聚氯乙烯/蒙脱土纳米复合材料的制备表征及性能研究
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摘要
聚合物纳米复合材料是一类新型的复合材料，由于纳米粒子的一些特性，使得该类材料具有许多优异的性能。目前在聚合物纳米复合材料领域中，无论是基础研究还是工业开发都十分活跃的是聚合物厂层状硅酸盐(Polymer／Layered Silicate，PLS)纳米复合材料。
本文首先采用乳液聚合法制备出了聚氯乙烯(PVC)／无机蒙脱土(MMT)纳米复合材料，通过XRD和TEM等手段对所制复合材料的形态结构进行了表征。结果表明通过乳液合成的方法，MMT能够以纳米尺度均匀分散于PVC基体中，形成部分剥离部分插层的结构。进一步对所制复合材料的乳胶粒径、分子量、力学性能及热性能进行了测试。发现MMT的加入和用量并不能明显影响复合乳液粒径的变化，而使聚合物的分子量变低，分子量分布指数减小。多项力学性能和热性能测试结果表明：适量MMT的加入使复合材料的性能有不同程度的提高。当MMT含量为2.1～3.5wt％时，复合材料的冲击强度比纯PVC的提高了近一倍。
为优选配方、降低产品成本，本文还采用乳液聚合的方法制备了不同乳化剂含量下的PVC／无机MMT纳米复合材料系列和PVC／国产无机MMT纳米复合材料。
此外，利用两种有机蒙脱土(OMMT)通过悬浮聚合的方法合成了PVC／OMMT纳米复合材料。一种为采用烷基季鏻盐有机化处理的MMT(pho-MMT)；另一种为采用烷基季铵盐处理的商品有机土(ammo-MMT)。对材料的形态结构、力学性能和热性能进行了测试和分析。结果表明：OMMT能够基本剥离并均匀分散于聚合物基体中。在适当土含量下两种复合材料的力学性均能得到提高。复合材料的玻璃化转变温度均高于纯PVC。然而不同种类的有机土对于材料热失重曲线和维卡软化点的影响较大。从整体上看，ammo-MMT使复合材料的热稳定性好于纯PVC，并且使材料的维卡软化点提高。而pho-MMT却加大了PVC脱HCl的速度，降低了复合材料在PVC分解第二阶段的热稳定性，直至PVC分解的第三、第四阶段，OMMT的加入才开始起到提高材料热稳定性作用，并且对材料维卡软化点的提高没有很大作用。
利用乳液聚合的方法制备了聚丙烯酸丁酯(PBA)／无机MMT复合胶乳，并在PBA／MMT复合胶乳存在下，采用悬浮聚合法制备了PVC／(PBA-MMT)纳米复合材料。发现MMT形成了部分剥离部分插层的结构，并且适量MMT的加入可以提高复合材料的力学性能和热稳定性。
Nanocomposites are a new class of composites, that are particle-filled polymers for which at least one dimension of the dispersed particles is in the nanometer range. Due to the special effect of the nanometer-size particles, the nanocomposites often exhibit remarkably improved properties. Nowadays, among all the potential nanocomposites, polymer/layered silicate (PLS) nanocomposites have attracted intensive interest from academic and industrial researchers.
In this thesis, PVC/Na+-montmorillonite(MMT) nanocomposites were synthesized by emulsion polymerization. The structure of the composites was characterized by X-ray diffraction(XRD) and transmission electric microscope(TEM). The experimental results revealed the formation of a mixture of intercalated and exfoliated nano-structure. The emulsion polymerization could realize the nanometer-size dispersion of MMT in the PVC matrix. The addition and amount of MMT could not apparently affect the mean particle diameters of PVC/ MMT nanocomposite latex. After the addition of MMT, the average molecular weights and PDI(Mw/Mn) of PVC matrix were lower than that of pure PVC. The proper amount of MMT could improve the mechanical and thermal properties of the nanocomposites. For systems containing clay in the range of 2.1wt% to 3.5wt%, the impact strength was almost two times as large as that of pure PVC.
We have also prepared PVC/MMT nanocomposites by emulsion polymerization under different emulsifier content. The effect of the emulsifier content on the properties of composites has been studied. Then the native MMT was used to prepare PVC/clay nanocomposites by emulsion polymerization.
Besides, PVC/organo-MMT (OMMT) nanocomposites were synthesized with two types of OMMT by suspension polymerization. The OMMT used in this study were prepared by replacing Na+ ions in layered silicates with alkylammonium or alkylphosphonium cations by ion exchange. The two kinds of OMMT can be represented by ammo-MMT and pho-MMT. The XRD and TEM results revealed that the silicate layers could be fully dispersed in the PVC matrix. The mechanical properties of the composites could be unproved under a proper amount
of OMMT. The glass transition temperature (Tg) of nanocomposites was higher than that of pure PVC. The modification of OMMT has greatly affected the Thermogravimetric analyses (TGA) curves and Vicat softening point(VSP) temperature of the materials. The addition of ammo-MMT could improve the composites thermal stability and VSP temperature. However, the pho-MMT speeded up the HC1 loss of PVC chains, and lower the thermal stability of the composites during the second stage of PVC thermal degradation. It wasn't until the third and fourth stages of PVC thermal degradation that the pho-MMT began to improve the thermal stability of the composites. Further more, the addition of pho-MMT have not apparently effect on the VSP of the composites.
Poly butyl acrylate (PBA)/MMT composites were prepared by emulsion polymerization. Then, PVC/(PBA-MMT) nanocomposites were prepared by suspension polymerization of Vinyl chloride in the presence of PBA/MMT composites. It could be found that MMT was partially exfoliated and partially intercalated in the matrix. A proper amount of MMT could improve the mechanical and thermal propertied of the PVC/(PB A-MMT) nanocomposites.
