膨胀型阻燃聚乙烯的研究
|
摘要
聚乙烯(PE)作为产量最大的通用塑料之一,由于重量轻、低毒性、良好的电气绝缘性和机械性能,被广泛应用于建筑、交通、家庭装饰和电线电缆等行业。然而它的极限氧指数很低极易燃烧,这一缺点严重影响了它的广泛应用。因此,提高聚乙烯的阻燃性成为一个挑战。
这一问题可以通过添加阻燃剂来解决,如卤素化合物和无机氢氧化物等。不幸的是,卤素化合物面临很大的环境问题,而无机添加剂效率都较低。近年来膨胀型阻燃剂因为具有无卤、低毒、生烟量少等特点而得到很大重视。膨胀型阻燃剂主要通过受热分解在材料表面生成多孔的膨胀炭层,起到隔绝热、氧及可燃气体产物等作用达到阻燃目的。
将金属化合物与膨胀型阻燃剂共同使用可以提高材料的阻燃性能。有研究表明金属盐类物质可以提高膨胀型阻燃聚丙烯的阻燃性能。某些金属络合物可以将烷基自由基转变为更稳定的物质。但还没有将其用于聚乙烯阻燃领域的报道,本论文采用多种有机金属络合物作为膨胀型阻燃剂的协效剂复配使用,取得了较好效果。
从无卤阻燃聚乙烯出发,本论文以1-氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷和季戊四醇为原料合成了一种新型膨胀型阻燃剂三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷-4-羰基)季戊四醇酯(CA);并对其合成条件进行了研究;通过红外光谱、核磁共振等方法对合成的产物进行了结构标征。当它与聚磷酸铵(APP)/三聚氰胺磷酸盐(MP)和有机金属络合物复配使用时具有很好的阻燃性能。
本论文还通过在一定温度下磷酸盐与多元醇的脱水酯化反应,运用反应挤
Polyethylene (PE), with characteristics of light-mass, lower-poison, excellent electric-insulation and mechanical durability, has been widely applied in many fields such as building, transport, furniture and electrical industries. However, it has a low limiting oxygen index (LOI) value and is flammable. The fateful drawback of polyethylene restricts its wider application. Therefore, how to improve its flame retardancy becomes a big challenge.
This problem can be solved by using flame-retardant additives, such as halogenated compounds and inorganic hydrated compounds. Unfortunately, halogenated compounds are serious environmentally problem, and inorganic additives have poor efficiency. Recently, intumescent flame retardants (IFRs) have received a considerable attention because they are non-halogen, low toxicity, and low smoke release. The IFRs are designed to swell and form a porous carbonaceous char layers on the surface of materials, which act as a barrier to heat, air and flammable pyrolysis products.
The presence of some metal-containing compounds with IFRs seemed to enhance the flame-retardant action. It was observed that the metal salt appeared to improve the performance of IFRs/PP. Some metal chelates have been proposed that they convert alkylperoxy radicals to more stable species.
In order to address the issue of halogen-free flame retardancy of PE, a novel intumescent flame retardant (CA) was synthesized based on
这一问题可以通过添加阻燃剂来解决,如卤素化合物和无机氢氧化物等。不幸的是,卤素化合物面临很大的环境问题,而无机添加剂效率都较低。近年来膨胀型阻燃剂因为具有无卤、低毒、生烟量少等特点而得到很大重视。膨胀型阻燃剂主要通过受热分解在材料表面生成多孔的膨胀炭层,起到隔绝热、氧及可燃气体产物等作用达到阻燃目的。
将金属化合物与膨胀型阻燃剂共同使用可以提高材料的阻燃性能。有研究表明金属盐类物质可以提高膨胀型阻燃聚丙烯的阻燃性能。某些金属络合物可以将烷基自由基转变为更稳定的物质。但还没有将其用于聚乙烯阻燃领域的报道,本论文采用多种有机金属络合物作为膨胀型阻燃剂的协效剂复配使用,取得了较好效果。
从无卤阻燃聚乙烯出发,本论文以1-氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷和季戊四醇为原料合成了一种新型膨胀型阻燃剂三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷-4-羰基)季戊四醇酯(CA);并对其合成条件进行了研究;通过红外光谱、核磁共振等方法对合成的产物进行了结构标征。当它与聚磷酸铵(APP)/三聚氰胺磷酸盐(MP)和有机金属络合物复配使用时具有很好的阻燃性能。
本论文还通过在一定温度下磷酸盐与多元醇的脱水酯化反应,运用反应挤
Polyethylene (PE), with characteristics of light-mass, lower-poison, excellent electric-insulation and mechanical durability, has been widely applied in many fields such as building, transport, furniture and electrical industries. However, it has a low limiting oxygen index (LOI) value and is flammable. The fateful drawback of polyethylene restricts its wider application. Therefore, how to improve its flame retardancy becomes a big challenge.
This problem can be solved by using flame-retardant additives, such as halogenated compounds and inorganic hydrated compounds. Unfortunately, halogenated compounds are serious environmentally problem, and inorganic additives have poor efficiency. Recently, intumescent flame retardants (IFRs) have received a considerable attention because they are non-halogen, low toxicity, and low smoke release. The IFRs are designed to swell and form a porous carbonaceous char layers on the surface of materials, which act as a barrier to heat, air and flammable pyrolysis products.
