一系列含不同长度亚甲基单元的液晶聚酯及新型环氧树脂固化促进剂与环氧树脂的固化研究
|
摘要
本文用对苯二甲酰双(4-氧基苯甲酰氯)(TOBC)和4,4'-双(ω-羟基烷氧基)联苯(nBP,n=2,4,6),通过溶液缩聚法合成了一系列含有联苯和三元芳香酯液晶基元及不同长度亚甲基链的主链型热致性液晶聚酯(PBTn, n=2,4,6),使用多种光谱技术和元素分析对单体和PBTn的结构进行了表征,利用差示扫描量热仪(DSC)、偏光显微镜(POM)、小角X光散射仪(SAXS)、热重分析(TG)和大角X光粉末衍射仪(WAXD)对PBTn的溶解能力、热性质、液晶性质和结晶度进行了研究。结果发现聚酯的性质与结构中亚甲基链的长度有关,亚甲基数量的增加会导致聚酯溶解度增加,液晶相温度范围变宽,液晶-各向同性相转变温度下降,热稳定性提高,结晶度降低。聚酯在氮气气氛中的热分解温度(5%质量损失)都超过了380℃。PBT2没有液晶相,PBT4和PBT6则具有近晶型液晶相并且在液晶相时表现出较高的粘度。
本文还成功制备了一系列新型的含有联苯和不同长度亚甲基单元的环氧树脂固化促进剂(LCECAn, n=2,4,6),用DSC分别研究了其固化双酚A二缩水甘油醚型环氧树脂(E-51)和一种合成的联苯二酚二缩水甘油醚型环氧树脂(LCE)的固化行为。在用Ozawa方程对其进行升温固化反应动力学研究的同时,还利用一种自催化固化动力学模型对各体系的恒温固化动力学数据进行了拟合。此外,通过二次升温DSC和TG测得了各体系固化产物的玻璃化转变温度(Tg)及热分解温度(Td)。结果表明,固化剂LCECAn中亚甲基的数量对E-51/LCECAn和LCE/LCECAn各体系的固化峰顶温度影响很小,升温固化法计算得到的反应活化能数值高于恒温法得到的活化能,并且E-51/LCECAn和LCE/LCECAn固化产物的Tg和Td值都随着LCECAn中亚甲基数量的增加而降低。
最后,本文还以DSC、动态热机械分析(DMA)、TG为手段,分别研究了LCECAn对LCE/DDM和LCE/Dicy固化体系的促进作用、升温固化反应动力学、动态力学行为和热稳定性进行了系统研究,并通过热台偏光显微镜对各固化体系的织态结构进行了观察。结果显示,添加10%LCECAn可使LCE/DDM和LCE/Dicy体系的固化峰顶温度降低15-20℃；各体系固化产物在偏光显微镜下都能显示出明显的液晶双折射,并且在DMA曲线上显示一个液晶结构单元引起的α’松弛峰,此液晶松弛峰有利于提高体系的冲击韧性；随着促进剂LCECAn中亚甲基数量的增加,LCE/DDM/LCECAn各固化试样的热稳定性逐渐提高,而LCE/Dicy/LCECAn固化产物的热稳定性则不断下降。
A homologous series of main-chain thermotropic polyesters (PBTn, n=2,4,6) containing biphenyl and triad aromatic ester mesogenic units interconnected by n-methylene spacers in the main chain were prepared from terephthaloyl bis(4-oxybenzoyl chloride) (TOBC) and 4,4'-bis(ω-hydroxyalkyloxy)biphenyls (nBP, n=2,4,6) by solution polycondensation. The chemical structures of the monomers and PBTn were characterized by spectroscopic techniques and elemental analysis. The solubility, crystallinity, thermal and liquid crystalline properties of PBTn were investigated by differential scanning calorimetry (DSC), polarizing microscopy (POM), small-angle X-ray scattering (SAXS), thermogravimetric analyses (TG) and wide-angle X-ray diffraction (WAXD), and they were found to be closely dependent on the length of the methylene spacers. The increasing methylene units led to improved solubility, broader liquid crystalline range, reduced mesophase-isotropic transition point, higher thermal stability and decreasing crystallinity. The decomposition temperatures (5% mass loss) of the polymers were above 380℃in nitrogen atmosphere and only PBT4 and PBT6 exhibited smectic mesophases as well as high viscosity in the mesophase.
A new homologous series of epoxy resin curing accelerators (LCECAn, n=2,4, 6) containing 4,4'-biphenyl and n-methylene units were also successfully synthesized. The curing behaviors of a commercial diglycidyl ether of bisphenol-A epoxy (E-51) and 4,4'-bis(2,3-epoxypropoxy)biphenyl (LCE) by using LCECAn as the curing agents have been investigated by DSC, respectively. The Ozawa equation was applied to the curing kinetics based upon the dynamic DSC data, and the isothermal DSC data was fitted using an autocatalytic curing model. The glass transition temperatures (Tg) of the cured epoxy systems were determined by DSC upon the second heating, and the thermal decomposition temperatures (Td) were obtained by TG. The results show that the number of methylene units in LCECAn has little influence on the curing peak temperatures of E-51/LCECAn and LCE/LCECAn systems. In addition, the activation energies obtained by the dynamic method proved to be larger than those by the isothermal method. Furthermore, both the Tg and Td of the cured E-51/LCECAn systems and LCE/LCECAn systems decreased with the increase in the number of methylene units in LCECAn.
Finally, the promoting effects of LCECAn on the cure of LCE/DDM and LCE/Dicy systems and their dynamic curing kinetics were studied by DSC. The textures of LCE/DDM/LCECAn and LCE/Dicy/LCECAn curing systems were observed by POM. The dynamic mechanical properties and thermal stabilities of their thermosets were also investigated by dynamic mechanical analysis (DMA) and TG, respectively. It was found that the add of LCECAn (10%) to LCE/DDM and LCE/Dicy systems decreased their curing peak temperatures by 15 to 20℃. When observed under POM, the cured products of LCE/DDM/LCECAn and LCE/Dicy/LCECAn showed obvious briefregence of liquid crystal. Moreover, aα' relaxation caused by liquid cyrstal was found on their DMA curves, suggesting an improved toughness. As the number of the methylene units in LCECAn increased, the thermal stability of LCE/DDM/LCECAn improved while the thermal stability of LCE/Dicy/LCECAn dropped.
本文还成功制备了一系列新型的含有联苯和不同长度亚甲基单元的环氧树脂固化促进剂(LCECAn, n=2,4,6),用DSC分别研究了其固化双酚A二缩水甘油醚型环氧树脂(E-51)和一种合成的联苯二酚二缩水甘油醚型环氧树脂(LCE)的固化行为。在用Ozawa方程对其进行升温固化反应动力学研究的同时,还利用一种自催化固化动力学模型对各体系的恒温固化动力学数据进行了拟合。此外,通过二次升温DSC和TG测得了各体系固化产物的玻璃化转变温度(Tg)及热分解温度(Td)。结果表明,固化剂LCECAn中亚甲基的数量对E-51/LCECAn和LCE/LCECAn各体系的固化峰顶温度影响很小,升温固化法计算得到的反应活化能数值高于恒温法得到的活化能,并且E-51/LCECAn和LCE/LCECAn固化产物的Tg和Td值都随着LCECAn中亚甲基数量的增加而降低。
最后,本文还以DSC、动态热机械分析(DMA)、TG为手段,分别研究了LCECAn对LCE/DDM和LCE/Dicy固化体系的促进作用、升温固化反应动力学、动态力学行为和热稳定性进行了系统研究,并通过热台偏光显微镜对各固化体系的织态结构进行了观察。结果显示,添加10%LCECAn可使LCE/DDM和LCE/Dicy体系的固化峰顶温度降低15-20℃；各体系固化产物在偏光显微镜下都能显示出明显的液晶双折射,并且在DMA曲线上显示一个液晶结构单元引起的α’松弛峰,此液晶松弛峰有利于提高体系的冲击韧性；随着促进剂LCECAn中亚甲基数量的增加,LCE/DDM/LCECAn各固化试样的热稳定性逐渐提高,而LCE/Dicy/LCECAn固化产物的热稳定性则不断下降。
A homologous series of main-chain thermotropic polyesters (PBTn, n=2,4,6) containing biphenyl and triad aromatic ester mesogenic units interconnected by n-methylene spacers in the main chain were prepared from terephthaloyl bis(4-oxybenzoyl chloride) (TOBC) and 4,4'-bis(ω-hydroxyalkyloxy)biphenyls (nBP, n=2,4,6) by solution polycondensation. The chemical structures of the monomers and PBTn were characterized by spectroscopic techniques and elemental analysis. The solubility, crystallinity, thermal and liquid crystalline properties of PBTn were investigated by differential scanning calorimetry (DSC), polarizing microscopy (POM), small-angle X-ray scattering (SAXS), thermogravimetric analyses (TG) and wide-angle X-ray diffraction (WAXD), and they were found to be closely dependent on the length of the methylene spacers. The increasing methylene units led to improved solubility, broader liquid crystalline range, reduced mesophase-isotropic transition point, higher thermal stability and decreasing crystallinity. The decomposition temperatures (5% mass loss) of the polymers were above 380℃in nitrogen atmosphere and only PBT4 and PBT6 exhibited smectic mesophases as well as high viscosity in the mesophase.
