聚甲基丙烯酰亚胺及其纳米复合材料研究
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摘要
聚酰亚胺是一类含有亚胺环的芳杂环聚合物,具有卓越的热力学性能,在高温环境中其性能优势更为明显。近四十年来,聚酰亚胺材料在许多高性能领域得到了迅速的发展和应用,如航空和微电子领域。聚甲基丙烯酰亚胺(PMI)是其中发展较快的一种,在具有聚酰亚胺材料优异性能的同时,具有良好的可加工性。
本文利用甲基丙烯腈(MAN)和甲基丙烯酸(MAA)的共聚反应,制备了MAN-MAA共聚物,并经过酰亚胺环化反应制得聚甲基丙烯酰亚胺(PMI);同时,为了提高PMI的性能,采用原位插层聚合制备了PMI/MMT纳米复合材料。利用FT-IR、DSC-TGA、SEM及力学性能测试等手段,分析表征了材料的结构与性能。
首先,以溶液聚合和本体聚合,制备了MAN-MAA共聚物,研究了反应温度、原料配比和引发体系对聚合过程的影响,通过对共聚物热性能和力学性能的分析表征,确定了适当的聚合方法,相应的反应体系组成和聚合工艺条件;并研究了环化反应的机理,通过控制环化时间和环化温度及PMI的性能研究,确定了共聚物的最佳环化工艺条件。
采用悬浮聚合制备了高分子量聚甲基丙烯酸甲酯(PMMA),研究了分散剂、反应温度和时间等对PMMA分子量的影响;将高分子量PMMA用于反应体系的增粘,有效解决了纳米蒙脱土在反应液中的沉降问题及其在共聚物中均匀分散的问题。对PMI/MMT纳米复合材料的结构和热力学性能研究的结果表明,所制备的PMI/MMT纳米复合材料中纳米MMT分散均匀,与纯PMI比较,其玻璃化转变温度由213℃提高到220℃,弯曲强度由51MPa提高到135MPa。
此外,本文还探索制备了AN-MAA共聚物/MMT纳米复合材料,并将AN-MAA共聚物环化后的产物称为半-聚甲基丙烯酰亚胺(半-PMI),与PMI/MMT纳米复合材料比较,半-PMI/MMT纳米复合材料的玻璃化转变温度略有下降,弯曲强度降低20%。
For recent 40 years, polyimides have been developed rapidly and applied in manyhigh performance fields, such as aerospace, microelectronics, and so on.Polyimide exhibitted outstanding thermal and mechanical properties, especially at elevated temperature.Polymethacrylimide(PMI) was a type developed rather rapidly among polyimides, good process ability was gained besides keeping function advantage.
In this thesis, MAN-MAA copolymer was prepared by copolymerization of methacrylic acid(MAA) and methacrylonitrile(MAN), PMI was formed via the imidation(cyclization, i.e.) of the copolymer to polyimide.PMI/montmorillorite nanocomposite was prepared by in-situ intercalate polymerization to enhance the properties of PMI afterwards.The stucture and property of the material mentioned above were characterized by FT-IR、DSC-TGA and SEM.The work was composed in following parts:
First of all, MAN-MAA copolymer were synthesized by solution polymerization and bulk polymerization, parameters such as reaction temperature, monomer ratio and initiator were investigated in polymerization.The preferable condition of polymerization was gained by characterization of thermal and mechanical properties.The mechanism of cyclization was studied at the mean time, and the preferable cyclization condition of the MAN-MAA copolymer was acquired via the controlling of time and temperature.
For the sake of nano MMT's homogeneous dispersion , high macromolecule poly(Methyl-Methacrylate) was synthesized via suspension polymerization, the influences of temperature, concentration of initiator, and conversion rate on molecular weight were analysed. In this way, the viscosity of the monomer reaction solution was improved.Based on the above work, influence of nano MMT to the property the copolymer was studied. Thanks to this special structure, the thermal and mechanical properties of the nano composite formed by PMI and MMT taken on a great improvement comparing to PMI.
