甲基丙烯酸甲酯-N-环己基马来酰亚胺—苯乙烯共聚物及其蒙脱土纳米复合材料的制备、结构和性能
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摘要
聚甲基丙烯酸甲酯(PMMA)是一种透明材料，与无机透明材料相比，它具有很多优异的性能，但耐热性差是其主要缺点。提高PMMA耐热性，拓宽其应用领域已成为当今众多科研工作者的热门研究课题。
本文采用两种途径对PMMA进行耐热改性：一是通过共聚在PMMA大分子链上引入刚性的N-环己基马来酰亚胺(CHMI)，增大链内旋转阻力，从而提高其耐热性；二是利用有机-无机纳米复合技术，通过性能互补，实现PMMA的高性能化。
本文首先研究了N-环己基马来酰亚胺单体合成的最佳条件，采用高温脱水法合成出了高产率、高纯度的单体(熔点为90.2℃，文献值90.2℃)。在此基础上，利用本体聚合法制备了MMA／CHMI二元共聚物。热分析测试表明，N-环己基马来酰亚胺的引入使PMMA的玻璃化转变温度、热分解温度显著提高。但随着CHMI用量的增加，产物的黄色指数增大。研究表明，导致产物变黄的主要原因是体系中CHMI的残留。为此，将苯乙烯(St)作为第三单体引入上述共聚体系，制备了MMA／CHMI／St三元共聚物。St的引入提高了CHMI参与共聚的活性，降低了产物的黄色指数，当St用量合适时，可得到热学性能、力学性能良好的透明材料。
本文研究的另一个重要内容是活性有机蒙脱土的制备。将水溶性阳离子自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)和十六烷基三甲基溴化铵(CTAB)或十六烷基三正丁基溴化鳞(HTPB)两次插层蒙脱土制备了既有较大层间距，又有引发活性的有机蒙脱土ANMMT(AIBA和CTAB改性MMT)和APMMT(AIBA和HTPB改性MMT)。AIBA在蒙脱土中的含量主要取决于两种插层剂的比值，与长碳链阳离子的种类关系不大。活性有机蒙脱土层间距的大小不仅与两种插层剂比值有关，还受阳离子种类的影响，在其它条件相同时，季鳞盐改性蒙脱土的层间距大于季铵盐。此种活性有机蒙脱土用于纳米复合材料的制备将从热力学和动力学两方面为蒙脱土片层的打开提供必要及充分的条件。
甲基内烯酸甲酷一N一环己基马来酞亚胺一苯乙烯共聚物及其蒙脱土纳米复合材料的制备、结构和性能
将MMA分别与上述两种活性有机蒙脱土进行原位本体聚合，制备了PMMA/
ANMMT和PMMA/APMMT纳米复合材料。XRD和TEM测试表明，两种复合材料均实
现了纳米复合;蒙脱土的加入使PMMA/ANMMT复合材料的玻璃化转变温度Tg提高，
而PMMA/APMMT复合材料未出现明显的玻璃化转变;两种复合材料都表现出较高的热
分解温度，尤其是PMMA/APMMT复合材料;PMMA/ANMMT复合材料的透光性变差，
而PMMA/APMMT表现出良好的透光率和雾度值。
为进一步提高蒙脱土片层的剥离程度，增大聚合物基体与蒙脱土片层的界面作用，采
用共聚插层复合，将耐热改性单体CHMI引入插层复合体系，制备了MMA一CHMI共聚
物/ANMMT和MMA一CHMI共聚物/APMMT复合材料。CHMI的引入使蒙脱土片层有
了更大程度的分散。共聚物/蒙脱土纳米复合材料的耐热性及透明性比均聚物/蒙脱土纳
米复合材料有明显的提高，而且MMA一CHMI/ APMMT复合材料的透明性优于MMA-
CHMI/ANMMT复合材料。
本文还探讨了无机蒙脱土存在下AIBA引发MMA一CHMI一St的三元共聚反应，考察
了MMT用量、AIBA浓度、反应温度对聚合反应速率、共聚物分子量和产物Tg的影响;
采用连续加料法制备了MMA一CHMI一St/MMT复合材料;将其作为耐热改性剂与PVC
共混，共混后PVC的耐热性有所提高。
Poly (methyl methacrylate) (PMMA) is a kind of transparent materials. It has a variety of interesting and desirable properties compared to inorganic materials. But the poor thermal properties of PMMA have been point out to be a main disadvantage of these materials. In order to extent it's application fields, more and more attentions have been focused on the research of improving heat resistence for PMMA.
In our work, two ways were adopted to improve the thermal properties of PMMA: incorporating rigid N-cyclohexyl maleimide into the chain of PMMA by copolymerization and compounding the organic-inorganic components by means of nanocompouding technique.
Firstly, N-cyclohexyl maleimide was synthesized in high yield and purity (mp: 90.2C, literature: 90.2C) by dehydration of maleimic acid at hight temperature. Binary copolymers of MMA / CHMI at different feed content were synthesized by bulk copolymerization. The results show that as the content ratio of CHMI increased, the glass transition temperature and thermal decomposition temperature of copolymers are all higher than PMMA, and the yellow index of the copolymer is also increased. The resident CHMI in the copolymer leads to the yellow index of the materials. The introduce of St as the third monomer into the copolymerization improves the activity of the CHMI, so the yellow index of the copolymer decreased. Transparent materials with well integration properties will be obtained by controlling the ratios of monomers properly.
Secondly, a new two-step intercalation with aqueous soluble cationic free-radical initiator 2,2'-azobi(2-methyl-propionamide) hydrochloride (AIBA) and hexadecyltrimethyammonium bromide (CTAB) or hexadecyltri-n-butylphosphonium bromide (HTPB) was used to modify montmorillonite (MMT), and two kinds of active organic montmorillonite ANMMT (AIBA-CTAB-MMT) and APMMT (AIBA-HTPB-MMT) were obtained. The absorption
amounts of AIBA in the above montmorillonite maining depended on the content ratio of AIBA, and the interlayer distance of the active organic montmorillonite was influenced by the ratio of intercalation agents and the cationic character.
PMMA / ANMMT and PMMA / APMMT nanocomposites were prepared by bulk intercalation polymerization. XRD and TEM studies showed that montmorillonite is as nanostructure in PMMA matrix. The glass transition temperature of PMMA / ANMMT nanocomposites was increased with the addition of ANMMT while no glass transition could be observed for PMMA / APMMT nanocomposites, but their heat decomposition temperature were all increased with the introduce of active organic montmorillonite. PMMA / APMMT nanocomposites exhibited better light transmittance than PMMA / ANMMT nanocomposites.
We introduced CHMI into the bulk intercalation copolymerization and prepared MMA-CHMI / ANMMT and MMA-CHMI / APMMT nanocomposites. It was found that the dispersibility of montmorillonite in polymer matrix and the interaction of between the montmorillonite layers with copolymer was greatly improved with the incorporation of polar unit CHMI. Thermal properties and light transmittance of copolymer nanocomposites were superior to those of the homopolymer nanocomposites .
Methyl methacrylate (MMA)-jV-cyclohexylmaleimide (CHMI)-styrene (St) copolymer / Na-montmorillonite (MMT) composites were prepared by soap-free emulsion copolymerization using 2,2'-azobi (2-methyl-propionamide) dehydrochloride (AIBA) as initiator. The influences of the amount of montmorillonite, initiator and the temperature of reaction on the copolymerization rate, molecular weight of copolymer and the glass transition temperature (Tg) of the composite were investigated. The results indicated that MMT can accelerate the copolymerization rate, increase the molecular weight of the copolymer, and enhance the thermal properties of composites. MMA-CHMI-St / MMT composites, using as heat resistance modifier, can improve the thermal property of PVC.