A new homologous series of epoxy resin curing accelerators (LCECAn, n=2,4, 6) containing 4,4'-biphenyl and n-methylene units were also successfully synthesized. The curing behaviors of a commercial diglycidyl ether of bisphenol-A epoxy (E-51) and 4,4'-bis(2,3-epoxypropoxy)biphenyl (LCE) by using LCECAn as the curing agents have been investigated by DSC, respectively. The Ozawa equation was applied to the curing kinetics based upon the dynamic DSC data, and the isothermal DSC data was fitted using an autocatalytic curing model. The glass transition temperatures (Tg) of the cured epoxy systems were determined by DSC upon the second heating, and the thermal decomposition temperatures (Td) were obtained by TG. The results show that the number of methylene units in LCECAn has little influence on the curing peak temperatures of E-51/LCECAn and LCE/LCECAn systems. In addition, the activation energies obtained by the dynamic method proved to be larger than those by the isothermal method. Furthermore, both the Tg and Td of the cured E-51/LCECAn systems and LCE/LCECAn systems decreased with the increase in the number of methylene units in LCECAn.
Finally, the promoting effects of LCECAn on the cure of LCE/DDM and LCE/Dicy systems and their dynamic curing kinetics were studied by DSC. The textures of LCE/DDM/LCECAn and LCE/Dicy/LCECAn curing systems were observed by POM. The dynamic mechanical properties and thermal stabilities of their thermosets were also investigated by dynamic mechanical analysis (DMA) and TG, respectively. It was found that the add of LCECAn (10%) to LCE/DDM and LCE/Dicy systems decreased their curing peak temperatures by 15 to 20℃. When observed under POM, the cured products of LCE/DDM/LCECAn and LCE/Dicy/LCECAn showed obvious briefregence of liquid crystal. Moreover, aα' relaxation caused by liquid cyrstal was found on their DMA curves, suggesting an improved toughness. As the number of the methylene units in LCECAn increased, the thermal stability of LCE/DDM/LCECAn improved while the thermal stability of LCE/Dicy/LCECAn dropped.
引文
[1]范星河.图解液晶聚合物——分子设计、合成和应用.北京：化学工业出版社,2005.3-3
[2]Singh S,Dunmur D A. Liquid crystals:fundamentals. Singapore:World Scientific,2002.1-1
[3]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.1-3
[4]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific,2004.2-2
[5]周其凤,王新久.液晶高分子.北京：科学出版社,1999.9-9
[6]Cladis P E. New Liquid-Crystal Phase Diagram. Phys Rev Lett,1975,35(1):48-48
[7]Cladis P E. The re-entrant nematic and the compounds of Gray. Liq Cryst,1998,24 (1): 15-20
[8]殷敬华,莫志深.现代高分物理学：上册.北京：科学出版社,2001.338-338
[9]Brown G H, Wolken J J. Liquid crystals and biological structures. New York:Academic Press,1979
[10]吴大诚,谢新光,徐建军.高分子液晶.成都：四川教育出版社,1988.8-8
[11]Seddon J, Templer R. Liquid crystals and the living cell. New Sci,1991,130(1769): 45-45
[12]Kwolek S L. Optically anisotropic aromatic polyamide dopes. United States Patent, 3,671,542.1972-01-20
[13]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific,2004.10-10
[14]Li C, Xie X, Cao S. Synthesis and characterization of liquid crystalline copolyesters containing horizontal and lateral rods in main chain. Polym Adv Technol,2002,13(3-4): 178-187
[15]Martins A F, Ferreira J B, Volino F, et al. NMR study of some thermotropic nematic polyesters with mesogenic elements and flexible spacers in the main chain. Macromolecules,1983,16(2):279-287
[16]Han H, Bhowmik P K, Frisch K C. Wholly aromatic thermotropic liquid crystalline polyesters of 3,3'-bis(phenyl)-4,4'-biphenol with 4,4'-benzophenone dicarboxylic acid. J Polym Sci, Part A:Polym Chem,1997,35(4):769-785
[17]Bhowmik P K, Han H, Cebe J J, et al. Thermotropic liquid-crystalline polyesters of 4,4'-biphenol and phenyl-substituted 4,4'-biphenols with 4,4'-oxybisbenzoic acid. J Polym Sci, Part A:Polym Chem,2002,40(1):141-155
[18]Van L D, Strzelecki L. Influence de la structure sur les proprietes mesomorphes des polyesters--Ⅱ. Eur Polym J,1980,16(4):303-306
[19]Strzelecki L, Liebert L. Influence de la structure sur les proprietes mesomorphes de polyesters--Ⅲ. Eur Polym J,1981,17(12):1271-1279
[20]Iimura K, Koide N, Ohta R, et al. Syntheses of thermotropic liquid crystalline polymers, 1.Azoxy and azo type polyesters. Makromol Chem,1981,182(10):2563-2568
[21]Meurisse P, Noel C, Monnerie L, et al. Polymers with mesogenic elements and flexible spacers in the main chain:Aromatic-aliphatic polyesters. Br Polym J,1981,13(2):55-63
[22]Ringsdorf H, Schneller A. Synthesis, structure and properties of liquid crystalline polymers. Br Polym J,1981,13(2):43-46
[23]Fradet A, Heitz W. Thermotropic polyesters, copolyesters and model compounds based on terephthalic acid and 4,4'-alkylenediphenols. Makromol Chem,1987,188(6):1233-1251
[24]Krigbaum W R, Watanabe J, Ishikawa T. Thermotropic polyesters.2. Investigation of the mesophase properties of polymers based on 4,4'-dihydroxybiphenyl. Macromolecules, 1983,16(8):1271-1279
[25]Meurisse P, Laupretre F, Noel C. Polyesters with Mesogenic Elements and Flexible Spacers in the Main Chain:A Further Investigation by Conformational Energy Calculations. Mol Cryst Liq Cryst,1984,110:41-58
[26]Zentel R, Reckert G. Liquid crystalline elastomers based on liquid crystalline side group, main chain and combined polymers. Makromol Chem,1986,187 (8):1915-1926
[27]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.102-102
[28]Ober C, Jin J -I, Zhou Q, et al. Liquid crystal polymers with flexible spacers in the main chain. Adv Polym Sci,1984,59:121-121
[29]Roviello A, Sirigu A. Odd-even effects in polymeric liquid crystals. Makromol Chem, 1982,183(4):895-904
[30]Griffin A C, Havens S J. Phase studies of polymer/small-molecule liquid-crystalline mixtures by differential scanning calorimetry. J Polym Sci, Part C:Polym Lett,1980, 18(4):259-263
[31]周其凤,王新久.液晶高分子.北京：科学出版社,1999.128-129
[32]董炎明.高分子分析手册.北京：中国石化出版社,2004.455-455
[33]殷敬华,莫志深.现代高分物理学：上册.北京：科学出版社,2001.330-330
[34]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.138-138
