜的热稳定性、力学性能及电击穿场强.结果表明,复合薄膜的热性能及电击穿场强均高于掺杂薄膜及未掺杂膜,当热失重达到10%时,复合薄膜的热分解温度达到了629.1℃;与掺杂薄膜相比,复合薄膜的力学性能得到明显提高,拉伸强度和断裂伸长率分别为117.4 MPa和18.5%.     

Preparation and properties of fluorine-containing colorless polyimide nanocomposite films with organo-modified montmorillonites for potential flexible substrate

We prepared transparent polyimide (PI) and organo-modified montmorillonite (OMMT) nanocomposite films from the solution of poly(amic acid) and various amounts (0.5-2 wt%) of OMMT in N,N-dimethylacetamide (DMAc). The Poly(amic acid) was prepared from the reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,2'-bis (trifluoromethyl)-4,4'-diamino phenyl (TFDB). Dodecylamine (C12-) and dodecyltriphenylphosphonium chloride (C12PPh-Cl-) were used as organic modifiers in OMMT. The PI/OMMT nanocomposite films were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscope (TEM), UV-Vis transmission spectra, thermomechanical analysis (TMA), and rheometric dynamic analysis (RDA). As the OMMT contents is increased, PI/OMMT nanocomposites generally show better properties compared to pristine PI films, although the transparency of the PI/OMMT nanocomposite films is sacrificed slightly. However, it is concluded that these nanocomposite films are good candidates for potential flexible substrates.     

高模量、低热膨胀系数聚酰亚胺杂化薄膜的制备

通过在聚酰胺酸中加入正硅酸乙酯(TEOS)和硅烷偶联剂(KH550),制备了不同SiO2含量的PI/SiO2杂化薄膜.采用FTIR、TMA、SEM以及TGA分析了PI/SiO2杂化薄膜的性能和结构.结果表明,TEOS经水解缩合与聚酰亚胺(PI)形成了有机-无机杂化网络结构,SiO2均匀分散在聚酰亚胺基体中;SiO2和偶联剂的引入提高了杂化薄膜的热稳定性;随着SiO2含量的增加,PI/SiO2杂化薄膜的拉伸强度降低,但当SiO2含量达到20%时,弹性模量增大到3.4GPa.