The presence of some metal-containing compounds with IFRs seemed to enhance the flame-retardant action. It was observed that the metal salt appeared to improve the performance of IFRs/PP. Some metal chelates have been proposed that they convert alkylperoxy radicals to more stable species.
In order to address the issue of halogen-free flame retardancy of PE, a novel intumescent flame retardant (CA) was synthesized based on
引文
1. Levchik S.V., Weil E.D., Flame retardancy of thermoplastic polyesters-a review of the recent literature. Polym Int. 2005, 54(1), 11-35.
2. Flame retardants: some new developments. Plastics Additives and Compounding. 2001, 2, 1-3.
3. Xie R.C., Qu B.J., Synergistic effects of expandable graphite with some halogen-free flame retardants in polyolefin blends, Polym Degrad Stab. 2001, 71(3), 375-380.
4. Camino G., Costa L., Luda di Cortemiglia M.P., Overview of fire retardant mechanism, Polym Degrad Stab. 1991, 33(2), 131-154.
5. 徐应麟,王元宏,高聚物材料的实用阻燃技术,北京:化学工业出版社,1994.
6. Delobel R., Le Bras M., Ouassou N., Alistiqsa F. J Fire Sci. 1990, 8, 85-108.
7. Chiu S.H., Wang W.K., Dynamic flame retardancy of polypropylene filled with ammonium polyphosphate, pentaerythritol and melamine additives, Polymer 1998, 39(10), 1951-1955.
8. Broadbent J.R.A., Hirschler M.M.. Eur Polym J. 1984, 20(11), 1087-1093.
9. Marosi G., Marton A., Anna P., Bertalan G., Ceramic precursor in flame retardant systems, Polym Degrad Stab. 2002, 77(2), 259-265.
10. Marosi G., Anna P., Marton A., Bertalan G.. Polym Adv Technol 2002, 13, 1103-1111.
11. Wilson J.O.C., et al., Surface and interfacial properties of polymer-intercalated layered double hydroxide nanocomposites. Appl Clay Sci. 1999, 15, 265-279.
12. Vaccari A., Clays and catalysis: a promising future, Appl Clay Sci. 1999, 14(4), 161-198.
13. Khan A.I., O`Hare D., Intercalation chemistry of layered double hydroxides: recent developments and applications. J Mater Chem. 2002, 12, 3191-3198.
14. Lerux F., Besse J.P., Polymer Interleaved Layered Double Hydroxide: A new emerging class of nanocomposites. Chem Mater. 2001, 13, 3507-3515.
15. 王玉忠 聚酯纤维阻燃化设计, 成都:四川科学技术出版社,1994.
16. 欧育湘,阻燃剂—制造、性能及应用,北京:兵器工业出版社,1997, 5.
17. 史翎,段雪,阻燃剂的发展及在塑料中的应用,塑料,2002, 31(3), 11-15.
18. Wang Z.Z., Qu B.J., Fan W.C., Huang P. Combustion characteristics of halogen-free flame-retarded polyethylene containing magnesium hydroxide and some synergists. J Appl Polym Sci. 2001, 81(1),206-214.
19. Lein Tange, Dieter Drohmann. Environmental issues related to end-of-life options of plastics containing brominated flame retardants. Fire and Mater. 2004, 28(5), 403-410.
20. 刘霞,阻燃剂的现状与发展趋势,广东化工,1999, 26(20), 111.
21. 陈宇,结合行业发展,推动助剂工业,塑料,2000, 29(5), 9.
22. Yang J.P., Brewer D.G., Venart J.E.S. Flame retardant polymeric materials, Fire and Mater. 1995, 15, 37-48.
23. 钱军民,李旭祥,聚乙烯改性研究进展,塑料,2001, 2(30), 38-41.
24. 肖鹏,腾人瑞,无卤阻燃原理及无毒阻燃技术的发展方向,阻燃材料与技术,1997, 1, 1-4.
25. 于永忠,吴启鸿,葛世成,阻燃材料手册,北京:群众出版社,1997
26. Innes J., Innes A., Compounding metal hydrate flame retardants. Plastics Additives and Compounding. 2002, April, 22-26.
27. 方征平,许承威,白雪冰,高填充聚乙烯/氢氧化铝体系的交联改性,中国塑料, 1998, 12(2), 49-51.
28. 王珂,李春江,HDPE/氢氧人镁复合体系力学性能及阻燃性的研究,塑料工业,1995, 5,34-38.
29. Shiinichi Akitaya, Toru Fukazawa. Flame retardant polypropylene resin composition, US 4966931, 1988. 83
30. 林明德,俞强等,LDPE熔融接枝的研究,塑料工业,1990, 1, 15-18.
31. 蓝方, 陈宁, 阻燃HDPE中氢氧化铝的表面处理和阻燃增效,塑料工业,1999, 27(1), 35-37.
32. Wu Q., Lü J.P., Qu B.J., Preparation and characterization of microcapsulated red phosphorus and its flame retardant mechanism in halogen-free flame retardant polyolefins, Polym Int. 2003, 52, 1326-1331.
