MC尼龙6/TiO_2原位纳米复合材料的制备、结构与性能研究
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摘要
采用阴离子原位聚合法制备MC尼龙6／TiO_2纳米复合材料，利用TEM研究了纳米TiO_2在MC尼龙6中的分散性，DSC、XRD、力学性能测试等方法研究了纳米复合材料的结晶与熔融及其结构与性能关系，得出了如下的结论：
(1)TEM研究纳米复合材料的分散性结果表明：纳米含量小于1％时，具有良好分散性；纳米含量大于1％时，纳米粒子开始出现团聚现象。XRD分析表明：纳米TiO_2不影响尼龙6的结晶形态。
(2)DSC法研究了纳米复合材料的等温结晶行为，采用Avrami方程研究其结晶动力学。复合材料等温DSC曲线表明，纳米TiO_2改变了尼龙6的等温结晶行为。Avrami法研究结晶动力学结果表明纳米TiO_2对尼龙6起到成核剂的作用，提高了其结晶速率，减小了半结晶时间。Hoffman结晶成核理论计算结果说明纳米TiO_2阻碍了尼龙6分子链的运动，使尼龙6由晶核生长占主导地位逐渐向成核机制占主导地位的转变。
(3)DSC研究了纳米复合材料非等温结晶行为，采用三种不同的处理方法研究复合材料的非等温结晶动力学。研究结果表明：Ozawa法不适用，Jeziomy法基本适用，Mo法是最佳处理方法；其结果表明纳米粒子对尼龙6有成核作用，改变了尼龙6成核机理，纳米粒子的引入提高了复合材料的结晶活化能，说明纳米粒子对尼龙6分子链具有阻碍作用。
(4)DSC法研究了纳米TiO_2对复合材料等温和非等温熔融行为的影响。研究结果表明：尼龙6及其纳米复合材料等温熔融为三重峰，非等温
摘要
熔融为二重峰。纳米TIO:提高了复合材料等温熔融的低温峰峰温，并随
纳米含量增加而增加，高温峰峰温基本不变。纳米Tio:加入提高了复合
材料非等温熔融低温峰峰温，而高温峰峰温基本不变。纳米Tio:粒子对
复合材料等温和非等温熔融行为的影响说明了纳米粒子对尼龙6的成核
作用提高了基体的晶粒完善性，同时提高了其平衡熔点。
(5)纳米TIO:提高了复合材料的热稳定性，提高了复合材料的拉伸
强度、弯曲强度、冲击强度，减小其断裂伸长率，起到了增强增韧的作用。
紫外辐照结果表明:辐照时间7一14天时，尼龙6和复合材料力学性能随
辐照时间延长而下降，辐照时间为21天时，辐照导致交联又提高了尼龙
6及纳米复合材料的力学性能。纳米含量为1%的复合材料抗辐照性能较
好.
MC nylon 6/TiO2 nanocomposites have been prepared by means of anion in-situ polymerization. The dispersity of nano-TiO2 in nylon 6 was studied by TEM, and the crystallization and melting behavior, structure and mechanical properties of nanocomposites was studied by DSC, XRD and mechanical properties methods. The conclusions as follows:
(1). When the nano-TiO2 content <1%, it has a good dispersity. When the nano-TiO2 content >1%, it begin to cluster. Nano-TiO2 doesn't influence on the crystal style of MC nylon 6.
(2). The results of isothermal DSC of nylon6 and nanocomposites show that nano-TiO2 influenced the behavior of isothermal crystallization of nylon 6. The results of Avrami equation show that nano-TiO2 were nucleation reagent of nylon 6, which raised the crystallization rate and decreased the half time of isothermal crystallization. The values of Kg of nanocomposites througing Hoffman equation increased with the increase of nano-TiO2 content.
(3). The results of non-isothermal DSC of nylon6 and nanocomposites show that nano-TiO2 influenced the behavior of non-isothermal crystallization of nylon 6. The non-isothermal crystallization of nylon 6 and nanocompsoites was analyzed by the methods of Ozawa, Jeziomy and Mo, the results show that the method of Mo is optimal method for nylon 6 and nanocompsoites. The results of the non-isothermal crystallization kinetics show that nano-TiO2 were nucleation reagent of nylon 6, which changed the nucleate mechanism of nylon 6 and increased the crystallization activation energy, indicating the nano-TiO2 baffled the movement of molecular segments of nylon 6.
(4). The isothermal and non-isothermal melting behaviors of nylon 6 and nanocomposites have been studied by means of DSC. The results show that the isothermal melting curves have three peaks and non-isothermal melting curves have two peaks. The values of temperature of the low temperature peaks increased and the high temperature peaks invariable, indicating that nano-TiO2 enhanced the perfection of crystal of nylon 6.