Furthermore, nano composite prepared by Acrylonitrile-Methacrylic acid(AN-MAA) copolymer/MMT was produced , after the same cyclization procedure as the methacrylonitrile-methacrylic acid copolymer, a structure named half-PMI was formed, compared to PMI/MMT nano composite , the glass-transition temperature of the half-PMI/MMT nano composite descended little, the bending intensity of the former descended 20%.
本文利用甲基丙烯腈(MAN)和甲基丙烯酸(MAA)的共聚反应,制备了MAN-MAA共聚物,并经过酰亚胺环化反应制得聚甲基丙烯酰亚胺(PMI);同时,为了提高PMI的性能,采用原位插层聚合制备了PMI/MMT纳米复合材料。利用FT-IR、DSC-TGA、SEM及力学性能测试等手段,分析表征了材料的结构与性能。
首先,以溶液聚合和本体聚合,制备了MAN-MAA共聚物,研究了反应温度、原料配比和引发体系对聚合过程的影响,通过对共聚物热性能和力学性能的分析表征,确定了适当的聚合方法,相应的反应体系组成和聚合工艺条件;并研究了环化反应的机理,通过控制环化时间和环化温度及PMI的性能研究,确定了共聚物的最佳环化工艺条件。
采用悬浮聚合制备了高分子量聚甲基丙烯酸甲酯(PMMA),研究了分散剂、反应温度和时间等对PMMA分子量的影响;将高分子量PMMA用于反应体系的增粘,有效解决了纳米蒙脱土在反应液中的沉降问题及其在共聚物中均匀分散的问题。对PMI/MMT纳米复合材料的结构和热力学性能研究的结果表明,所制备的PMI/MMT纳米复合材料中纳米MMT分散均匀,与纯PMI比较,其玻璃化转变温度由213℃提高到220℃,弯曲强度由51MPa提高到135MPa。
此外,本文还探索制备了AN-MAA共聚物/MMT纳米复合材料,并将AN-MAA共聚物环化后的产物称为半-聚甲基丙烯酰亚胺(半-PMI),与PMI/MMT纳米复合材料比较,半-PMI/MMT纳米复合材料的玻璃化转变温度略有下降,弯曲强度降低20%。
For recent 40 years, polyimides have been developed rapidly and applied in manyhigh performance fields, such as aerospace, microelectronics, and so on.Polyimide exhibitted outstanding thermal and mechanical properties, especially at elevated temperature.Polymethacrylimide(PMI) was a type developed rather rapidly among polyimides, good process ability was gained besides keeping function advantage.
In this thesis, MAN-MAA copolymer was prepared by copolymerization of methacrylic acid(MAA) and methacrylonitrile(MAN), PMI was formed via the imidation(cyclization, i.e.) of the copolymer to polyimide.PMI/montmorillorite nanocomposite was prepared by in-situ intercalate polymerization to enhance the properties of PMI afterwards.The stucture and property of the material mentioned above were characterized by FT-IR、DSC-TGA and SEM.The work was composed in following parts:
First of all, MAN-MAA copolymer were synthesized by solution polymerization and bulk polymerization, parameters such as reaction temperature, monomer ratio and initiator were investigated in polymerization.The preferable condition of polymerization was gained by characterization of thermal and mechanical properties.The mechanism of cyclization was studied at the mean time, and the preferable cyclization condition of the MAN-MAA copolymer was acquired via the controlling of time and temperature.
For the sake of nano MMT's homogeneous dispersion , high macromolecule poly(Methyl-Methacrylate) was synthesized via suspension polymerization, the influences of temperature, concentration of initiator, and conversion rate on molecular weight were analysed. In this way, the viscosity of the monomer reaction solution was improved.Based on the above work, influence of nano MMT to the property the copolymer was studied. Thanks to this special structure, the thermal and mechanical properties of the nano composite formed by PMI and MMT taken on a great improvement comparing to PMI.
Furthermore, nano composite prepared by Acrylonitrile-Methacrylic acid(AN-MAA) copolymer/MMT was produced , after the same cyclization procedure as the methacrylonitrile-methacrylic acid copolymer, a structure named half-PMI was formed, compared to PMI/MMT nano composite , the glass-transition temperature of the half-PMI/MMT nano composite descended little, the bending intensity of the former descended 20%.
