含芴基二胺单体及其聚酰亚胺的合成与表征

利用水合肼法成功合成了含芴基、醚键及烷基的二胺单体9,9-双(3,5-二甲基-4氨基苯氧基苯基)芴,并对其熔点、红外、核磁表征。结构表明,该单体具较高的纯度,并且熔点较高。采用该二胺和双酚A型二酐聚合,合成了较高分子量的聚酰亚胺前驱体聚酰胺酸,通过热亚胺化和化学亚胺化得到了聚酰亚胺薄膜,通过红外(FT-IR)、特性黏度的测试,说明合成了含芴基及醚键的新型聚酰亚胺,同时从溶解度的测试结果来看,在有机溶剂中的溶解性较好。     

基于硅桥的V形有机凝胶因子的合成及性能研究

以对氯甲苯和二氯二甲基硅烷为原料,经偶联、氧化、酯化、酰肼化等系列反应,得到中间体二(4′-酰肼基苯基)-二甲基硅烷,将其与3,4,5-三辛氧基苯甲酸反应,合成了含有二甲基硅的V形二酰肼衍生物--N,N′-(4,4′-二甲基硅烷二基)双(苯甲酰基)双(3,4,5-三辛氧基苯并酰肼)。利用核磁共振氢谱仪、核磁共振碳谱仪、飞行时间质谱仪、傅里叶变换红外光谱仪对其结构进行了表征。合成的目标化合物只能在四氯化碳溶液中热可逆凝胶化,扫描电子显微镜分析表明干凝胶形貌类似火山岩结构。利用热重分析仪测定了目标化合物的热稳定性,其热分解温度为397℃,表明该化合物具有良好的热稳定性。     

一种可溶性双酮酐型共聚酰亚胺的合成及性能

以均苯四甲酸二酐(PMDA)和4,4’-对苯二甲酰二邻苯二甲酸酐(TDPA)为二酐单体,4,4’-(3-氨基苯氧基)二苯甲酮(BABP)为二胺单体,采用两步法低温溶液缩聚合成了系列双酮酐型共聚酰亚胺。采用红外光谱、X射线衍射、差示扫描量热分析、热重分析、拉伸测试和溶解性能测试对聚合物的结构与性能进行了表征,考察了TDPA/PMDA不同摩尔比对共聚酰亚胺溶解性、耐热性和力学性能的影响。结果表明,双酮酐型聚酰亚胺的玻璃化转变温度随TDPA摩尔含量的增加逐渐下降,溶解性能则逐渐提高,当TDPA/PMDA摩尔比为7/3时,共聚酰亚胺具有优良的耐热性能及力学性能,可溶于N,N-二甲基甲酰胺(DMF)等极性溶剂。     

二(p-氨基苯氧基)二甲基硅烷的合成及其聚酰亚胺的制备

采用二甲基二氯硅烷和对氨基苯酚作为主要原料,一步法合成了二(p-氨基苯氧基)二甲基硅烷,使用核磁共振光谱,红外光谱及质谱对产物结构进行了表征.以新合成的二(p-氨基苯氧基)二甲基硅烷(SIDA)为原料和ODA,与PMDA反应合成有机硅氧烷聚酰胺酸,并分别采用热酰胺化与化学酰胺化制得了有机硅氧烷改性聚酰亚胺,使用FT-I...     

PMDA/ODA型聚酰亚胺的共聚改性研究

以1,3-双(4-氨基苯氧基)苯(队PB134)和4,4'-二氨基二苯醚(ODA)为二胺单体,与均苯四甲酸二酐(PM-DA)进行共聚,合成了一系列具有一定溶解性的聚酰亚胺(PI).采用IR、TGA、DSC、XRD和拉伸实验等手段,对其结构和性能进行了研究.结果表明:共聚酰亚胺(CoPI)薄膜为非晶态结构,其热性能和拉伸强度与均聚物相当,模量有所降低,而断裂伸长率显著提高.     