本文首先采用乳液聚合法制备出了聚氯乙烯(PVC)／无机蒙脱土(MMT)纳米复合材料，通过XRD和TEM等手段对所制复合材料的形态结构进行了表征。结果表明通过乳液合成的方法，MMT能够以纳米尺度均匀分散于PVC基体中，形成部分剥离部分插层的结构。进一步对所制复合材料的乳胶粒径、分子量、力学性能及热性能进行了测试。发现MMT的加入和用量并不能明显影响复合乳液粒径的变化，而使聚合物的分子量变低，分子量分布指数减小。多项力学性能和热性能测试结果表明：适量MMT的加入使复合材料的性能有不同程度的提高。当MMT含量为2.1～3.5wt％时，复合材料的冲击强度比纯PVC的提高了近一倍。
为优选配方、降低产品成本，本文还采用乳液聚合的方法制备了不同乳化剂含量下的PVC／无机MMT纳米复合材料系列和PVC／国产无机MMT纳米复合材料。
此外，利用两种有机蒙脱土(OMMT)通过悬浮聚合的方法合成了PVC／OMMT纳米复合材料。一种为采用烷基季鏻盐有机化处理的MMT(pho-MMT)；另一种为采用烷基季铵盐处理的商品有机土(ammo-MMT)。对材料的形态结构、力学性能和热性能进行了测试和分析。结果表明：OMMT能够基本剥离并均匀分散于聚合物基体中。在适当土含量下两种复合材料的力学性均能得到提高。复合材料的玻璃化转变温度均高于纯PVC。然而不同种类的有机土对于材料热失重曲线和维卡软化点的影响较大。从整体上看，ammo-MMT使复合材料的热稳定性好于纯PVC，并且使材料的维卡软化点提高。而pho-MMT却加大了PVC脱HCl的速度，降低了复合材料在PVC分解第二阶段的热稳定性，直至PVC分解的第三、第四阶段，OMMT的加入才开始起到提高材料热稳定性作用，并且对材料维卡软化点的提高没有很大作用。
利用乳液聚合的方法制备了聚丙烯酸丁酯(PBA)／无机MMT复合胶乳，并在PBA／MMT复合胶乳存在下，采用悬浮聚合法制备了PVC／(PBA-MMT)纳米复合材料。发现MMT形成了部分剥离部分插层的结构，并且适量MMT的加入可以提高复合材料的力学性能和热稳定性。
Nanocomposites are a new class of composites, that are particle-filled polymers for which at least one dimension of the dispersed particles is in the nanometer range. Due to the special effect of the nanometer-size particles, the nanocomposites often exhibit remarkably improved properties. Nowadays, among all the potential nanocomposites, polymer/layered silicate (PLS) nanocomposites have attracted intensive interest from academic and industrial researchers.
In this thesis, PVC/Na+-montmorillonite(MMT) nanocomposites were synthesized by emulsion polymerization. The structure of the composites was characterized by X-ray diffraction(XRD) and transmission electric microscope(TEM). The experimental results revealed the formation of a mixture of intercalated and exfoliated nano-structure. The emulsion polymerization could realize the nanometer-size dispersion of MMT in the PVC matrix. The addition and amount of MMT could not apparently affect the mean particle diameters of PVC/ MMT nanocomposite latex. After the addition of MMT, the average molecular weights and PDI(Mw/Mn) of PVC matrix were lower than that of pure PVC. The proper amount of MMT could improve the mechanical and thermal properties of the nanocomposites. For systems containing clay in the range of 2.1wt% to 3.5wt%, the impact strength was almost two times as large as that of pure PVC.
We have also prepared PVC/MMT nanocomposites by emulsion polymerization under different emulsifier content. The effect of the emulsifier content on the properties of composites has been studied. Then the native MMT was used to prepare PVC/clay nanocomposites by emulsion polymerization.
Besides, PVC/organo-MMT (OMMT) nanocomposites were synthesized with two types of OMMT by suspension polymerization. The OMMT used in this study were prepared by replacing Na+ ions in layered silicates with alkylammonium or alkylphosphonium cations by ion exchange. The two kinds of OMMT can be represented by ammo-MMT and pho-MMT. The XRD and TEM results revealed that the silicate layers could be fully dispersed in the PVC matrix. The mechanical properties of the composites could be unproved under a proper amount
of OMMT. The glass transition temperature (Tg) of nanocomposites was higher than that of pure PVC. The modification of OMMT has greatly affected the Thermogravimetric analyses (TGA) curves and Vicat softening point(VSP) temperature of the materials. The addition of ammo-MMT could improve the composites thermal stability and VSP temperature. However, the pho-MMT speeded up the HC1 loss of PVC chains, and lower the thermal stability of the composites during the second stage of PVC thermal degradation. It wasn't until the third and fourth stages of PVC thermal degradation that the pho-MMT began to improve the thermal stability of the composites. Further more, the addition of pho-MMT have not apparently effect on the VSP of the composites.
Poly butyl acrylate (PBA)/MMT composites were prepared by emulsion polymerization. Then, PVC/(PBA-MMT) nanocomposites were prepared by suspension polymerization of Vinyl chloride in the presence of PBA/MMT composites. It could be found that MMT was partially exfoliated and partially intercalated in the matrix. A proper amount of MMT could improve the mechanical and thermal propertied of the PVC/(PB A-MMT) nanocomposites.