本文采用两种途径对PMMA进行耐热改性：一是通过共聚在PMMA大分子链上引入刚性的N-环己基马来酰亚胺(CHMI)，增大链内旋转阻力，从而提高其耐热性；二是利用有机-无机纳米复合技术，通过性能互补，实现PMMA的高性能化。
本文首先研究了N-环己基马来酰亚胺单体合成的最佳条件，采用高温脱水法合成出了高产率、高纯度的单体(熔点为90.2℃，文献值90.2℃)。在此基础上，利用本体聚合法制备了MMA／CHMI二元共聚物。热分析测试表明，N-环己基马来酰亚胺的引入使PMMA的玻璃化转变温度、热分解温度显著提高。但随着CHMI用量的增加，产物的黄色指数增大。研究表明，导致产物变黄的主要原因是体系中CHMI的残留。为此，将苯乙烯(St)作为第三单体引入上述共聚体系，制备了MMA／CHMI／St三元共聚物。St的引入提高了CHMI参与共聚的活性，降低了产物的黄色指数，当St用量合适时，可得到热学性能、力学性能良好的透明材料。
本文研究的另一个重要内容是活性有机蒙脱土的制备。将水溶性阳离子自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)和十六烷基三甲基溴化铵(CTAB)或十六烷基三正丁基溴化鳞(HTPB)两次插层蒙脱土制备了既有较大层间距，又有引发活性的有机蒙脱土ANMMT(AIBA和CTAB改性MMT)和APMMT(AIBA和HTPB改性MMT)。AIBA在蒙脱土中的含量主要取决于两种插层剂的比值，与长碳链阳离子的种类关系不大。活性有机蒙脱土层间距的大小不仅与两种插层剂比值有关，还受阳离子种类的影响，在其它条件相同时，季鳞盐改性蒙脱土的层间距大于季铵盐。此种活性有机蒙脱土用于纳米复合材料的制备将从热力学和动力学两方面为蒙脱土片层的打开提供必要及充分的条件。
甲基内烯酸甲酷一N一环己基马来酞亚胺一苯乙烯共聚物及其蒙脱土纳米复合材料的制备、结构和性能
将MMA分别与上述两种活性有机蒙脱土进行原位本体聚合，制备了PMMA/
ANMMT和PMMA/APMMT纳米复合材料。XRD和TEM测试表明，两种复合材料均实
现了纳米复合;蒙脱土的加入使PMMA/ANMMT复合材料的玻璃化转变温度Tg提高，
而PMMA/APMMT复合材料未出现明显的玻璃化转变;两种复合材料都表现出较高的热
分解温度，尤其是PMMA/APMMT复合材料;PMMA/ANMMT复合材料的透光性变差，
而PMMA/APMMT表现出良好的透光率和雾度值。
为进一步提高蒙脱土片层的剥离程度，增大聚合物基体与蒙脱土片层的界面作用，采
用共聚插层复合，将耐热改性单体CHMI引入插层复合体系，制备了MMA一CHMI共聚
物/ANMMT和MMA一CHMI共聚物/APMMT复合材料。CHMI的引入使蒙脱土片层有
了更大程度的分散。共聚物/蒙脱土纳米复合材料的耐热性及透明性比均聚物/蒙脱土纳
米复合材料有明显的提高，而且MMA一CHMI/ APMMT复合材料的透明性优于MMA-
CHMI/ANMMT复合材料。
本文还探讨了无机蒙脱土存在下AIBA引发MMA一CHMI一St的三元共聚反应，考察
了MMT用量、AIBA浓度、反应温度对聚合反应速率、共聚物分子量和产物Tg的影响;
采用连续加料法制备了MMA一CHMI一St/MMT复合材料;将其作为耐热改性剂与PVC
共混，共混后PVC的耐热性有所提高。
Poly (methyl methacrylate) (PMMA) is a kind of transparent materials. It has a variety of interesting and desirable properties compared to inorganic materials. But the poor thermal properties of PMMA have been point out to be a main disadvantage of these materials. In order to extent it's application fields, more and more attentions have been focused on the research of improving heat resistence for PMMA.
In our work, two ways were adopted to improve the thermal properties of PMMA: incorporating rigid N-cyclohexyl maleimide into the chain of PMMA by copolymerization and compounding the organic-inorganic components by means of nanocompouding technique.
Firstly, N-cyclohexyl maleimide was synthesized in high yield and purity (mp: 90.2C, literature: 90.2C) by dehydration of maleimic acid at hight temperature. Binary copolymers of MMA / CHMI at different feed content were synthesized by bulk copolymerization. The results show that as the content ratio of CHMI increased, the glass transition temperature and thermal decomposition temperature of copolymers are all higher than PMMA, and the yellow index of the copolymer is also increased. The resident CHMI in the copolymer leads to the yellow index of the materials. The introduce of St as the third monomer into the copolymerization improves the activity of the CHMI, so the yellow index of the copolymer decreased. Transparent materials with well integration properties will be obtained by controlling the ratios of monomers properly.
Secondly, a new two-step intercalation with aqueous soluble cationic free-radical initiator 2,2'-azobi(2-methyl-propionamide) hydrochloride (AIBA) and hexadecyltrimethyammonium bromide (CTAB) or hexadecyltri-n-butylphosphonium bromide (HTPB) was used to modify montmorillonite (MMT), and two kinds of active organic montmorillonite ANMMT (AIBA-CTAB-MMT) and APMMT (AIBA-HTPB-MMT) were obtained. The absorption
amounts of AIBA in the above montmorillonite maining depended on the content ratio of AIBA, and the interlayer distance of the active organic montmorillonite was influenced by the ratio of intercalation agents and the cationic character.
PMMA / ANMMT and PMMA / APMMT nanocomposites were prepared by bulk intercalation polymerization. XRD and TEM studies showed that montmorillonite is as nanostructure in PMMA matrix. The glass transition temperature of PMMA / ANMMT nanocomposites was increased with the addition of ANMMT while no glass transition could be observed for PMMA / APMMT nanocomposites, but their heat decomposition temperature were all increased with the introduce of active organic montmorillonite. PMMA / APMMT nanocomposites exhibited better light transmittance than PMMA / ANMMT nanocomposites.
We introduced CHMI into the bulk intercalation copolymerization and prepared MMA-CHMI / ANMMT and MMA-CHMI / APMMT nanocomposites. It was found that the dispersibility of montmorillonite in polymer matrix and the interaction of between the montmorillonite layers with copolymer was greatly improved with the incorporation of polar unit CHMI. Thermal properties and light transmittance of copolymer nanocomposites were superior to those of the homopolymer nanocomposites .
Methyl methacrylate (MMA)-jV-cyclohexylmaleimide (CHMI)-styrene (St) copolymer / Na-montmorillonite (MMT) composites were prepared by soap-free emulsion copolymerization using 2,2'-azobi (2-methyl-propionamide) dehydrochloride (AIBA) as initiator. The influences of the amount of montmorillonite, initiator and the temperature of reaction on the copolymerization rate, molecular weight of copolymer and the glass transition temperature (Tg) of the composite were investigated. The results indicated that MMT can accelerate the copolymerization rate, increase the molecular weight of the copolymer, and enhance the thermal properties of composites. MMA-CHMI-St / MMT composites, using as heat resistance modifier, can improve the thermal property of PVC.