引文
[1]丁孟贤.聚酰亚胺-化学、结构与性能的关系及材料[M].北京:科学出版社,2006.
[2]J.E.Mark.Hybrid organic-inorganic composites containing mixed-oxide ceramics and hi gh-temperature polymers[J].J.Master.Sc.Pure Appl.Chem.1996,33(12):2005.
[3]Fusher H,et al.Cross linking of polyimidesviaspirodi lactone unit in polymer back bone[J].Journal of polym science,partA:PolymChem,1999,37(19):3680-3695.
[4]Sun Yuan Tsay,Bor Kuan Chen,C P Chen.Synthesis and properties ofpol～mide(co ntainingnaphthalene)nanoeomposites with organo-modifiedmontmoriUonites[J].Journal o f applied polymer science,2006,99:2966-2972.
[5]刘勇,王世敏等.聚酰亚胺的改性研究新进展[J].胶体与聚合物,2006,24(1):43-45.
[6]胡轶喆,吴利平等.含硅聚酰亚胺的合成及性能研究[J].热固性树脂,2006,21(6)21-24.
[7]杨金田等.可溶性共聚酰亚胺的合成与性能研究[J].高分子学报,2006,(4):609-613.
[8]胡爱军等.功能性聚酰亚胺薄膜的研制[J].宇航材料工艺,2006,(2):23-26.
[9]吴伟,郭曼芬.聚酰亚胺单体二酐的合成方法[J].化学与粘合,2002,(4):173-175.
[10]Scherble Jonas,Geyer Werner,Seibert Hermann,et al.Thermally stable,microporous polymethacrylimide foams[P].DE 10350971A1,2005.
[11]P.斯坦,et al.高分子量聚甲基丙烯酰亚胺的衍生[P].中国国家专利,200380106731.
[12]Yamamoto,Naoki et al.Methacrylimide group-containing polymer[P].US Patent 5225496.
[13]Yamamoto,Naoki et al.Thermoplastic polymethacrylimide resin composition[P].US Patent 4902742.
[14]Stein,Peter et al.Method for the synthesis of copolymers for producing polymethacrylimides[P].US Patent 20070142588
[15]Manfred Krieg et al.Method for producing block-shaped polymethacrylimide foamed materials[P].US Patent 6670405.
[16]Method of producing polymethacrylimide foams[P].US Patent 486361.
[17]Polymethacrylimide plastic foam materials with reduced inflammability in addition to a method for the production thereof.US Patent 20050090568.
[18]Agag T,Koga T,Takeiehi.Estimation ofthe surfacefree energy ofpolymem[J],polymer , 2001, 42(15):3399-3342.
[19]PralayM, PhamHoaiN , MasamiO, et al.Influence of Crystallization on Intercalation, Morphology , and Mechanical Properties of Polypropylene/Clay Nanocomposites[J].Macromolecules, 2002, (35):2042-2049.
[20]Tony M, W.Raymond M, Chun YL, et al.Polyamide～12 layered silicate nanocomposites by meltblending[J].Polymer, 2003, (44):2761-2772.
[21]Naoki H, Hirotaka O, Makoto K, et al.Nylon6/Na～montmorillonite nanocomposites prepared by compounding Nylon6 withNa～montmorillonite slurry[J].Polym., 2003 ,(44):2933-2937.
[22]Vaia, R.A., Farmer, B.L. Interaction energy and surface reconstruction between sheets of layered silicates[J].Journal of Chemical Physics, 2006, 124(22):2244-2247.
[23]Theng B .K.G., The Chemistry of Clay～Organic Reactions[M]].Adam kilger, London, 1974.
[24]M. Okamoto, S. Morita, Y. H. Kim, T. Kotaka and H. Tateyama.Dispersed structure change of smectic clay/poly(methyl methacrylate) nanocomposites by copolymerization with polar comonomers[J].Polymer, 42(3): 1201-1206.
[25] Michael Alexandre, Philippe Dubois.Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials[J].Materials Science and Engineering: R:Reports, 2000, 28(1-2):1-63.
[26]Filippi, Sara, Mameli, et al.Comparison of solution-blending and melt-intercalation for the preparation of poly(ethylene-co-acrylic acid)/organoclay nanocomposites[J].European Polymer Journal, 2007, 43(5): 1645-1659.