33. Nishihara H. Interactions between phosphorous and nitrogen-containing flame retardants. Polymer J. 1998, 30(3), 163-170.
34. Edward N.P. Phosphorous flame retardants thermoplastics. J Appl Polym Sci. 1982, 20, 1680-1685.
35. Ulrike Braun, Bernhard Schartel. Flame Retardant Mechanisms of Red Phosphorus and Magnesium Hydroxide in High Impact Polystyrene. Macromolecular Chemistry and Physics.2004, 205(16), 2185-2196.
36. Baillet C., Gandi S., Fire retardants of polyethylene: study of a formulation involving phosphorous and polyol systems. Polym Degrad Stab. 1992, 35, 149-158
37. Prasad V.S., Pillai C.K.S., Flame retardation of polyethylene: Effect of a phosphorus flame retardant having both hydrophobic and hydrophilic groups in the same molecule. J Appl Polym Sci. 2000, 77, 2631-2640.
38. Camino G., Martinasso G., Costa L. Thermal degradation of penterythritol diphosphate. Polym Degrad Stab. 1990, 27, 285-296.
39. Camino G., Polym Degrad Stab. 1988, 20, 271-279
40. Zhang S., Horrocks A. R., Substantive intumescence from phosphorylated 1,3-propanediol derivatives substituted on to cellulose. J. Appl. Polym. Sci. 2003, 90, 3165-3172.
41. Duquesne S., Le Bras M., et al., X-ray photoelectron spectroscopy investigation of fire retarded polymeric materials: application to the study of an intumescent system, Polym Degrad Stab. 2002, 77, 203-211.
42. Nakayama, Y., Soeda, F., Ishitani, A. Carbon. 1990, 28: 21.
43. Pels, JR., Kapteijn, F., Moulijn, JA., Zhu, Q., Thomas, KM. Carbon. 1995, 33: 1641.
44. Le Bras M., Bourbigot S., In: Le Bras M., Camino G., Bourbigot S., Delobel R., Fire retardancy of polymers-the use of intumescence. Cambridge: The Royal Sociey of Chemistry, 1998, p.64.
45. Baljinder K.K., Horrocks A.R., Complex char formation in flame retarded fibre – intumescent combinations -Ⅱ. Thermal analytical studies, Polym. Degrad. Stab. 1996, 54(2-3), 289-303.
46. Camino G., Polym Degrad Stab. 1984, 4, 243-254.
47. Almeras X., Dabrowski F., Le Bras M., Poutch F., Bourbigot S., Marosi G., Anna P., Polym Degrad Stab. 2002, 77(2), 305-313.
48. Levchik G.F., Levchik S.V., Sachok P.D., Selevich A.F., Lyakhov A.S., Lesnikoovich AI. Thermal behaviour of ammonium polyphosphate-inorganic compound mixtures. Part 2. Manganese dioxide. Thermochim Acta. 1995, 257, 117-125.
49. 李伟,李晖,冯开才等, 高分子材料科学与工程, 1998, 14(3), 59.
50. Pearce M., Pure Appl. Chem. 1986, 58, 925-930.
51. Cost L., Polym Degrad Stab. 1989, 23, 259-269.
52. Le Bras M., Bourbigot S., Synergy in intumescence-application to cyclodextrin carbonization agent in intumescent additives for fire retardant polyethylene formulations. Polym Degrad Stab. 1997, 56, 11-21.
53. 李斌,张秀成,孙才英,淀粉对聚乙烯膨胀阻燃体系热降解和阻燃的影响,高分子材料科学与工程,2000, 16(2), 155-157.
54. Devaux E., Rochery M., Bourbigot S., Polyurethane/clay and polyurethane/POSS nanocomposites as flame retarded coating for polyester and cotton fabrics, Fire and Mater. 2002, 26(4-5), 149-154.
55. Scharff P., New carbon materials for research and technology, Carbon. 1998, 36(5- 6), 481- 486.
56. Qin L.C., Zhao x.l., et al, Materials science-The smallest carbon nanotube, Nature. 2000, 408, 50- 50.
57. Hamada Sawada N., et al., Phys Rev Lett. 1992, 68, 1579- 1581.
58. Sandler J., Shaffer M. S. P., Prasse T., et al., Development of a dispersion process for carbon nanotubes in an epoxy matrix and the resulting electrical properties, Polymer. 1999, 40(21), 5967- 5971.
59. Takashi, Eric Grulkd, Jenny Hilding, et al., Thermal degradation and flammability properties of polypropylene/carbon nanotube composites, Macromol Rapid Commun. 2002, 23, 761-765.
60. 欧育湘.未来的高效阻燃系统,化工进展,1998(4):14-16
61. Chine J C W, Kiang J Y. Macromol, 1980,13:280～288
62. A. W. Benbow, C. F. Cullis, H. S. Laver, Polymer 1978, 19, 824.
63. Bourgigot S., Le Bras M., Delobel R., Bréant P., Trémillon J.M., Zeolite: new synergistic agents for intumescent fire retardant thermoplastic formulations-criteria for the choice of the zeolite, Fire and Mater. 1996, 20(3), 145-154.