引文
[1] 宋焕成，赵时熙．聚合物基复合材料．北京：国防工业出版社，1986．200
[2] 张立德，纳米材料．北京：化学工业出版社，2000．39-42
[3] 陈光明，李强，漆宗能，等．聚合物／层状硅酸盐纳米复合材料研究进展．高分子通报，1999，(4)：1-10
[4] Enzel P, Bein T. Inclusion of polyanitine filameuts in zeolite molecular sieves. J Phys Chem, 1989, 93: 6270-6278
[5] Tawney PO, Snyder RH, Conger RP, et al. maleimide and derivatives Ⅱ maleimide and Nmethylolmaleimide. J Org Chem, 1961, 26:15-21
[6] 松永藤尚，福原浩，小林正夫．N-制造方法．日本公开特许，JP昭62-273952．1987．11．28．
[7] Matsumoto A, Kubota T, Otsu T, et al. Radical polymerization of N- lalkyl- substituted phenylmaleimides: synthesis of thermally stable polymers soluble in nonpolar solvents. Macromolecules, 1990, 23:4508-4513
[8] Cubbon RC. Free radical and anionic polymerization of some N- substituted maleimides. Polymer, 1965, 6(8): 419-426
[9] Barilett, PD, Nozake KJ. Chem Soc, 1946, 68:1495
[10] 汪昆华等．聚合物近代仪器分析．北京：清华大学出版社，1992．39，67，136
[11] 单国荣，翁志学，黄志明，等．苯乙烯／N-苯基马来酰亚胺共聚物分子量模型．浙江大学学报，1997．31(1)：1
[12] 吴培熙，张留成．聚合物共混改性．北京：轻工业出版社，1996．72-76
[13] 钱保功，许观藩，等．高聚物的转变与松弛．北京：科学出版社，1986．141-146
[14] Schneider HA, Rieger J, Penzel E. Glass transition temperature of random copolymers: 2.extension of the gordon-taylor equation for asymmetric tg vs composition curves. Polym, 1997, 38: 1323-1337
[15] Johnston NW. Sequence distribution-glass transition effects of acrylonitrile co-and terpolymers. Applied Polymer Symposium, 1974, 25:19-26
[16] Cloudhary L, Varma DS, Varma IK, et al. Thermal behavior of methyl methacrytate and N-phenylmaleimide copolymers. J Therm Anal, 1993, 39(5): 633-642
[17] Aoki Y. Miscibility of poly(acrylonitrile-co-styrene) with poly[styrene-co-(maleic anhydride)] and poly[styrene-co-(N-phenylmaleimide)]. Macromolecules, 1988, 21(5): 1277-1282
[18] Iwatsuki A, Kubo M, Wakita M, et al. Polymerization thermodynamics of N-phenylmaleimide and its copolymerization with styrene and phenylvinyl sulfide. Macromolecules, 1991, 24(8): 5009-5014
[19] Oishi T, Kawamoto T. Synthesis and polymerization of optically active N-[4 - N' - (2 - methylbenzyl) aminocarbonylphenyl] itaconimide. J POlym, 1994, 26(8): 920-929
[20] Doi T, Sugiure Y, Yukioka S, et al. A new glass of transparent polymeric materials. Ⅰ . Production and properties of an alternating copolymer of N-methylmaleimide and isobutene. J Appl Polym Sci, 1996, 61(5): 853-858
[21] Doi T, Ishikawa N, Akimoto A. A new glass of transparent polymeric materials. Ⅱ. synthesis and properties of poly(N-cyclohexylmaleimide-alt-isobutene) modified with lauryl methacrylate. J Appl Polym Sci, 1996, 61(5): 859-863
[22] 董绍胜，张志谦，苏荣军，等．N-取代马来酰亚胺在开发新材料中的应用．中国塑料，1998，12(3)：24-29
[23] Yuan Y, Siegmann A, Narkis M, et al. Emulsion copolymerization of N-phenylmaleimide with styrene. J Appl Polym Sci, 1996, 61:1049-1054
[24] Zhang X, James PB, Narkis M. The electro polymerization of poly(styrene-co-4-carboxyphenylmaleimide) coatings on tosteel. J Appl Polym Sci, 1996, 62: 1303-1312
[25] Takao I,Rsutomu N, Wakichi F. Effect of matrix compositions on modifilation of bismaleimide resin by N-phenylmaleimide-styrene copolymers. J Appl Polym Sci, 1996, 60:37-45
[26] Yui CK, Kazuo K, Kinichi N. Coloration me chanism of the acrylonitrile solution of N-phenylmaleimide and it stabilization method. J Appl Polym Sci, 1995, 64:2037-2045
[27] Abbate M, Martuscelli E, Musto P. A novel reactive liquid rubber with maleimide end groups for the toughening of vusaturated polyesterresins. J Appl Polym Sci, 1996, 62:2107-2119
[28] Toru D, Satoshi, Yukioka, Hiroshi I. A new glass of transparent polymeric materials. Ⅲ. miscible blends of poly)N-methylmaleimide-alt-isobutene with poly(acrylonitrile-co-styrene) and the properties of the blends. J Appl Polym Sci, 1997, 63:925-929
[29] 杨丽庭，张留成．N-取代马来酰亚胺共聚反应及共聚物性能、结构与应用的研究进展．河北大学学报(自然科学版)，1998，18(4)：417-422
[30] 汪璐霞．耐热透明高功能树脂．化工新型材料，1993，(7)：33-36
[31] 干睦铿．功能有机玻璃．化工新型材料，1993，(11)：24-28
[32] 吴岩．提高有机玻璃耐热性的研究．沈阳化工，1998，27(3)：37-39
[33] Hitachi Chemical Co Ltd, JP01-87651
[34] 董绍胜，王清民，魏月贞，等．不同聚合方法对耐热有机玻璃结构与性能的影响．材料科学与工艺，1998，6(4)：64-67
[35] 王清民，董绍胜，于广义，等．甲基丙烯酸甲酯-N-环己基马来酰亚胺二元共聚物的研究．高分子材料科学与工程，2000，16(3)：160-162
[36] Dong SS, Wei YZ, Zheng ZQ, et al. Study on the sythesis of heat-resistant PMMA. J Appl Polym Sci, 1998, 72:1335-1339
[37] 夏平，蒋序林，颜德岳．耐热星形甲基丙烯酸甲酯共聚物的合成．高等学校化学学报，2002，23(2)：336-338
[38] 张桂玲，戴柏青，韦永德，等．CHMI／MMA共聚物结构与性能的量子化学研究．高等学校化学学报，2002，(2)：249-251
[39] Jiang XL, Yan DY, Zhang YL, et al. Atom transfer radical copolymerization of methyl methacrylate with N-cyclohexylmaleimide. Polym Int 2000, 49:893-897
[40] Gao JG, Liu GD, Yang LT, et al. Thermoanalysis and rheological behavior of emulsion copolymers of methyl methacrylate, N-phenylmaleimide and styrene. Polym Eng Sci, 2000, 40(5): 1226-1231
[41] 朱勤勤，封麟先．光学用透明高分子材料．高分子材料科学与工程，1995，11(5)：1-6
[42] 刘世雄，顾陈斌，刘新厚，等．耐热性有机高分子的性能研究及其在塑料光纤中的应用．感光科学与光化学，2001，19(4)：304-309
[43] 李悦生，翁志学，潘祖仁，等．N-取代马来酰亚胺改性的MMA树脂．化工新型材料，1994，(5)：20-24
[44] Roy R, Komarneni S, Roy DM. Multi-phase ceramic composites made by sol-gel technique. Mater Res Sic Symp Proc, 1984, 32:347
[45] Okada A, Kawasumi M, Kurauchi T, et al. Synthesis and characterization of a nylon 6-clay hybrid. Polym Prepr, 1987, 28(2): 447-448
[46] Usuki A, Kato M, Okada A, et al. Synthesis of polypropylene-clay hybrid. J Appl Polym Sci, 1997, 63: 137-139
[47] Burnside SD, Giannelis EP. Synthesis and properties of new poly (dimethylsiloxane) nanocomposites. Chem Mater, 1995, 7(9): 1597-1600
[48] Guillermo J, Nobuo O, Hidekazu K, et al. Structure and thermal/mechanical properties of poly (ε-caprolactone) - clay blend. J Appl Polym Sci, 1997, 64:2211-2220
[49] Mesersmith PB, Giannelis EP. Polymer-layered silicate nanocomposites: in situ intercalative polymerization of ε-caperolactone in layered silicates. Chem Mater, 1993, 5(8): 1064-1066
[50] Wang MS, Pinnavaia YJ. Clay- polymer nanocomposites formed fuom acidic derivatives of montmorillonite and an epoxy resin. Chem Mater, 1994, 6(4): 468-474
[51] Lan T, Pinnavaia TJ. Clay-reinforced epoxy nanocomposltes. Chem Motet, 1994, 6(12): 2216-2219
