偶联剂对PI/SiO2杂化薄膜微观结构的影响

采用溶胶-凝胶路线制备了偶联剂分别为3-氨丙基三乙氧基硅烷(APrTEOS)、3-缩水甘油丙基醚三甲氧基硅烷(GPTMOS)、乙烯基三乙氧基硅烷(TEVS)的3种PI/SiO2杂化薄膜,并对其微观结构进行了研究。研究结果表明:在这3种偶联剂中,采用APrTEOS为偶联剂,偶联效果最好。其次为GPTMOS,当采用TEVS为偶联剂时,几乎没有偶联效果。     

PI/T-SiO2杂化薄膜的制备及偶联剂的影响

利用模板法制备了纳米管状SiO2(T—SiO2),在此基础上合成了聚酰亚胺(T-SiO2杂化薄膜。采用透射电子显微镜和扫描电子显微镜对T—SiO2的形态进行了研究,用红外光谱分析了硅烷偶联剂对杂化薄膜微观结构的影响,并讨论了偶联剂加入方式、用量等因素对杂化薄膜力学性能的影响。结果表明,所制备的SiO2主要为管口直径分布在100-500nm,长径比在10～500的T—SiO2;在聚酰胺酸形成后,加入经偶联剂改性的T—SiO2,且偶联剂用量为填料质量的10％时,杂化薄膜的拉伸强度和弹性模量取得最佳值,分别为111．8MPa和1．42GPa。     

杂化聚酰亚胺薄膜耐电晕性能的研究

用均苯四甲酸二酐和4,4＇-二氨基二苯醚合成聚酰亚胺（PI）树脂,以甲基三乙氧基硅烷为无机前驱体原位产生二氧化硅（SiO2）粒子,并以3-氨丙基三乙氧基硅烷为偶联剂制备了PI／SiO2杂化薄膜。分析和讨论了无机成分的含量和两相间界面形态的变化对PI／SiO2薄膜耐电晕性能的影响结果表明,无机组分的引入对杂化PI／SiO2薄膜的耐电晕性能产生很大的影响,薄膜的耐电晕性能随SiO含量的增加而提高;偶联刑的引入对无机粒子的分散、两相相容性,以及界面形态具有明显的改善作用,对薄膜耐电晕性能的改善更为明显：并提出了一个耐电晕模型。     

含芳杂环结构的聚酰亚胺/SiO2杂化薄膜及性能研究

以均苯四甲酸二酐(PMDA)为二酐单体,对苯二胺(p-PDA)、2-(4-氨基苯基)-5-氨基苯并噁唑(BOA)和2-(4-氨基苯基)-5-氨基苯并咪唑(BIA)为二胺单体,制备了聚酰亚胺(PI)树脂和薄膜,又采用三辊机制备了PI/SiO_2杂化树脂和薄膜。利用傅里叶红外光谱对材料的结构进行了表征,结果表明薄膜完全亚胺化,且SiO_2存在于PI基体中。此外,还研究了PI和PI/SiO_2杂化薄膜的热学性能和力学性能。随着2种不同粒径SiO_2的加入,PI/SiO_2杂化薄膜的耐热性能得到明显改善。与纯PI相比,PI/SiO_2杂化薄膜的玻璃化转变温度上升3～16℃,1%热失重温度提高了14～30℃,而且线性热膨胀得到抑制,PI-R106-5的线性热膨胀系数(CTE)仅为2.59×10~(-6)/℃。但是,PI/SiO_2杂化薄膜的力学性能相对于纯PI薄膜有所降低,未来应继续提高其相容性。     

聚酰亚胺/纳米氧化硅氧化铝杂化膜的制备

研究了用溶胶凝胶法制得的二氧化硅及三氧化二铝溶胶,将其掺入到聚酰胺酸基体中,得到SiO2-Al2O3/聚酰亚胺杂化膜,并采用FTIR、SEM和TGA表征了所制备的杂化膜的结构微观形态和热性能。结果表明,薄膜材料中SiO2和Al2O3粒子分散均匀,与有机相存在键合,材料热分解温度有所提高。     