[35]周其凤,王新久.液晶高分子.北京：科学出版社,1999.101-101
[36]Qian R Y, Shen D Y, Li H M. Fourier Transform Infrared Studies of Poly (Ethylene Terephthalate) Film in the Glass Transition Region. Chin J Polym Sci,1989,7(2):150-158
[37]殷敬华,莫志深.现代高分物理学：下册.北京：科学出版社,2001.969-969
[38]Dierking I. Textures of Liquid Crystals. Weinheim:Wiley-Vch Verlag,2004.163-165
[39]董炎明.高分子分析手册.北京：中国石化出版社,2004.570-570
[40]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.19-20
[41]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.238-238
[42]闻再庆,沈德言,周其凤.主链型热致性液晶高分子芳香共聚酯的红外光谱研究.分析测试学报,1988,7(6)：14-19
[43]Owens F J, Poole C P, Farach H A. Magnetic resonance of phase transitions. New York: Academic Press,1979
[44]Blinc R, Vilfan M, Rutar V. On the nature of spin-lattice relaxation in nematic MBBA. Solid State Commun,1975,17(2):171-174
[45]孟庆安,胡传民,曹琪娟,等.热致液晶CPHOB的有序参数与核磁共振弛豫.物理学报,1997,46(10)：1961-1964
[46]陈群,杨光,王源身,等.固体变温高分辨核磁共振碳谱研究聚氨醋型热致液晶高聚物.高等学校化学学报,1996,17(8)：1300-1304
[47]Papadimitrakopoulos F, Hsu S L, MacKnight W J. Investigation of a monotropic liquid crystal polyurethane based on biphenol,2,6-tolylene diisocyanate, and a six methylene containing flexible spacer.1. Thermal and structure characterization. Macromolecules, 1992,25(18):4671-4681
[48]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.3-3
[49]Guo Q, Huang Y, Zhang Y -Y, et al. Curing behavior of epoxy resins with a series of novel curing agents containing 4,4'-biphenyl and varying methylene units. J Therm Anal Calorim, DOI:10.1007/s10973-010-0764-2
[50]张进.环氧树脂工业的现状及发展建议.化学工业与工程技术,2005,26(1)：38-41
[51]孙曼灵.环氧树脂应用原理与技术.北京：机械工业出版社,2003.669-675
[52]Carfagna C, Amendola E, Giamberini M. Liquid crystalline epoxy based thermosetting Polymers. Prog Polym Sci,1997,22(8):1607-1647
[53]李桂林.环氧树脂与环氧涂料.北京：化学工业出版社,2003.1-42
[54]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.14-24
[55]Mimura K, Ito H. Characteristics of epoxy resin cured with in situ polymerized curing agent. Polymer,2002,43(26):7559-7566
[56]陈清松,李晓燕,柯金炼,等.松香改性酚醛环氧树脂的合成与表征.广州化学,2007,32(4)：6-11
[57]张军营,张孝阿.新型有机硅化环氧树脂的合成与表征.北京化工大学学报,2008,35(2)：38-41
[58]陈立新,蓝立文,王汝敏.液晶环氧树脂的研究概况.材料导报,200,14(9)：41-43
[59]Muller H -P, Gipp R, Heine H. Liquid-crystalline diglycidyl compounds, their preparation and use in curable epoxide mixtures. German Patent, C07D3622610.1986-07-05
[60]Muller H P, Gipp R, Heine H. Liquid-crystalline diglycidyl compounds, the preparation of these, and the use of these in curable epoxide mixtures. United States Patent, 4,764,581.1988-08-16
[61]刘国栋,李卿,张广林,等.一种液晶环氧树脂改性双酚A环氧树脂的方法.中国专利,CN200810052793.6.2008-04-18
[62]Szczepaniak B, Penczek P, Warchaowska M, et al. Liquid crystalline epoxy resins by polyaddition of diglycidyl ether of 4,4prime-dihydroxybiphenyl and difunctional aromatic compounds. J Polym Sci, Part A:Polym Chem,1998,36(1):21-29
[63]刘伟昌,申胜军,周其庠,等.含偶氮介晶基元的环氧化合物的合成.清华大学学报(自然科学版),1998,38(12)：104-106
[64]Barclay G G, Ober C K, Papathomas K I, et al. Liquid crystalline epoxy thermosets based on dihydroxymethylstilbene:Synthesis and characterization. J Polym Sci, Part A:Polym Chem,1992,30(9):1831-1843
[65]Ashida T, Katoh A, Handa K, et al. Structure and properties of epoxy resins modified with acrylic particles. J Appl Polym Sci,1999,74(12):2955-2962
[66]郭宝春,贾德民,傅伟文,等.聚醚酰亚胺对氰酸酯树脂/环氧树脂共混物的增韧作用.材料研究学报,2002,16(1)：99-104
[67]Mimura K, Ito H, Fujioka H. Improvement of thermal and mechanical properties by control of morphologies in PES-modified epoxy resins. Polymer,2000,41(12):4451-4459
[68]Varley R J, Hodgkin J H, Simon G P. Toughening of a trifunctional epoxy system:Part VI. Structure property relationships of the thermoplastic toughened system. Polymer,2001, 42(8):3847-3858
[69]朱永群,胡巧玲,付晏彬,等.同步互穿和顺序互穿对PU/EPIPN性能及微结构的影响.高分子材料科学与工程,1999,15(6)：148-150
[70]黄增芳,谭松庭,王霞瑜.热致性液晶聚酯的合成及与环氧树脂共混物的性能研究.中国塑料,2003,17(12)：32-35
[71]蔡辉,闫逢元,薛群基.环氧树脂研究与应用进展.材料导报,2003,17(2)：46-48
[72]梁威,杨青芳,马爱洁.环氧树脂增韧改性新技术.工程塑料应用,2004,32(8)：68-71
[73]侯雪光,王卫华.环氧固化剂的研究现状与未来.粘接,2008,29(1)：49-51
[74]胡幼华,高辉,叶士标,等.环氧树脂材料的研究概况.绍兴文理学院学报,2000,20(6)：93-99
[75]胡玉明,吴良义.固化剂.北京：化学工业出版社,2004.477-478
[76]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.199-199
[77]王承霞,徐泽晶,黄晓天,等.环氧树脂固化剂的研究现状.河南建材,2005,2005(5)：42-43
[78]焦剑,蓝立文,宁荣昌.一种中温固化环氧树脂的研究.复合材料学报,2000,17(2)： 8-11
[79]胡玉明,吴良义.固化剂.北京：化学工业出版社,2004.144-144
[80]李清秀,张炜,周红卫.环氧树脂的韧性固化剂的合成.复旦学报(自然科学版),1997,36(4)：469-475
[81]王青.环氧树脂固化剂研究进展.全面腐蚀控制,2001,15(6)：18-20
[82]韦春,钟文斌,谭松庭,等.热致性液晶固化剂增韧环氧树脂的研究.中国塑料,2001,15(5)：42-45
[83]Kamal M R, Ryan M E. The behavior of thermosetting compounds in injection molding cavities. Polym Eng Sci,1980,20(13):859-867
[84]Kamal M R, Ryan M E. Reactive polymer processing:Techniques and trends. Adv Polym Tech,1984,4(3-4):323-348
[85]Batch G L, Macosko C W. Kinetic model for crosslinking free radical polymerization including diffusion limitations. J Appl Polym Sci,1992,44(10):1711-1729
[86]Patel P S, Shah P P, Patel S R. Differential scanning calorimetry investigation of curing of bisphenolfurfural resins. Polym Eng Sci,1986,26(17):1186-1190
[87]Vinnik R, Roznyatovsky V. Kinetic method by using calorimetry to mechanism of epoxy-amine cure reaction. J Therm Anal Calorim,2003,73(3):807-817
[88]Liu X, Sheng X, Lee J, et al. Isothermal cure characterization of dicyclopentadiene. J Therm Anal Calorim,2007,89(2):453-457
[89]张竞,黄培.环氧树脂固化动力学研究进展.材料导报,2009,23(7)：58-61
[90]Kissinger H E. Reaction Kinetics in Differential Thermal Analysis. Anal Chem,1957, 29(11):1702-1706
[91]Ozawa T. Kinetic analysis of derivative curves in thermal analysis. J Therm Anal Calorim, 1970,2(3):301-324
[92]Friedman H L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci, Part C:Polym Symp, 1964,6(1):183-195
[93]Vyazovkin S. Alternative description of process kinetics. Thermochim Acta,1992,211: 181-187
[94]Yousefi A, Lafleur P G, Gauvin R. Kinetic studies of thermoset cure reactions:A review. Polym Compos,1997,18(2):157-168
[95]王遵,邢素丽,曾竟成,等.热固性树脂固化反应动力学模型研究进展.高分子材料科学与工程,2007,23(4)：11-14
[96]Flory P J. Principles of Polymer Chemistry. New York:Cornell University Press,1953
