新型石墨层间化合物的制备及其膨胀与阻燃机理的研究
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摘要
以硫酸为插层剂所制造的一类石墨层间化合物(硫酸-GIC)作为膨胀型阻燃剂获得了广泛的研究和应用。尽管此类GIC具有良好的阻燃性能,但在很多实际应用中,阻燃能力仍显不足,而且,较低的初始膨胀温度也在一定程度上限制了它在聚合物阻燃领域中的应用。迄今,有关GIC用作阻燃剂的试验结果均来自于硫酸-GIC,有关其他化合物插层GIC的阻燃性能与阻燃机理的研究极少。
本文期望能够通过对不同化合物插层GIC的膨胀与阻燃性能的研究,提高GIC的初始膨胀温度,改善其阻燃性能。为此,本文利用正交实验设计方法对直接插层法和分步插层法制备GIC的反应因素进行了研究,通过GIC的结构和膨胀体积的分析,确立了制备硝酸盐-硫酸-GIC和含磷化合物-硫酸-GIC的较佳反应条件,分析了石墨插层反应原理,探讨了膨胀体积的影响因素,以及GIC的膨胀原理,并将所制备的GIC用于阻燃聚乙烯,对其阻燃性能及其阻燃机理进行了研究,确定了影响GIC膨胀及阻燃性能的关键因素。
本文的研究结果表明,通过选择插层剂的热稳定性和氧化性、采用不同插层方法调整GIC的阶结构能够控制GIC的初始膨胀温度、热稳定性、膨胀体积等重要性能参数;所研究的分步插层法更适于制备多元GIC,所制备的GIC具有更低阶结构,其膨胀体积与热稳定性均优于直接插层法所制备的产物;由此制备的含有不同插层剂的GIC具有不同的阻燃性能,其中,多聚磷酸铵-硫酸-GIC因具有自协同阻燃作用而表现出较高阻燃性能;TG-FTIR的试验结果证明,GIC的膨胀机理的关键在于膨胀过程中发生的氧化还原反应,其阻燃机理主要在于形成膨胀石墨阻挡层和促进聚合物成炭的作用。
Graphite intercalation compounds (GIC) intercalated with sulphuric acid (SA-GIC) were widely used as intumescent flame retardants, but such GIC showed limited applications in flame retardant polymers because of the lower flame retardant properties and the lower initial expansion temperature. By now, few literatures have been delivered on the flame retardant properties and flame retardant mechanism of GIC intercalated with other compounds.
The paper aims at the preparation of GIC intercalated with different compounds and the investigation of their flame retardant properties and flame retardant mechanism. For that, direct and two-step intercalation methods were used to prepare GIC. According to the results of orthogonal experiments, the optimal reaction conditions were obtained to prepare nitrate-sulphuric acid-GIC and phosphorous compounds-sulphuric acid-GIC. The structure and expansion volume of GIC were analyzed by means of XRD, SEM, XPS and EDS, based on the results of which, the intercalation theory and expansion process were proposed. GICs as prepared were applied in flame retardant polyethylene (PE) whose flame retardant properties and mechanism were studied. As a result, the key factors on expansion properties and flame retardant properties were determined.
The following results can be concluded. Initial expansion temperature, thermal stability and expansion volume of GIC can be controlled by stage structure of GIC and intercalating agents. Compared with direct method, two-step one was in favor of the preparation of muli-components GIC with lower stage structure and better expansion properties. GIC with different intercalating agents possessed different flame retardant properties, among which ammonium polyphosphate-sulphuric acid-GIC had the best flame retardant properties because of its self-synergistic effect. GIC underwent redox process during its expansion. The flame retardant mechanism of GIC can be attributed to two main factors, that is expanded graphite layers formed during expansion of GIC and enhanced charring process by GIC.