引文
1. Ray, S S; Okamoto, M.. Polymer/layered silicate nanocomposites: a review from preparation to processing. Progress in polymer science, 2003, 28, 1539-1641
2. Zhu, J; Wilkie, C A. Thermal and fire studies on polystyrene-clay nanocomposites. Polymer International, 2000, 49, 1158-1163
3. Hwu, J M; Jiang, G J; Gao, Z M, et al. The characterization of Organic Modified Clay and Clay-filled PMMA Nanocomposite. Journal of Applied Polymer Science, 2002,83,1702-1710
4. Yang, Y; Zhu, Z K; Yin, J, et al. Preparation and properties of hybrids of organo-soluble polyimide and montmodllonite with various chemical surface modification methods. Polymer, 1999,40, 4407-4414
5. Lan, T; Kaviratna, P D; Pinnavaia, T J. Mechanism of Clay Tactoid Exfoliation in Epoxy-Clay Nanocomposites. Chemistry of Materials, 1995, 7, 2144-2150
6. Kornmann, X; Lindberg, H; Berglund, L A. Synthesis of epoxy-clay nanocomposites:influence of the nature of the clay on structure. Polymer, 2001, 42, 1303-1310
7. Lan, T; Kaviratna, P D; Pinnavaia, T J. Epoxy self-polymerization in smectite clays. Journal of physics of Chemical Solids, 1996, 57,1005-1010
8. Maiti, P; Nam, P H; Okamoto M, et al. Influence of Crystallization on Intercalation, Morphology, and Mechanical Properties of Polypropylene/Clay Nanocomposites. Macromolecules 2002,35,2042-2049
9. Li, X C; Kang, T, Cho; W J, et al. Preparaton and Characterization of poly(butyleneterephalate)/Organoclay Nanocomposites. Macromolecules Rapid Communication, 2001, 22, 1306-1312
10. Hong, S H; Kim, B H; Joo, J, et al. Polypyrrole-montmodllonite nanocomposites synthesized by emulsion polymerization. Current Applied Physics, 2001, 1,447-450
11. Kim, J W; Liu, F, Choi; H J, et al. Intercalated polypyrrole/Na~+-montmorillonite nanocomposite via an inverted emulsion pathway method. Polymer, 2003, 44, 289-293
12. Kim, B H; Jung, J H; Hong, S H, et al. Physical characterization of emulsion intercalated polyaniline-caly nanocomposite. Current Applied Physics, 2001, 1, 112-115
13. Choi, H J; Kim, J W; Joo, J, et al. Synthesis and electrorheology of emulsion intercalated PANI-clay nanocomposite. Synthesis Metals, 2001,121, 1325-1326
14. Wang, H S; Zhao, T; Zhi, L J, et al. Synthesis of Novolac/Layered Silicate Nanocomposites by Reaction Exfoliation Using Acid-Modified Montmorillonite. Macromolecules Rapid Communication, 2002, 23, 44-48
15. Takeichi, T; Zeidam, R; Agag, T. Polybenzoxazine/clay hybrid nanocomposites: influence of preparation method on the curing behavior and properties of polybenzoxazines. Polymer, 2002, 43,45-53
16. Ray, S S; Yamada, K; Okamoto, M, et al. New polylactide/layered silicate nanocomposieds.5.Designing of materials with desired properties. Polymer, 2003, 44, 6633-6646
17. Krishnamoorti, R; Vaia, R A; Giannelis, E P. Structure and Dynamics of Polymer-Layered Silicate Nanocomposites.Chemistry of Materials, 1996,8,1728-1734
18．漆宗能，尚文字著．聚合物／层状硅酸盐纳米复合材料理论与实践．北京：化学工业出版社，2002，1-78
19. Alexandre, M; Dubois, P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Materials Science and Engineering, 2000,28,1-63
20. Tong, X; Zhao, H C;Tang, T, et al. Preparation and Characterization of Poly(ethyl acrylate Bentonite Nanocomposites by In Situ Emulsion Polymerization. Journal of Polymer Science: Part A: Polymer Chemistry, 2002, 40, 1706-1711
21. Lye, D C; Jang, L W; Preparation and Characterization of PMMA-Clay Hybrid Composite by Emulsion Polymerization. Journal of Applied Polymer Science, 1996, 61, 1117-1122,
22. Lee, D C; Jang, L W; Characterization of Epoxy-Clay Hybrid Composite prepared by Emulsion Polymerization. Journal of Applied Polymer Science, 1996, 68, 1997-2005
23. Nob, M H; Jang, L W;Lee, D C. Intercalation of Styrene-Acrylonitrile Copolymer in Layered Silicate by Emulsion Polymrization, Journal of Applied Polymer Science, 1999, (74), 179-188
24. Kim, J W; Nob, M H; Choi, H J, et al. Electrorheological Characteristics of Emulsion Polymerizaed SAN-Clay Nanocomposite Suspensions. Polymer Bulletin, 1998,41,512-513
25. Kim, B H; Jung, J H; Hong, S H, et al. Nanocomposite of Polyaniline and Na~+- Montmorillonite Clay. Macromolecules, 2002, 35, 1419-1423
26. Kim, T H; Jang, L W; Lee, D C, et al. Synthesis and Rheology of Intercalated Polystyrene/ Montmorillonite Nanocomposites. Macromolecules Rapid Communication, 2002, 23(3), 191-195