可溶性透明含氟聚酰亚胺薄膜的合成与性能

利用3种二胺单体1,4-双(4-氨基-2-三氟甲基苯氧基)苯、4,4’-双(4-氨基-2-三氟甲基苯氧基)二苯醚和4,4’-双(4-氨基-2-三氟甲基苯氧基)六氟丙烷分别与3种二酐单体1,2,3,4-环丁烷四酸二酐(CBDA)、均苯四甲酸二酐(PMDA)和3,3’,4,4’-二苯醚四酸二酐(ODPA)进行低温溶液缩聚反应,再经热酰亚胺化制备出9种聚酰亚胺(PI)薄膜。结果表明,这些PI具有较好的溶解性,可溶解于氨型强极性溶剂,在弱极性溶剂中也有一定的溶解性;CBDA和ODPA基PI在450 nm处的透光率超过80%,且CBDA基PI的紫外截止波长为310 nm,更接近无色,但其热稳定性最差,5%热分解温度在420℃左右,而PMDA和ODPA基PI的热稳定性较好。     

一类含四甲氧基芴结构可溶性聚酰亚胺的合成及表征

通过三步有机反应合成了一种新型含四甲氧基芴结构的芳香型二胺单体——9,9-双(3,5-二甲氧基-4-(4-氨基苯氧基)苯基)芴,由这种单体分别与4种商品化芳香二酐经过高温缩聚反应,制得一系列含芴结构聚酰亚胺(PI 4a~4d)。分别用傅里叶红外光谱、核磁共振波谱、差示扫描量热及热失重分析等对聚合物的结构和性能进行了表征和研究。该类聚酰亚胺在甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等高沸点溶剂及CHCl_3、CH_2Cl_2等低沸点溶剂中具有优异的溶解性;所制得的薄膜具有良好的力学性能,其拉伸强度为62.1~75.6 MPa,断裂伸长率在16.0%~20.7%之间,弹性模量为1.8~2.6 GPa。该系列聚酰亚胺的玻璃化转变温度在244~256℃之间,空气和氮气中10%热失重温度均在430℃以上,表现出优异的热学性能。     

可溶性含羟基聚酰亚胺的制备及其性能研究

合成了含羟基的二胺单体4,4′-二氨基-4″-羟基三苯甲烷(DHTM),并将该单体分别同六氟异叉丙基二苯四羧酸二酐(6FDA),3,3′,4,4′-二苯醚四羧酸二酐(ODPA)和4,4′,-二(4,4′,-异丙叉二苯氧基)四羧酸二酐(BPADA)反应制备了3种结构的聚酰亚胺。溶解性实验表明,这3种聚合物在非质子极性溶剂中均显示出良好的溶解性。此外,还对聚酰亚胺薄膜进行了拉伸和动态机械热性能测试。     

一类同时含二甲基、双苯侧基和芴结构聚芳酰胺的合成与性能EI北大核心CSCD

以2-苯基苯酚和9-芴酮为原料,于60℃进行羰基偶合反应得到含双苯侧基芴结构双酚单体9,9-双(3-苯基-4-(4-羟基)苯基)芴,进一步经芳香亲核取代、氧化还原得到一种同时含二甲基、双苯侧基和芴结构的新型芳香二胺单体——9,9-双(3-苯基-4-(4-氨基-2-甲基苯氧基)苯基)芴二胺单体。由该二胺分别与对苯二酸、2,2-双(4-羧基苯基)六氟丙烷、4,4-二苯醚二甲酸通过磷酰化缩合反应合成一系列聚芳酰胺,分别利用核磁共振氢谱、红外光谱、X射线衍射对所合成的聚芳酰胺的分子结构和聚集体结构进行了表征,并对聚合物的溶解性、特性黏数、热性能、力学性能等进行了研究分析。研究结果表明,该类含二甲基、双苯侧基和芴结构的聚芳酰胺为无定形态,且具有优异的溶解性能,能溶于二甲基乙酰胺、二甲基甲酰胺、甲基吡咯烷酮、四氢呋喃、吡啶等有机溶剂。聚合物具有良好的热性能和力学性能(空气和氮气中10%的热失重温度均达到450℃以上,玻璃化转变温度在216~234℃,拉伸强度最高达到85. 6 MPa)。刚性扭曲非共平面结构及二取代甲基的存在赋予了该系列聚芳酰胺良好的综合性能。     