[27]T. Agag, T. Koga and T. Takeichi.Studies on thermal and mechanical properties of polyimide-clay nanocomposites[J].Polymer, 2001, 42(8):3399-3408.
[28]PralayM, Pham Hoai N , Masami O, et al.Influence of Crystallization on Intercalation,Morphology , and Mechanical Properties of Polypropylene/Clay Nanocomposites[J].Macromolecules, 2002, (35): 2042-2049.
[29]Naoki H, Hirotaka O, Makoto K, et aI.Nylon6/Na～montmorillonite nanocomposites prepared by compounding Nylon6 withNa～montmorillonite slurry[J].Polym , 2003 ,44:2933-2937.
[30]Tony M,W.Raymond M,Chun YL,et al.Polyamide～12 layered silicate nanocomposites by meltblending.Polymer,2003,44:2761-2772.
[31]Usuki A,Kojima Y,Okada A,et al.Synthesis of Nylon6～Clay Hybrid[J].J.Mater.Res,1993,8(5):179-1184.
[32]王海,陶龙忠.聚酰亚胺/MMT纳米复合材料的合成及形成机理研究.硅酸盐通报,2006,25(3):38-41.
[33]聂玉梅.聚丙烯/层状硅酸盐纳米复合材料研究进展.化学工程师,2006,(7):44-46.
[34]Youngjae Yoo,Sung～Su Kim,et al.Enhancement of the thermal stability,mechanicalproperties and morphologies of recycled PVC/claynanocomposites[J].Polymer Bulletin,2004,(52):373-380.
[35]李春生等.聚台物/MMT纳米复合材料的研究进展[J].化工生产与技术,2002,9(4):22-26.
[36]Richard A.Vaia,Emmanuel P.Giannelis.latice model of polymer melt intercalation in organically～modified layered silicates[J].Macromolecules,1997,(30):7990-7999.
[37]Yulia Lyatskaya,Anna C,Balaza.Modeling the phase behavior of polymer～clay composites[J].Macromolecules,1998,(31):6676-6680.
[38]Arma C.Balazs,Chandralekha Singh,Ekaterina Zhulina.Modeling the interaction between polymers and clay surface through self-consistent field theory[J].Macromolecules,1998,(31):8370-8381.
[39]Richard A.Vaia,Emmanuel P.Giannelis.latice model of polymer melt intercalation in organically～modified layered silicates[J].Macromolecules,1997,(30):7990-7999.
[40]J.M.Gloaguen,J.M.Lefebvre.Plastic deformation behavior of thermoplastic/clay nanocomposites[J].Polymer,2001,(42):5841-5847.
[41]Richard A.Vaia,Emmanuel P.Gianneilis.polymer melt intercalation in organically～modified layeredsilicates:Model predications and Experiment[J].Macromolecules,1997,(30):8000-8009.
[42]Goettler,L.A.,Lee,K.Y.,Thakkar,H..Layered silicate reinforced polymer nanocomposites:Development and applications[J].Polymer Reviews,2007,47(2):291-317.
[43]漆宗能.尚文宇著聚合物/层状硅酸盐纳米复合材料理论与实践[M].北京:化学工业出版 社,2002。
[44]杨海洋,朱平平,任峰.粘度法研究高分子溶液行为的实验改进[J].化学通报.1999,(5):47-49.
[45]潘祖仁.高分子化学[M].化学工业出版社,1997.
[46]应圣康,余丰年.共聚合原理.北京,化学工业出版社,1984.
[47]Ignacio Rintoul,Christine Wandrey.Polymerization of ionic monomers in polar solventskinetics and mechanism of the free radical copolymerization of acrylamide acrylic acid[J].Polymer,2005,46(13):4525-4532.
[48]Paul G.Brown and Kiyohisa Fujimori.Solvent effects on the copolymerization of p-methoxystyrene with maleic anhydride:aninvestigation into the mechanism ofaltemating copolymerization[J].Polymer,1995,36(5):1053-1059.
[49]R.Makushka,G.Bajoras,S.Budriene,M.Balevicius,Vysokomol.Soedin.29A(1987)685.