[52] Kormann X, Berglund LA, Sterte J, et al. Nanocomposltes based on montemorillonite and unsaturated polyester. Polymer Engineering and Science, 1998, 38(8): 1351-1358
[53] Vaia RA, Vasudevan S, Krawiec W, et al. New polymer electrolyte nanocomposites: meltintercalation of poly(ethylene oxide) in mica-type silicates. Adv Mater, 1995, 7(2): 154-156
[54] Lan T, Kaviratna PD, Pinnavaia TJ. Synthesis, characterization and C_(12) permeability of polyimide-clay composites. Polymer Preprints, 1994, 35(1): 823-824
[55] Mehrotra V, Giannelis EP. Nanometer scale multilayers of electroactive polymer: intercalation of polypyrrole in mica-type silicates. Solid State lonics, 1992, 51: 115-122
[56] Reichert P, Kressler J, Thomann R. Nanocomposite based on a synthetic layer silicate and polyamide-12. Acta Polym, 1998, 49(2-3): 116-123
[57] Olson BG, Peng ZL, Srithawatpong R, et al. Free volume in layered organosilicate-polystyrene nanocomposites. Material Science Forum, 1997, 250:336-338
[58] Choi HJ, Kim JW, Kim SG, et al. Synthesis and electrorheological characterization of polyaniline-Na+ -montmorillonite clay suspensions. Polymer Preprints, 1999, 40(2): 813-814
[59] Uemoto M, Furuya T. Polyurethane-coated cloth for label printing sheet with washability. JP2000 17579, 日本专利, 2000
[60] 乔放，李强，漆宗能，等．聚酰胺／粘土纳米复合材料的制备、结构表征及性能研究．高分子通报，1997，(3)：135-143
[61] 朱笑初，景肃，孟娟，等．PBT／粘土纳米复合材料的制备和性能表征．塑料工业，2000，28(20)：45-47
[62] 漆宗能，柯杨船，丁幼康．一种聚对苯二甲酸丁二酯／层状硅酸盐纳米复合材料及其制备方法．CNI187506，中国专利，1998
[63] 王一中，武保华．聚氧乙烯／蒙脱土嵌入化合物的制备与结构表征．高等学校化学学报，1999，29(7)：1143-1147
[64] 顾群，吴大诚，易国祯，等．聚醚酯／蒙脱土复合材料的结晶动力学和结晶形态．高等学校化学学报，1999，20，(2)：324-326
[65] 蒋殿录，翁永良．聚苯胺／膨润土纳米复合材料的合成与表征．物理化学学报，1999，15(1)：69-72
[66] 封禄田，田一光，石爽，等．蒙脱土／聚丙烯酰胺复合材料的制备和性能研究．沈阳化工学院学报，1999，13(1)：1-5
[67] 石爽，田一光．聚丙烯腈／蒙脱土纳米复合材料的制备．沈阳化丁学院学报，1999，13(3)：164-167
[68] 孙维林，王铁军，刘庆旺．粘土的理化性能．北京：地质出版社，1992
[69] 武保华，王一中，余鼎声．有机蒙脱土的制备与表征．石油化工，1999，28(3)：153-156
[70] 傅万里，刘竞超．环氧树脂／粘土纳米复合材料的研究．工程塑料应用，2002，30(5)：1-4
[71] 李同年，周持兴，庐文奎，等．聚苯乙烯-蒙脱土插层复合材料的制备与性能．塑料工业，2000，28(2)：33-35
[72] 王立新，张楷亮，袁金凤，等．环氧树脂对脂肪胺阳离子交换蒙脱石浸润行为的研究．河北工业大学学报，2000，29(4)：24-28
[73] 程爱民，田艳，韩冰．聚氨酯／蒙脱士纳米复合材料的制各与性能研究．高分子学报，2003，(4)：591-594
[74] Yang HH, Sung TL. Rheology of poly(ethlence oxide/organoclay nanocomposites. Macromolecues, 2001, 34:8084
[75] Kornmann X, Lindberg H, Berglund LA. Synthesis of epoxy-clay nanocomposites: influence of the nature of the curing agent on structure. Polym, 2001, 42(10): 4493-4499
[76] 郑华，张隐西，张勇，等．合成橡胶工业，2003，26(2)：115-118
[77] Fu X, Qutubuddin S. Polymer-clay nanocomposites., exfoliation of organophilic montmorillonite nanolayers in polystyrene. 2001, 42(2): 807-813
[78] 章永化，龚克成．可聚合性季铵盐-膨润土嵌入复合物的制备．硅酸盐通报，1998，(1)：24-28
[79] Masami O, Satoshi M, Hideyuki T, et al. Synthesis and Structure of Smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites viain situ intercalative polymerization. Polymer, 2000, 41:3887-3890
[80] Zhu J, Morgan AB, Frank JL, et al. Chem Mater, 2001, 13:3774-3780
[81] Jui MY, Shir J, Ching Y, et al. Anticorrosively enhanced pmma-clay nanocomposite materials with quaternary alkylphosphonium salt as an intercalating agent. Chem Mater, 2002, 14:154-161
[82] Horng LT, Kung HW. J Polym. Sci, Part B: Polymer Physics, 2000, 38:2873-2878
[83] Blasci L, Aglietto M, Ruggeri G. Functionalization of montmorillonite by methyl methacrylate polymers containing side-chain ammonium cations. Polym, 1994, 35(15): 3296-3304
[84] Dekking HGG. Propagation of vinyl polymers on day surfaces. (Ⅰ). preparation structure, and decomposition of clay initiators. J Appl Polym Sci, 1965, 9(5): 1641-1651
[85] Lan T, Kaviratna PD, Pinnavaia T. Mechanism of clay exfoliation in epoxy-clay nanocomposites. J Chem Mater, 1995, 7(11): 2144-2150
[86] 陈光明，马永梅，漆宗能．甲苯-2，4-二异氰酸酯修饰蒙脱士及聚苯乙烯／蒙脱土纳米复合材料的制备与表征．高分子学报，2000，5：599-603
[87] 赵春贵，阳明书，冯猛．氯硅烷改性蒙脱土的制备与性能．高等学校化学学报，2003，24(5)：928-931
[88] Zhu J, Start P, Mauritz KA, et al. Silicon-methoxide-modified clays and their polystyrene nanocomposites. J Appl Polymer Sci, Part A: Polyme Chem, 2002, 40:1498-1503
[89] 周宁琳，夏小仙，王延儒，等．剥离型硅橡胶／粘土纳米复合材料研究．高分子学报，2002，(2)：253-255
[90] 赵伟安，侯万国，孙德军．聚苯乙烯／硅烷偶联剂修饰蒙脱土纳米复合材料的制备与表征．功能高分子学报，2003，16(1)：81-84
[91] 张径，杨玉昆．插层法恳浮聚合制备PMMA／蒙脱土纳米复合材料．高分子学报，2001(1)：79-82
[92] 张楠，徐日炜，余鼎声．石油化工，2002，31(10)：807-809
[93] 王柯，朱湛，郭炳南．有机蒙脱土的制备及其结构表征．北京理工大学学报，2002，22(2)：240-243
[94] Vaia RA, Giannelis EP. Lattice model of polymer melt intercalation in organically-modified layered silicates. Macromolecules, 1997, 30(25): 7990-7999
[95] Vaia RA, Giannelis EP. Polymer melt intercalation in organically-modified layered silicates: model predictions and experiment. Macromolecules, 1997, 30(25): 8000-8009
[96] Vaia RA, Jandt KD, Kramer EJ, et al. Microstructural evolution of melt intercalated polymerorganically modified layered silicates nanocomposites. Chem Mater, 1996, 8(11): 2628-2635
[97] Giannelis EP. Polymer layered silicate nanocomposites. Adv Mater, 1996, 8(1): 29-35
[98] Balazs AC, Singh C, Zhulina E. Stabilizing properties of copolymers adsorbed on heterogeneous surfaces: a model for the interactions between a polymer-coated influenza virus and a cell. Macromolecules, 1998, 31(18): 6369-6379
[99] Sikka M., Cerini LN, Ghosh SS, et al. Melt intercalation of polystyrene in layered silicates. J Polym Sci, Part B: Polym Phys, 1996, 34:1443-1449
[100] Lee JY, Baljon ARC, Loring RF. Modelling intercalation kinetics of polymer silicate nanocomposites. J Chem Phys, 1999, 111(21): 9754-9760
[101] Lyatskaya Y, Balazs AC. Modeling the phase behavior of polymer-clay composites. Macromolecules, 1998, 31(19): 6676-6680
[102] Vaia RA, Vasudevan S, Krawiec W, et al. New polymer electrolyte nanocomposites melt intercalation of poly(ethylene oxide) in mica-type silicates. Adv Mater, 1995, 7(2): 154-156
[103] 漆宗能，李强，赵竹弟，等．一种聚酰胺／粘土纳米复合材料及其制备方法．中国专利，申请号：96105362．3
[104] Chen GM, Liu SH, Chert SJ, et al. FTIR spectra, thermal properties, and dispersibility of a polystyrene/montmorillonite nanocomposite. Macromol Chem Phys, 2001, 202:1189-1193
[105] Kojima Y, Usuki A, Kawasumi M, et al. Synthesis of nylon- 6- clay hybrid by monomorillonite intercalated with ε-caprolactam. J Polym Sci Part A Polymer Chemistry, 1993, 31:983-986