本文期望能够通过对不同化合物插层GIC的膨胀与阻燃性能的研究,提高GIC的初始膨胀温度,改善其阻燃性能。为此,本文利用正交实验设计方法对直接插层法和分步插层法制备GIC的反应因素进行了研究,通过GIC的结构和膨胀体积的分析,确立了制备硝酸盐-硫酸-GIC和含磷化合物-硫酸-GIC的较佳反应条件,分析了石墨插层反应原理,探讨了膨胀体积的影响因素,以及GIC的膨胀原理,并将所制备的GIC用于阻燃聚乙烯,对其阻燃性能及其阻燃机理进行了研究,确定了影响GIC膨胀及阻燃性能的关键因素。
本文的研究结果表明,通过选择插层剂的热稳定性和氧化性、采用不同插层方法调整GIC的阶结构能够控制GIC的初始膨胀温度、热稳定性、膨胀体积等重要性能参数;所研究的分步插层法更适于制备多元GIC,所制备的GIC具有更低阶结构,其膨胀体积与热稳定性均优于直接插层法所制备的产物;由此制备的含有不同插层剂的GIC具有不同的阻燃性能,其中,多聚磷酸铵-硫酸-GIC因具有自协同阻燃作用而表现出较高阻燃性能;TG-FTIR的试验结果证明,GIC的膨胀机理的关键在于膨胀过程中发生的氧化还原反应,其阻燃机理主要在于形成膨胀石墨阻挡层和促进聚合物成炭的作用。
Graphite intercalation compounds (GIC) intercalated with sulphuric acid (SA-GIC) were widely used as intumescent flame retardants, but such GIC showed limited applications in flame retardant polymers because of the lower flame retardant properties and the lower initial expansion temperature. By now, few literatures have been delivered on the flame retardant properties and flame retardant mechanism of GIC intercalated with other compounds.
The paper aims at the preparation of GIC intercalated with different compounds and the investigation of their flame retardant properties and flame retardant mechanism. For that, direct and two-step intercalation methods were used to prepare GIC. According to the results of orthogonal experiments, the optimal reaction conditions were obtained to prepare nitrate-sulphuric acid-GIC and phosphorous compounds-sulphuric acid-GIC. The structure and expansion volume of GIC were analyzed by means of XRD, SEM, XPS and EDS, based on the results of which, the intercalation theory and expansion process were proposed. GICs as prepared were applied in flame retardant polyethylene (PE) whose flame retardant properties and mechanism were studied. As a result, the key factors on expansion properties and flame retardant properties were determined.
The following results can be concluded. Initial expansion temperature, thermal stability and expansion volume of GIC can be controlled by stage structure of GIC and intercalating agents. Compared with direct method, two-step one was in favor of the preparation of muli-components GIC with lower stage structure and better expansion properties. GIC with different intercalating agents possessed different flame retardant properties, among which ammonium polyphosphate-sulphuric acid-GIC had the best flame retardant properties because of its self-synergistic effect. GIC underwent redox process during its expansion. The flame retardant mechanism of GIC can be attributed to two main factors, that is expanded graphite layers formed during expansion of GIC and enhanced charring process by GIC.