[50]陈厚,刘军深等.不同共聚体系对丙烯腈与丙烯酸单体竞聚率的影响.高分子材料科学与工程.2005,21(6):66-68.
[51]张旺玺.碳纤维前躯体高分子量聚丙烯腈的合成工艺研究与结构性能表征.山东大学博士学位论文.2003.
[52]焦健,雷渭媛.高聚物的结构、性能与测试[M].化学工业出版社,2003.
[53]刘铁民等.甲基丙烯酸/丙烯腈.“原位成环”法制备高性能MAA/AN泡沫塑料的研究[J].工程塑料应用,2006,34(7):9-12.
[54]C.McNeill,Tarique Mahmood.Thermal degradation studies of methacrylonitrile polymers and copolymers-3.Polymers capable of chain end～initiated colouration[J].Polymer Degradation and Stability,1998,(60):449-458.
[55]西鹏,高晶等.高技术纤维[M].北京:化学工业出版社,2004.
[56]陈志彦,林鹤鸣,王澜.发泡剂分解温度的研究[J].浙江工程学院学报,2000,17(4):225-229.
[57]张翠,张广成等.AN/MAA/AM三元共聚物的合成及性能研究.热固性树脂,2006,21(4):9-13,17.
[58]冯仰婕,袁军.热分析法研究固体热分解动力学处理方法的比较[J].高分子材料科学与 工程,1995,11(2):66-70.
[59]陈厚,刘军深.AN/AA共聚物热解反应表观活化能的计算.高分子材料科学与工程,2005,21(5):242-244.
[60]Beltz LA,Gustafson R R.Carbon,1996,(34):561-566.
[61]N.Grassie,I.C.McNeill.Thermal degradation of polymethacrylonitrile.Part Ⅴ.The mechanism of the initiation step in coloration reactions[J].Journal of Polymer Science,1959,39(135):211-222.
[62]赵藻藩,周性尧,张悟铭等.仪器分析.北京:高等教育出版社,1990.
[63]邓芹英,刘岚,邓慧敏.波谱分析教程.北京:科学出版社,2003.
[64]马占镖.甲基丙烯酸酯树脂及其应用.化学工业出版社,2002.
[65]祝爱兰,钟宏.悬浮聚合法制取不同分子量级别的聚甲基丙烯酸甲酯[J].应用化工.2001,30(5):21-23.
[66]潘祖仁,翁志学.悬浮聚合[M].化学工业出版社,2003.
[67]赵彬.分散聚合法制备微米级单分散PMMA微球.北京化工大学硕士学位论文,2001.
[68]何曼君,陈维孝,董西侠.高分子物理(修订版).复旦大学出版社,2001.
[69]龙敬伟.甲基丙烯酸甲酯-N-环己基马来酰亚胺共聚物/蒙脱土纳米复合材料的研究.河北工业大学硕士学位论文.
[70]Woo,Tim;Halley,Peter;Martin,Darren;Dae,Su Kim.Effect of different preparation routes on the structure and properties of rigid polyurethane-layered silicate nanocomposites[J].Journal of Applied Polymer Science,2006,102(3):2894-2903.
[71]黄俊超.特种聚酰亚胺-无机物纳米复合材料制备及结构与性能研究[D].上海交通大学博士学位论文,2000.
[72]Yibing Cai,et al.Preparation and characterization of poly(styrene～acrylonitrile)(SAN)_clay nanocomposites by melt intercalation[J].J Mater Sci,DOI 10.1007/s 10853-006-1077-5.
[73]Xie W,Gao Z M,Pan W P,et al.Thermal degradation chemistryof alkyl quaternary ammonium montmorillonite[J].Chem Mater,2001,13(9):2979-2990.
[74]Onal,Muserref,Celik,Meltem.Polymethacrylamide/Na-montmorillonite nanocomposites synthesized by free-radical polymerization[J].Materials Letters,2006,60(1):48-52.
[75]N.Llaleque～Mignard,J.P.Montheard,B.Boinon.Thermal degradation of copolymers of acrylonitrile, methacrylonitrile and vinylidene cyanide with vinyl acetate. Journal of Analytical and Applied Pyrolysis, 1998, (47):145-164.