64. Bourgigot S., Le Bras M., Delobel R., Décressain R., Amoureux J.P., J Chem Soc Faraday Trans. 1996, 92(1), 149.
65. Le Bras M., Bourbigot S., Félix E., Pouille C.Siat, Traisnel M. Characterization of a polyamide-6-based intumescent additive for thermoplastic formulations. Polymer. 2000, 41, 5283-5296.
66. Cullis C F, Hirschler M M. Eur Polym J 1984; 20: 53-60.
67. Lewin M, Makoto E. Polym Adv Technol 2003; 14:3-11.
68. Verkade J G, Roynolds L I, J. Org. Chem., 1960,25:663
69. Brown, NMD., Hewitt, JA., Meenan, BJ. Surf. Interf. Anal. 1992, 18: 187.
70. 钟世云,许乾慰,王公善,聚合物降解与稳定化, 北京:化学工业出版社,2002, 3-5.
71. Kandola Horrocks S, Horrocks AR. Thermochim Acta. 1997,294:113.
72. X. Li, Y. X. Ou, Y. H. Zhang, D. J. Lian, Chin. Chem. Lett. 2000, 11, 887.
73. Y. G. Li, J. J. Wang, T. Han, Y. S. Liu, Acta. Chimica. Sinica. 1988, 46, 679
74. 化工百科全书(第10卷),北京:化学工业出版社,1996.
75. 徐旭荣,陈关喜,胡耿源等,磷杂螺环化合物的合成及表征. 精细化工 1997,(14): 35-38
76. Morice L, Bourbigot S and Leroy J-M, J Fire Sci 15:358-374(1997)
77. Zhu WM, Weil ED and Mukhopadhyay S, J Appl Polym Sci 62:2267-2280(1996),
78. Halpern Y, Mott DM and Niswarder RH, Ind Eng Chem Prod Res Dev 23:233-238(1984)
79. Chiang W-Y, Hu HC-H, J Appl Polym Sci 81:1125-1135(2001)
80. Le bras M, Bugajny M, Lefebvre J-M, Bourbigot S, Polym Int 49:1115-1124(2000)
81. Le Bras M and Bourbigot S, J Mater Sci 34:5777-5782(1999)
82. Wang Q, Chen YH, Liu Y, Yin H, Aelmans N, Kierkels R. Polym Int 53:439-448(2004)
83. Chen YH, Liu Y, Wang Q, Yin H, Aelmans N, Kierkels R. Polym Degrad Stab 81:215-224(2003)
84. Camino G, Costa L and Trossarelli L, Polym Degrad Stabil 8:13-22(1984)
85. Liu T.S., Wang C.S., Synergistic effect of a phosphorus-nitrogen flame retardant on engineering plastics, J Appl Polym Sci. 2004, 91(1), 410-417.
86. Marchal A., Delobel R., Le Bras M., Leroy J.M., Effect of intumescence on polymer degradation, Polym Degrad and Stab. 1994, 44, 263-272.
87. Bourbigot, S., Le Bras, M., Gengembre, L., Delobel, R. Appl. Surf. Sci.1994,81:299.
88. Hirschler M.M., Electric cable fire hazard assessment with the cone calorimeter, Fire hazard and fire risk assessment(ASTM STP 1150) 1992, 44-65, American society for testing and materials, Philadelphia.
89. Babrauskas V.,Peacock R.D. Heat release rate: the single most important variable in fire hazard, Fire Safety J. 1992, 18, 255-272.
90. Bourbigot, S., Le Bras, M., Delobel, R., Gengembre, L. Appl. Surf. Sci.1997,120: 15.
91. Elliot P.J., Whiteley R.H., A cone calorimeter test for the measurement of flammability properties of insulated wire. Polymer Testing. 1999, 64, 577-584.
92. Sekiguchi, Y., Frye, JS., Shafizadeh, F. J. Appl. Polym. Sci. 1983, 28: 31513
93. Wu, OH., Qu, BJ., Xu, YH., Wu, Q. Polym. Degrad. Stab. 2000, 68: 97
94. R. P. R. Ranaweera, G. Scott, Eur. Polym. J. 1976, 12, 825.
95. Zhu, SW., Shi, WF. Synthesis, characterization and flame retardancy of methacrylated phosphate/diphosphate. Polym. Int. 2004, 53: 266–271.
96. Bugajny M., Le Bras M., Bourbigot S., Thermoplastic polyurethanes as carbonization agents in intumescent blents. Part 2: thermal behavior of polypropylene/thermoplastic polyurethane/ammonium polyphosphate blends, J Fire Sci. 1999, 18, 7-26.
97. K. Ismet, G. Murat, Eur. Polym. J. 2004, 40, 2025.
98. M. Hasan, R. V. Adalet, Polym. Degrad. Stab. 2004, 83,255.
99. H. M. Cao, ‘‘Handbook of Inorganic Compounds’’, 1st edition, Chemical Industry Press, Beijing 1988.
100. Shih Y.C., Cheung F.B., Koo J.H., Theoretical modeling of intumescent fire-retardant materials, J Fire Sci. 1998, 16, 46-71.
101. N. S. Allen, “Degradation and Stabilization of Polyolefins”, Applied Science, New York 1983.
102. 舒中俊,漆宗能,聚合物及其复合材料火灾危险与对策, 工程塑料与应用, 1999, 11, 37-39.