引文
1 李士贤,姚建,林定浩.石墨.北京:化学工业出版社,1991:34
2 倪文,李建平等.矿物材料学导论.北京:科学出版社,1998:223
3 赖盛刚,奚晕.膨胀石墨密封材料及其制品.北京:中国石化出版社,1994:20
4 Duquesne s,Bourbigot S,Bourbigot S.Thermal Degradation of Polyurethane and Polyurethane/Expandable Graphite Coatings.Polymer Degradation and Stability,2001,74:493-499
5 黄颖霞,周宁琳,李利等.石墨层间化合物的合成及其结构研究.南京师大学报(自然科学版),2005,(4):57-59
6 关正辉.石墨层间化合物的特性及应用前景.甘肃科技,2002,(10):48-49
7 时虎.石墨的开发及其应用.化工科技,2001,12:24-27
8 金为群,张华蓉,权新军等.石墨插层复合材料制备及应用现状.中国非金属矿工业导刊,2005,4(48):8-12
9 卢锦花,李贺军.石墨层间化合物的制备、结构与应用.炭素技术,2003,(1):21-24
10 时虎,胡源,赵华伟.石墨层间化合物在阻燃防火上的应用.非金属矿,2001,24(5):31-33
11 Jin Tong-Shou,MA Yan-Ran,Li Tong-Shang.An efficient and simple procedure for acylation of alcohols and phenols with acetic anhydride catalysed by expansive graphite.Indian Journal of Chemistry,1999,38B:109-110
12 张进.可膨胀微粉石墨的制备及应用.南京理工大学硕士论文,2005
13 陈志刚,张勇,杨娟等.膨胀石墨的制备、结构和应用.江苏大学学报(自然科学版),2005,26(3):248-252
14 M S Dresselhaus,G Dresslhaus.Intercalation compounds of graphite.Advanced in Physics,1981,30(2):139-326
15 N Daumas,A Herold.Domain model of graphite intercalation compounds in higher stage.C.R.Acad.Sci.Ser.C.1969,268:272-378
16 Hawrylak P,Subbaswamy K R.Kinetic model of stage transformation and intercalation in graphite.Phys Rev Lett,1984,53(22):2098-2101
17 吴翠玲,翁文桂等.膨胀石墨的多层次结构.华侨大学学报(自然科学版),2003,24(2):147-150
18 陈宇飞.可膨胀石墨生产中的技术问题探讨.炭素,1996,2:38-40
19 于仁光.乔小晶等.低硫可膨胀石墨制备新工艺.精细石油化工进展,2003,4(10):8-10
20 Reinheimer Arne,Wenzel Antje.Expandable graphite intercalation compounds,method for synthesizing them and their use.US 7118725,2006
21 Kaschak David M,Robert A,et al.Graphite intercalation and exfoliation process.US 7105108,2006
22 Barsukov Igor V,Zaleski Peter L.Method of preparing graphite intercalation compounds and resultant products.US 6756027,2004
23 Greinke Ronald Alfred,Intercalated graphite flakes exhibiting improved expansion characteristics and process therefore.US 6669919,2003
24 Greinke Ronald Alfred,Robert Anderson.Expandable graphite and method.US 6416815,2002
25 M Inagaki.Applications of graphite intercalation compounds.J.Mater.Res,1989,4(6):1560-1568
26 M Posternak,A Baldereschi,et al.Prediction of Electronic Interlayer States in Graphite and Reinterpretation of Alkali Bands in Graphite Intercalation Compounds.Phys.Rev.Lett.,1983,50(10):761-764
27 Tsutomu Ohzuku,Yasunobu Iwakoshi,Keijiro Sawai.Formation of Lithium-Graphite Intercalation Compounds in Nonaqueous Electrolytes and Their Application as a Negative Electrode for a Lithium Ion(Shuttlecock) Cell.J.Electrochem.Soc.,1993,140(9):2490-2498
28 Chung D.D.L.Flexible Graphite for Gasketing,Adsorption,Electromagnetic Interference Shielding,Vibration Damping,Electrochemical Applications,and Stress Sensing.Journal of Materials Engineering and Performance,2000,9(2):161-163
29 Robert Angelo Mercuri,Jeffrey John Gough.Flexible graphite composite for use in the form of a fuel cell flow field plate.US 6037074,1998
30 Yang L,Jialin G,Wenquan C,Zhang T.Influences of density and flake size on the mechanical properties of flexible graphite.Carbon,1998,36(7):875-881