[2]J.E.Mark.Hybrid organic-inorganic composites containing mixed-oxide ceramics and hi gh-temperature polymers[J].J.Master.Sc.Pure Appl.Chem.1996,33(12):2005.
[3]Fusher H,et al.Cross linking of polyimidesviaspirodi lactone unit in polymer back bone[J].Journal of polym science,partA:PolymChem,1999,37(19):3680-3695.
[4]Sun Yuan Tsay,Bor Kuan Chen,C P Chen.Synthesis and properties ofpol～mide(co ntainingnaphthalene)nanoeomposites with organo-modifiedmontmoriUonites[J].Journal o f applied polymer science,2006,99:2966-2972.
[5]刘勇,王世敏等.聚酰亚胺的改性研究新进展[J].胶体与聚合物,2006,24(1):43-45.
[6]胡轶喆,吴利平等.含硅聚酰亚胺的合成及性能研究[J].热固性树脂,2006,21(6)21-24.
[7]杨金田等.可溶性共聚酰亚胺的合成与性能研究[J].高分子学报,2006,(4):609-613.
[8]胡爱军等.功能性聚酰亚胺薄膜的研制[J].宇航材料工艺,2006,(2):23-26.
[9]吴伟,郭曼芬.聚酰亚胺单体二酐的合成方法[J].化学与粘合,2002,(4):173-175.
[10]Scherble Jonas,Geyer Werner,Seibert Hermann,et al.Thermally stable,microporous polymethacrylimide foams[P].DE 10350971A1,2005.
[11]P.斯坦,et al.高分子量聚甲基丙烯酰亚胺的衍生[P].中国国家专利,200380106731.
[12]Yamamoto,Naoki et al.Methacrylimide group-containing polymer[P].US Patent 5225496.
[13]Yamamoto,Naoki et al.Thermoplastic polymethacrylimide resin composition[P].US Patent 4902742.
[14]Stein,Peter et al.Method for the synthesis of copolymers for producing polymethacrylimides[P].US Patent 20070142588
[15]Manfred Krieg et al.Method for producing block-shaped polymethacrylimide foamed materials[P].US Patent 6670405.
[16]Method of producing polymethacrylimide foams[P].US Patent 486361.
[17]Polymethacrylimide plastic foam materials with reduced inflammability in addition to a method for the production thereof.US Patent 20050090568.
[18]Agag T,Koga T,Takeiehi.Estimation ofthe surfacefree energy ofpolymem[J],polymer , 2001, 42(15):3399-3342.
[19]PralayM, PhamHoaiN , MasamiO, et al.Influence of Crystallization on Intercalation, Morphology , and Mechanical Properties of Polypropylene/Clay Nanocomposites[J].Macromolecules, 2002, (35):2042-2049.
[20]Tony M, W.Raymond M, Chun YL, et al.Polyamide～12 layered silicate nanocomposites by meltblending[J].Polymer, 2003, (44):2761-2772.
[21]Naoki H, Hirotaka O, Makoto K, et al.Nylon6/Na～montmorillonite nanocomposites prepared by compounding Nylon6 withNa～montmorillonite slurry[J].Polym., 2003 ,(44):2933-2937.
[22]Vaia, R.A., Farmer, B.L. Interaction energy and surface reconstruction between sheets of layered silicates[J].Journal of Chemical Physics, 2006, 124(22):2244-2247.
[23]Theng B .K.G., The Chemistry of Clay～Organic Reactions[M]].Adam kilger, London, 1974.
[24]M. Okamoto, S. Morita, Y. H. Kim, T. Kotaka and H. Tateyama.Dispersed structure change of smectic clay/poly(methyl methacrylate) nanocomposites by copolymerization with polar comonomers[J].Polymer, 42(3): 1201-1206.
[25] Michael Alexandre, Philippe Dubois.Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials[J].Materials Science and Engineering: R:Reports, 2000, 28(1-2):1-63.
[26]Filippi, Sara, Mameli, et al.Comparison of solution-blending and melt-intercalation for the preparation of poly(ethylene-co-acrylic acid)/organoclay nanocomposites[J].European Polymer Journal, 2007, 43(5): 1645-1659.