27. Choi, Y S; Wang, K H; Xu, M Z, et al. Synthesis of Exfoliated Polyacrylonitrile/Na-MMT Nanocomposites via Emulsion Polymerization. Chemistry of Materials, 2002,14, 2936-2939
28. Yano, K; Usuki, A; Okada, A, et al. Synthesis and Properties of Polyimide-Clay Hydrid. Journal of Polymer Science: Part A: Polymer Chemistry, 1993, 31, 2493-2498
29. Vaia, R A; Jandt, K D; Kramer, E J, et al. Microstructural Evolution of Melt Inercalated Polymer Organically Modified Layered Silicates Nanocomposites. Chemistry of Materials, 1996, 8, 2628-2635
30. Vaia, R A; Ishii, H; Giannelis, E P, et al. Synthesis and properties of two-dimensional nanostructures by direct intercalation of polymer melts in layered silicates. Chemistry of Materials, 1993,5,1694-1696
31. Vaia, R A; Jandt, K D; Kramer, E G, et al. Kinetics of Polymer Melt Intercalation. Macromolecules, 1995, 28, 8080-8085
32. Vaia, R A; Giannelis, E P. Polymer Melt Intercalation in Organically-Modified Layered Silicates: Model Predictions and Experiment. Macromolecules, 1997, 30, 8000-8009
33. Kim, S W; Jo, W H; Lee, M S, et al. Effects of Shear on Melt Exfoliation of Clay in Preparation of Nylon
6/Organoclay Nanocomposites. Polymer Journal, 2002, 34(3), 103-111
34. Tony, M N; Murphy, W R; Lew, C Y, et al. Polyamide-12 layered silicate nanocomposites by melt blending. Polymer, 2003,44, 2761-2772
35. Kato, M; Usuki, A; Okada, A. Synthesis ofpolypropylene oligomer - clay intercalation compounds. Journal of Applied Polymer Science, 1997, 66, 1781-1785
36. Kojima, Y; Usuki, A; Kawasumi, M, et al. Mechanical properties of nylon 6-clay hybrid. Journal of Material Research, 1993, 8(5), 1185-1189
37. Bharadwaj, R K; Mehrabi, A R; Hamilton, C, et al. Polymer, 2002, 43, 3699-3705
38．[美]H·范·奥尔芬．粘土胶体化学导论，1982，66-68
39．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，1999，2，1-5
40. Zhu, J; Start, P; Mauritz, K A, et al. Silicon-Methoxide-Modified Clays and Their Polystyrene Nanocomposites.Journal of Polymer Science: Part A, 2002, 40, 1498-1503
41．徐寿昌主编．有机化学．第二版．高等教育出版社，1993，4，452-453
42. Okada, A; Kawasumi, M; Kurauchi, T, et al. Synthesis and Characterization of a Nylon 6-Clay Hybrid. Polymer Preprint ,1987, 28, 447-448
43. Usuki, A. Kawasumi, M. Kojima, Y, et al. Swelling behavior of montmorillonite cation exchanged "for ω-amino acids by ε-caprolactam.. Journal of Material Research, 1993, 8(5), 1174-1182
44. Chen, T K; Tien, Y I; Wei, K H. Synthesis and Characterization of Novel Segmented Polyurethane/Clay Nanocomposite via Poly(ε-caprolactone)/Clay. Journal of Polymer Science:Part A, 1999, 37, 2225-2233,
45. Chen, T K; Tien, Y I; Wei, K H. Synthesis and characterization of novel segmented polyurethane/clay nanocomposites. Polymer, 2000, 41, 1345-1353
46. Messersmith, P B; Giannelis, E E Synthesis and barrier properties ofpoly(ε-caprolactone)-layered silicate nanocomposites. Journal of Polymer Science Part A: Polymer Chemistry, 1995, 33(7), 1047-1057
47. Ogawa, M; Kuroda, K. Preparation of Inorganic-Organic Nanocomposites through Intercalation of Organoammonium Ions into Layered Silicates. Bulll.Chem.Soc.Jpn, 1997,70, 2593-2618
48. Xie, W; Gao, Z M; Pan, W P, et al. Thermal Degradation chemistry of alkyl quaternary ammonium montmorillonite. Chemistry of Materials, 2001, 13, 2979-2990
49. Zhu, J; Morgan, A B; Lamelas, F J, et al. Fire properties of polystyrene-clay nanocomposites. Chemistry of Materials, 2001, 13, 3774-3780
50. Zhu, J; Uhl, F M; Morgan, A B, et al. Studies on the mechanical by which the formation of nanocomposites enhances thermal stability. Chemistry of Materials, 2001, 13, 4649-4654
51. Yeh, J M; Liou, S J; Lin, C Y, et aI. Anticorrosively enhanced PMMA-clay nanocomposite materials with quaternary alkylphosphonium salt as an intercalating agent. Chemistry of Materials, 2002, 14, 154-161
52. Kommann, X; Berglund, L A; Sterte, J. Nanocomposites Based on Montmorillonite and Unsaturated Polyester. Polymer Engineering and Science, 1998, 38(8), 1351-1357
53. Furuichi, N; Kurokawa, Y; Fujita, K, et al. Preparation and properties of polypropylene reinforced by smectite. Journal of Materials Science, 1996, 31, 4307-4310
54．吴成泰等著．冠醚化学．科学出版社，1992，12，116-118
55. Hitzky, E R; Casal, B. Crown ether intercalations with phyllosilicates. Nature, 1978,276,596-597