PMDA-6FHP-DR1／SiO2杂化纳米材料的结构设计和合成

以含氟的二胺5，5′—(六氟异丙基)—二—(2—氨基苯酚)及均苯四甲酸酐(PMDA)为单体，首先合成了经酰胺化的主链上带有活性羟基的含氟聚酰亚胺，再通过Mitsunobu反应将活性生色分子分散红1(DR1)共价链接到聚酰亚胺的侧链骨架上，合成了含氟聚酰亚胺．采用溶胶—凝胶(SOl—Gel)技术，并利用偶联剂γ—氨丙基三乙氧基硅烷(AFTES)制备带有发色团的和含有硅氧烷端分子的聚酰胺酸，其中的Si(OR)3基经水解、缩合后，与正硅酸乙酯(TEOS)在催化剂作用下反应，经杂化、凝胶后，得到光学透明且热稳定性高的有机／无机杂化材料．将制得的含氟聚酰亚胺／SiO2杂化材料，采用红外光谱(FT—IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、示差扫描量热法(DSC)，对材料的结构、表面形貌、热性能进行了表征．     

聚酰亚胺/二氧化钛杂化材料的制备及性能研究

采用超声分散-原位聚合工艺制备了聚酰亚胺(PI)/二氧化钛(TiO2)杂化膜。通过傅里叶转换红外光谱、紫外-可见光谱、扫描电子显微镜等对杂化膜进行了表征,探讨了杂化膜中TiO2含量对杂化膜的热性能、吸湿性能和力学性能的影响。结果表明,纳米TiO2粒子均匀分散在PI基体中,TiO2的掺入及与有机基体的杂化提高了材料的热分解温度与玻璃化转变温度,降低了材料的吸湿性能,改善了材料的力学性能。当TiO2含量为6%时,杂化膜的拉伸弹性模量和断裂强度达到最大值,分别为纯PI膜的2.17倍和1.63倍。     

聚酰亚胺/二氧化硅杂化膜的制备与介电性能的研究

采用溶胶-凝胶法制备了BTDA-ODA聚酰亚胺/SiO2杂化膜,利用红外分光光度计（FTIR）、热重分析仪（TGA）和透射电镜（TEM）研究了杂化膜的微观结构和热性能,并对杂化膜的介电常数（e）和介电损耗（tand）随SiO2粒子含量和电场频率的变化进行了分析和讨论。结果表明：杂化膜的介电常数和介电损耗随SiO2粒子含量的增加而增大,随电场频率的升高而逐渐降低,用考虑到粒子的形状因素和两相间相互作用的EMT模型可以预测聚酰亚胺/SiO2杂化膜的介电常数。     

聚酰亚胺/无机纳米杂化材料的研究

聚酰亚胺是一种综合性能优异的材料,现已被广泛应用于航空航天及微电子领域.但是其明显的性能缺陷限制了其在高温和精密状态下的应用;而无机纳米粒子的引入,大大弥补了其性能缺陷（如较高的热膨胀系数和较低的吸水性）,非常适合对PI改性.本文阐述了PI纳米杂化材料的制备方法,介绍了纳米杂化材料的特点及应用.     

水含量对PI/SiO2纳米杂化薄膜热稳定性的影响

以TEOS为无机前躯体,采用溶胶-凝胶路线成功制备了水含量不同的3种聚酰亚胺/二氧化硅(P1/SiO2)纳米杂化薄膜.采用傅立叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、热重分析(TGA)等方法研究了杂化薄膜的结构与热稳定性.研究结果表明:水含量对PI/SiO2杂化薄膜热稳定性影响很大.在水含量不同的3种杂化薄膜中,当水含量为1:6时,热稳定性最高.在质量损失为5％时,杂化薄膜的热分解温度为592.1℃.与纯PI相比,热稳定性升高.     

Effect of chemical interaction on morphology and mechanical properties of CPI‐OH/SiO2 hybrid films with coupling agent

A novel hybrid film composed of copolyimide with hydroxyl group, silica and γ‐glycidyloxypropyltrimethoxysilane (CPI‐OH/SiO₂/GOTMS) was prepared by the sol–gel process based on hydrolyzed tetraethoxysilane (TEOS) under acidic condition. GOTMS, as the coupling agent, and hydroxyl group in PI chain were used to improve the compatibility between the PI and SiO₂. The components, morphologies, and mechanical properties of the hybrids were investigated by FTIR, UV–vis, SEM, stress–strain tests, and DMA. The results showed that SiO₂ particle size significantly decreased, fractured cross sections of hybrid were rougher, and the surfaces of spherical SiO₂ particles were more widely covered by PI component. The tensile mechanical properties of hybrids increased when adding GOTMS. The critical points of maximum tensile strength and elongation at break move from 11 to 16 wt % SiO₂ content. DMA results showed that the storage moduli of hybrids with GOTMS, when above 260°C, were obviously higher than those without GOTMS; the tan δ transition temperature of hybrid films went up from 317 to 337°C. It suggests that chemical interaction between CPI‐OH and SiO₂ is formed and the PI molecular mobility is restricted by the chemical interaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3530–3538, 2007     