[97]Stevenson J K. Free radical polymerization models for simulating reactive processing. Polym Eng Sci,1986,26(11):746-759
[98]Sourour S, Kamal M R. Differential scanning calorimetry of epoxy cure:isothermal cure kinetics. Thermochim Acta,1976,14(1-2):41-59
[99]Gonzalez-Romero V M. Studies of Reactive Polymer Processing with Fiber Glass Reinforcements:[dissertation]. Twin Cities:University of Minnesota,1983
[100]Gonzalez-Romero V M, Casillas N. Isothermal and temperature programmed kinetic studies of thermosets. Polym Eng Sci,1989,29(5):295-301
[101]Kamal M R, Sourour S. Kinetics and thermal characterization of thermoset cure. Polym Eng Sci,1973,13(1):59-64
[102]Kamal M R. Thermoset characterization for moldability analysis. Polym Eng Sci,1974, 14(3):231-239
[103]Dispenza C, Spadaro G. Cure Kinetics of a Tetrafunctional Rubber Modified Epoxy-amine System. J Therm Anal Calorim,2000,61(2):579-587
[104]Fraga F, Soto V, Rodriguez-Nunez E, et al. Cure kinetic of the epoxy network diglycidyl ether of bisphenol A (BADGE n=0)/amantidine. J Therm Anal Calorim,2007,87 (1): 97-100
[105]代晓青,肖加余,曾竟成,等.等温DSC法研究RFI用环氧树脂固化动力学.复合材料学报,2008,25(4)：18-23
[106]李正莉,张有智,王煊军,苟小莉.潜伏性环氧树脂/胺基酰亚胺体系的固化动力学.高分子材料科学与工程,2010,26(1)：85-87
[107]陈梦雪,胡国贞.联苯型环氧-酚醛树脂的恒温固化动力学研究.化工新型材料,2008,36(7)：61-62
[108]孙文兵,张超灿.等温DSC法研究聚酰胺与环氧树脂的固化动力学.武汉理工大学学报,2009,31(6)：28-31
[109]Ober C, Jin J I, Lenz R W. Liquid Crystal Polymers. V. Thermotropic Polyesters with Either Dyad or Triad Aromatic Ester Mesogenic Units and Flexible Polymethylene Spacers in the Main Chain. Polym J,1982,14(1):9-17
[110]Ober C, JinJ -I, Zhou Q, et al. Liquid crystal polymers with flexible spacers in the main chain. Adv Polym Sci,1984,59:103-146
[111]Mix R, Gahde J, Goering H, et al. Segmented polyurethanes with 4,4'-bis-(6-hydroxyhexoxy)biphenyl as chain extender. Part 2. Synthesis and properties of MDI-polyurethanes in comparison with 2,4-TDI-polyurethanes. J Polym Sci, Part A: Polym Chem,1996,34(1):33-44
[112]Ojha U P, Kumar A. Design, synthesis, and characterization of main-chain, aromatic polyesters based on 3,4-ethylenedioxythiophene. J Polym Sci, Part A:Polym Chem,2006, 44(11):3479-3486
[113]Rao V S, Samui A B. Structure-property relationship of photoactive liquid crystalline polyethers containing benzylidene moiety. J Polym Sci, Part A:Polym Chem,2009, 47(8):2143-2155
[114]Stickfort L, Poersch G, Hess M, et al. Liquid-crystalline polyesters based on branched propylene spacers. J Polym Sci, Part A:Polym Chem,1996,34(7):1325-1330
[115]Hoshino H, Jin J I, Lenz R W. Liquid crystalline behavior of polymeric glycols terminated with aromatic diester and diacid mesogenic groups. J Appl Polym Sci,1984,29 (2):547- 554
[116]Kent S L, Geil P H. Folded chain crystallization of random terpolymer liquid crystal polymers from the nematic state. J Polym Sci, Part B:Polym Phys,1992,30(13): 1489-1506
[117]Bagheri M, Rad R Z. Synthesis and characterization of thermotropic liquid crystalline polyesters with biphenyl unit in the main chain. React Funct Polym,2008,68(2):613-622
[118]Volksen W, Jr. J R L, Economy J, et al. Liquid-crystalline copolyesters based on poly(p-oxybenzoate) and poly(p,p-biphenylene terephthalate). J Polym Sci, Part A:Polym Chem,1983,21(8):2249-2259
[119]Ober C, Lenz R W, Galli G, et al. Liquid-crystalline polymers.12. Polyesters with either alternating or random orientation of mesogenic units. Macromolecules,1983,16(7): 1034-1036
[120]Martin P G, Stupp S I. Contrasting behavior of chemically ordered versus chemically disordered liquid-crystal polymers. Macromolecules,1988,21(5):1222-1227
[121]Aharoni S M. Hydrogen-bonded highly regular strictly alternating aliphatic-aromatic liquid-crystalline poly(ester amides). Macromolecules,1988,21(7):1941-1961
[122]Aharoni S M. The first-order transitions of hydrogen-bonded liquid-crystalline poly(esteramides). Macromolecules,1989,22(2):686-693
[123]Sudha J D, Pillai C K S. Hydrogen-bonded thermotropic liquid-crystalline polyester-amides from bis(hydroxy alkamido)aranes:Synthesis and properties. J Polym Sci, Part A:Polym Chem,2003,41(2):335-346
[124]Kent S L, Rybnikar F, Geilt P H, et al. Morphology of a thermotropic random terpolymer liquid crystal polymer crystallized in the bulk:compression mouldings, extrudates and fibres. Polymer,1994,35(9):1869-1879
[125]Kent S L, Geil P H. Annealing Effects in Solution Grown Single Crystals of a Random Terpolymer Liquid Crystal Polymer. J Macromol Sci, Pure Appl Chem,1992,29(11): 315-320
[126]Kent S L, Geil P H. Solution Grown Folded Chain Crystals of a Random Terpolymer Thermotropic Liquid Crystal Polymer. J Macromol Sci, Pure Appl Chem,1991,28 (11): 203-208
[127]Kent S L, Geil P H. Chain folding in single crystals and sheared ("fiber") samples of a liquid crystal polymer. Polym Bull,1991,26(5):579-585
[128]Kent S L, Geil P H. Solution-grown single crystals of random terpolymer liquid crystal polymers:Chain folding, morphology, and effect of annealing. J Macromol Sci, Phys 1992,31(4):413-437
[129]Chandrasekhar S. Liquid crystals. Cambridge University Press,1992.48-51
[130]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.139-139
[131]Zhang B -L, Tang G -L, ShiK -Y, et al. A study on properties of epoxy resin toughened by functionalized polymer containing rigid, rod-like moiety. Eur Polym J,2000,36(1): 205-213
[132]He S, Shi K, Bai J, et al. Studies on the properties of epoxy resins modified with chain-extended ureas. Polymer,2001,42(23):9641-9647
[133]HeSJ, Shi K Y, Guo X Z, et al. Properties of methyltetrahydrophthalic anhydride-cured epoxy resin modified with MITU. Polym Adv Technol,2009,20(2):130-134
[134]Ma S, Liu W, Su Q, et al. Studies on the Thermal Properties of Epoxy Resins Modified with Two Kinds of Silanes. J Macromol Sci, Phys,2010,49(1):43-56
[135]Villanueva M, Fraga I, Rodriguez-Anon J, et al. Study of the influence of a reactive diluent on the rheological properties of an epoxy-diamine system. J Therm Anal Calorim,2009, 98(2):521-525