103. Bourbigot S., Le Bras M., Duqesne S., Rochery M., Recent advances for intumescent polymers, Macromol Mater Eng. 2004, 289, 499-511.
104. 李斌,孙才英,张秀成,用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性,高等学校化学学报,1999, 20(1), 146-149.
105. 欧育湘,陈宇,王晓梅,阻燃高分子材料,北京:国防工业出版社,2001.
106. 林建军,郑丽敏,傅岩,高等学校化学学报,1994(15)1110～1113
107. Jakab E., Uddin M.A., Bhaskar T., Sakata Y., Thermal decomposition of flame-retarded high-impact polystyrene, Journal of Analytical and Applied Pyrolysis, 2003, 68-69, 83-99.
108. Zhao H., Wang Y.Z., Wang D.Y., Wu B., Chen D.Q., Wang X.L., Yang K.K., Kinetics of thermal degradation of flame retardant copolyesters containing phosphorus linked pendent groups, Polym Degrad Stab. 2003, 80(1), 135-140.
109. Dahiya J.B., Rana S., Thermal degradation and morphological studies on cotton cellulose modified with various arylphosphorodichloridites, Polym Int. 2004, 53(7), 995-1002.
110. Lin C.H., Synthesis of novel phosphorus-containing cyanate esters and their curing reaction with epoxy resin, Polymer. 2004, 45, 7911-7926.
111. Wang J.Q., Du J.X., Zhu J., Wilkie C.A., An XPS study of the thermal degradation and flame retardant mechanism of polystyrene-clay nanocomposites, Polym Degrad Stab. 2002, 77(2), 249-252.
112. Miklós M., András T., Peter R. H., Paul A. C., Matthew Cross, Gy?rgy Marosi, XPS analysis of zinc hydroxystannate-coated hydrated fillers, Surface and Interface Analysis. 2002, 34(1), 735-739.
113. Wei P., Hao J.W., Du J.X., Han Z.D., Wang J.Q., An investigation on synergism of an intumescent flame retardant based on silica and alumina, J Fire Sci. 2003, 21(1), 17-28.
114. Marosi G., Anna P., Balogh I., et al., Thermoanalytical study of nucleating effects in polypropylene composites .3. Intumescent flame retardant containing polypropylene, Journal of Thermal Analysis. 1997, 48(4), 717-726.
115. Le Bras M., Bourbigot S., Delporte C., et al., New Intumescent Formulations of Fire-retardant Polypropylene - Discussion of the Free Radical Mechanism of the Formation of Carbonaceous Protective Material During the Thermo-oxidative Treatment of the Additives. Fire and Mater. 1996, 20(4), 191-203.
116. Ravadits, I., Tóth, A., Marosi, G., et al., Organosilicon surface layer on polyolefins to achieve improved flame retardancy through an oxygen barrier effect, Polym Degrad Stab. 2001, 74(3), 419-422.
2. Flame retardants: some new developments. Plastics Additives and Compounding. 2001, 2, 1-3.
3. Xie R.C., Qu B.J., Synergistic effects of expandable graphite with some halogen-free flame retardants in polyolefin blends, Polym Degrad Stab. 2001, 71(3), 375-380.
4. Camino G., Costa L., Luda di Cortemiglia M.P., Overview of fire retardant mechanism, Polym Degrad Stab. 1991, 33(2), 131-154.
5. 徐应麟,王元宏,高聚物材料的实用阻燃技术,北京:化学工业出版社,1994.
6. Delobel R., Le Bras M., Ouassou N., Alistiqsa F. J Fire Sci. 1990, 8, 85-108.
7. Chiu S.H., Wang W.K., Dynamic flame retardancy of polypropylene filled with ammonium polyphosphate, pentaerythritol and melamine additives, Polymer 1998, 39(10), 1951-1955.
8. Broadbent J.R.A., Hirschler M.M.. Eur Polym J. 1984, 20(11), 1087-1093.
9. Marosi G., Marton A., Anna P., Bertalan G., Ceramic precursor in flame retardant systems, Polym Degrad Stab. 2002, 77(2), 259-265.
10. Marosi G., Anna P., Marton A., Bertalan G.. Polym Adv Technol 2002, 13, 1103-1111.
11. Wilson J.O.C., et al., Surface and interfacial properties of polymer-intercalated layered double hydroxide nanocomposites. Appl Clay Sci. 1999, 15, 265-279.
12. Vaccari A., Clays and catalysis: a promising future, Appl Clay Sci. 1999, 14(4), 161-198.
13. Khan A.I., O`Hare D., Intercalation chemistry of layered double hydroxides: recent developments and applications. J Mater Chem. 2002, 12, 3191-3198.
14. Lerux F., Besse J.P., Polymer Interleaved Layered Double Hydroxide: A new emerging class of nanocomposites. Chem Mater. 2001, 13, 3507-3515.
15. 王玉忠 聚酯纤维阻燃化设计, 成都:四川科学技术出版社,1994.
16. 欧育湘,阻燃剂—制造、性能及应用,北京:兵器工业出版社,1997, 5.
17. 史翎,段雪,阻燃剂的发展及在塑料中的应用,塑料,2002, 31(3), 11-15.