(5). Nano-TiO2 increased thermal stability of composites and mechanical properties, but decreased elongation at break, which indicate nano-TiO2 has strengthening and toughening ability. The results of UV-irradiation show that the mechanical properties of nylon 6 and nanocomposites decreased with the increase of UV-irradiation time at the beginning, but when the UV-irradiation time is 21 day which leaded to crosslink and made the mechanical properties of nylon 6 and nanocomposites increased. The nanocomposite with 1% TiO2 is the optimal composite to resist UV-irradiation.
(1)TEM研究纳米复合材料的分散性结果表明：纳米含量小于1％时，具有良好分散性；纳米含量大于1％时，纳米粒子开始出现团聚现象。XRD分析表明：纳米TiO_2不影响尼龙6的结晶形态。
(2)DSC法研究了纳米复合材料的等温结晶行为，采用Avrami方程研究其结晶动力学。复合材料等温DSC曲线表明，纳米TiO_2改变了尼龙6的等温结晶行为。Avrami法研究结晶动力学结果表明纳米TiO_2对尼龙6起到成核剂的作用，提高了其结晶速率，减小了半结晶时间。Hoffman结晶成核理论计算结果说明纳米TiO_2阻碍了尼龙6分子链的运动，使尼龙6由晶核生长占主导地位逐渐向成核机制占主导地位的转变。
(3)DSC研究了纳米复合材料非等温结晶行为，采用三种不同的处理方法研究复合材料的非等温结晶动力学。研究结果表明：Ozawa法不适用，Jeziomy法基本适用，Mo法是最佳处理方法；其结果表明纳米粒子对尼龙6有成核作用，改变了尼龙6成核机理，纳米粒子的引入提高了复合材料的结晶活化能，说明纳米粒子对尼龙6分子链具有阻碍作用。
(4)DSC法研究了纳米TiO_2对复合材料等温和非等温熔融行为的影响。研究结果表明：尼龙6及其纳米复合材料等温熔融为三重峰，非等温
摘要
熔融为二重峰。纳米TIO:提高了复合材料等温熔融的低温峰峰温，并随
纳米含量增加而增加，高温峰峰温基本不变。纳米Tio:加入提高了复合
材料非等温熔融低温峰峰温，而高温峰峰温基本不变。纳米Tio:粒子对
复合材料等温和非等温熔融行为的影响说明了纳米粒子对尼龙6的成核
作用提高了基体的晶粒完善性，同时提高了其平衡熔点。
(5)纳米TIO:提高了复合材料的热稳定性，提高了复合材料的拉伸
强度、弯曲强度、冲击强度，减小其断裂伸长率，起到了增强增韧的作用。
紫外辐照结果表明:辐照时间7一14天时，尼龙6和复合材料力学性能随
辐照时间延长而下降，辐照时间为21天时，辐照导致交联又提高了尼龙
6及纳米复合材料的力学性能。纳米含量为1%的复合材料抗辐照性能较
好.
MC nylon 6/TiO2 nanocomposites have been prepared by means of anion in-situ polymerization. The dispersity of nano-TiO2 in nylon 6 was studied by TEM, and the crystallization and melting behavior, structure and mechanical properties of nanocomposites was studied by DSC, XRD and mechanical properties methods. The conclusions as follows:
(1). When the nano-TiO2 content <1%, it has a good dispersity. When the nano-TiO2 content >1%, it begin to cluster. Nano-TiO2 doesn't influence on the crystal style of MC nylon 6.
(2). The results of isothermal DSC of nylon6 and nanocomposites show that nano-TiO2 influenced the behavior of isothermal crystallization of nylon 6. The results of Avrami equation show that nano-TiO2 were nucleation reagent of nylon 6, which raised the crystallization rate and decreased the half time of isothermal crystallization. The values of Kg of nanocomposites througing Hoffman equation increased with the increase of nano-TiO2 content.
(3). The results of non-isothermal DSC of nylon6 and nanocomposites show that nano-TiO2 influenced the behavior of non-isothermal crystallization of nylon 6. The non-isothermal crystallization of nylon 6 and nanocompsoites was analyzed by the methods of Ozawa, Jeziomy and Mo, the results show that the method of Mo is optimal method for nylon 6 and nanocompsoites. The results of the non-isothermal crystallization kinetics show that nano-TiO2 were nucleation reagent of nylon 6, which changed the nucleate mechanism of nylon 6 and increased the crystallization activation energy, indicating the nano-TiO2 baffled the movement of molecular segments of nylon 6.