[136]Villanueva M, Martin-lglesias J, Rodriguez-Anon J, et al. Thermal study of an epoxy system DGEBA (n=0)/mXDA modified with POSS. J Therm Anal Calorim,2009,96 (2): 575-582
[137]Lopez J, Rico M, Montero B, et al. Polymer blends based on an epoxy-amine thermoset and a thermoplastic. J Therm Anal Calorim,2009,95(2):369-376
[138]Zhang B -L, Tang G -L, Shi K -Y, et al. A study on the properties of epoxy resin toughened by a liquid crystal-type oligomer. J Appl Polym Sci,1999,71(1):177-184
[139]张保龙,石可瑜,由英才,等.取代脲促进环氧树脂/双氰胺固化体系反应机理.应用化学,1998,15(4)：95-97
[140]Son P -N, Weber C D. Some aspects of monuron-accelerated dicyandiamide cure of epoxy resins. J Appl Polym Sci,1973,17(5):1305-1313
[141]Mehdipour-Ataei S, Einollahy P. Synthesis, Characterization and Properties of Novel Poly(Ester-Amide-Urethane)s. Macromol Symp,2004,214(1):339-350
[142]Ando M, Uryu T. Synthesis of polymer materials by low energy electron beam. XIII. Structure and properties of EB-cured polymers of bifunctional monomer with biphenyl moiety as mesogenic group. J Polym Sci, Part A:Polym Chem,1990,28(9):2575-2584
[143]李迎法,单书香.4-(1-乙氧乙氧基)正丁基溴的合成.四川化工,1991(1)：10-11
[144]Hsu T -F, Lee Y -D. Properties of thermoplastic polyurethane elastomers containing liquid crystalline chain extender (Ⅰ) synthesis and properties of hard segments. Polymer,1999, 40(3):577-587
[145]Bagheri M, Didehban K, Rezvani Z, et al. Thermotropic polyesters.1:Synthesis, characterization and thermal transition of poly[4,4'-bis(ω-alkoxy)biphenyl isophthalate]. Eur Polym J,2004,40(4):865-871
[146]周其凤,王新久.液晶高分子.北京：科学出版社,1999.106-107
[147]Dewar M J S, Goldberg R S. Effects of central and terminal groups on nematic mesophase stability. J Org Chem,1970,35(8):2711-2715
[148]Bilibin A Y, Tenkovtsev AV, Piraner ON, et al. Thermotropic polyesters,2. Synthesis of regular polyesters from aromatic dicarboxylic acids and phenols or aliphatic diols, and study of their mesomorphic properties. Makromol Chem,1985,186(8):1575-1591
[149]Wei C, Gong Y, Yang X, et al. Synthesis and characterization of thermotropic liquid crystalline polyurethanes from 4,4'-bis(6-hydroxyhexoxy) biphenyl and aliphatic diols. Polym Adv Technol,2009,20(12):1006-1009
[150]Mormann W, Brocher M. "Liquid crystalline" thermosets from 4,4'-bis(2,3-epoxypropoxy)biphenyl and aromatic diamines. Macromol Chem Phys,1996, 197(6):1841-1851
[151]Giamberjni M, Amendola E, Carfagna C. Liquid Crystalline Epoxy Thermosets. Mol Cryst Liq Cryst,1995,266:9-22
[152]Barton J M. Monitoring the curing reaction of an aromatic amine/epoxide resin system by differential scanning calorimetry (DSC):Determination and significance of the activation energy. Makromol Chem,1973,171(1):247-251
[153]Punchaipetch P, Ambrogi V, Giamberini M, et al. Epoxy+liquid crystalline epoxy coreacted networks:I. Synthesis and curing kinetics. Polymer,2001,42 (5):2067-2075
[154]Khanna U, Chanda M. Kinetics of anhydride curing of isophthalic diglycidyl ester using differential scanning calorimetry. J Appl Polym Sci,1993,49(2):319-329
[155]Prime R B. Differential scanning calorimetry of the epoxy cure reaction. Polym Eng Sci, 1973,13(5):365-371
[156]Riccardi CC, Dupuy J, Williams R J J. A simple model to explain the complex kinetic behavior of epoxy/anhydride systems. J Polym Sci, Part B:Polym Phys,1999,37(19): 2799-2805
[157]Peyser P, Bascom W D. Kinetics of epoxy resin polymerization using differential scanning calorimetry. J Appl Polym Sci,1977,21(9):2359-2373
[158]Hale A, Macosko C W, Bair H E. Glass transition temperature as a function of conversion in thermosetting polymers. Macromolecules,1991,24(9):2610-2621
[159]Mathew A P, Packirisamy S, Thomas S. Studies on the thermal stability of natural rubber/polystyrene interpenetrating polymer networks:thermogravimetric analysis. Polym Degrad Stab,2001,72(3):423-439
[160]Gupta A, Singhal R, Nagpal A K. Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam:Process of epoxy cure and kinetics of decomposition. J Appl Polym Sci,2004,92(2):687-697
[2]Singh S,Dunmur D A. Liquid crystals:fundamentals. Singapore:World Scientific,2002.1-1
[3]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.1-3
[4]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific,2004.2-2
[5]周其凤,王新久.液晶高分子.北京：科学出版社,1999.9-9
[6]Cladis P E. New Liquid-Crystal Phase Diagram. Phys Rev Lett,1975,35(1):48-48
[7]Cladis P E. The re-entrant nematic and the compounds of Gray. Liq Cryst,1998,24 (1): 15-20
[8]殷敬华,莫志深.现代高分物理学：上册.北京：科学出版社,2001.338-338
[9]Brown G H, Wolken J J. Liquid crystals and biological structures. New York:Academic Press,1979
[10]吴大诚,谢新光,徐建军.高分子液晶.成都：四川教育出版社,1988.8-8
[11]Seddon J, Templer R. Liquid crystals and the living cell. New Sci,1991,130(1769): 45-45
[12]Kwolek S L. Optically anisotropic aromatic polyamide dopes. United States Patent, 3,671,542.1972-01-20
[13]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific,2004.10-10
[14]Li C, Xie X, Cao S. Synthesis and characterization of liquid crystalline copolyesters containing horizontal and lateral rods in main chain. Polym Adv Technol,2002,13(3-4): 178-187
[15]Martins A F, Ferreira J B, Volino F, et al. NMR study of some thermotropic nematic polyesters with mesogenic elements and flexible spacers in the main chain. Macromolecules,1983,16(2):279-287
[16]Han H, Bhowmik P K, Frisch K C. Wholly aromatic thermotropic liquid crystalline polyesters of 3,3'-bis(phenyl)-4,4'-biphenol with 4,4'-benzophenone dicarboxylic acid. J Polym Sci, Part A:Polym Chem,1997,35(4):769-785
[17]Bhowmik P K, Han H, Cebe J J, et al. Thermotropic liquid-crystalline polyesters of 4,4'-biphenol and phenyl-substituted 4,4'-biphenols with 4,4'-oxybisbenzoic acid. J Polym Sci, Part A:Polym Chem,2002,40(1):141-155
[18]Van L D, Strzelecki L. Influence de la structure sur les proprietes mesomorphes des polyesters--Ⅱ. Eur Polym J,1980,16(4):303-306
[19]Strzelecki L, Liebert L. Influence de la structure sur les proprietes mesomorphes de polyesters--Ⅲ. Eur Polym J,1981,17(12):1271-1279