18. Wang Z.Z., Qu B.J., Fan W.C., Huang P. Combustion characteristics of halogen-free flame-retarded polyethylene containing magnesium hydroxide and some synergists. J Appl Polym Sci. 2001, 81(1),206-214.
19. Lein Tange, Dieter Drohmann. Environmental issues related to end-of-life options of plastics containing brominated flame retardants. Fire and Mater. 2004, 28(5), 403-410.
20. 刘霞,阻燃剂的现状与发展趋势,广东化工,1999, 26(20), 111.
21. 陈宇,结合行业发展,推动助剂工业,塑料,2000, 29(5), 9.
22. Yang J.P., Brewer D.G., Venart J.E.S. Flame retardant polymeric materials, Fire and Mater. 1995, 15, 37-48.
23. 钱军民,李旭祥,聚乙烯改性研究进展,塑料,2001, 2(30), 38-41.
24. 肖鹏,腾人瑞,无卤阻燃原理及无毒阻燃技术的发展方向,阻燃材料与技术,1997, 1, 1-4.
25. 于永忠,吴启鸿,葛世成,阻燃材料手册,北京:群众出版社,1997
26. Innes J., Innes A., Compounding metal hydrate flame retardants. Plastics Additives and Compounding. 2002, April, 22-26.
27. 方征平,许承威,白雪冰,高填充聚乙烯/氢氧化铝体系的交联改性,中国塑料, 1998, 12(2), 49-51.
28. 王珂,李春江,HDPE/氢氧人镁复合体系力学性能及阻燃性的研究,塑料工业,1995, 5,34-38.
29. Shiinichi Akitaya, Toru Fukazawa. Flame retardant polypropylene resin composition, US 4966931, 1988. 83
30. 林明德,俞强等,LDPE熔融接枝的研究,塑料工业,1990, 1, 15-18.
31. 蓝方, 陈宁, 阻燃HDPE中氢氧化铝的表面处理和阻燃增效,塑料工业,1999, 27(1), 35-37.
32. Wu Q., Lü J.P., Qu B.J., Preparation and characterization of microcapsulated red phosphorus and its flame retardant mechanism in halogen-free flame retardant polyolefins, Polym Int. 2003, 52, 1326-1331.
33. Nishihara H. Interactions between phosphorous and nitrogen-containing flame retardants. Polymer J. 1998, 30(3), 163-170.
34. Edward N.P. Phosphorous flame retardants thermoplastics. J Appl Polym Sci. 1982, 20, 1680-1685.
35. Ulrike Braun, Bernhard Schartel. Flame Retardant Mechanisms of Red Phosphorus and Magnesium Hydroxide in High Impact Polystyrene. Macromolecular Chemistry and Physics.2004, 205(16), 2185-2196.
36. Baillet C., Gandi S., Fire retardants of polyethylene: study of a formulation involving phosphorous and polyol systems. Polym Degrad Stab. 1992, 35, 149-158
37. Prasad V.S., Pillai C.K.S., Flame retardation of polyethylene: Effect of a phosphorus flame retardant having both hydrophobic and hydrophilic groups in the same molecule. J Appl Polym Sci. 2000, 77, 2631-2640.
38. Camino G., Martinasso G., Costa L. Thermal degradation of penterythritol diphosphate. Polym Degrad Stab. 1990, 27, 285-296.
39. Camino G., Polym Degrad Stab. 1988, 20, 271-279
40. Zhang S., Horrocks A. R., Substantive intumescence from phosphorylated 1,3-propanediol derivatives substituted on to cellulose. J. Appl. Polym. Sci. 2003, 90, 3165-3172.
41. Duquesne S., Le Bras M., et al., X-ray photoelectron spectroscopy investigation of fire retarded polymeric materials: application to the study of an intumescent system, Polym Degrad Stab. 2002, 77, 203-211.
42. Nakayama, Y., Soeda, F., Ishitani, A. Carbon. 1990, 28: 21.
43. Pels, JR., Kapteijn, F., Moulijn, JA., Zhu, Q., Thomas, KM. Carbon. 1995, 33: 1641.
44. Le Bras M., Bourbigot S., In: Le Bras M., Camino G., Bourbigot S., Delobel R., Fire retardancy of polymers-the use of intumescence. Cambridge: The Royal Sociey of Chemistry, 1998, p.64.
45. Baljinder K.K., Horrocks A.R., Complex char formation in flame retarded fibre – intumescent combinations -Ⅱ. Thermal analytical studies, Polym. Degrad. Stab. 1996, 54(2-3), 289-303.
46. Camino G., Polym Degrad Stab. 1984, 4, 243-254.
47. Almeras X., Dabrowski F., Le Bras M., Poutch F., Bourbigot S., Marosi G., Anna P., Polym Degrad Stab. 2002, 77(2), 305-313.
48. Levchik G.F., Levchik S.V., Sachok P.D., Selevich A.F., Lyakhov A.S., Lesnikoovich AI. Thermal behaviour of ammonium polyphosphate-inorganic compound mixtures. Part 2. Manganese dioxide. Thermochim Acta. 1995, 257, 117-125.
49. 李伟,李晖,冯开才等, 高分子材料科学与工程, 1998, 14(3), 59.