(4). The isothermal and non-isothermal melting behaviors of nylon 6 and nanocomposites have been studied by means of DSC. The results show that the isothermal melting curves have three peaks and non-isothermal melting curves have two peaks. The values of temperature of the low temperature peaks increased and the high temperature peaks invariable, indicating that nano-TiO2 enhanced the perfection of crystal of nylon 6.
(5). Nano-TiO2 increased thermal stability of composites and mechanical properties, but decreased elongation at break, which indicate nano-TiO2 has strengthening and toughening ability. The results of UV-irradiation show that the mechanical properties of nylon 6 and nanocomposites decreased with the increase of UV-irradiation time at the beginning, but when the UV-irradiation time is 21 day which leaded to crosslink and made the mechanical properties of nylon 6 and nanocomposites increased. The nanocomposite with 1% TiO2 is the optimal composite to resist UV-irradiation.
引文
1．吴人杰著．复合材料．天津：天津大学出版社，2000．3
2. Roy R. Ceramics by the solution sol-gel route. Science, 1987,238:1664
3．王世敏，许祖勋，傅晶著．纳米材料制备技术．北京：化学工业出版社，2002．220
4．王铀，沈静姝．制备聚合物纳米复合材料展望．化工新型材料．1998，(1)：8
5. Green N C, Peng X G, Alivisatos A R Charge separation and transport in conjugatedpolymer/semiconductor nanocrystal composites studies by photoluminescence quenchingand photoconductivity. Phys Rev B, 1996,25:17628
6. Jeffrey G, Winiarz D, Zhang L M, et al. Photogeneration, charge transport and photoconductivity of a novel PVK/CdS-nanocrystal polymer composite. Chem Physi,1999, 245:417
7. Yoshita M, Lal M, Kumar N, et al. TiO_2 nano-particle-dispersed polyimide composites
optical waveguide materials through reverse micelles. J Mater Sci,1997,32(15):4047
8．李侃社，王琪．磨盘碾磨制各PP／石墨复合粉末的研究．高分子学报．2002，(6)：707
9. Masao S, Yasuyoshi T. Tensile yield stress of polypropylene composites filled withultrafine particles. J Mater Sci, 1983, 18:1758
10．章永化，龚克成．Sol-Gel法制备有机／无机纳米复合材料的进展．高分子材料科学与工程．1997，13(4)：14
11．曹立新，袁迅道．溶胶-凝胶法制备有机-无机纳米复合材料．应用化学．1998，15(3)：1
12. Novak B M. Hybrid nanocomposite materials-between inorganic glasses and organicpolymers. Adv Mater, 1993,5(6):422
13．陈艳，王新宇，高宗明．聚酰亚胺／二氧化硅纳米尺度复合材料的研究．高分子学报．1997(1)：73
14．周文，董建华，丘坤元．3-氨丙基三乙氧基硅烷对溶胶-凝胶法苯乙烯-顺丁烯二酸酐共聚物／TiO_2杂化材料的制备与性能的影响．高分子学报．1998，(6)：730
15．杜宏伟，孔瑛．气体分离用PI／TiO_2纳米复合膜的制备．应用化学．2003，20(5)：462
16. Suzuki F, Onozato K, Kurokawa Y. Formation of compatible poly(vinylalcohol)/alumina gel composites and its properties. J Appl Polym Sci, 1990,39:371
17. Pope E J A, Asami M,Mackenzie J D.Transparent silica gel-PMMA composites. JMater Res, 1989,(4):1018
18．赵竹第，高宗明，欧玉春等．苯乙烯-马来酸酐共聚物／聚硅氧烷纳米尺度复合材料的研究．高分子学报．1996，(2)：228
19．张启卫，章永化，陈守明等．聚甲基丙烯酸丁酯-二氧化硅杂化材料的制备及性能．高分子材料科学与工程．2003，15(9)：197
20. Novak B M, Ellsworth M W. Mutually inlerppanetraing inorganic-organic networks,new routes into nonshriking sol-gel composites material. J Am ChemSoc,1991,113(7):2756