[106] Mesersmith PB, Giannelis EP. Polymer- layered silicate nanocomposites: in site intercalative polymerization of ε-caprolactone in layered silicates. Chem Mater, 1993, 5(8): 1064-1066
[107] Yano K, Usuki A., Okada A, et al. Synthesis and properties of polyimide - clay hybrid, J. Polym. Sci, Part A: Polymer Chemistry, 1993, 31 : 2493-2498
[108] 王新宇，漆宗能，王佛松．聚合物-层状硅酸盐纳米复合材料制备及应用．工程塑料应用，1999，27(2)：1-5
[109] Dekking HGG. Propagation Vinyl polymers on clay surfaces, ⅱ. polymerization of monomers initiated by free radicals attached to clay. J Appl Polym Sci, 1967, 11: 23-26
[110] 官同华，瞿雄伟，张留成．乳液法甲基丙烯酸甲酯／蒙脱土纳米复合材料的合成与表征．中国塑料，2001，15(11)：15-19
[111] 李青山，白德安，王慧敏．PMMA／MT纳米复合材料的研究．齐齐哈尔大学学报，2001，17(4)：4-5
[112] 李青山，白德安，蔡传英，等．甲基丙烯酸甲酯-蒙脱土纳米复合材料的研究．中国粉体技术，2000，6：273-275
[113] Luca B. Functionalization of montmorillonite by methyl methacrylate polymers containing side-chain ammonium cations. Polymer, 1994, 35(15): 3296-3304
[114] Okamoto M, Morita S, Kim YH, et al. Dispersed structure change of smetic clay/poly(methyl methacrylate) nanocomposites by copolymerization with polar comonomers. Polym, 2001, 42: 1201-1206
[115] Frark D, Yi T, Ralf T, et al. Translucent acrylic nanocomposites containing anisotropic laminated nanoparticles derived from intercalated layered silicates. 2000, 75:396-405
[116] 王一中，武保华，余鼎声．乳液聚合法制备聚甲基丙烯酸甲酯／蒙脱土嵌入混杂材料．北京化工大学学报，2000，27(2)：25-28
[117] Dong CL, Lee WJ. Preparation and characterization of pmma-clay composite by emusison polymerization. J Appl Polym Sci, 1996, 61 : 1117-1122
[118] AL - ESAIMI MM. Studies on the polymerization of pmma in the presence of mmt. J Appl Polym Sci, 1997, 64:367-372
[119] 邹纲，方堑，盛夏，等．动态扭振法研究聚甲基丙烯酸甲酯／蒙脱土纳米复合材料的本体插层聚合．高等学校化学学报，2003，24(3)：537-540
[120] Bhattacharya, J, Saha SK. Aqueous polymerization on clay surfaces. J Polym Sci, part A: Polym Chem, 1990, 28:2249-2254
[121] 张径，杨玉昆．以SiO_2纳米粒子为种子的甲基丙烯酸甲酯乳液聚合．化学与粘合，2001，1：1-3
[122] 张启卫，章永化，陈守明，等．聚甲基丙烯酸甲酯／二氧化硅杂化材料制备与性能．应用化学，2002，19(9)：874-877
[123] Yuich K, Kazuo K, Koichi N. Synthesis of N-cyclohexylmaleimide for heat-resistant trans parent methacrylic resin. J Appl Polym Sci, 1997, 63:363-368
[124] [美]RM西尔弗斯著．有机化合物光谱鉴定．北京：科学出版社，1988
[125] Aida H, Kimura M, Fukuoka A, et al. Glass transition temperatures of copolymers of maleimides with methyl acrylate or methacrylate. Kobunshi Kagaku, 1971,28(312): 354-361
[126] Bharel R, Cloudhary V, Varma IK. Thermal and mechanical properties of copolymers of methyl methcrylate with N-phenylmaleimide. J Appl Polym Sci, 1993, 49(1): 31-38
[127] Nakai Y, Sato F. Heat-resistant copolymer resins for optical elements. Jpn Kokai Tokkyo Koho JP 61, 141, 715186, 141,715]
[128] Grassie N , Farish E. Thermal degradation of copolymers of styrene and methyl methacrylate. Eur Polym J, 1967, 3(2): 305-315
[129] 胡孝东，罗时剑，颜德岳．甲基丙烯酸甲酯-苯乙烯-N苯基马来酰亚胺三元共聚物的研究．高分子学报，1992，6：696-699
[130] Mayo FR., Lewis, FM. J Am Chem Soc, 1944, 66:1894
[131] Elsabee MA, Sabaa MW, Naguib HF, et al. Copolymerization of methyl rnethacrylate with N-phenylmaleimide in different solvents. J Macromol Sci Chem, 1987, A24(10): 1207-1221
[132] Barrales-Rienda JM, Gonzalez de la Campa JI, Gonzalez RJ. Free-radical copolymerization of N-phehylmaleimide. J Macromol Sci, 1997, 11:267-286
[133] 单国荣．乙烯基单体／N-取代马来酰亚胺共聚合．[博士学位论文]．浙江：浙江大学，1996
[134] 柯扬船，[美]皮特·斯壮主编，聚合物-无机纳米复合材料，北京：化学工业出版社，2003
[135] 傅万里，刘竞超．环氧树脂／粘土纳米复合材料的研究(Ⅰ)有机蒙脱土的制备与表征．湘潭大学自然科学学报，2002，24(1)：68-70
[136] Ortego JD, Kowalska M, Cocke DL. Interactions of montmorillonite with organic compounds-adsorptive and catalytic properties. Chemosphere, 1991, 22(8): 769-798
[137] Gungor N. Effect of the Adsorption of Surfactants on the rheology of Na-Bentonite Slurries. J Appl. Poly Sci, 2000, 75:107-110
[138] Pan G, Yang B, Han HY. Studies on interaction of dodecyltrimethylammonium btomide with Na - and Al - montmorillonite, J Colloid Interface Science, 1997, 197:276-280
[139] Dekking HGG. Propagation of vinyl polymers on clay surfaces. Ⅱ. polymerization of monomers initiated by free radicals attached to clay, J. Appl. Polym. Sci. 1967, 11:23-26
[140] Makoto O, Kazuyuki K. Preparation of inorganic-organic nanocomposites through intercalation of organoammoniumions into layered silicates. Bull Chem Soc Jpn, 1997, 70:2593
[141] 官建国，黄俊，袁润章．光学透明材料的现状和研究进展．武汉工业大学学报，1998，20(3)：11-13
[142] 徐洪耀．塑料透镜的耐磨膜．工程塑料应用，1994，22(5)：47-49
[143] 徐国财，张立德编著．纳米复合材料．北京：化学工业出版社，2002，225
[144] Cholocl MS, Parker HY. Encyclopedia of Polymer Science and Engineering, 1995, 6385-6390
[145] 上海市模具技术协会．塑料技术标准大全．杭州：浙江科学技术出版社，1993
[146] Vaia RA, Ishii H, Giannelis EP. Symttosis and properties of two dimensional nanostructures by direct intercalation of polymer melts in layered Silicates. Chem Mater, 1993, 5(12): 1694-1696
[147] Vaia RA, Sauer BB, Tse K, et al. Relaxations of confised chains in Polymer nanocomposits: Glass transition Properties of Polycethylene oxide, intercalated in montmorillonite. J Polym Sci B Polym Phys, 1997, 35:59-67
[148] Girish G, Ramesh C, Ashish LA. Rheological study on the kinetics of hybrid rormathon in polypropylene nanocomposites. Macromolecues, 2001, 34:852
[149] 吕建坤，柯毓才，漆宗能，等．环氧／粘土纳米复合材料过程中粘土剥离行为的研究．高分子通报，2000，2：18-26
[150] 唐业全，罗是忠，吴正翠，等．微波辐照制备无皂阳离子PMMA胶乳粒子．高分子学报，2002，4：443-446
[151] 杨丽庭．N-取代马来酰亚胺共聚反应、共聚物性能、结构与应用研究及其共混物性能与群子标度之间关系的研究：[博士学位论文]．北京：北京化工大学，2000
[152] 李克友．涂料工业，1986，3
[153] 北京大学化学系高分子教研室编．高分子实验与专论．北京：北京大学出版社，1990
[154] Xingyu H, William JB. Synthesis of a PMMA-layered silicate namocomposite by suspension polymerization Polymer Preprints 2000, 41(1): 521
[155] Vaia RA, et al. Microstructural Euvolution of Melt intercalated polymer-organically modified layered sillicates nanocomposites, Chem Mater, 1996, 8:2628
[156] Dritis VA, Tchoubar C. X-ray diffraction by disordered lamellar structures, springer-verlag: New York, 1990:21
[157] Cullity BD. Principles of X-ray diffraction, Addison-Wesley. Reading, MA, 1987
[158] Yang LT, Liu GD, Sun DH, et al. Mechanical properties and theological behavior of PVC blended with terpolymers containg N-phenylmaleimide. J Vinyl Additive Technol, 2002, 8(2): 151-158