一类同时含二甲基、双苯侧基和芴结构聚芳酰胺的合成与性能

以2-苯基苯酚和9-芴酮为原料,于60℃进行羰基偶合反应得到含双苯侧基芴结构双酚单体9,9-双(3-苯基-4-(4-羟基)苯基)芴,进一步经芳香亲核取代、氧化还原得到一种同时含二甲基、双苯侧基和芴结构的新型芳香二胺单体——9,9-双(3-苯基-4-(4-氨基-2-甲基苯氧基)苯基)芴二胺单体。由该二胺分别与对苯二酸、2,2-双(4-羧基苯基)六氟丙烷、4,4-二苯醚二甲酸通过磷酰化缩合反应合成一系列聚芳酰胺,分别利用核磁共振氢谱、红外光谱、X射线衍射对所合成的聚芳酰胺的分子结构和聚集体结构进行了表征,并对聚合物的溶解性、特性黏数、热性能、力学性能等进行了研究分析。研究结果表明,该类含二甲基、双苯侧基和芴结构的聚芳酰胺为无定形态,且具有优异的溶解性能,能溶于二甲基乙酰胺、二甲基甲酰胺、甲基吡咯烷酮、四氢呋喃、吡啶等有机溶剂。聚合物具有良好的热性能和力学性能(空气和氮气中10%的热失重温度均达到450℃以上,玻璃化转变温度在216~234℃,拉伸强度最高达到85. 6 MPa)。刚性扭曲非共平面结构及二取代甲基的存在赋予了该系列聚芳酰胺良好的综合性能。     

添加剂对聚酰亚胺液晶垂直取向剂性能的影响

研究了添加剂对PI取向性能、耐摩擦性、热稳定性以及透光率的影响。用均苯四甲酸二酐(PM-DA),对苯二胺(PDA),4-已氧基联苯酚-3’,5’-二胺基苯甲酸酯(C6-BBDA),制备了三元共聚型PI取向膜,并采用添加剂(封端剂和交联剂)对PI改性。通过调节添加剂的组成制备了4种PI。利用红外光谱仪(FT-IR)、热失重分析仪(TGA)、紫外分光光度计(UV-Vis)、偏光显微镜(POM)和预倾角测试仪对合成的PI进行了结构表征和性能测试。研究发现LC分子在4种PI膜上都获得了均匀的垂直取向;添加交联剂的PI膜具有良好的耐摩擦性,经摩擦强度为600mm摩擦后,仍对LC分子具有垂直取向的能力;加入添加剂的PI膜具有良好的热稳定性,此外,加入添加剂的PI膜仍具有较高的透光率。     

耐高温聚酰亚胺导电复合材料的性能

采用涂膜法制备了以碳纳米管(CNTs)、乙炔黑和石墨粉为导电填料的聚酰亚胺(PI)导电复合材料,研究了其电学性能、力学性能和粘接性能。结果显示,PI/CNTs导电复合材料有较好的综合性能。     

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.     