21. Ellsworth M W, Novak B M. Elegant synthetic route for preparation oforganic-inorganic hybrid by sol-gel reactions without significant volume shrinkage. ChemMater, 1993,5:839
22．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
23．王立新，张开亮，任丽等．聚合物／层状硅酸盐纳米复合材料的研究进展．复合材料学报．2001，18(3)：5
24. Okada A,Kawasumi M, Kurauchi T, et al. Synthesis and characterization of a nylon
6-clay hybrid. Polym Prepr, 1987,28:447
25. Giannelis P E. A new strategy for synthesizing polymer-ceramic nanocomposites.1992,JOM, (3):28
26. Usudi A, Kawasumi M , Kojima Y, et al. Swelling behavior of montmorillonite cationexchanged for ω -amino acids by caprolactam. J Mater Res, 1993,8(5): 1174
27．李强，漆宗能．尼龙6／蒙脱土纳米复合材料的结晶行为．高分子学报．1997，(2)：188
28. Noh M H, Lee D C. Comparison of characteristics of SAN-MMT nanocompositespreparared by emulsion and solution polymerization.J Appl Polym Sci, 1999,74:2811
29 Tyan H L, Liu Y C. Thermally and mechanically enchanted clay/polyimidenanocomposite via reactivity organclay. Chem Mater, 1999,11:1942
30. Vaia R A, Giannlis E P. Relaxations of confined chains in polymer nanocomposites:glass transition properties of poly(ethylene oxide) intercalated in montmorillonite. J PolymSci, Part B:Polym Physi, 1997,35:59
31．朱结东，廖明义，李杨等．熔体插层聚合物／粘土纳米复合材料．高分子通报．2003，(2)：29
32．王传洋，黄汉雄，黄有发等．熔融插层制备聚合物／层状粘土纳米复合材料研究进展．中国塑料．2002，16(4)：1
33. Vaia R A, Iahii H, Giannelis E RSynthesis and properties of two-dimensionalnanostructures by direct intercalation of polymer melts in layered silicates. Chem MaterRev, 1993, 5:1694
34. Walter P, Reichert E Novel polypropylene materials.J MS-Pure ApplChem,1999,A36(11):1613
35. Hasegawa N, Okamoto H, Kato M, et al. Preparation and mechanical properties of polypropylene-clay hybrids based on motified polypropylene and organphilic clay. J Appl Polym Sci, 2000,78(11): 1918
36. Cho J W, Paul D R. Nylon 6 nanocomposites by melt compounding. Polymer,2001,42(3): 1083
37. Hoffmann B, et al. Morphology and rheology of polystyrene nanocomposites based upon organoclay. Macronol rapid commun, 2000, 21: 57
38．刘立敏，乔放，漆宗能等．熔体插层制备尼龙6／蒙脱土纳米复合材料的性能表征．高分子学报．1998，(3)：304
39．王胜杰，李强，王新宇等．聚苯乙烯／蒙脱土熔融插层复合的研究．高分子学报．1998，(2)：129
40. Fornes T D, Yoon P J, Keskkula H. Nylon 6 nanocomposites: the effect of matrix molecular weight. Polymer, 2001,42:9929
41. Kawasumi M, Hasegawa N, Kato M, et al. Preparation and mechanical properties of polypropylene-clay hybrids. Macromolecules, 1997,30(20):6333
42. Godovsky D Y.Electron behavior and magnetic properties polymer-nanocomposites. Adv Polym Sci,1995,119:79
43. Conslaves K E,Carlson G. Surface functionalized nanocstructured gold/polymer composites.Polym Mater Sci Eng, 1995,73:298
44．杨凤，赵海超，张学全等．原位聚合制备聚乙烯／蒙脱土(MMT)纳米复合材料的研究．高等学校化学学报．2003，24(4)：711
45．张晟卯，张志军，党洪辛等．TiO_2／聚丙烯酸丁酯纳米复合薄膜的制备及结构表征．物理化学学报．2003，19(2)：171
46．贾志杰，王正元，徐才录等．原位法制取碳纳米管／尼龙-6复合材料．清华大学学报(自然版)．2000，40(4)：14
47．王丽萍，吴宗斌，洪广言．稀土硫化物-聚苯乙烯纳米复合材料的制备与表征．化学研究．2001，12(4)：1
48．官文超，吴春炜，卢海峰．碳纳米管-乙烯基吡咯烷酮聚合物的合成研究．华中科技大学学报(自然科学版)．2002，30(9)：114
49．奚强，赵春芳，李蕾等．反相微乳液模板原位聚合制备纳米氯化银／聚甲基丙烯酸甲酯及其结构表征．化学物理学报．2003，16(2)：136