[20]Iimura K, Koide N, Ohta R, et al. Syntheses of thermotropic liquid crystalline polymers, 1.Azoxy and azo type polyesters. Makromol Chem,1981,182(10):2563-2568
[21]Meurisse P, Noel C, Monnerie L, et al. Polymers with mesogenic elements and flexible spacers in the main chain:Aromatic-aliphatic polyesters. Br Polym J,1981,13(2):55-63
[22]Ringsdorf H, Schneller A. Synthesis, structure and properties of liquid crystalline polymers. Br Polym J,1981,13(2):43-46
[23]Fradet A, Heitz W. Thermotropic polyesters, copolyesters and model compounds based on terephthalic acid and 4,4'-alkylenediphenols. Makromol Chem,1987,188(6):1233-1251
[24]Krigbaum W R, Watanabe J, Ishikawa T. Thermotropic polyesters.2. Investigation of the mesophase properties of polymers based on 4,4'-dihydroxybiphenyl. Macromolecules, 1983,16(8):1271-1279
[25]Meurisse P, Laupretre F, Noel C. Polyesters with Mesogenic Elements and Flexible Spacers in the Main Chain:A Further Investigation by Conformational Energy Calculations. Mol Cryst Liq Cryst,1984,110:41-58
[26]Zentel R, Reckert G. Liquid crystalline elastomers based on liquid crystalline side group, main chain and combined polymers. Makromol Chem,1986,187 (8):1915-1926
[27]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.102-102
[28]Ober C, Jin J -I, Zhou Q, et al. Liquid crystal polymers with flexible spacers in the main chain. Adv Polym Sci,1984,59:121-121
[29]Roviello A, Sirigu A. Odd-even effects in polymeric liquid crystals. Makromol Chem, 1982,183(4):895-904
[30]Griffin A C, Havens S J. Phase studies of polymer/small-molecule liquid-crystalline mixtures by differential scanning calorimetry. J Polym Sci, Part C:Polym Lett,1980, 18(4):259-263
[31]周其凤,王新久.液晶高分子.北京：科学出版社,1999.128-129
[32]董炎明.高分子分析手册.北京：中国石化出版社,2004.455-455
[33]殷敬华,莫志深.现代高分物理学：上册.北京：科学出版社,2001.330-330
[34]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.138-138
[35]周其凤,王新久.液晶高分子.北京：科学出版社,1999.101-101
[36]Qian R Y, Shen D Y, Li H M. Fourier Transform Infrared Studies of Poly (Ethylene Terephthalate) Film in the Glass Transition Region. Chin J Polym Sci,1989,7(2):150-158
[37]殷敬华,莫志深.现代高分物理学：下册.北京：科学出版社,2001.969-969
[38]Dierking I. Textures of Liquid Crystals. Weinheim:Wiley-Vch Verlag,2004.163-165
[39]董炎明.高分子分析手册.北京：中国石化出版社,2004.570-570
[40]张其锦.聚合物液晶导论.合肥：中国科学技术大学出版社,1994.19-20
[41]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.238-238
[42]闻再庆,沈德言,周其凤.主链型热致性液晶高分子芳香共聚酯的红外光谱研究.分析测试学报,1988,7(6)：14-19
[43]Owens F J, Poole C P, Farach H A. Magnetic resonance of phase transitions. New York: Academic Press,1979
[44]Blinc R, Vilfan M, Rutar V. On the nature of spin-lattice relaxation in nematic MBBA. Solid State Commun,1975,17(2):171-174
[45]孟庆安,胡传民,曹琪娟,等.热致液晶CPHOB的有序参数与核磁共振弛豫.物理学报,1997,46(10)：1961-1964
[46]陈群,杨光,王源身,等.固体变温高分辨核磁共振碳谱研究聚氨醋型热致液晶高聚物.高等学校化学学报,1996,17(8)：1300-1304
[47]Papadimitrakopoulos F, Hsu S L, MacKnight W J. Investigation of a monotropic liquid crystal polyurethane based on biphenol,2,6-tolylene diisocyanate, and a six methylene containing flexible spacer.1. Thermal and structure characterization. Macromolecules, 1992,25(18):4671-4681
[48]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.3-3
[49]Guo Q, Huang Y, Zhang Y -Y, et al. Curing behavior of epoxy resins with a series of novel curing agents containing 4,4'-biphenyl and varying methylene units. J Therm Anal Calorim, DOI:10.1007/s10973-010-0764-2
[50]张进.环氧树脂工业的现状及发展建议.化学工业与工程技术,2005,26(1)：38-41
[51]孙曼灵.环氧树脂应用原理与技术.北京：机械工业出版社,2003.669-675
[52]Carfagna C, Amendola E, Giamberini M. Liquid crystalline epoxy based thermosetting Polymers. Prog Polym Sci,1997,22(8):1607-1647
[53]李桂林.环氧树脂与环氧涂料.北京：化学工业出版社,2003.1-42
[54]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.14-24
[55]Mimura K, Ito H. Characteristics of epoxy resin cured with in situ polymerized curing agent. Polymer,2002,43(26):7559-7566
[56]陈清松,李晓燕,柯金炼,等.松香改性酚醛环氧树脂的合成与表征.广州化学,2007,32(4)：6-11
[57]张军营,张孝阿.新型有机硅化环氧树脂的合成与表征.北京化工大学学报,2008,35(2)：38-41
[58]陈立新,蓝立文,王汝敏.液晶环氧树脂的研究概况.材料导报,200,14(9)：41-43
[59]Muller H -P, Gipp R, Heine H. Liquid-crystalline diglycidyl compounds, their preparation and use in curable epoxide mixtures. German Patent, C07D3622610.1986-07-05
[60]Muller H P, Gipp R, Heine H. Liquid-crystalline diglycidyl compounds, the preparation of these, and the use of these in curable epoxide mixtures. United States Patent, 4,764,581.1988-08-16
[61]刘国栋,李卿,张广林,等.一种液晶环氧树脂改性双酚A环氧树脂的方法.中国专利,CN200810052793.6.2008-04-18
[62]Szczepaniak B, Penczek P, Warchaowska M, et al. Liquid crystalline epoxy resins by polyaddition of diglycidyl ether of 4,4prime-dihydroxybiphenyl and difunctional aromatic compounds. J Polym Sci, Part A:Polym Chem,1998,36(1):21-29
[63]刘伟昌,申胜军,周其庠,等.含偶氮介晶基元的环氧化合物的合成.清华大学学报(自然科学版),1998,38(12)：104-106
[64]Barclay G G, Ober C K, Papathomas K I, et al. Liquid crystalline epoxy thermosets based on dihydroxymethylstilbene:Synthesis and characterization. J Polym Sci, Part A:Polym Chem,1992,30(9):1831-1843
[65]Ashida T, Katoh A, Handa K, et al. Structure and properties of epoxy resins modified with acrylic particles. J Appl Polym Sci,1999,74(12):2955-2962
[66]郭宝春,贾德民,傅伟文,等.聚醚酰亚胺对氰酸酯树脂/环氧树脂共混物的增韧作用.材料研究学报,2002,16(1)：99-104
[67]Mimura K, Ito H, Fujioka H. Improvement of thermal and mechanical properties by control of morphologies in PES-modified epoxy resins. Polymer,2000,41(12):4451-4459
[68]Varley R J, Hodgkin J H, Simon G P. Toughening of a trifunctional epoxy system:Part VI. Structure property relationships of the thermoplastic toughened system. Polymer,2001, 42(8):3847-3858
[69]朱永群,胡巧玲,付晏彬,等.同步互穿和顺序互穿对PU/EPIPN性能及微结构的影响.高分子材料科学与工程,1999,15(6)：148-150
[70]黄增芳,谭松庭,王霞瑜.热致性液晶聚酯的合成及与环氧树脂共混物的性能研究.中国塑料,2003,17(12)：32-35
[71]蔡辉,闫逢元,薛群基.环氧树脂研究与应用进展.材料导报,2003,17(2)：46-48
[72]梁威,杨青芳,马爱洁.环氧树脂增韧改性新技术.工程塑料应用,2004,32(8)：68-71
[73]侯雪光,王卫华.环氧固化剂的研究现状与未来.粘接,2008,29(1)：49-51
[74]胡幼华,高辉,叶士标,等.环氧树脂材料的研究概况.绍兴文理学院学报,2000,20(6)：93-99
[75]胡玉明,吴良义.固化剂.北京：化学工业出版社,2004.477-478