球磨共混制备优异抗原子氧性能的氧化石墨烯/聚酰亚胺复合薄膜

通过简单的机械共混（球磨共混）和高温压制的方法,制备了一系列具有良好抗原子氧（AO）性能的氧化石墨烯/聚酰亚胺（GO/PI）复合薄膜。微量（0.5wt%） GO的引入可使GO/PI复合薄膜的抗AO性能提高17.9%。同时,含0.5wt% GO的GO/PI复合薄膜也表现出良好的热稳定性能和力学性能。热重分析表明,含0.5wt% GO的GO/PI复合薄膜在质量损失为5%时的温度（T_d5）为519.4℃,比纯PI薄膜高14.7℃;拉伸强度为111.9 MPa,杨氏模量为2.1 GPa,与纯PI薄膜相比,分别提高了4.3 MPa和0.1 GPa。与传统的原位聚合法相比,机械共混-高温压制的方式更易于操作和控制,使具有优异综合性能的GO/PI复合薄膜的大规模量产成为可能。     

A facile assembly of polyimide/graphene core–shell structured nanocomposites with both high electrical and thermal conductivities

Polyimide/reduced graphene oxide (PI/r-GO) core–shell structured microspheres were fabricated by in-situ reduction of graphene oxide (GO), which was coated on the surface of PI microspheres via hydrogen bonding and π–π stacking interaction. The highly ordered 3D core–shell structure of PI/r-GO microspheres with graphene shell thickness of 3 nm was well characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and Raman spectra. The glass transition temperature (T_g) of PI/r-GO microspheres was slightly increased because of the interaction of r-GO and PI matrix while the temperature at 5% weight loss (T_5%) of PI/r-GO microspheres was decreased due to the side effect of reductant hydrazine hydrate. The PI/r-GO nanocomposites exhibited highly electrical conductivity with percolation threshold of 0.15 vol% and ultimate conductivity of 1.4 × 10⁻² S/m. Besides, the thermal conductivity of PI/r-GO nanocomposites with 2% weight content of r-GO could reach up to 0.26 W/m K.     

Effect of side-chain structure of rigid polyimide dispersant on mechanical properties of single-walled carbon nanotube/cyanate ester composite

Three kinds of polymer, polyimide without side-chain (PI), polyimide-graft-glyceryl 4-nonylphenyl ether (PI-GNE), and polyimide-graft-bisphenol A diglyceryl acrylate (PI-BDA), have been synthesized and used to disperse single-walled carbon nanotubes (SWNTs) and to improve the interfacial bonding between SWNTs and cyanate ester (CE) matrix. Visual observation, UV-vis-near-IR (UV-vis-NIR) spectra, and atomic force microscopy (AFM) images show that both PI-GNE and PI-BDA are highly effective at dispersing and debundling SWNTs in DMF, whereas PI is less effective. Interaction between SWNTs and PI, PI-GNE or PI-BDA was confirmed by computer simulation and Raman spectra. A series of CE-based composite films reinforced with different loadings of SWNTs, SWNTs/PI, SWNTs/PI-GNE and SWNTs/PI-BDA were prepared by solution casting. It was found that, because of the unique side-chain structure of PI-BDA, SWNTs/PI-BDA disperse better in CE matrix than do SWNTs/PI-GNE, SWNTs/PI, and SWNTs. As a result, SWNTs/PI-BDA/CE composites have the greatest improvement in mechanical properties of the materials tested. These results imply that the choice of side-chain on a dispersant is very important to the dispersion of SWNTs in matrix and the filler/matrix interfacial adhesion, which are two key requirements for achieving effective reinforcement.     

Intercalation behavior of polyimide/organoclay nanocomposites during thermal imidization

To understand the intercalation behavior of polyimide (PI)/clay nanocomposites during thermal imidization, two different types of poly(amic acid) (PAA) were synthesized, and the corresponding hybrids with organically treated clays (O-MMT) were also prepared. The changes in molecular structure of the polymer matrix, interlayer spacing, and fracture morphology with a series of thermal imidization steps were investigated. The PAA/clay nanocomposites initially showed two X-ray diffraction peaks, indicating two levels of intercalation. As the temperature at which the thermal imidization step was performed increased, the peak intensity of the higher angle peak increased, and it remained as a unique peak at 2θ=6.70 (d-spacing of 13.2 Å) for both PI(1), based on pyromellitic dianhydride (PMDA)+4,4′-oxydianiline (ODA), and PI(2), based on PMDA+4,4′-(9-fluorenylidene)-dianiline (9FDA). However, the lower angle peak became smaller and broader, and the angle became higher. This peak finally disappeared after thermal treatment at 300 °C for PI(1), but did not disappear completely for PI(2), although the peak showed a marked decrease in intensity and became broader.     