50．杨利营，盛京，王雪梅等．功能高分子学报．2002，15(3)：245
51．胜淼，杜中杰，荣峻峰等．原位聚合法制备新型有机／无机聚烯烃纳米复合材料．高分子材料科学与工程．2003，19(1)：128
52. Ou Y C, Yang F, Yu Z Z. A new conception on the toughness of nylon 6/silicananocomposites prepared via in situ polymerization. J Polym Sci, Polym Phys, 1998,36:789
53. Watkins J J, McCarthy T J. Ploym Mater Sci Eng, 1995,73:158
54. Tsukruk V V. Assembly of supramolecular polymers in ultrathin films. Progr in PolymSci, 1997,22:247
55．殷亚东，张志成，徐相凌等．纳米材料的辐射合成法制备．化学通报．1998，12：21
56．徐国财，张立德著．纳米复合材料．北京：化学工业出版社．2002，323
57．陈光明，马永梅，漆宗能．聚苯乙烯／蒙脱土纳米复合材料的自组装行为．高等学校化学学报．2001，22(5)：872
58．赵伟安，候万国，孙德军等．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
59．奚强，李亮，赵雷等．反相微乳液模板原位聚合制备和表征纳米AgCl／PMMA复合材料．高分子材料科学与工程．2003，19(2)：213
60. Burdon J, Calvert R Nanophase and nanocomposites materials. Mater Res Soc Symp
Pro, 1993, 286:315
61．金燕苹，征茂苹，金国良等．原位合成纳米Ag掺杂PVP薄膜的AFM研究．电子显微学报．2000，19(4)：477
62．盛淼，杜中杰，荣峻峰等．DSC法研究原位聚合聚乙烯／凹凸棒石纳米复合材料的结晶行为．高分子材料科学与工程．2003，19(3)：168
63．刘立敏，朱晓光，漆宗能．尼龙6／蒙脱土纳米复合材料的等温结晶动力学研究．高分子学报．1999，(3)：274
64. Noh M W, Lee D C. Synthesis and characterization of PS-clay nanocomposite byemulsion polymerization. Ploymer Bulletin, 1999,42:619
65．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
66．李强，赵竹第，欧玉春等．尼龙6／蒙脱土纳米复合材料的结晶行为．高分子学报．1997，(2)：188
67．赵竹第，李强，欧玉春等．尼龙6／蒙脱土纳米复合材料的制备、结构与力学性能的研究．高分子学报．1997，(5)：519
68．余鼎声，张楠，徐日炜等．阴离子开环原位聚合法制备尼龙6／蒙脱土混杂复合材料．北京化工大学学报(自然科学版)．2000，27(4)：32
69．王娜，张劲松，田一光等．尼龙6／蒙脱土纳米复合材料的合成新方法．应用化工．2003，32(3)：9
70. Kojoma Y, Usuki A, Kawasumi M, et al. Synthesis nylon 6-clay hybrid by montmorillonite intercalated withe-carprolactam. J Polym Sci, Part A:Polym Chem,1993,31:983
71. Kojoma Y, Usuki A, Kawasumi M, et al. Synthesis of Nylon 6- Clay Hybrid. J Polym Sci, Part A, Polym Chem,1993,31:1755
72. Usuki A, Kojoma Y, Kawasumi M, et al. Swelling behavior of montmorillonite cation exchanged for omega-amino acids by epsilon-caprolactam. J Mater Res, 1993,8:1174
73. Fornes T D, Paul D R. Crystallization behavior of nylon 6 nanocomposites Polymer,2003,44(14):3945
74. Cho J W, Paul D R. Nylon 6 Nanocomposites by Melt Compounding. Polymer, 2001,42:1083
75. Fornes T D, Yoon P J, Paul D R. Polymer matrix degradation and color formation in melt processed nylon 6/clay nanocomposites. Polymer, 2003, 44(24):7545
76. Fomes T D, Yoon P J, Hunter D L, et al. Effect of organoclay structure on nylon 6 nanocomposite morphology and properties. Polymer, 2002,43 (22):5915
77. Hasegawa N, Okamoto H, Kato M, et al. Nylon 6/Na-montmorillonite nanocomposites prepared by compounding Nylon 6 with Na-montmorillonite slurry. Polymer, 44 (10):2933
78．黎华明，沈志刚，王进等．sPS／PA／蒙脱土纳米复合材料的制备与性能．高分子学报．2003，(1)：78
79．潘玉珣，于中振，欧玉春等．尼龙6／石墨纳米导电复合材料的制备与性能高分子学报．2001，(1)：42
80．余颖，贾志杰，曾艳等．碳纳米管增强PA6复合材料的机理．高分子材料科学与工程．2003，19(3)：198
81．李莹，于建，郭朝霞．纳米TiO_2粒子表面官能团对尼龙6原位聚合的影响．高分子学报．2003，(2)：235
82. Pan Y X,Yu Z Z, Ou Y C, et al. A new process of fabricating electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization. J Polym Sci, Part B:Polym Physi, 2000,38(12): 1626