[27]T. Agag, T. Koga and T. Takeichi.Studies on thermal and mechanical properties of polyimide-clay nanocomposites[J].Polymer, 2001, 42(8):3399-3408.
[28]PralayM, Pham Hoai N , Masami O, et al.Influence of Crystallization on Intercalation,Morphology , and Mechanical Properties of Polypropylene/Clay Nanocomposites[J].Macromolecules, 2002, (35): 2042-2049.
[29]Naoki H, Hirotaka O, Makoto K, et aI.Nylon6/Na～montmorillonite nanocomposites prepared by compounding Nylon6 withNa～montmorillonite slurry[J].Polym , 2003 ,44:2933-2937.
[30]Tony M,W.Raymond M,Chun YL,et al.Polyamide～12 layered silicate nanocomposites by meltblending.Polymer,2003,44:2761-2772.
[31]Usuki A,Kojima Y,Okada A,et al.Synthesis of Nylon6～Clay Hybrid[J].J.Mater.Res,1993,8(5):179-1184.
[32]王海,陶龙忠.聚酰亚胺/MMT纳米复合材料的合成及形成机理研究.硅酸盐通报,2006,25(3):38-41.
[33]聂玉梅.聚丙烯/层状硅酸盐纳米复合材料研究进展.化学工程师,2006,(7):44-46.
[34]Youngjae Yoo,Sung～Su Kim,et al.Enhancement of the thermal stability,mechanicalproperties and morphologies of recycled PVC/claynanocomposites[J].Polymer Bulletin,2004,(52):373-380.
[35]李春生等.聚台物/MMT纳米复合材料的研究进展[J].化工生产与技术,2002,9(4):22-26.
[36]Richard A.Vaia,Emmanuel P.Giannelis.latice model of polymer melt intercalation in organically～modified layered silicates[J].Macromolecules,1997,(30):7990-7999.
[37]Yulia Lyatskaya,Anna C,Balaza.Modeling the phase behavior of polymer～clay composites[J].Macromolecules,1998,(31):6676-6680.
[38]Arma C.Balazs,Chandralekha Singh,Ekaterina Zhulina.Modeling the interaction between polymers and clay surface through self-consistent field theory[J].Macromolecules,1998,(31):8370-8381.
[39]Richard A.Vaia,Emmanuel P.Giannelis.latice model of polymer melt intercalation in organically～modified layered silicates[J].Macromolecules,1997,(30):7990-7999.
[40]J.M.Gloaguen,J.M.Lefebvre.Plastic deformation behavior of thermoplastic/clay nanocomposites[J].Polymer,2001,(42):5841-5847.
[41]Richard A.Vaia,Emmanuel P.Gianneilis.polymer melt intercalation in organically～modified layeredsilicates:Model predications and Experiment[J].Macromolecules,1997,(30):8000-8009.
[42]Goettler,L.A.,Lee,K.Y.,Thakkar,H..Layered silicate reinforced polymer nanocomposites:Development and applications[J].Polymer Reviews,2007,47(2):291-317.
[43]漆宗能.尚文宇著聚合物/层状硅酸盐纳米复合材料理论与实践[M].北京:化学工业出版 社,2002。
[44]杨海洋,朱平平,任峰.粘度法研究高分子溶液行为的实验改进[J].化学通报.1999,(5):47-49.
[45]潘祖仁.高分子化学[M].化学工业出版社,1997.
[46]应圣康,余丰年.共聚合原理.北京,化学工业出版社,1984.
[47]Ignacio Rintoul,Christine Wandrey.Polymerization of ionic monomers in polar solventskinetics and mechanism of the free radical copolymerization of acrylamide acrylic acid[J].Polymer,2005,46(13):4525-4532.
[48]Paul G.Brown and Kiyohisa Fujimori.Solvent effects on the copolymerization of p-methoxystyrene with maleic anhydride:aninvestigation into the mechanism ofaltemating copolymerization[J].Polymer,1995,36(5):1053-1059.
[49]R.Makushka,G.Bajoras,S.Budriene,M.Balevicius,Vysokomol.Soedin.29A(1987)685.