Friction and wear studies of polyimide composites filled with short carbon fibers and graphite and micro SiO2

Polyimide (PI) composites filled with short carbon fibers (SCFs), micro SiO₂, and graphite (Gr) particles were prepared by means of hot press molding technique. The friction and wear properties of the resulting composites sliding against GCr15 steel were investigated on a model ring-on-block test rig. Experimental results revealed that single incorporation of graphite and SCF significantly improve the tribological properties of the PI composites, but micro SiO₂ was harmful to the improvement of the friction and wear behavior of the PI composite. It is found that a combinative addition of Gr, SCF and micro SiO₂ was the most effective in improving the friction-reducing and anti-wear abilities of the PI composites. Research results also show that the filled PI composites exhibited better tribological properties under higher PV-product.     

高强高模聚酰亚胺纤维/改性氰酸酯树脂复合材料制备及性能

以4,5-环氧己烷-1,2-二甲酸二缩水甘油酯（TDE-85）、苯基缩水甘油醚（PGE）、壬基酚（NP）作为改性剂改性双酚A氰酸酯（BCE）得到改性氰酸酯树脂（TPNCE）,通过湿法缠绕制备预浸料,并采用热压罐成型工艺制备S30M型高强高模聚酰亚胺纤维/TPNCE（PI/TPNCE）复合材料,对TPNCE树脂及PI/TPNCE复合材料的介电、力学等性能进行了分析。结果表明,TPNCE树脂冲击强度达到14.2 kJ/m2,比BCE提高近一倍,固化温度下降了约43℃,与PI纤维界面结合较好,且保持较低的介电常数和介电损耗;PI/TPNCE复合材料0°拉伸强度达到1 485 MPa,弯曲强度达到758 MPa,压缩强度达到322 MPa,7~18 GHz范围内介电常数保持在3.15左右,介电损耗因子在0.005~0.0075之间,玻璃化转变温度为197℃,密度为1.28 g/cm3。本研究实现了高强高模PI纤维与氰酸酯树脂复合的重要突破,为轻质高强结构-功能一体化复合材料的设计和选材提供了新思路。      

聚苯胺-石墨烯/聚酰亚胺复合导电纱的制备及其超电容特性

为了提高石墨烯/聚酰亚胺(rGO/PI)复合纱线电极的电化学性能,采用电化学聚合法在rGO/PI复合纱线表面沉积聚苯胺(PANI)颗粒,研究了沉积时间对PANI-rGO/PI复合导电纱的形貌及增重的影响。结果表明, PANI在rGO/PI复合纱线表面均匀沉积,且沉积量随着沉积时间的增加而增大。采用循环伏安法(CV)、恒流充放电法(GCD)研究了PANI-rGO/PI复合导电纱线的电化学行为。结果表明, PANI沉积时间对纱线电极的循环伏安特性、恒流充放电曲线等有很大的影响,当PANI沉积时间为900 s时,所得PANI-rGO/PI复合纱线电极的循环伏安特性和恒流充放电性能表现均最优,比电容为81.22 F·cm^-3,而rGO/PI纱线电极仅为16.4 F·cm^-3。以最优工艺制得的PANI-rGO/PI复合导电纱作为电极组装了纤维状超级电容器,采用交流阻抗谱法(EIS)、 CV及GCD对器件进行电化学性能表征。结果表明,该器件体积比电容可达41.73 F·cm^-3,在充放电3 000次后比电容依然能够维持在85%左右,所得纤维状超级电容器经过串联可成功驱动LED灯。