56. Gilman, J W; Kashiwage,T;Morgan, A B, et al. Proceedings of Additives 2001,March, 2001
57．陈光明，马永梅，漆宗能．甲苯-2,4-二异氰酸酯修饰蒙脱土及聚苯乙烯／蒙脱土纳米复合材料的制备与表征．高分子学报，2000，10(5)，119-122
58. Chen, G M; Ma, Y M; Qi, Z N. Preparation of Polystyrene/Toluene-2,4-di-isocyanate-Modified Montmorillonite Hybrid. Journal of Applied Polymer Science, 2000, 77, 2201-2205
59. Ogata, N; Kawakage, S; Ogihara, T, et al. Poly(vinyl alcohol)-elay and poly(ethylene oxide)-elay blend prepared using water as solvent.Journal of Applied Polymer Science, 1997, 66, 573-581
60. Hasegawa, N; Okamoto, H; Kato, M, et al. Nylon 6/Na-montmorillonite nanoeomposites prepared by compounding Nylon6 with Na-montmorillonite slurry. Polymer, 2003, 44, 2933-2937
61．吴培熙，张留成编著．聚合物共混改性．中国轻工业出版社，1996，2，207-208
62．罗艳红．聚氯乙烯／粘土纳米复合材料的制备及性能研究：[硕士学位论文]．天津：河北工业大学，2000，6
63．宋洪祥，吴承训，袁茂全．纳米复合技术在聚氯乙烯增韧改性中的应用．合成技术及应用，2000，15(4)，22-26
64．严海标，潘国元．PVC／无机纳米复合材料的研究进展及应用．现代塑料加工应用，2003，15(5)，43-46
65．韩和良，钱锦文，徐雨尧．纳米CaCO_3微乳液存在下的万吨级氯乙烯原位聚合技术．聚氯乙烯，2001，(4)， 11-27
66．郝五棉，王耀斌，辛经萍．工业化生产纳米碳酸钙原位聚合聚氯乙烯树脂．聚氯乙烯，2002，(3)，15-17
67．田满红，郭少云．纳米SiO_2增强增韧聚氯乙烯复合材料的研究．聚氯乙烯，2003，(1)，26-32
68．王光辉，张玲．PVC／粘土纳米复合材料的研究进展．聚氯乙烯，2003，(5)，1-10
69. Ishida H; Campbell S; Blackwell J. General Approach to Nanocomposites Preparation. Chemistry of Materials, 2000,12,1260-1267
70. Wang, D Y; Parlow, D; Yao, Q, et al. PVC-Clay Nanocomposites: Preparation, Thermal and Mechanical Properties. Journal of Vinyl & Additive Technology, 2001, 7(4), 203-213
71. Du, J X; Wang, D Y; Wilkie, C A, et al. An XPS investigation of thermal degradation and charring on poly(vinyl chlodde)-clay nanoeomposites. Polymer Degradation and Stability, 2003, 79, 319-324
72．王平华，宋功品，徐国永，等．PVC／蒙脱土复合材料的制备与结构研究．中国塑料，2003， 17(1)，35-38
73．戈明亮，徐卫兵．聚氯乙烯／蒙脱土纳米复合材料的开发及研究．化工新型材料，2002，30(9)，20-29
74．巩方玲，赵春贵，杨明书．剥离型PVC／蒙脱石纳米复合材料的研究．全国高分子学术论文报告会论
文集，杭州，2003，F332
75. Wan, C Y; Qiao, X Y; Zhang, Y, et al. Effect of different clay treatment on morphology and mechanical properties of PVC-clay nanocompoistes. Polymer Testing, 2003, 22, 453-461
76. Wan, C Y; Qiao, X Y; Zhang, Y, et al. Effect of Epoxy Resin on Morphology and Physical Properties of PVC/Organophilic Montmofillonite Nanocomposites.Journal of Applied Polymer Science, 2003, Vol.89, 2184-2192
77. Wan, CY; Qiao, X Y; Zhang Y, et al. Structures and Mechanical Properties of PVC/Na+- Montmorillonite Nanocompositesm.Chinese Chemical Letters, 2003, 14 (4) , 417-418,
78．万超瑛，乔秀颖，张勇，等．聚氯乙烯／蒙脱土纳米复合材料的结构与力学性能．上海交通大学学报，2003，37(5)，636-639
79．万超瑛，乔秀颖，张勇，等．增韧聚氯乙烯／蒙脱土复合材料的结构与性能．中国塑料，2003，17(4)，39-42
80．刘青喜，周兴平，解孝林，等．原位插层聚合制备PVC／蒙脱土纳米复合材料．聚氯乙烯，2002，3(2)，11-13
81．瞿雄伟，罗艳红，丁会利，等．．聚氯乙烯／粘土熔融插层复合的研究．材料工程，2002，(4)，9-23
82. Hu, H Y; Pan, M W; Li, X C, et al. Polymer International, in press
83．胡海彦．原位插层法聚氯乙烯／粘土纳米复合材料的制备及性能研究：[硕士学位论文]．天津：河北工业大学，2003，1
84．胡金生，曹同玉，刘庆普编．乳液聚合．化学工业出版社，1987，1，126-127
85．刘晓辉，范家起，李强，等．聚丙烯／蒙脱土纳米复合材料Ⅰ．制备、表征及动态力学性能．高分子学报，2000，(5)，563-567
86．周宁琳，夏小仙，王延儒．剥离型硅橡胶／黏土纳米复合材料研究．高分子学报，2002，(2)，253-256
87．史彰悠著．聚氯乙烯高分子化学的理论与实践．第二版，浙江科学技术出版社，1990，8，188-192
88．马继盛，漆宗能，张树范．聚氨酯弹性体／蒙脱土纳米复合材料的合成结构与性能．高分子学报，2001，(3)，325-328
89. Pan, M W; Zhang, L C. Preparation and characterization of poly(butyl acrylate-co-2-ethylhexyl acrylate) gaffing of vinyl chloride resin with good impact resistance. Journal of Applied Polymer Science, 2003, 90, 643-649
90．何曼军，陈维孝，董西侠编．高分子物理(修订版)．复旦大学出版社，1990，10，244-245
91. Yua, Y H; Lina, C Y; Yeh, J M, et al. Preparation and properties of poly(vinyl alcohol)-clay nanocomposite materials. Polymer, 2003, 44, 3553-3560
92. Yeh, J M; Chen,C L; Chen, Y C, et al. Enhancement of corrosion protection effeet of poly(o-ethoxyaniline) via the formation of poly(o-ethoxyaniline)-clay nanocomposite materials. Polymer, 2002, 43, 2729-2736
93．严福英等主编．中国氯碱工业协会组织编写．聚氯乙烯工艺学．化学工业出版社，1996，1，4-5
94．舒中俊，漆宗能，王佛松．聚合物阻燃新途径——聚合物／粘土纳米复合材料的特殊阻燃性．高分子通报，2000，(4)，65-70
95．高家武主编，雷渭嫒，张复盛等编．高分子材料近代测试技术．北京航空航天大学出版社，1994，12，35-36
96．侯梅芳，马北雁，万洪富，等．我国各地膨润土的矿物学性质．岩矿测试，2002，21(3)，190-194
97. Ishida. General approach to nanocomposite preparation. U.S., United States Patent, 6,271,297. Aug. 7, 2001
98．郑震．聚氯乙烯降解理论的进展．塑料，1999，28(3)，8-14
99．沈德言，胡兴洲，英新芳，等．聚氯乙烯树脂的不饱和度和热稳定性的关系．高分子学报，1997，(2)， 183-187
100．潘才元主编．高分子化学．中国科学技术大学出版社，1997，7，327
101．郑增勇，丁超，贾德民，等．插层型NBR／膨润土混杂材料及其对PVC增韧作用的研究．广州化学，2001，26(4)，11-16
102．万超瑛，乔秀颖，张勇，等．增韧聚氯乙烯／蒙脱土复合材料的结构与性能．中国塑料，2003，17(4)，39-42