83. Takayuki H, Komasawa I. Preparation of nano-CdS-polyurethane composites via in situ polymerization in reverse micellar systems. J Mater Chem, 2000, 10 ( 10): 2234
84. Reynaud E, Jouen T, Gauthier C. Nanofillers in polymeric matrix: a study on silica reinforced PA6. Polymer, 2001,42(21):8759
85. Li Y, Yu J. The influence of silane treatment on nylon 6/nano-SiO_2in situ polymerization. J Appl Polym Sci, 2002,84(4):827
86．左都罗，李道火，郑兆佳等．非晶氮化硅纳米粒子的制备及量子限制效应．无机材料学报．1994，9(3)：351
2. Roy R. Ceramics by the solution sol-gel route. Science, 1987,238:1664
3．王世敏，许祖勋，傅晶著．纳米材料制备技术．北京：化学工业出版社，2002．220
4．王铀，沈静姝．制备聚合物纳米复合材料展望．化工新型材料．1998，(1)：8
5. Green N C, Peng X G, Alivisatos A R Charge separation and transport in conjugatedpolymer/semiconductor nanocrystal composites studies by photoluminescence quenchingand photoconductivity. Phys Rev B, 1996,25:17628
6. Jeffrey G, Winiarz D, Zhang L M, et al. Photogeneration, charge transport and photoconductivity of a novel PVK/CdS-nanocrystal polymer composite. Chem Physi,1999, 245:417
7. Yoshita M, Lal M, Kumar N, et al. TiO_2 nano-particle-dispersed polyimide composites
optical waveguide materials through reverse micelles. J Mater Sci,1997,32(15):4047
8．李侃社，王琪．磨盘碾磨制各PP／石墨复合粉末的研究．高分子学报．2002，(6)：707
9. Masao S, Yasuyoshi T. Tensile yield stress of polypropylene composites filled withultrafine particles. J Mater Sci, 1983, 18:1758
10．章永化，龚克成．Sol-Gel法制备有机／无机纳米复合材料的进展．高分子材料科学与工程．1997，13(4)：14
11．曹立新，袁迅道．溶胶-凝胶法制备有机-无机纳米复合材料．应用化学．1998，15(3)：1
12. Novak B M. Hybrid nanocomposite materials-between inorganic glasses and organicpolymers. Adv Mater, 1993,5(6):422
13．陈艳，王新宇，高宗明．聚酰亚胺／二氧化硅纳米尺度复合材料的研究．高分子学报．1997(1)：73
14．周文，董建华，丘坤元．3-氨丙基三乙氧基硅烷对溶胶-凝胶法苯乙烯-顺丁烯二酸酐共聚物／TiO_2杂化材料的制备与性能的影响．高分子学报．1998，(6)：730
15．杜宏伟，孔瑛．气体分离用PI／TiO_2纳米复合膜的制备．应用化学．2003，20(5)：462
16. Suzuki F, Onozato K, Kurokawa Y. Formation of compatible poly(vinylalcohol)/alumina gel composites and its properties. J Appl Polym Sci, 1990,39:371
17. Pope E J A, Asami M,Mackenzie J D.Transparent silica gel-PMMA composites. JMater Res, 1989,(4):1018
18．赵竹第，高宗明，欧玉春等．苯乙烯-马来酸酐共聚物／聚硅氧烷纳米尺度复合材料的研究．高分子学报．1996，(2)：228
19．张启卫，章永化，陈守明等．聚甲基丙烯酸丁酯-二氧化硅杂化材料的制备及性能．高分子材料科学与工程．2003，15(9)：197
20. Novak B M, Ellsworth M W. Mutually inlerppanetraing inorganic-organic networks,new routes into nonshriking sol-gel composites material. J Am ChemSoc,1991,113(7):2756
21. Ellsworth M W, Novak B M. Elegant synthetic route for preparation oforganic-inorganic hybrid by sol-gel reactions without significant volume shrinkage. ChemMater, 1993,5:839
22．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
23．王立新，张开亮，任丽等．聚合物／层状硅酸盐纳米复合材料的研究进展．复合材料学报．2001，18(3)：5
24. Okada A,Kawasumi M, Kurauchi T, et al. Synthesis and characterization of a nylon
6-clay hybrid. Polym Prepr, 1987,28:447
25. Giannelis P E. A new strategy for synthesizing polymer-ceramic nanocomposites.1992,JOM, (3):28