Synthesis and characterization of polyimide/silica hybrid nanocomposites

Polyimide/silica (PI/SiO₂) hybrid nanocomposites were prepared by the sol‐gel process directly from a soluble polyimide. This soluble PI was synthesized from a diamine with a pendant phenyl hydroxyl group, 4,4′‐diamino‐4″‐hydroxy triphenyl methane (DHTM) and a dianhydride, pyromellitic dianhydride (PMDA), followed by cyclodehydration. Three ways of preparing PI/SiO₂ hybrid nanocomposites were investigated in this study. Two of them used the coupling agent 3‐glycidyloxy propyl trimethoxysilane (GPTMOS) to enhance the compatibility between PI and silica. The coupling agent can react with the PI to form covalent bonds. The structures of the modified hybrid nanocomposites were identified with a FTIR, whereas the size of the silica in polyimides was characterized with a scanning electron microscope. The size of silica particles in the modified system was <100 nm. The covalently bonded PI/SiO₂ hybrid nanocomposites prepared by the novel third approach exhibited good transparency when the silica content was <15%. Moreover, their thermal and mechanical properties exhibited a significant improvement. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 382–393, 2004     

Preparation and properties of organosoluble montmorillonite/polyimide hybrid materials

Organosoluble montmorillonite/polyimide hybrids were prepared using a monomer solution intercalation polymerization method. Montmorillonite was organo-treated with p-aminobenzoic acid and the organosoluble polyimide was based on pyromellitic dianhydride and 4,4′-diamino-3,3′-dimethyldiphenylmethane. The particle size of montmorillonite in the hybrid containing 1 wt % of montmorillonite is about 400 nm. The strength and the toughness of montmorillonite/polyimide hybrids are improved simultaneously when the montmorillonite content is below 5 wt %. The thermal stabilities of montmorillonite/polyimide hybrids are obviously improved and their thermal expansion coefficients are reduced. When the montmorillonite content is below 5 wt %, the montmorillonite/polyimide hybrids are soluble in strong aprotonic polar organic solvents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2063–2068, 1999     

Synthesis and properties of low‐color polyimide/silica hybrid films

A series of polyimide precursors, poly(amic acid)s, containing propyltrimethoxysliane at two chain ends were prepared from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( I ) with six commercially available dianhydrides, followed by end‐capping with 3‐aminopropyltrimethoxysilane (APrTMOS). A new class of fluorine‐containing polyimide/silica composite films ( III ) with chemical bonds between the fluorinated polyimide backbone and the silica network has been synthesized from the APrTMOS‐terminated precursors with tetramethoxysilane via the sol‐gel process and thermal cyclodehydration. The resultant hybrid films were light‐colored, flexible, and tough. They had high levels of thermal stability associated with high glass‐transition temperatures (>251°C), 10% weight‐loss temperatures in excess of 527°C, and char yields at 800°C in nitrogen higher than 60%. For a comparative study, the analogous nonfluorinated polyimide/silica hybrid films ( III′ ), based on 4,4′‐bis(4‐aminophenoxy)biphenyl ( I′ ), and the neat fluorinated polyimide films ( IV ), based on diamine I , were also synthesized and characterized. The hybrid films of the fluorinated series III showed a higher transparency and less color intensity when compared with the nonfluorinated III′ analogs. They also revealed a lower refraction index and birefringence than pure polyimides ( IV ). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4046–4052, 2007     

Wear,thermal, and physical properties of fluorine-containing polyimide/silica hybrid nanocomposite coatings

This study prepared fluorine and SiO₂ particles containing organic–inorganic hybrid polyimide nanocomposite coatings (PISFs) with inorganic content in the range of 5–20% in pure polyimide solutions via the sol–gel process. Polyimide hybrid structures containing fluorine and SiO₂ particles were synthesized by using perfluorooctyltriethoxysilane and tetraethyl orthosilicate. These formulations were applied on aluminum sheets by using a 75 μm wire wound applicator, and the coatings were cured for 8 h at room temperature and then 24 h at 100 °C. Increased inorganic contents caused slight decreases in the initial decomposition temperatures, but the char yield values increased for PISF15 and PISF20. All samples exhibited hydrophobic properties. When all samples were compared, PISF5 and PISF10 exhibited hydrophobicity, high wear resistance and thermal properties. Additionally, PISF5 and PISF10 showed high adhesion, hardness, and methyl ethyl ketone solvent resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47399.     