103．权英，杨明山，严庆，等．纳米刚性粒子对硬质PVC的增韧增强效果．北京化工大学学报，2002，29(6)． 24-26
2. Zhu, J; Wilkie, C A. Thermal and fire studies on polystyrene-clay nanocomposites. Polymer International, 2000, 49, 1158-1163
3. Hwu, J M; Jiang, G J; Gao, Z M, et al. The characterization of Organic Modified Clay and Clay-filled PMMA Nanocomposite. Journal of Applied Polymer Science, 2002,83,1702-1710
4. Yang, Y; Zhu, Z K; Yin, J, et al. Preparation and properties of hybrids of organo-soluble polyimide and montmodllonite with various chemical surface modification methods. Polymer, 1999,40, 4407-4414
5. Lan, T; Kaviratna, P D; Pinnavaia, T J. Mechanism of Clay Tactoid Exfoliation in Epoxy-Clay Nanocomposites. Chemistry of Materials, 1995, 7, 2144-2150
6. Kornmann, X; Lindberg, H; Berglund, L A. Synthesis of epoxy-clay nanocomposites:influence of the nature of the clay on structure. Polymer, 2001, 42, 1303-1310
7. Lan, T; Kaviratna, P D; Pinnavaia, T J. Epoxy self-polymerization in smectite clays. Journal of physics of Chemical Solids, 1996, 57,1005-1010
8. Maiti, P; Nam, P H; Okamoto M, et al. Influence of Crystallization on Intercalation, Morphology, and Mechanical Properties of Polypropylene/Clay Nanocomposites. Macromolecules 2002,35,2042-2049
9. Li, X C; Kang, T, Cho; W J, et al. Preparaton and Characterization of poly(butyleneterephalate)/Organoclay Nanocomposites. Macromolecules Rapid Communication, 2001, 22, 1306-1312
10. Hong, S H; Kim, B H; Joo, J, et al. Polypyrrole-montmodllonite nanocomposites synthesized by emulsion polymerization. Current Applied Physics, 2001, 1,447-450
11. Kim, J W; Liu, F, Choi; H J, et al. Intercalated polypyrrole/Na~+-montmorillonite nanocomposite via an inverted emulsion pathway method. Polymer, 2003, 44, 289-293
12. Kim, B H; Jung, J H; Hong, S H, et al. Physical characterization of emulsion intercalated polyaniline-caly nanocomposite. Current Applied Physics, 2001, 1, 112-115
13. Choi, H J; Kim, J W; Joo, J, et al. Synthesis and electrorheology of emulsion intercalated PANI-clay nanocomposite. Synthesis Metals, 2001,121, 1325-1326
14. Wang, H S; Zhao, T; Zhi, L J, et al. Synthesis of Novolac/Layered Silicate Nanocomposites by Reaction Exfoliation Using Acid-Modified Montmorillonite. Macromolecules Rapid Communication, 2002, 23, 44-48
15. Takeichi, T; Zeidam, R; Agag, T. Polybenzoxazine/clay hybrid nanocomposites: influence of preparation method on the curing behavior and properties of polybenzoxazines. Polymer, 2002, 43,45-53
16. Ray, S S; Yamada, K; Okamoto, M, et al. New polylactide/layered silicate nanocomposieds.5.Designing of materials with desired properties. Polymer, 2003, 44, 6633-6646
17. Krishnamoorti, R; Vaia, R A; Giannelis, E P. Structure and Dynamics of Polymer-Layered Silicate Nanocomposites.Chemistry of Materials, 1996,8,1728-1734
18．漆宗能，尚文字著．聚合物／层状硅酸盐纳米复合材料理论与实践．北京：化学工业出版社，2002，1-78
19. Alexandre, M; Dubois, P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Materials Science and Engineering, 2000,28,1-63
20. Tong, X; Zhao, H C;Tang, T, et al. Preparation and Characterization of Poly(ethyl acrylate Bentonite Nanocomposites by In Situ Emulsion Polymerization. Journal of Polymer Science: Part A: Polymer Chemistry, 2002, 40, 1706-1711
21. Lye, D C; Jang, L W; Preparation and Characterization of PMMA-Clay Hybrid Composite by Emulsion Polymerization. Journal of Applied Polymer Science, 1996, 61, 1117-1122,
22. Lee, D C; Jang, L W; Characterization of Epoxy-Clay Hybrid Composite prepared by Emulsion Polymerization. Journal of Applied Polymer Science, 1996, 68, 1997-2005
23. Nob, M H; Jang, L W;Lee, D C. Intercalation of Styrene-Acrylonitrile Copolymer in Layered Silicate by Emulsion Polymrization, Journal of Applied Polymer Science, 1999, (74), 179-188
24. Kim, J W; Nob, M H; Choi, H J, et al. Electrorheological Characteristics of Emulsion Polymerizaed SAN-Clay Nanocomposite Suspensions. Polymer Bulletin, 1998,41,512-513
25. Kim, B H; Jung, J H; Hong, S H, et al. Nanocomposite of Polyaniline and Na~+- Montmorillonite Clay. Macromolecules, 2002, 35, 1419-1423
26. Kim, T H; Jang, L W; Lee, D C, et al. Synthesis and Rheology of Intercalated Polystyrene/ Montmorillonite Nanocomposites. Macromolecules Rapid Communication, 2002, 23(3), 191-195