50. Pearce M., Pure Appl. Chem. 1986, 58, 925-930.
51. Cost L., Polym Degrad Stab. 1989, 23, 259-269.
52. Le Bras M., Bourbigot S., Synergy in intumescence-application to cyclodextrin carbonization agent in intumescent additives for fire retardant polyethylene formulations. Polym Degrad Stab. 1997, 56, 11-21.
53. 李斌,张秀成,孙才英,淀粉对聚乙烯膨胀阻燃体系热降解和阻燃的影响,高分子材料科学与工程,2000, 16(2), 155-157.
54. Devaux E., Rochery M., Bourbigot S., Polyurethane/clay and polyurethane/POSS nanocomposites as flame retarded coating for polyester and cotton fabrics, Fire and Mater. 2002, 26(4-5), 149-154.
55. Scharff P., New carbon materials for research and technology, Carbon. 1998, 36(5- 6), 481- 486.
56. Qin L.C., Zhao x.l., et al, Materials science-The smallest carbon nanotube, Nature. 2000, 408, 50- 50.
57. Hamada Sawada N., et al., Phys Rev Lett. 1992, 68, 1579- 1581.
58. Sandler J., Shaffer M. S. P., Prasse T., et al., Development of a dispersion process for carbon nanotubes in an epoxy matrix and the resulting electrical properties, Polymer. 1999, 40(21), 5967- 5971.
59. Takashi, Eric Grulkd, Jenny Hilding, et al., Thermal degradation and flammability properties of polypropylene/carbon nanotube composites, Macromol Rapid Commun. 2002, 23, 761-765.
60. 欧育湘.未来的高效阻燃系统,化工进展,1998(4):14-16
61. Chine J C W, Kiang J Y. Macromol, 1980,13:280～288
62. A. W. Benbow, C. F. Cullis, H. S. Laver, Polymer 1978, 19, 824.
63. Bourgigot S., Le Bras M., Delobel R., Bréant P., Trémillon J.M., Zeolite: new synergistic agents for intumescent fire retardant thermoplastic formulations-criteria for the choice of the zeolite, Fire and Mater. 1996, 20(3), 145-154.
64. Bourgigot S., Le Bras M., Delobel R., Décressain R., Amoureux J.P., J Chem Soc Faraday Trans. 1996, 92(1), 149.
65. Le Bras M., Bourbigot S., Félix E., Pouille C.Siat, Traisnel M. Characterization of a polyamide-6-based intumescent additive for thermoplastic formulations. Polymer. 2000, 41, 5283-5296.
66. Cullis C F, Hirschler M M. Eur Polym J 1984; 20: 53-60.
67. Lewin M, Makoto E. Polym Adv Technol 2003; 14:3-11.
68. Verkade J G, Roynolds L I, J. Org. Chem., 1960,25:663
69. Brown, NMD., Hewitt, JA., Meenan, BJ. Surf. Interf. Anal. 1992, 18: 187.
70. 钟世云,许乾慰,王公善,聚合物降解与稳定化, 北京:化学工业出版社,2002, 3-5.
71. Kandola Horrocks S, Horrocks AR. Thermochim Acta. 1997,294:113.
72. X. Li, Y. X. Ou, Y. H. Zhang, D. J. Lian, Chin. Chem. Lett. 2000, 11, 887.
73. Y. G. Li, J. J. Wang, T. Han, Y. S. Liu, Acta. Chimica. Sinica. 1988, 46, 679
74. 化工百科全书(第10卷),北京:化学工业出版社,1996.
75. 徐旭荣,陈关喜,胡耿源等,磷杂螺环化合物的合成及表征. 精细化工 1997,(14): 35-38
76. Morice L, Bourbigot S and Leroy J-M, J Fire Sci 15:358-374(1997)
77. Zhu WM, Weil ED and Mukhopadhyay S, J Appl Polym Sci 62:2267-2280(1996),
78. Halpern Y, Mott DM and Niswarder RH, Ind Eng Chem Prod Res Dev 23:233-238(1984)
79. Chiang W-Y, Hu HC-H, J Appl Polym Sci 81:1125-1135(2001)
80. Le bras M, Bugajny M, Lefebvre J-M, Bourbigot S, Polym Int 49:1115-1124(2000)
81. Le Bras M and Bourbigot S, J Mater Sci 34:5777-5782(1999)
82. Wang Q, Chen YH, Liu Y, Yin H, Aelmans N, Kierkels R. Polym Int 53:439-448(2004)
83. Chen YH, Liu Y, Wang Q, Yin H, Aelmans N, Kierkels R. Polym Degrad Stab 81:215-224(2003)
84. Camino G, Costa L and Trossarelli L, Polym Degrad Stabil 8:13-22(1984)
85. Liu T.S., Wang C.S., Synergistic effect of a phosphorus-nitrogen flame retardant on engineering plastics, J Appl Polym Sci. 2004, 91(1), 410-417.
86. Marchal A., Delobel R., Le Bras M., Leroy J.M., Effect of intumescence on polymer degradation, Polym Degrad and Stab. 1994, 44, 263-272.