[2] 张立德，纳米材料．北京：化学工业出版社，2000．39-42
[3] 陈光明，李强，漆宗能，等．聚合物／层状硅酸盐纳米复合材料研究进展．高分子通报，1999，(4)：1-10
[4] Enzel P, Bein T. Inclusion of polyanitine filameuts in zeolite molecular sieves. J Phys Chem, 1989, 93: 6270-6278
[5] Tawney PO, Snyder RH, Conger RP, et al. maleimide and derivatives Ⅱ maleimide and Nmethylolmaleimide. J Org Chem, 1961, 26:15-21
[6] 松永藤尚，福原浩，小林正夫．N-制造方法．日本公开特许，JP昭62-273952．1987．11．28．
[7] Matsumoto A, Kubota T, Otsu T, et al. Radical polymerization of N- lalkyl- substituted phenylmaleimides: synthesis of thermally stable polymers soluble in nonpolar solvents. Macromolecules, 1990, 23:4508-4513
[8] Cubbon RC. Free radical and anionic polymerization of some N- substituted maleimides. Polymer, 1965, 6(8): 419-426
[9] Barilett, PD, Nozake KJ. Chem Soc, 1946, 68:1495
[10] 汪昆华等．聚合物近代仪器分析．北京：清华大学出版社，1992．39，67，136
[11] 单国荣，翁志学，黄志明，等．苯乙烯／N-苯基马来酰亚胺共聚物分子量模型．浙江大学学报，1997．31(1)：1
[12] 吴培熙，张留成．聚合物共混改性．北京：轻工业出版社，1996．72-76
[13] 钱保功，许观藩，等．高聚物的转变与松弛．北京：科学出版社，1986．141-146
[14] Schneider HA, Rieger J, Penzel E. Glass transition temperature of random copolymers: 2.extension of the gordon-taylor equation for asymmetric tg vs composition curves. Polym, 1997, 38: 1323-1337
[15] Johnston NW. Sequence distribution-glass transition effects of acrylonitrile co-and terpolymers. Applied Polymer Symposium, 1974, 25:19-26
[16] Cloudhary L, Varma DS, Varma IK, et al. Thermal behavior of methyl methacrytate and N-phenylmaleimide copolymers. J Therm Anal, 1993, 39(5): 633-642
[17] Aoki Y. Miscibility of poly(acrylonitrile-co-styrene) with poly[styrene-co-(maleic anhydride)] and poly[styrene-co-(N-phenylmaleimide)]. Macromolecules, 1988, 21(5): 1277-1282
[18] Iwatsuki A, Kubo M, Wakita M, et al. Polymerization thermodynamics of N-phenylmaleimide and its copolymerization with styrene and phenylvinyl sulfide. Macromolecules, 1991, 24(8): 5009-5014
[19] Oishi T, Kawamoto T. Synthesis and polymerization of optically active N-[4 - N' - (2 - methylbenzyl) aminocarbonylphenyl] itaconimide. J POlym, 1994, 26(8): 920-929
[20] Doi T, Sugiure Y, Yukioka S, et al. A new glass of transparent polymeric materials. Ⅰ . Production and properties of an alternating copolymer of N-methylmaleimide and isobutene. J Appl Polym Sci, 1996, 61(5): 853-858
[21] Doi T, Ishikawa N, Akimoto A. A new glass of transparent polymeric materials. Ⅱ. synthesis and properties of poly(N-cyclohexylmaleimide-alt-isobutene) modified with lauryl methacrylate. J Appl Polym Sci, 1996, 61(5): 859-863
[22] 董绍胜，张志谦，苏荣军，等．N-取代马来酰亚胺在开发新材料中的应用．中国塑料，1998，12(3)：24-29
[23] Yuan Y, Siegmann A, Narkis M, et al. Emulsion copolymerization of N-phenylmaleimide with styrene. J Appl Polym Sci, 1996, 61:1049-1054
[24] Zhang X, James PB, Narkis M. The electro polymerization of poly(styrene-co-4-carboxyphenylmaleimide) coatings on tosteel. J Appl Polym Sci, 1996, 62: 1303-1312
[25] Takao I,Rsutomu N, Wakichi F. Effect of matrix compositions on modifilation of bismaleimide resin by N-phenylmaleimide-styrene copolymers. J Appl Polym Sci, 1996, 60:37-45
[26] Yui CK, Kazuo K, Kinichi N. Coloration me chanism of the acrylonitrile solution of N-phenylmaleimide and it stabilization method. J Appl Polym Sci, 1995, 64:2037-2045
[27] Abbate M, Martuscelli E, Musto P. A novel reactive liquid rubber with maleimide end groups for the toughening of vusaturated polyesterresins. J Appl Polym Sci, 1996, 62:2107-2119
[28] Toru D, Satoshi, Yukioka, Hiroshi I. A new glass of transparent polymeric materials. Ⅲ. miscible blends of poly)N-methylmaleimide-alt-isobutene with poly(acrylonitrile-co-styrene) and the properties of the blends. J Appl Polym Sci, 1997, 63:925-929
[29] 杨丽庭，张留成．N-取代马来酰亚胺共聚反应及共聚物性能、结构与应用的研究进展．河北大学学报(自然科学版)，1998，18(4)：417-422
[30] 汪璐霞．耐热透明高功能树脂．化工新型材料，1993，(7)：33-36
[31] 干睦铿．功能有机玻璃．化工新型材料，1993，(11)：24-28
[32] 吴岩．提高有机玻璃耐热性的研究．沈阳化工，1998，27(3)：37-39
[33] Hitachi Chemical Co Ltd, JP01-87651
[34] 董绍胜，王清民，魏月贞，等．不同聚合方法对耐热有机玻璃结构与性能的影响．材料科学与工艺，1998，6(4)：64-67
[35] 王清民，董绍胜，于广义，等．甲基丙烯酸甲酯-N-环己基马来酰亚胺二元共聚物的研究．高分子材料科学与工程，2000，16(3)：160-162
[36] Dong SS, Wei YZ, Zheng ZQ, et al. Study on the sythesis of heat-resistant PMMA. J Appl Polym Sci, 1998, 72:1335-1339
[37] 夏平，蒋序林，颜德岳．耐热星形甲基丙烯酸甲酯共聚物的合成．高等学校化学学报，2002，23(2)：336-338
[38] 张桂玲，戴柏青，韦永德，等．CHMI／MMA共聚物结构与性能的量子化学研究．高等学校化学学报，2002，(2)：249-251
[39] Jiang XL, Yan DY, Zhang YL, et al. Atom transfer radical copolymerization of methyl methacrylate with N-cyclohexylmaleimide. Polym Int 2000, 49:893-897
[40] Gao JG, Liu GD, Yang LT, et al. Thermoanalysis and rheological behavior of emulsion copolymers of methyl methacrylate, N-phenylmaleimide and styrene. Polym Eng Sci, 2000, 40(5): 1226-1231
[41] 朱勤勤，封麟先．光学用透明高分子材料．高分子材料科学与工程，1995，11(5)：1-6
[42] 刘世雄，顾陈斌，刘新厚，等．耐热性有机高分子的性能研究及其在塑料光纤中的应用．感光科学与光化学，2001，19(4)：304-309
[43] 李悦生，翁志学，潘祖仁，等．N-取代马来酰亚胺改性的MMA树脂．化工新型材料，1994，(5)：20-24
[44] Roy R, Komarneni S, Roy DM. Multi-phase ceramic composites made by sol-gel technique. Mater Res Sic Symp Proc, 1984, 32:347
[45] Okada A, Kawasumi M, Kurauchi T, et al. Synthesis and characterization of a nylon 6-clay hybrid. Polym Prepr, 1987, 28(2): 447-448
[46] Usuki A, Kato M, Okada A, et al. Synthesis of polypropylene-clay hybrid. J Appl Polym Sci, 1997, 63: 137-139
[47] Burnside SD, Giannelis EP. Synthesis and properties of new poly (dimethylsiloxane) nanocomposites. Chem Mater, 1995, 7(9): 1597-1600
[48] Guillermo J, Nobuo O, Hidekazu K, et al. Structure and thermal/mechanical properties of poly (ε-caprolactone) - clay blend. J Appl Polym Sci, 1997, 64:2211-2220
[49] Mesersmith PB, Giannelis EP. Polymer-layered silicate nanocomposites: in situ intercalative polymerization of ε-caperolactone in layered silicates. Chem Mater, 1993, 5(8): 1064-1066
[50] Wang MS, Pinnavaia YJ. Clay- polymer nanocomposites formed fuom acidic derivatives of montmorillonite and an epoxy resin. Chem Mater, 1994, 6(4): 468-474
[51] Lan T, Pinnavaia TJ. Clay-reinforced epoxy nanocomposltes. Chem Motet, 1994, 6(12): 2216-2219
[52] Kormann X, Berglund LA, Sterte J, et al. Nanocomposltes based on montemorillonite and unsaturated polyester. Polymer Engineering and Science, 1998, 38(8): 1351-1358