[76]王德中.环氧树脂生产与应用(第二版).北京：化学工业出版社,2001.199-199
[77]王承霞,徐泽晶,黄晓天,等.环氧树脂固化剂的研究现状.河南建材,2005,2005(5)：42-43
[78]焦剑,蓝立文,宁荣昌.一种中温固化环氧树脂的研究.复合材料学报,2000,17(2)： 8-11
[79]胡玉明,吴良义.固化剂.北京：化学工业出版社,2004.144-144
[80]李清秀,张炜,周红卫.环氧树脂的韧性固化剂的合成.复旦学报(自然科学版),1997,36(4)：469-475
[81]王青.环氧树脂固化剂研究进展.全面腐蚀控制,2001,15(6)：18-20
[82]韦春,钟文斌,谭松庭,等.热致性液晶固化剂增韧环氧树脂的研究.中国塑料,2001,15(5)：42-45
[83]Kamal M R, Ryan M E. The behavior of thermosetting compounds in injection molding cavities. Polym Eng Sci,1980,20(13):859-867
[84]Kamal M R, Ryan M E. Reactive polymer processing:Techniques and trends. Adv Polym Tech,1984,4(3-4):323-348
[85]Batch G L, Macosko C W. Kinetic model for crosslinking free radical polymerization including diffusion limitations. J Appl Polym Sci,1992,44(10):1711-1729
[86]Patel P S, Shah P P, Patel S R. Differential scanning calorimetry investigation of curing of bisphenolfurfural resins. Polym Eng Sci,1986,26(17):1186-1190
[87]Vinnik R, Roznyatovsky V. Kinetic method by using calorimetry to mechanism of epoxy-amine cure reaction. J Therm Anal Calorim,2003,73(3):807-817
[88]Liu X, Sheng X, Lee J, et al. Isothermal cure characterization of dicyclopentadiene. J Therm Anal Calorim,2007,89(2):453-457
[89]张竞,黄培.环氧树脂固化动力学研究进展.材料导报,2009,23(7)：58-61
[90]Kissinger H E. Reaction Kinetics in Differential Thermal Analysis. Anal Chem,1957, 29(11):1702-1706
[91]Ozawa T. Kinetic analysis of derivative curves in thermal analysis. J Therm Anal Calorim, 1970,2(3):301-324
[92]Friedman H L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci, Part C:Polym Symp, 1964,6(1):183-195
[93]Vyazovkin S. Alternative description of process kinetics. Thermochim Acta,1992,211: 181-187
[94]Yousefi A, Lafleur P G, Gauvin R. Kinetic studies of thermoset cure reactions:A review. Polym Compos,1997,18(2):157-168
[95]王遵,邢素丽,曾竟成,等.热固性树脂固化反应动力学模型研究进展.高分子材料科学与工程,2007,23(4)：11-14
[96]Flory P J. Principles of Polymer Chemistry. New York:Cornell University Press,1953
[97]Stevenson J K. Free radical polymerization models for simulating reactive processing. Polym Eng Sci,1986,26(11):746-759
[98]Sourour S, Kamal M R. Differential scanning calorimetry of epoxy cure:isothermal cure kinetics. Thermochim Acta,1976,14(1-2):41-59
[99]Gonzalez-Romero V M. Studies of Reactive Polymer Processing with Fiber Glass Reinforcements:[dissertation]. Twin Cities:University of Minnesota,1983
[100]Gonzalez-Romero V M, Casillas N. Isothermal and temperature programmed kinetic studies of thermosets. Polym Eng Sci,1989,29(5):295-301
[101]Kamal M R, Sourour S. Kinetics and thermal characterization of thermoset cure. Polym Eng Sci,1973,13(1):59-64
[102]Kamal M R. Thermoset characterization for moldability analysis. Polym Eng Sci,1974, 14(3):231-239
[103]Dispenza C, Spadaro G. Cure Kinetics of a Tetrafunctional Rubber Modified Epoxy-amine System. J Therm Anal Calorim,2000,61(2):579-587
[104]Fraga F, Soto V, Rodriguez-Nunez E, et al. Cure kinetic of the epoxy network diglycidyl ether of bisphenol A (BADGE n=0)/amantidine. J Therm Anal Calorim,2007,87 (1): 97-100
[105]代晓青,肖加余,曾竟成,等.等温DSC法研究RFI用环氧树脂固化动力学.复合材料学报,2008,25(4)：18-23
[106]李正莉,张有智,王煊军,苟小莉.潜伏性环氧树脂/胺基酰亚胺体系的固化动力学.高分子材料科学与工程,2010,26(1)：85-87
[107]陈梦雪,胡国贞.联苯型环氧-酚醛树脂的恒温固化动力学研究.化工新型材料,2008,36(7)：61-62
[108]孙文兵,张超灿.等温DSC法研究聚酰胺与环氧树脂的固化动力学.武汉理工大学学报,2009,31(6)：28-31
[109]Ober C, Jin J I, Lenz R W. Liquid Crystal Polymers. V. Thermotropic Polyesters with Either Dyad or Triad Aromatic Ester Mesogenic Units and Flexible Polymethylene Spacers in the Main Chain. Polym J,1982,14(1):9-17
[110]Ober C, JinJ -I, Zhou Q, et al. Liquid crystal polymers with flexible spacers in the main chain. Adv Polym Sci,1984,59:103-146
[111]Mix R, Gahde J, Goering H, et al. Segmented polyurethanes with 4,4'-bis-(6-hydroxyhexoxy)biphenyl as chain extender. Part 2. Synthesis and properties of MDI-polyurethanes in comparison with 2,4-TDI-polyurethanes. J Polym Sci, Part A: Polym Chem,1996,34(1):33-44
[112]Ojha U P, Kumar A. Design, synthesis, and characterization of main-chain, aromatic polyesters based on 3,4-ethylenedioxythiophene. J Polym Sci, Part A:Polym Chem,2006, 44(11):3479-3486
[113]Rao V S, Samui A B. Structure-property relationship of photoactive liquid crystalline polyethers containing benzylidene moiety. J Polym Sci, Part A:Polym Chem,2009, 47(8):2143-2155
[114]Stickfort L, Poersch G, Hess M, et al. Liquid-crystalline polyesters based on branched propylene spacers. J Polym Sci, Part A:Polym Chem,1996,34(7):1325-1330
[115]Hoshino H, Jin J I, Lenz R W. Liquid crystalline behavior of polymeric glycols terminated with aromatic diester and diacid mesogenic groups. J Appl Polym Sci,1984,29 (2):547- 554
[116]Kent S L, Geil P H. Folded chain crystallization of random terpolymer liquid crystal polymers from the nematic state. J Polym Sci, Part B:Polym Phys,1992,30(13): 1489-1506
[117]Bagheri M, Rad R Z. Synthesis and characterization of thermotropic liquid crystalline polyesters with biphenyl unit in the main chain. React Funct Polym,2008,68(2):613-622
[118]Volksen W, Jr. J R L, Economy J, et al. Liquid-crystalline copolyesters based on poly(p-oxybenzoate) and poly(p,p-biphenylene terephthalate). J Polym Sci, Part A:Polym Chem,1983,21(8):2249-2259
[119]Ober C, Lenz R W, Galli G, et al. Liquid-crystalline polymers.12. Polyesters with either alternating or random orientation of mesogenic units. Macromolecules,1983,16(7): 1034-1036
[120]Martin P G, Stupp S I. Contrasting behavior of chemically ordered versus chemically disordered liquid-crystal polymers. Macromolecules,1988,21(5):1222-1227
[121]Aharoni S M. Hydrogen-bonded highly regular strictly alternating aliphatic-aromatic liquid-crystalline poly(ester amides). Macromolecules,1988,21(7):1941-1961
[122]Aharoni S M. The first-order transitions of hydrogen-bonded liquid-crystalline poly(esteramides). Macromolecules,1989,22(2):686-693
[123]Sudha J D, Pillai C K S. Hydrogen-bonded thermotropic liquid-crystalline polyester-amides from bis(hydroxy alkamido)aranes:Synthesis and properties. J Polym Sci, Part A:Polym Chem,2003,41(2):335-346