Preparation and properties of ternary polyimide/SiO2/polydiphenylsiloxane composite films

A series of novel ternary polyimide/SiO₂/polydiphenylsiloxane (PI/SiO₂/PDPhS) composite films were prepared through co‐hydrolysis and condensation between tetramethoxysilane, diphenyldimethoxysilane (DDS) and aminopropyltriethoxysilane‐terminated polyamic acid, using an in situ sol–gel method. The composite films exhibited good optical transparency up to 30 wt% of total content of DDS and SiO₂. SEM analysis showed that the PDPhS and SiO₂ were well dispersed in the PI matrix without macroscopic separation of the composite films. TGA analysis indicated that the introduction of SiO₂ could improve the thermal stability of the composite films. Dynamic mechanical thermal analysis showed that the composite films with low DDS content (5 wt%) had a higher glass transition temperature (T_g) than pure PI matrix. When the content of DDS was above 10 wt%, the T_g of the composite decreased slightly due to the plasticizing effect of flexible PDPhS linkages on the rigid PI chains. The composite films with high SiO₂ content exhibited higher values of storage modulus. Tensile measurements also showed that the modulus and tensile strength of the composite films increased with increasing SiO₂ content, and the composite films still retained a high elongation at break due the introduction of DDS. The density and water absorption of the composite films were also characterized. Copyright © 2006 Society of Chemical Industry     

偶联剂对SiO_2/CE复合材料热学及摩擦性能的影响

利用纳米SiO2对氰酸酯树脂(CE)进行改性,通过热失重分析(TGA)、摩擦磨损性能测试及扫描电镜(SEM)分析研究了纳米SiO2及其表面处理(分别选用小分子偶联剂KH-560和大分子偶联剂SEA-171)对纳米SiO2/CE复合材料热学及摩擦性能的影响,并初步探讨了其作用机理。结果表明,经SEA-171表面处理的纳米SiO2质量分数为3.0%时,其CE复合材料的热分解温度比纯CE树脂提高了将近75℃,摩擦系数降低了约25%,磨损率降低了77%。偶联剂的加入增加了纳米SiO2与CE树脂之间的界面粘结作用,因而复合材料的耐热性能和摩擦性能等得以提高。     

偶联剂对白炭黑／SBR复合材料力学性能的影响

研究了4种偶联剂KH-550、KH-792、WD-60和HG-305对白炭黑／SBR复合材料力学性能和热空气老化性能的影响。研究结果表明：当KH-550用量为4．0份时,复合材料的综合力学性能最好,与未改的白炭黑／SBR复合材料相比,其拉伸强度和撕裂强度分别提高了77％和24％;复合材料的老化实验结果表明,经偶联剂改性的复合材料的耐热老化性能有所下降,其中HG-305改性的复合材料抗老化性较好。     

Study on morphology control and how to affect mechanical properties of polyimide/silica hybrid films

A series of polyimide (PI)/silica hybrid films were prepared by sol–gel method, using hydrolyzed tetraethoxysilane and poly amic acid‐imides (PAA‐Is), which were different imidization degree controlled by chemical imidization method. The imidization degree was characterized by Fourier transform infrared spectra and their corresponding morphology was characterized by scanning electron microscopy. The results show that there are two kinds of silica particles and their formative morphology obeys the double phase separation mechanism. According to the increase of PAA‐I imidization degree, amount of nano silica particles decreased and the diameter of macro silica particles increased in the hybrid films. Tensile testing, dynamic mechanical analysis, and thermal mechanical analysis results show that, according to the amount of nano silica particles increasing, the hybrids have the higher the mechanical properties, glass transition temperature (T_g), and thermal expansion coefficient. Through controlling PI/silica hybrid films microstructure, its mechanical properties can be controlled. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010