26. Usudi A, Kawasumi M , Kojima Y, et al. Swelling behavior of montmorillonite cationexchanged for ω -amino acids by caprolactam. J Mater Res, 1993,8(5): 1174
27．李强，漆宗能．尼龙6／蒙脱土纳米复合材料的结晶行为．高分子学报．1997，(2)：188
28. Noh M H, Lee D C. Comparison of characteristics of SAN-MMT nanocompositespreparared by emulsion and solution polymerization.J Appl Polym Sci, 1999,74:2811
29 Tyan H L, Liu Y C. Thermally and mechanically enchanted clay/polyimidenanocomposite via reactivity organclay. Chem Mater, 1999,11:1942
30. Vaia R A, Giannlis E P. Relaxations of confined chains in polymer nanocomposites:glass transition properties of poly(ethylene oxide) intercalated in montmorillonite. J PolymSci, Part B:Polym Physi, 1997,35:59
31．朱结东，廖明义，李杨等．熔体插层聚合物／粘土纳米复合材料．高分子通报．2003，(2)：29
32．王传洋，黄汉雄，黄有发等．熔融插层制备聚合物／层状粘土纳米复合材料研究进展．中国塑料．2002，16(4)：1
33. Vaia R A, Iahii H, Giannelis E RSynthesis and properties of two-dimensionalnanostructures by direct intercalation of polymer melts in layered silicates. Chem MaterRev, 1993, 5:1694
34. Walter P, Reichert E Novel polypropylene materials.J MS-Pure ApplChem,1999,A36(11):1613
35. Hasegawa N, Okamoto H, Kato M, et al. Preparation and mechanical properties of polypropylene-clay hybrids based on motified polypropylene and organphilic clay. J Appl Polym Sci, 2000,78(11): 1918
36. Cho J W, Paul D R. Nylon 6 nanocomposites by melt compounding. Polymer,2001,42(3): 1083
37. Hoffmann B, et al. Morphology and rheology of polystyrene nanocomposites based upon organoclay. Macronol rapid commun, 2000, 21: 57
38．刘立敏，乔放，漆宗能等．熔体插层制备尼龙6／蒙脱土纳米复合材料的性能表征．高分子学报．1998，(3)：304
39．王胜杰，李强，王新宇等．聚苯乙烯／蒙脱土熔融插层复合的研究．高分子学报．1998，(2)：129
40. Fornes T D, Yoon P J, Keskkula H. Nylon 6 nanocomposites: the effect of matrix molecular weight. Polymer, 2001,42:9929
41. Kawasumi M, Hasegawa N, Kato M, et al. Preparation and mechanical properties of polypropylene-clay hybrids. Macromolecules, 1997,30(20):6333
42. Godovsky D Y.Electron behavior and magnetic properties polymer-nanocomposites. Adv Polym Sci,1995,119:79
43. Conslaves K E,Carlson G. Surface functionalized nanocstructured gold/polymer composites.Polym Mater Sci Eng, 1995,73:298
44．杨凤，赵海超，张学全等．原位聚合制备聚乙烯／蒙脱土(MMT)纳米复合材料的研究．高等学校化学学报．2003，24(4)：711
45．张晟卯，张志军，党洪辛等．TiO_2／聚丙烯酸丁酯纳米复合薄膜的制备及结构表征．物理化学学报．2003，19(2)：171
46．贾志杰，王正元，徐才录等．原位法制取碳纳米管／尼龙-6复合材料．清华大学学报(自然版)．2000，40(4)：14
47．王丽萍，吴宗斌，洪广言．稀土硫化物-聚苯乙烯纳米复合材料的制备与表征．化学研究．2001，12(4)：1
48．官文超，吴春炜，卢海峰．碳纳米管-乙烯基吡咯烷酮聚合物的合成研究．华中科技大学学报(自然科学版)．2002，30(9)：114
49．奚强，赵春芳，李蕾等．反相微乳液模板原位聚合制备纳米氯化银／聚甲基丙烯酸甲酯及其结构表征．化学物理学报．2003，16(2)：136
50．杨利营，盛京，王雪梅等．功能高分子学报．2002，15(3)：245
51．胜淼，杜中杰，荣峻峰等．原位聚合法制备新型有机／无机聚烯烃纳米复合材料．高分子材料科学与工程．2003，19(1)：128
52. Ou Y C, Yang F, Yu Z Z. A new conception on the toughness of nylon 6/silicananocomposites prepared via in situ polymerization. J Polym Sci, Polym Phys, 1998,36:789
53. Watkins J J, McCarthy T J. Ploym Mater Sci Eng, 1995,73:158
54. Tsukruk V V. Assembly of supramolecular polymers in ultrathin films. Progr in PolymSci, 1997,22:247
55．殷亚东，张志成，徐相凌等．纳米材料的辐射合成法制备．化学通报．1998，12：21