[124]Kent S L, Rybnikar F, Geilt P H, et al. Morphology of a thermotropic random terpolymer liquid crystal polymer crystallized in the bulk:compression mouldings, extrudates and fibres. Polymer,1994,35(9):1869-1879
[125]Kent S L, Geil P H. Annealing Effects in Solution Grown Single Crystals of a Random Terpolymer Liquid Crystal Polymer. J Macromol Sci, Pure Appl Chem,1992,29(11): 315-320
[126]Kent S L, Geil P H. Solution Grown Folded Chain Crystals of a Random Terpolymer Thermotropic Liquid Crystal Polymer. J Macromol Sci, Pure Appl Chem,1991,28 (11): 203-208
[127]Kent S L, Geil P H. Chain folding in single crystals and sheared ("fiber") samples of a liquid crystal polymer. Polym Bull,1991,26(5):579-585
[128]Kent S L, Geil P H. Solution-grown single crystals of random terpolymer liquid crystal polymers:Chain folding, morphology, and effect of annealing. J Macromol Sci, Phys 1992,31(4):413-437
[129]Chandrasekhar S. Liquid crystals. Cambridge University Press,1992.48-51
[130]Wang X J, Zhou Q F. Liquid Crystalline Polymers. Singapore:World Scientific, 2004.139-139
[131]Zhang B -L, Tang G -L, ShiK -Y, et al. A study on properties of epoxy resin toughened by functionalized polymer containing rigid, rod-like moiety. Eur Polym J,2000,36(1): 205-213
[132]He S, Shi K, Bai J, et al. Studies on the properties of epoxy resins modified with chain-extended ureas. Polymer,2001,42(23):9641-9647
[133]HeSJ, Shi K Y, Guo X Z, et al. Properties of methyltetrahydrophthalic anhydride-cured epoxy resin modified with MITU. Polym Adv Technol,2009,20(2):130-134
[134]Ma S, Liu W, Su Q, et al. Studies on the Thermal Properties of Epoxy Resins Modified with Two Kinds of Silanes. J Macromol Sci, Phys,2010,49(1):43-56
[135]Villanueva M, Fraga I, Rodriguez-Anon J, et al. Study of the influence of a reactive diluent on the rheological properties of an epoxy-diamine system. J Therm Anal Calorim,2009, 98(2):521-525
[136]Villanueva M, Martin-lglesias J, Rodriguez-Anon J, et al. Thermal study of an epoxy system DGEBA (n=0)/mXDA modified with POSS. J Therm Anal Calorim,2009,96 (2): 575-582
[137]Lopez J, Rico M, Montero B, et al. Polymer blends based on an epoxy-amine thermoset and a thermoplastic. J Therm Anal Calorim,2009,95(2):369-376
[138]Zhang B -L, Tang G -L, Shi K -Y, et al. A study on the properties of epoxy resin toughened by a liquid crystal-type oligomer. J Appl Polym Sci,1999,71(1):177-184
[139]张保龙,石可瑜,由英才,等.取代脲促进环氧树脂/双氰胺固化体系反应机理.应用化学,1998,15(4)：95-97
[140]Son P -N, Weber C D. Some aspects of monuron-accelerated dicyandiamide cure of epoxy resins. J Appl Polym Sci,1973,17(5):1305-1313
[141]Mehdipour-Ataei S, Einollahy P. Synthesis, Characterization and Properties of Novel Poly(Ester-Amide-Urethane)s. Macromol Symp,2004,214(1):339-350
[142]Ando M, Uryu T. Synthesis of polymer materials by low energy electron beam. XIII. Structure and properties of EB-cured polymers of bifunctional monomer with biphenyl moiety as mesogenic group. J Polym Sci, Part A:Polym Chem,1990,28(9):2575-2584
[143]李迎法,单书香.4-(1-乙氧乙氧基)正丁基溴的合成.四川化工,1991(1)：10-11
[144]Hsu T -F, Lee Y -D. Properties of thermoplastic polyurethane elastomers containing liquid crystalline chain extender (Ⅰ) synthesis and properties of hard segments. Polymer,1999, 40(3):577-587
[145]Bagheri M, Didehban K, Rezvani Z, et al. Thermotropic polyesters.1:Synthesis, characterization and thermal transition of poly[4,4'-bis(ω-alkoxy)biphenyl isophthalate]. Eur Polym J,2004,40(4):865-871
[146]周其凤,王新久.液晶高分子.北京：科学出版社,1999.106-107
[147]Dewar M J S, Goldberg R S. Effects of central and terminal groups on nematic mesophase stability. J Org Chem,1970,35(8):2711-2715
[148]Bilibin A Y, Tenkovtsev AV, Piraner ON, et al. Thermotropic polyesters,2. Synthesis of regular polyesters from aromatic dicarboxylic acids and phenols or aliphatic diols, and study of their mesomorphic properties. Makromol Chem,1985,186(8):1575-1591
[149]Wei C, Gong Y, Yang X, et al. Synthesis and characterization of thermotropic liquid crystalline polyurethanes from 4,4'-bis(6-hydroxyhexoxy) biphenyl and aliphatic diols. Polym Adv Technol,2009,20(12):1006-1009
[150]Mormann W, Brocher M. "Liquid crystalline" thermosets from 4,4'-bis(2,3-epoxypropoxy)biphenyl and aromatic diamines. Macromol Chem Phys,1996, 197(6):1841-1851
[151]Giamberjni M, Amendola E, Carfagna C. Liquid Crystalline Epoxy Thermosets. Mol Cryst Liq Cryst,1995,266:9-22
[152]Barton J M. Monitoring the curing reaction of an aromatic amine/epoxide resin system by differential scanning calorimetry (DSC):Determination and significance of the activation energy. Makromol Chem,1973,171(1):247-251
[153]Punchaipetch P, Ambrogi V, Giamberini M, et al. Epoxy+liquid crystalline epoxy coreacted networks:I. Synthesis and curing kinetics. Polymer,2001,42 (5):2067-2075
[154]Khanna U, Chanda M. Kinetics of anhydride curing of isophthalic diglycidyl ester using differential scanning calorimetry. J Appl Polym Sci,1993,49(2):319-329
[155]Prime R B. Differential scanning calorimetry of the epoxy cure reaction. Polym Eng Sci, 1973,13(5):365-371
[156]Riccardi CC, Dupuy J, Williams R J J. A simple model to explain the complex kinetic behavior of epoxy/anhydride systems. J Polym Sci, Part B:Polym Phys,1999,37(19): 2799-2805
[157]Peyser P, Bascom W D. Kinetics of epoxy resin polymerization using differential scanning calorimetry. J Appl Polym Sci,1977,21(9):2359-2373
[158]Hale A, Macosko C W, Bair H E. Glass transition temperature as a function of conversion in thermosetting polymers. Macromolecules,1991,24(9):2610-2621
[159]Mathew A P, Packirisamy S, Thomas S. Studies on the thermal stability of natural rubber/polystyrene interpenetrating polymer networks:thermogravimetric analysis. Polym Degrad Stab,2001,72(3):423-439
[160]Gupta A, Singhal R, Nagpal A K. Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam:Process of epoxy cure and kinetics of decomposition. J Appl Polym Sci,2004,92(2):687-697