27. Choi, Y S; Wang, K H; Xu, M Z, et al. Synthesis of Exfoliated Polyacrylonitrile/Na-MMT Nanocomposites via Emulsion Polymerization. Chemistry of Materials, 2002,14, 2936-2939
28. Yano, K; Usuki, A; Okada, A, et al. Synthesis and Properties of Polyimide-Clay Hydrid. Journal of Polymer Science: Part A: Polymer Chemistry, 1993, 31, 2493-2498
29. Vaia, R A; Jandt, K D; Kramer, E J, et al. Microstructural Evolution of Melt Inercalated Polymer Organically Modified Layered Silicates Nanocomposites. Chemistry of Materials, 1996, 8, 2628-2635
30. Vaia, R A; Ishii, H; Giannelis, E P, et al. Synthesis and properties of two-dimensional nanostructures by direct intercalation of polymer melts in layered silicates. Chemistry of Materials, 1993,5,1694-1696
31. Vaia, R A; Jandt, K D; Kramer, E G, et al. Kinetics of Polymer Melt Intercalation. Macromolecules, 1995, 28, 8080-8085
32. Vaia, R A; Giannelis, E P. Polymer Melt Intercalation in Organically-Modified Layered Silicates: Model Predictions and Experiment. Macromolecules, 1997, 30, 8000-8009
33. Kim, S W; Jo, W H; Lee, M S, et al. Effects of Shear on Melt Exfoliation of Clay in Preparation of Nylon
6/Organoclay Nanocomposites. Polymer Journal, 2002, 34(3), 103-111
34. Tony, M N; Murphy, W R; Lew, C Y, et al. Polyamide-12 layered silicate nanocomposites by melt blending. Polymer, 2003,44, 2761-2772
35. Kato, M; Usuki, A; Okada, A. Synthesis ofpolypropylene oligomer - clay intercalation compounds. Journal of Applied Polymer Science, 1997, 66, 1781-1785
36. Kojima, Y; Usuki, A; Kawasumi, M, et al. Mechanical properties of nylon 6-clay hybrid. Journal of Material Research, 1993, 8(5), 1185-1189
37. Bharadwaj, R K; Mehrabi, A R; Hamilton, C, et al. Polymer, 2002, 43, 3699-3705
38．[美]H·范·奥尔芬．粘土胶体化学导论，1982，66-68
39．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，1999，2，1-5
40. Zhu, J; Start, P; Mauritz, K A, et al. Silicon-Methoxide-Modified Clays and Their Polystyrene Nanocomposites.Journal of Polymer Science: Part A, 2002, 40, 1498-1503
41．徐寿昌主编．有机化学．第二版．高等教育出版社，1993，4，452-453
42. Okada, A; Kawasumi, M; Kurauchi, T, et al. Synthesis and Characterization of a Nylon 6-Clay Hybrid. Polymer Preprint ,1987, 28, 447-448
43. Usuki, A. Kawasumi, M. Kojima, Y, et al. Swelling behavior of montmorillonite cation exchanged "for ω-amino acids by ε-caprolactam.. Journal of Material Research, 1993, 8(5), 1174-1182
44. Chen, T K; Tien, Y I; Wei, K H. Synthesis and Characterization of Novel Segmented Polyurethane/Clay Nanocomposite via Poly(ε-caprolactone)/Clay. Journal of Polymer Science:Part A, 1999, 37, 2225-2233,
45. Chen, T K; Tien, Y I; Wei, K H. Synthesis and characterization of novel segmented polyurethane/clay nanocomposites. Polymer, 2000, 41, 1345-1353
46. Messersmith, P B; Giannelis, E E Synthesis and barrier properties ofpoly(ε-caprolactone)-layered silicate nanocomposites. Journal of Polymer Science Part A: Polymer Chemistry, 1995, 33(7), 1047-1057
47. Ogawa, M; Kuroda, K. Preparation of Inorganic-Organic Nanocomposites through Intercalation of Organoammonium Ions into Layered Silicates. Bulll.Chem.Soc.Jpn, 1997,70, 2593-2618
48. Xie, W; Gao, Z M; Pan, W P, et al. Thermal Degradation chemistry of alkyl quaternary ammonium montmorillonite. Chemistry of Materials, 2001, 13, 2979-2990
49. Zhu, J; Morgan, A B; Lamelas, F J, et al. Fire properties of polystyrene-clay nanocomposites. Chemistry of Materials, 2001, 13, 3774-3780
50. Zhu, J; Uhl, F M; Morgan, A B, et al. Studies on the mechanical by which the formation of nanocomposites enhances thermal stability. Chemistry of Materials, 2001, 13, 4649-4654
51. Yeh, J M; Liou, S J; Lin, C Y, et aI. Anticorrosively enhanced PMMA-clay nanocomposite materials with quaternary alkylphosphonium salt as an intercalating agent. Chemistry of Materials, 2002, 14, 154-161
52. Kommann, X; Berglund, L A; Sterte, J. Nanocomposites Based on Montmorillonite and Unsaturated Polyester. Polymer Engineering and Science, 1998, 38(8), 1351-1357
53. Furuichi, N; Kurokawa, Y; Fujita, K, et al. Preparation and properties of polypropylene reinforced by smectite. Journal of Materials Science, 1996, 31, 4307-4310
54．吴成泰等著．冠醚化学．科学出版社，1992，12，116-118
55. Hitzky, E R; Casal, B. Crown ether intercalations with phyllosilicates. Nature, 1978,276,596-597
56. Gilman, J W; Kashiwage,T;Morgan, A B, et al. Proceedings of Additives 2001,March, 2001