31 Robert Schlogl,Harald Werner,Michael Wohlers.Metal-fullerene intercalation compounds,process for their preparation and use as catalysts.US 5523438,1996
32 M S.Dresselhaus,G Dresselhaus.Intercalation compounds of graphite.Advances in Physics,2002,51(1):1-186
33 Emmanuelle Alain,Dominique Begin,et al.Pyrolysis of coal tar pitch mixed in the presence of a graphite intercalation compound:A kinetic study.Fuel,1998,77(6):533-541
34 中岛刚,杨学元.石墨层间化合物的功能和应用.新型碳材料,1993,(3):26-29
35 方守狮,董远达.高容量贮氢材料的最新进展.自然杂志,2001,23(5):259-261
36 边福利,陈栋梁等.无卤膨胀型防火密封胶的研究.消防科学与技术,2004,23(4):379-381
37 时虎,赵华伟.石墨插层化合物的合成及在塑料阻燃中的应用.消防技术与产品信息,2001,(10):27-31
38 康飞宇.石墨层间化合物和膨胀石墨.新型碳材料,2000,15(4):80
39 于仁光,乔小晶等.新型环保材料膨胀石墨的电化学法制备及性能.化工生产与技术,2003,10(6):6-8
40 Xie Hai-ming,Yan Xue-dong,et al.A New Tin Graphite Intercalation Compound for Lithium Ion Batteries.Chemical Research in Chinese University,2006,10(5):639-642
41 M Noel,R Santhanam.Electrochemistry of graphite intercalation compounds.Journal of Power Sources,1998,72(1):53-65
42 M Endo,C Kim,K Nishimura,et al.Recent development of carbon materials for Li ion batteries.Carbon,2000,38:183-197
43 田金星,杨华.柔性石墨功能材料的应用研究.矿产保护与利用,1999,(5):14-17
44 于德胜.柔性石墨—新型的发热材料.建材工业信息,1998,(4):40-41
45 于仁光,乔小晶.纳米复合材料——可膨胀石墨的合成及应用.材料导报,2003,17(9):125-126
46 任京成,沈万慈.柔性石墨材料和膨胀石墨材料的现状及发展趋势.非金属矿,1999,22(5):5-7.
47 沈万慈,祝力.石墨层间化合物(GICs)材料的研究动向与展望.炭素技术,1993,(6):26-32
48 邢玉梅,田军.稀土—石墨层间化合物的合成和应用前景.稀土,2000,21(6):52-57
49 薛恩钰.曾敏修.阻燃科学及应用.北京:国防工业出版社,1988.264
50 Schilling B.Expandierbarer graphit:Ein physikalisch wirkender D(a|¨)mmschichtbildner als Brandschutz.Kunststoffe,1997,87(8):1004-1006
51 欧育湘.阻燃剂——制造、性能及应用.北京:兵器工业出版社,1997.169
52 张旭东.张玉军等.无机非金属材料学.济南:山东大学出版社,2000.309
53 J BEYER,HG von REICHENBACH.An extended revision of the interlayer structures of one-and two-layer hydrates of Na-vermiculite.Clay minerals,2002,37(1):157-168
54 M Roulia,K Chassapis,et al.Dispersion and Sorption of Oil Spills by Emulsifier-Modified Expanded Perlite.Spill science and technology bulletin,2003,8(5-6):425-431
55 倪文.李建平等.矿物材料学导论.北京:科学出版社,1998.223
56 时虎,赵华伟.可膨胀石墨的合成及其阻燃应用.阻燃材料与技术,2002,(3):6-15
57 Heitmann U,Rossel H.Process for preparing a flame-resistant,elastic soft polyurethane foam.US 5192811,1993
58 Terao M,Tsujimoto M.Flame-retardant polyethylene compositon.JP 09059439,1997
59 Okisaki F,Hamada A.Fire-retardant polymer composition.US 5760115,1998
60 Okisaki F.Hamada A,et al.Fire-retardant polymer composition.US 5942561,1999
61 Modesti M.Lorenzetti A.Expandable graphite as an intumescent flame retardant in polyisocyanurate-polyurethane foams,polymer degradation and stability,2002,77(2):195-202
62 Okisaki F.Hamada A.Obasa M.Flame-retardant engineering plastic composition.US 5810914,1998
63 Knox C L.Intumescent nonhalogenated flame retardant polystyrene composition.US 5414031,1995
64 Shen K.Schilling B.RECENT ADVANCES WITH EXPANDABLE GRAPHITE IN INTUMESCENT FLAME RETARDANT TECHNOLOGY.www.nyacol.com