56．徐国财，张立德著．纳米复合材料．北京：化学工业出版社．2002，323
57．陈光明，马永梅，漆宗能．聚苯乙烯／蒙脱土纳米复合材料的自组装行为．高等学校化学学报．2001，22(5)：872
58．赵伟安，候万国，孙德军等．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
59．奚强，李亮，赵雷等．反相微乳液模板原位聚合制备和表征纳米AgCl／PMMA复合材料．高分子材料科学与工程．2003，19(2)：213
60. Burdon J, Calvert R Nanophase and nanocomposites materials. Mater Res Soc Symp
Pro, 1993, 286:315
61．金燕苹，征茂苹，金国良等．原位合成纳米Ag掺杂PVP薄膜的AFM研究．电子显微学报．2000，19(4)：477
62．盛淼，杜中杰，荣峻峰等．DSC法研究原位聚合聚乙烯／凹凸棒石纳米复合材料的结晶行为．高分子材料科学与工程．2003，19(3)：168
63．刘立敏，朱晓光，漆宗能．尼龙6／蒙脱土纳米复合材料的等温结晶动力学研究．高分子学报．1999，(3)：274
64. Noh M W, Lee D C. Synthesis and characterization of PS-clay nanocomposite byemulsion polymerization. Ploymer Bulletin, 1999,42:619
65．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
66．李强，赵竹第，欧玉春等．尼龙6／蒙脱土纳米复合材料的结晶行为．高分子学报．1997，(2)：188
67．赵竹第，李强，欧玉春等．尼龙6／蒙脱土纳米复合材料的制备、结构与力学性能的研究．高分子学报．1997，(5)：519
68．余鼎声，张楠，徐日炜等．阴离子开环原位聚合法制备尼龙6／蒙脱土混杂复合材料．北京化工大学学报(自然科学版)．2000，27(4)：32
69．王娜，张劲松，田一光等．尼龙6／蒙脱土纳米复合材料的合成新方法．应用化工．2003，32(3)：9
70. Kojoma Y, Usuki A, Kawasumi M, et al. Synthesis nylon 6-clay hybrid by montmorillonite intercalated withe-carprolactam. J Polym Sci, Part A:Polym Chem,1993,31:983
71. Kojoma Y, Usuki A, Kawasumi M, et al. Synthesis of Nylon 6- Clay Hybrid. J Polym Sci, Part A, Polym Chem,1993,31:1755
72. Usuki A, Kojoma Y, Kawasumi M, et al. Swelling behavior of montmorillonite cation exchanged for omega-amino acids by epsilon-caprolactam. J Mater Res, 1993,8:1174
73. Fornes T D, Paul D R. Crystallization behavior of nylon 6 nanocomposites Polymer,2003,44(14):3945
74. Cho J W, Paul D R. Nylon 6 Nanocomposites by Melt Compounding. Polymer, 2001,42:1083
75. Fornes T D, Yoon P J, Paul D R. Polymer matrix degradation and color formation in melt processed nylon 6/clay nanocomposites. Polymer, 2003, 44(24):7545
76. Fomes T D, Yoon P J, Hunter D L, et al. Effect of organoclay structure on nylon 6 nanocomposite morphology and properties. Polymer, 2002,43 (22):5915
77. Hasegawa N, Okamoto H, Kato M, et al. Nylon 6/Na-montmorillonite nanocomposites prepared by compounding Nylon 6 with Na-montmorillonite slurry. Polymer, 44 (10):2933
78．黎华明，沈志刚，王进等．sPS／PA／蒙脱土纳米复合材料的制备与性能．高分子学报．2003，(1)：78
79．潘玉珣，于中振，欧玉春等．尼龙6／石墨纳米导电复合材料的制备与性能高分子学报．2001，(1)：42
80．余颖，贾志杰，曾艳等．碳纳米管增强PA6复合材料的机理．高分子材料科学与工程．2003，19(3)：198
81．李莹，于建，郭朝霞．纳米TiO_2粒子表面官能团对尼龙6原位聚合的影响．高分子学报．2003，(2)：235
82. Pan Y X,Yu Z Z, Ou Y C, et al. A new process of fabricating electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization. J Polym Sci, Part B:Polym Physi, 2000,38(12): 1626
83. Takayuki H, Komasawa I. Preparation of nano-CdS-polyurethane composites via in situ polymerization in reverse micellar systems. J Mater Chem, 2000, 10 ( 10): 2234
84. Reynaud E, Jouen T, Gauthier C. Nanofillers in polymeric matrix: a study on silica reinforced PA6. Polymer, 2001,42(21):8759
85. Li Y, Yu J. The influence of silane treatment on nylon 6/nano-SiO_2in situ polymerization. J Appl Polym Sci, 2002,84(4):827
86．左都罗，李道火，郑兆佳等．非晶氮化硅纳米粒子的制备及量子限制效应．无机材料学报．1994，9(3)：351