57．陈光明，马永梅，漆宗能．甲苯-2,4-二异氰酸酯修饰蒙脱土及聚苯乙烯／蒙脱土纳米复合材料的制备与表征．高分子学报，2000，10(5)，119-122
58. Chen, G M; Ma, Y M; Qi, Z N. Preparation of Polystyrene/Toluene-2,4-di-isocyanate-Modified Montmorillonite Hybrid. Journal of Applied Polymer Science, 2000, 77, 2201-2205
59. Ogata, N; Kawakage, S; Ogihara, T, et al. Poly(vinyl alcohol)-elay and poly(ethylene oxide)-elay blend prepared using water as solvent.Journal of Applied Polymer Science, 1997, 66, 573-581
60. Hasegawa, N; Okamoto, H; Kato, M, et al. Nylon 6/Na-montmorillonite nanoeomposites prepared by compounding Nylon6 with Na-montmorillonite slurry. Polymer, 2003, 44, 2933-2937
61．吴培熙，张留成编著．聚合物共混改性．中国轻工业出版社，1996，2，207-208
62．罗艳红．聚氯乙烯／粘土纳米复合材料的制备及性能研究：[硕士学位论文]．天津：河北工业大学，2000，6
63．宋洪祥，吴承训，袁茂全．纳米复合技术在聚氯乙烯增韧改性中的应用．合成技术及应用，2000，15(4)，22-26
64．严海标，潘国元．PVC／无机纳米复合材料的研究进展及应用．现代塑料加工应用，2003，15(5)，43-46
65．韩和良，钱锦文，徐雨尧．纳米CaCO_3微乳液存在下的万吨级氯乙烯原位聚合技术．聚氯乙烯，2001，(4)， 11-27
66．郝五棉，王耀斌，辛经萍．工业化生产纳米碳酸钙原位聚合聚氯乙烯树脂．聚氯乙烯，2002，(3)，15-17
67．田满红，郭少云．纳米SiO_2增强增韧聚氯乙烯复合材料的研究．聚氯乙烯，2003，(1)，26-32
68．王光辉，张玲．PVC／粘土纳米复合材料的研究进展．聚氯乙烯，2003，(5)，1-10
69. Ishida H; Campbell S; Blackwell J. General Approach to Nanocomposites Preparation. Chemistry of Materials, 2000,12,1260-1267
70. Wang, D Y; Parlow, D; Yao, Q, et al. PVC-Clay Nanocomposites: Preparation, Thermal and Mechanical Properties. Journal of Vinyl & Additive Technology, 2001, 7(4), 203-213
71. Du, J X; Wang, D Y; Wilkie, C A, et al. An XPS investigation of thermal degradation and charring on poly(vinyl chlodde)-clay nanoeomposites. Polymer Degradation and Stability, 2003, 79, 319-324
72．王平华，宋功品，徐国永，等．PVC／蒙脱土复合材料的制备与结构研究．中国塑料，2003， 17(1)，35-38
73．戈明亮，徐卫兵．聚氯乙烯／蒙脱土纳米复合材料的开发及研究．化工新型材料，2002，30(9)，20-29
74．巩方玲，赵春贵，杨明书．剥离型PVC／蒙脱石纳米复合材料的研究．全国高分子学术论文报告会论
文集，杭州，2003，F332
75. Wan, C Y; Qiao, X Y; Zhang, Y, et al. Effect of different clay treatment on morphology and mechanical properties of PVC-clay nanocompoistes. Polymer Testing, 2003, 22, 453-461
76. Wan, C Y; Qiao, X Y; Zhang, Y, et al. Effect of Epoxy Resin on Morphology and Physical Properties of PVC/Organophilic Montmofillonite Nanocomposites.Journal of Applied Polymer Science, 2003, Vol.89, 2184-2192
77. Wan, CY; Qiao, X Y; Zhang Y, et al. Structures and Mechanical Properties of PVC/Na+- Montmorillonite Nanocompositesm.Chinese Chemical Letters, 2003, 14 (4) , 417-418,
78．万超瑛，乔秀颖，张勇，等．聚氯乙烯／蒙脱土纳米复合材料的结构与力学性能．上海交通大学学报，2003，37(5)，636-639
79．万超瑛，乔秀颖，张勇，等．增韧聚氯乙烯／蒙脱土复合材料的结构与性能．中国塑料，2003，17(4)，39-42
80．刘青喜，周兴平，解孝林，等．原位插层聚合制备PVC／蒙脱土纳米复合材料．聚氯乙烯，2002，3(2)，11-13
81．瞿雄伟，罗艳红，丁会利，等．．聚氯乙烯／粘土熔融插层复合的研究．材料工程，2002，(4)，9-23
82. Hu, H Y; Pan, M W; Li, X C, et al. Polymer International, in press
83．胡海彦．原位插层法聚氯乙烯／粘土纳米复合材料的制备及性能研究：[硕士学位论文]．天津：河北工业大学，2003，1
84．胡金生，曹同玉，刘庆普编．乳液聚合．化学工业出版社，1987，1，126-127
85．刘晓辉，范家起，李强，等．聚丙烯／蒙脱土纳米复合材料Ⅰ．制备、表征及动态力学性能．高分子学报，2000，(5)，563-567
86．周宁琳，夏小仙，王延儒．剥离型硅橡胶／黏土纳米复合材料研究．高分子学报，2002，(2)，253-256
87．史彰悠著．聚氯乙烯高分子化学的理论与实践．第二版，浙江科学技术出版社，1990，8，188-192
88．马继盛，漆宗能，张树范．聚氨酯弹性体／蒙脱土纳米复合材料的合成结构与性能．高分子学报，2001，(3)，325-328
89. Pan, M W; Zhang, L C. Preparation and characterization of poly(butyl acrylate-co-2-ethylhexyl acrylate) gaffing of vinyl chloride resin with good impact resistance. Journal of Applied Polymer Science, 2003, 90, 643-649
90．何曼军，陈维孝，董西侠编．高分子物理(修订版)．复旦大学出版社，1990，10，244-245
91. Yua, Y H; Lina, C Y; Yeh, J M, et al. Preparation and properties of poly(vinyl alcohol)-clay nanocomposite materials. Polymer, 2003, 44, 3553-3560
92. Yeh, J M; Chen,C L; Chen, Y C, et al. Enhancement of corrosion protection effeet of poly(o-ethoxyaniline) via the formation of poly(o-ethoxyaniline)-clay nanocomposite materials. Polymer, 2002, 43, 2729-2736
93．严福英等主编．中国氯碱工业协会组织编写．聚氯乙烯工艺学．化学工业出版社，1996，1，4-5
94．舒中俊，漆宗能，王佛松．聚合物阻燃新途径——聚合物／粘土纳米复合材料的特殊阻燃性．高分子通报，2000，(4)，65-70
95．高家武主编，雷渭嫒，张复盛等编．高分子材料近代测试技术．北京航空航天大学出版社，1994，12，35-36
96．侯梅芳，马北雁，万洪富，等．我国各地膨润土的矿物学性质．岩矿测试，2002，21(3)，190-194
97. Ishida. General approach to nanocomposite preparation. U.S., United States Patent, 6,271,297. Aug. 7, 2001
98．郑震．聚氯乙烯降解理论的进展．塑料，1999，28(3)，8-14
99．沈德言，胡兴洲，英新芳，等．聚氯乙烯树脂的不饱和度和热稳定性的关系．高分子学报，1997，(2)， 183-187
100．潘才元主编．高分子化学．中国科学技术大学出版社，1997，7，327
101．郑增勇，丁超，贾德民，等．插层型NBR／膨润土混杂材料及其对PVC增韧作用的研究．广州化学，2001，26(4)，11-16
102．万超瑛，乔秀颖，张勇，等．增韧聚氯乙烯／蒙脱土复合材料的结构与性能．中国塑料，2003，17(4)，39-42
103．权英，杨明山，严庆，等．纳米刚性粒子对硬质PVC的增韧增强效果．北京化工大学学报，2002，29(6)． 24-26