87. Bourbigot, S., Le Bras, M., Gengembre, L., Delobel, R. Appl. Surf. Sci.1994,81:299.
88. Hirschler M.M., Electric cable fire hazard assessment with the cone calorimeter, Fire hazard and fire risk assessment(ASTM STP 1150) 1992, 44-65, American society for testing and materials, Philadelphia.
89. Babrauskas V.,Peacock R.D. Heat release rate: the single most important variable in fire hazard, Fire Safety J. 1992, 18, 255-272.
90. Bourbigot, S., Le Bras, M., Delobel, R., Gengembre, L. Appl. Surf. Sci.1997,120: 15.
91. Elliot P.J., Whiteley R.H., A cone calorimeter test for the measurement of flammability properties of insulated wire. Polymer Testing. 1999, 64, 577-584.
92. Sekiguchi, Y., Frye, JS., Shafizadeh, F. J. Appl. Polym. Sci. 1983, 28: 31513
93. Wu, OH., Qu, BJ., Xu, YH., Wu, Q. Polym. Degrad. Stab. 2000, 68: 97
94. R. P. R. Ranaweera, G. Scott, Eur. Polym. J. 1976, 12, 825.
95. Zhu, SW., Shi, WF. Synthesis, characterization and flame retardancy of methacrylated phosphate/diphosphate. Polym. Int. 2004, 53: 266–271.
96. Bugajny M., Le Bras M., Bourbigot S., Thermoplastic polyurethanes as carbonization agents in intumescent blents. Part 2: thermal behavior of polypropylene/thermoplastic polyurethane/ammonium polyphosphate blends, J Fire Sci. 1999, 18, 7-26.
97. K. Ismet, G. Murat, Eur. Polym. J. 2004, 40, 2025.
98. M. Hasan, R. V. Adalet, Polym. Degrad. Stab. 2004, 83,255.
99. H. M. Cao, ‘‘Handbook of Inorganic Compounds’’, 1st edition, Chemical Industry Press, Beijing 1988.
100. Shih Y.C., Cheung F.B., Koo J.H., Theoretical modeling of intumescent fire-retardant materials, J Fire Sci. 1998, 16, 46-71.
101. N. S. Allen, “Degradation and Stabilization of Polyolefins”, Applied Science, New York 1983.
102. 舒中俊,漆宗能,聚合物及其复合材料火灾危险与对策, 工程塑料与应用, 1999, 11, 37-39.
103. Bourbigot S., Le Bras M., Duqesne S., Rochery M., Recent advances for intumescent polymers, Macromol Mater Eng. 2004, 289, 499-511.
104. 李斌,孙才英,张秀成,用锥形量热仪研究聚乙烯膨胀阻燃体系的燃烧性,高等学校化学学报,1999, 20(1), 146-149.
105. 欧育湘,陈宇,王晓梅,阻燃高分子材料,北京:国防工业出版社,2001.
106. 林建军,郑丽敏,傅岩,高等学校化学学报,1994(15)1110～1113
107. Jakab E., Uddin M.A., Bhaskar T., Sakata Y., Thermal decomposition of flame-retarded high-impact polystyrene, Journal of Analytical and Applied Pyrolysis, 2003, 68-69, 83-99.
108. Zhao H., Wang Y.Z., Wang D.Y., Wu B., Chen D.Q., Wang X.L., Yang K.K., Kinetics of thermal degradation of flame retardant copolyesters containing phosphorus linked pendent groups, Polym Degrad Stab. 2003, 80(1), 135-140.
109. Dahiya J.B., Rana S., Thermal degradation and morphological studies on cotton cellulose modified with various arylphosphorodichloridites, Polym Int. 2004, 53(7), 995-1002.
110. Lin C.H., Synthesis of novel phosphorus-containing cyanate esters and their curing reaction with epoxy resin, Polymer. 2004, 45, 7911-7926.
111. Wang J.Q., Du J.X., Zhu J., Wilkie C.A., An XPS study of the thermal degradation and flame retardant mechanism of polystyrene-clay nanocomposites, Polym Degrad Stab. 2002, 77(2), 249-252.
112. Miklós M., András T., Peter R. H., Paul A. C., Matthew Cross, Gy?rgy Marosi, XPS analysis of zinc hydroxystannate-coated hydrated fillers, Surface and Interface Analysis. 2002, 34(1), 735-739.
113. Wei P., Hao J.W., Du J.X., Han Z.D., Wang J.Q., An investigation on synergism of an intumescent flame retardant based on silica and alumina, J Fire Sci. 2003, 21(1), 17-28.
114. Marosi G., Anna P., Balogh I., et al., Thermoanalytical study of nucleating effects in polypropylene composites .3. Intumescent flame retardant containing polypropylene, Journal of Thermal Analysis. 1997, 48(4), 717-726.
115. Le Bras M., Bourbigot S., Delporte C., et al., New Intumescent Formulations of Fire-retardant Polypropylene - Discussion of the Free Radical Mechanism of the Formation of Carbonaceous Protective Material During the Thermo-oxidative Treatment of the Additives. Fire and Mater. 1996, 20(4), 191-203.
116. Ravadits, I., Tóth, A., Marosi, G., et al., Organosilicon surface layer on polyolefins to achieve improved flame retardancy through an oxygen barrier effect, Polym Degrad Stab. 2001, 74(3), 419-422.