[53] Vaia RA, Vasudevan S, Krawiec W, et al. New polymer electrolyte nanocomposites: meltintercalation of poly(ethylene oxide) in mica-type silicates. Adv Mater, 1995, 7(2): 154-156
[54] Lan T, Kaviratna PD, Pinnavaia TJ. Synthesis, characterization and C_(12) permeability of polyimide-clay composites. Polymer Preprints, 1994, 35(1): 823-824
[55] Mehrotra V, Giannelis EP. Nanometer scale multilayers of electroactive polymer: intercalation of polypyrrole in mica-type silicates. Solid State lonics, 1992, 51: 115-122
[56] Reichert P, Kressler J, Thomann R. Nanocomposite based on a synthetic layer silicate and polyamide-12. Acta Polym, 1998, 49(2-3): 116-123
[57] Olson BG, Peng ZL, Srithawatpong R, et al. Free volume in layered organosilicate-polystyrene nanocomposites. Material Science Forum, 1997, 250:336-338
[58] Choi HJ, Kim JW, Kim SG, et al. Synthesis and electrorheological characterization of polyaniline-Na+ -montmorillonite clay suspensions. Polymer Preprints, 1999, 40(2): 813-814
[59] Uemoto M, Furuya T. Polyurethane-coated cloth for label printing sheet with washability. JP2000 17579, 日本专利, 2000
[60] 乔放，李强，漆宗能，等．聚酰胺／粘土纳米复合材料的制备、结构表征及性能研究．高分子通报，1997，(3)：135-143
[61] 朱笑初，景肃，孟娟，等．PBT／粘土纳米复合材料的制备和性能表征．塑料工业，2000，28(20)：45-47
[62] 漆宗能，柯杨船，丁幼康．一种聚对苯二甲酸丁二酯／层状硅酸盐纳米复合材料及其制备方法．CNI187506，中国专利，1998
[63] 王一中，武保华．聚氧乙烯／蒙脱土嵌入化合物的制备与结构表征．高等学校化学学报，1999，29(7)：1143-1147
[64] 顾群，吴大诚，易国祯，等．聚醚酯／蒙脱土复合材料的结晶动力学和结晶形态．高等学校化学学报，1999，20，(2)：324-326
[65] 蒋殿录，翁永良．聚苯胺／膨润土纳米复合材料的合成与表征．物理化学学报，1999，15(1)：69-72
[66] 封禄田，田一光，石爽，等．蒙脱土／聚丙烯酰胺复合材料的制备和性能研究．沈阳化工学院学报，1999，13(1)：1-5
[67] 石爽，田一光．聚丙烯腈／蒙脱土纳米复合材料的制备．沈阳化丁学院学报，1999，13(3)：164-167
[68] 孙维林，王铁军，刘庆旺．粘土的理化性能．北京：地质出版社，1992
[69] 武保华，王一中，余鼎声．有机蒙脱土的制备与表征．石油化工，1999，28(3)：153-156
[70] 傅万里，刘竞超．环氧树脂／粘土纳米复合材料的研究．工程塑料应用，2002，30(5)：1-4
[71] 李同年，周持兴，庐文奎，等．聚苯乙烯-蒙脱土插层复合材料的制备与性能．塑料工业，2000，28(2)：33-35
[72] 王立新，张楷亮，袁金凤，等．环氧树脂对脂肪胺阳离子交换蒙脱石浸润行为的研究．河北工业大学学报，2000，29(4)：24-28
[73] 程爱民，田艳，韩冰．聚氨酯／蒙脱士纳米复合材料的制各与性能研究．高分子学报，2003，(4)：591-594
[74] Yang HH, Sung TL. Rheology of poly(ethlence oxide/organoclay nanocomposites. Macromolecues, 2001, 34:8084
[75] Kornmann X, Lindberg H, Berglund LA. Synthesis of epoxy-clay nanocomposites: influence of the nature of the curing agent on structure. Polym, 2001, 42(10): 4493-4499
[76] 郑华，张隐西，张勇，等．合成橡胶工业，2003，26(2)：115-118
[77] Fu X, Qutubuddin S. Polymer-clay nanocomposites., exfoliation of organophilic montmorillonite nanolayers in polystyrene. 2001, 42(2): 807-813
[78] 章永化，龚克成．可聚合性季铵盐-膨润土嵌入复合物的制备．硅酸盐通报，1998，(1)：24-28
[79] Masami O, Satoshi M, Hideyuki T, et al. Synthesis and Structure of Smectic clay/poly(methyl methacrylate) and clay/polystyrene nanocomposites viain situ intercalative polymerization. Polymer, 2000, 41:3887-3890
[80] Zhu J, Morgan AB, Frank JL, et al. Chem Mater, 2001, 13:3774-3780
[81] Jui MY, Shir J, Ching Y, et al. Anticorrosively enhanced pmma-clay nanocomposite materials with quaternary alkylphosphonium salt as an intercalating agent. Chem Mater, 2002, 14:154-161
[82] Horng LT, Kung HW. J Polym. Sci, Part B: Polymer Physics, 2000, 38:2873-2878
[83] Blasci L, Aglietto M, Ruggeri G. Functionalization of montmorillonite by methyl methacrylate polymers containing side-chain ammonium cations. Polym, 1994, 35(15): 3296-3304
[84] Dekking HGG. Propagation of vinyl polymers on day surfaces. (Ⅰ). preparation structure, and decomposition of clay initiators. J Appl Polym Sci, 1965, 9(5): 1641-1651
[85] Lan T, Kaviratna PD, Pinnavaia T. Mechanism of clay exfoliation in epoxy-clay nanocomposites. J Chem Mater, 1995, 7(11): 2144-2150
[86] 陈光明，马永梅，漆宗能．甲苯-2，4-二异氰酸酯修饰蒙脱士及聚苯乙烯／蒙脱土纳米复合材料的制备与表征．高分子学报，2000，5：599-603
[87] 赵春贵，阳明书，冯猛．氯硅烷改性蒙脱土的制备与性能．高等学校化学学报，2003，24(5)：928-931
[88] Zhu J, Start P, Mauritz KA, et al. Silicon-methoxide-modified clays and their polystyrene nanocomposites. J Appl Polymer Sci, Part A: Polyme Chem, 2002, 40:1498-1503
[89] 周宁琳，夏小仙，王延儒，等．剥离型硅橡胶／粘土纳米复合材料研究．高分子学报，2002，(2)：253-255
[90] 赵伟安，侯万国，孙德军．聚苯乙烯／硅烷偶联剂修饰蒙脱土纳米复合材料的制备与表征．功能高分子学报，2003，16(1)：81-84
[91] 张径，杨玉昆．插层法恳浮聚合制备PMMA／蒙脱土纳米复合材料．高分子学报，2001(1)：79-82
[92] 张楠，徐日炜，余鼎声．石油化工，2002，31(10)：807-809
[93] 王柯，朱湛，郭炳南．有机蒙脱土的制备及其结构表征．北京理工大学学报，2002，22(2)：240-243
[94] Vaia RA, Giannelis EP. Lattice model of polymer melt intercalation in organically-modified layered silicates. Macromolecules, 1997, 30(25): 7990-7999
[95] Vaia RA, Giannelis EP. Polymer melt intercalation in organically-modified layered silicates: model predictions and experiment. Macromolecules, 1997, 30(25): 8000-8009
[96] Vaia RA, Jandt KD, Kramer EJ, et al. Microstructural evolution of melt intercalated polymerorganically modified layered silicates nanocomposites. Chem Mater, 1996, 8(11): 2628-2635
[97] Giannelis EP. Polymer layered silicate nanocomposites. Adv Mater, 1996, 8(1): 29-35
[98] Balazs AC, Singh C, Zhulina E. Stabilizing properties of copolymers adsorbed on heterogeneous surfaces: a model for the interactions between a polymer-coated influenza virus and a cell. Macromolecules, 1998, 31(18): 6369-6379
[99] Sikka M., Cerini LN, Ghosh SS, et al. Melt intercalation of polystyrene in layered silicates. J Polym Sci, Part B: Polym Phys, 1996, 34:1443-1449
[100] Lee JY, Baljon ARC, Loring RF. Modelling intercalation kinetics of polymer silicate nanocomposites. J Chem Phys, 1999, 111(21): 9754-9760
[101] Lyatskaya Y, Balazs AC. Modeling the phase behavior of polymer-clay composites. Macromolecules, 1998, 31(19): 6676-6680
[102] Vaia RA, Vasudevan S, Krawiec W, et al. New polymer electrolyte nanocomposites melt intercalation of poly(ethylene oxide) in mica-type silicates. Adv Mater, 1995, 7(2): 154-156
[103] 漆宗能，李强，赵竹弟，等．一种聚酰胺／粘土纳米复合材料及其制备方法．中国专利，申请号：96105362．3
[104] Chen GM, Liu SH, Chert SJ, et al. FTIR spectra, thermal properties, and dispersibility of a polystyrene/montmorillonite nanocomposite. Macromol Chem Phys, 2001, 202:1189-1193
[105] Kojima Y, Usuki A, Kawasumi M, et al. Synthesis of nylon- 6- clay hybrid by monomorillonite intercalated with ε-caprolactam. J Polym Sci Part A Polymer Chemistry, 1993, 31:983-986