[50]陈厚,刘军深等.不同共聚体系对丙烯腈与丙烯酸单体竞聚率的影响.高分子材料科学与工程.2005,21(6):66-68.
[51]张旺玺.碳纤维前躯体高分子量聚丙烯腈的合成工艺研究与结构性能表征.山东大学博士学位论文.2003.
[52]焦健,雷渭媛.高聚物的结构、性能与测试[M].化学工业出版社,2003.
[53]刘铁民等.甲基丙烯酸/丙烯腈.“原位成环”法制备高性能MAA/AN泡沫塑料的研究[J].工程塑料应用,2006,34(7):9-12.
[54]C.McNeill,Tarique Mahmood.Thermal degradation studies of methacrylonitrile polymers and copolymers-3.Polymers capable of chain end～initiated colouration[J].Polymer Degradation and Stability,1998,(60):449-458.
[55]西鹏,高晶等.高技术纤维[M].北京:化学工业出版社,2004.
[56]陈志彦,林鹤鸣,王澜.发泡剂分解温度的研究[J].浙江工程学院学报,2000,17(4):225-229.
[57]张翠,张广成等.AN/MAA/AM三元共聚物的合成及性能研究.热固性树脂,2006,21(4):9-13,17.
[58]冯仰婕,袁军.热分析法研究固体热分解动力学处理方法的比较[J].高分子材料科学与 工程,1995,11(2):66-70.
[59]陈厚,刘军深.AN/AA共聚物热解反应表观活化能的计算.高分子材料科学与工程,2005,21(5):242-244.
[60]Beltz LA,Gustafson R R.Carbon,1996,(34):561-566.
[61]N.Grassie,I.C.McNeill.Thermal degradation of polymethacrylonitrile.Part Ⅴ.The mechanism of the initiation step in coloration reactions[J].Journal of Polymer Science,1959,39(135):211-222.
[62]赵藻藩,周性尧,张悟铭等.仪器分析.北京:高等教育出版社,1990.
[63]邓芹英,刘岚,邓慧敏.波谱分析教程.北京:科学出版社,2003.
[64]马占镖.甲基丙烯酸酯树脂及其应用.化学工业出版社,2002.
[65]祝爱兰,钟宏.悬浮聚合法制取不同分子量级别的聚甲基丙烯酸甲酯[J].应用化工.2001,30(5):21-23.
[66]潘祖仁,翁志学.悬浮聚合[M].化学工业出版社,2003.
[67]赵彬.分散聚合法制备微米级单分散PMMA微球.北京化工大学硕士学位论文,2001.
[68]何曼君,陈维孝,董西侠.高分子物理(修订版).复旦大学出版社,2001.
[69]龙敬伟.甲基丙烯酸甲酯-N-环己基马来酰亚胺共聚物/蒙脱土纳米复合材料的研究.河北工业大学硕士学位论文.
[70]Woo,Tim;Halley,Peter;Martin,Darren;Dae,Su Kim.Effect of different preparation routes on the structure and properties of rigid polyurethane-layered silicate nanocomposites[J].Journal of Applied Polymer Science,2006,102(3):2894-2903.
[71]黄俊超.特种聚酰亚胺-无机物纳米复合材料制备及结构与性能研究[D].上海交通大学博士学位论文,2000.
[72]Yibing Cai,et al.Preparation and characterization of poly(styrene～acrylonitrile)(SAN)_clay nanocomposites by melt intercalation[J].J Mater Sci,DOI 10.1007/s 10853-006-1077-5.
[73]Xie W,Gao Z M,Pan W P,et al.Thermal degradation chemistryof alkyl quaternary ammonium montmorillonite[J].Chem Mater,2001,13(9):2979-2990.
[74]Onal,Muserref,Celik,Meltem.Polymethacrylamide/Na-montmorillonite nanocomposites synthesized by free-radical polymerization[J].Materials Letters,2006,60(1):48-52.
[75]N.Llaleque～Mignard,J.P.Montheard,B.Boinon.Thermal degradation of copolymers of acrylonitrile, methacrylonitrile and vinylidene cyanide with vinyl acetate. Journal of Analytical and Applied Pyrolysis, 1998, (47):145-164.