[106] Mesersmith PB, Giannelis EP. Polymer- layered silicate nanocomposites: in site intercalative polymerization of ε-caprolactone in layered silicates. Chem Mater, 1993, 5(8): 1064-1066
[107] Yano K, Usuki A., Okada A, et al. Synthesis and properties of polyimide - clay hybrid, J. Polym. Sci, Part A: Polymer Chemistry, 1993, 31 : 2493-2498
[108] 王新宇，漆宗能，王佛松．聚合物-层状硅酸盐纳米复合材料制备及应用．工程塑料应用，1999，27(2)：1-5
[109] Dekking HGG. Propagation Vinyl polymers on clay surfaces, ⅱ. polymerization of monomers initiated by free radicals attached to clay. J Appl Polym Sci, 1967, 11: 23-26
[110] 官同华，瞿雄伟，张留成．乳液法甲基丙烯酸甲酯／蒙脱土纳米复合材料的合成与表征．中国塑料，2001，15(11)：15-19
[111] 李青山，白德安，王慧敏．PMMA／MT纳米复合材料的研究．齐齐哈尔大学学报，2001，17(4)：4-5
[112] 李青山，白德安，蔡传英，等．甲基丙烯酸甲酯-蒙脱土纳米复合材料的研究．中国粉体技术，2000，6：273-275
[113] Luca B. Functionalization of montmorillonite by methyl methacrylate polymers containing side-chain ammonium cations. Polymer, 1994, 35(15): 3296-3304
[114] Okamoto M, Morita S, Kim YH, et al. Dispersed structure change of smetic clay/poly(methyl methacrylate) nanocomposites by copolymerization with polar comonomers. Polym, 2001, 42: 1201-1206
[115] Frark D, Yi T, Ralf T, et al. Translucent acrylic nanocomposites containing anisotropic laminated nanoparticles derived from intercalated layered silicates. 2000, 75:396-405
[116] 王一中，武保华，余鼎声．乳液聚合法制备聚甲基丙烯酸甲酯／蒙脱土嵌入混杂材料．北京化工大学学报，2000，27(2)：25-28
[117] Dong CL, Lee WJ. Preparation and characterization of pmma-clay composite by emusison polymerization. J Appl Polym Sci, 1996, 61 : 1117-1122
[118] AL - ESAIMI MM. Studies on the polymerization of pmma in the presence of mmt. J Appl Polym Sci, 1997, 64:367-372
[119] 邹纲，方堑，盛夏，等．动态扭振法研究聚甲基丙烯酸甲酯／蒙脱土纳米复合材料的本体插层聚合．高等学校化学学报，2003，24(3)：537-540
[120] Bhattacharya, J, Saha SK. Aqueous polymerization on clay surfaces. J Polym Sci, part A: Polym Chem, 1990, 28:2249-2254
[121] 张径，杨玉昆．以SiO_2纳米粒子为种子的甲基丙烯酸甲酯乳液聚合．化学与粘合，2001，1：1-3
[122] 张启卫，章永化，陈守明，等．聚甲基丙烯酸甲酯／二氧化硅杂化材料制备与性能．应用化学，2002，19(9)：874-877
[123] Yuich K, Kazuo K, Koichi N. Synthesis of N-cyclohexylmaleimide for heat-resistant trans parent methacrylic resin. J Appl Polym Sci, 1997, 63:363-368
[124] [美]RM西尔弗斯著．有机化合物光谱鉴定．北京：科学出版社，1988
[125] Aida H, Kimura M, Fukuoka A, et al. Glass transition temperatures of copolymers of maleimides with methyl acrylate or methacrylate. Kobunshi Kagaku, 1971,28(312): 354-361
[126] Bharel R, Cloudhary V, Varma IK. Thermal and mechanical properties of copolymers of methyl methcrylate with N-phenylmaleimide. J Appl Polym Sci, 1993, 49(1): 31-38
[127] Nakai Y, Sato F. Heat-resistant copolymer resins for optical elements. Jpn Kokai Tokkyo Koho JP 61, 141, 715186, 141,715]
[128] Grassie N , Farish E. Thermal degradation of copolymers of styrene and methyl methacrylate. Eur Polym J, 1967, 3(2): 305-315
[129] 胡孝东，罗时剑，颜德岳．甲基丙烯酸甲酯-苯乙烯-N苯基马来酰亚胺三元共聚物的研究．高分子学报，1992，6：696-699
[130] Mayo FR., Lewis, FM. J Am Chem Soc, 1944, 66:1894
[131] Elsabee MA, Sabaa MW, Naguib HF, et al. Copolymerization of methyl rnethacrylate with N-phenylmaleimide in different solvents. J Macromol Sci Chem, 1987, A24(10): 1207-1221
[132] Barrales-Rienda JM, Gonzalez de la Campa JI, Gonzalez RJ. Free-radical copolymerization of N-phehylmaleimide. J Macromol Sci, 1997, 11:267-286
[133] 单国荣．乙烯基单体／N-取代马来酰亚胺共聚合．[博士学位论文]．浙江：浙江大学，1996
[134] 柯扬船，[美]皮特·斯壮主编，聚合物-无机纳米复合材料，北京：化学工业出版社，2003
[135] 傅万里，刘竞超．环氧树脂／粘土纳米复合材料的研究(Ⅰ)有机蒙脱土的制备与表征．湘潭大学自然科学学报，2002，24(1)：68-70
[136] Ortego JD, Kowalska M, Cocke DL. Interactions of montmorillonite with organic compounds-adsorptive and catalytic properties. Chemosphere, 1991, 22(8): 769-798
[137] Gungor N. Effect of the Adsorption of Surfactants on the rheology of Na-Bentonite Slurries. J Appl. Poly Sci, 2000, 75:107-110
[138] Pan G, Yang B, Han HY. Studies on interaction of dodecyltrimethylammonium btomide with Na - and Al - montmorillonite, J Colloid Interface Science, 1997, 197:276-280
[139] Dekking HGG. Propagation of vinyl polymers on clay surfaces. Ⅱ. polymerization of monomers initiated by free radicals attached to clay, J. Appl. Polym. Sci. 1967, 11:23-26
[140] Makoto O, Kazuyuki K. Preparation of inorganic-organic nanocomposites through intercalation of organoammoniumions into layered silicates. Bull Chem Soc Jpn, 1997, 70:2593
[141] 官建国，黄俊，袁润章．光学透明材料的现状和研究进展．武汉工业大学学报，1998，20(3)：11-13
[142] 徐洪耀．塑料透镜的耐磨膜．工程塑料应用，1994，22(5)：47-49
[143] 徐国财，张立德编著．纳米复合材料．北京：化学工业出版社，2002，225
[144] Cholocl MS, Parker HY. Encyclopedia of Polymer Science and Engineering, 1995, 6385-6390
[145] 上海市模具技术协会．塑料技术标准大全．杭州：浙江科学技术出版社，1993
[146] Vaia RA, Ishii H, Giannelis EP. Symttosis and properties of two dimensional nanostructures by direct intercalation of polymer melts in layered Silicates. Chem Mater, 1993, 5(12): 1694-1696
[147] Vaia RA, Sauer BB, Tse K, et al. Relaxations of confised chains in Polymer nanocomposits: Glass transition Properties of Polycethylene oxide, intercalated in montmorillonite. J Polym Sci B Polym Phys, 1997, 35:59-67
[148] Girish G, Ramesh C, Ashish LA. Rheological study on the kinetics of hybrid rormathon in polypropylene nanocomposites. Macromolecues, 2001, 34:852
[149] 吕建坤，柯毓才，漆宗能，等．环氧／粘土纳米复合材料过程中粘土剥离行为的研究．高分子通报，2000，2：18-26
[150] 唐业全，罗是忠，吴正翠，等．微波辐照制备无皂阳离子PMMA胶乳粒子．高分子学报，2002，4：443-446
[151] 杨丽庭．N-取代马来酰亚胺共聚反应、共聚物性能、结构与应用研究及其共混物性能与群子标度之间关系的研究：[博士学位论文]．北京：北京化工大学，2000
[152] 李克友．涂料工业，1986，3
[153] 北京大学化学系高分子教研室编．高分子实验与专论．北京：北京大学出版社，1990
[154] Xingyu H, William JB. Synthesis of a PMMA-layered silicate namocomposite by suspension polymerization Polymer Preprints 2000, 41(1): 521
[155] Vaia RA, et al. Microstructural Euvolution of Melt intercalated polymer-organically modified layered sillicates nanocomposites, Chem Mater, 1996, 8:2628
[156] Dritis VA, Tchoubar C. X-ray diffraction by disordered lamellar structures, springer-verlag: New York, 1990:21
[157] Cullity BD. Principles of X-ray diffraction, Addison-Wesley. Reading, MA, 1987
[158] Yang LT, Liu GD, Sun DH, et al. Mechanical properties and theological behavior of PVC blended with terpolymers containg N-phenylmaleimide. J Vinyl Additive Technol, 2002, 8(2): 151-158