65 Li Z.Qu B.Flammability characterization and synergistic effects of expandable graphite with magnesium hydroxide in halogen-free flame-retardant EVA blends.Polymer degradation and stability,2003,81(3):401-408
66 Dietzen Franz-Josef,Gluck Guiscard.Flame-proofed polystyrene foamed materials.US 6420442,2002
67 Burgun Sandrine,Kammerer Jonathan,et al.Fire resistance acoustic foam.US 7144925,2006
68 Wallace W R.Baumforth R J,et al.Flame retardant flexible foam.US 5719199,1998
69 Wallace W R.Baumforth R J.Flame retardant flexible foam.US 5650448,1996
70 Xie R C.Expandable Graphite Systems for Halogen-Free Flame-Retarding of Polyolefins.I.Flammability Characterization and Synergistic Effect.Journal of Applied Polymer Science,2001,80:1181-1189
71 Duquesne S,Bourbigot S,Bourbigot S.Expandable Graphite:a Fire Retardant Additive for Polyurethane Coatings.Fire and Materials,2003,27(3):103-117
72 Chuang T H,Guo W J,Guo W J.Application of Expandable Graphite as a Flame Retardant and Smoke-Suppressing Additive for Ethylene-Propylene-Dieneterpolymer.Journal of Polymer Research,1997,4(3): 153-158
73 王建祺等.无卤阻燃聚合物基础与应用.北京:科学出版社,2005
74 Reinheimer A.Wenzel A.Expandable graphite intercalation compounds,method for synthesizing them and their use.US 20030157015,2003
75 Wang J Q.Han Z D.In:M Le Bras et al.Fire retardancy of polymer.American Chemical Society,2004:161-176
76 Wang J Q.Han Z D.TGA-FTIR Study on Thermal Degradation and Flammability of Polymer Layered Graphite Oxide(PLGO) Composites.Presented at 228th ACS meeting,2004
77 朱继平.硫酸石墨插层化合物的物性研究.合肥工业大学学报:自然科学版,2001,24(6):1158-1162
78 勒通收,马艳然.可膨胀石墨的制备.无机化学学报,1997,13(2):231-233
79 Herold A,Petitjean D,et al.Exfoliation of graphite intercalation compounds:classification and discussion of the processes from new experimental data relative to graphite-acid compounds.Materials science forum,1994,152-153:281
80 Camino G,Delobel R,Delobel R.Mechanism of Expandable Graphite Fire Retardant Action in Polyurethanes.Fires and Polymers:Materials and Solutions for Hazard Prevention(Symposium Seres No.797)
2 倪文,李建平等.矿物材料学导论.北京:科学出版社,1998:223
3 赖盛刚,奚晕.膨胀石墨密封材料及其制品.北京:中国石化出版社,1994:20
4 Duquesne s,Bourbigot S,Bourbigot S.Thermal Degradation of Polyurethane and Polyurethane/Expandable Graphite Coatings.Polymer Degradation and Stability,2001,74:493-499
5 黄颖霞,周宁琳,李利等.石墨层间化合物的合成及其结构研究.南京师大学报(自然科学版),2005,(4):57-59
6 关正辉.石墨层间化合物的特性及应用前景.甘肃科技,2002,(10):48-49
7 时虎.石墨的开发及其应用.化工科技,2001,12:24-27
8 金为群,张华蓉,权新军等.石墨插层复合材料制备及应用现状.中国非金属矿工业导刊,2005,4(48):8-12
9 卢锦花,李贺军.石墨层间化合物的制备、结构与应用.炭素技术,2003,(1):21-24
10 时虎,胡源,赵华伟.石墨层间化合物在阻燃防火上的应用.非金属矿,2001,24(5):31-33
11 Jin Tong-Shou,MA Yan-Ran,Li Tong-Shang.An efficient and simple procedure for acylation of alcohols and phenols with acetic anhydride catalysed by expansive graphite.Indian Journal of Chemistry,1999,38B:109-110
12 张进.可膨胀微粉石墨的制备及应用.南京理工大学硕士论文,2005
13 陈志刚,张勇,杨娟等.膨胀石墨的制备、结构和应用.江苏大学学报(自然科学版),2005,26(3):248-252
14 M S Dresselhaus,G Dresslhaus.Intercalation compounds of graphite.Advanced in Physics,1981,30(2):139-326
15 N Daumas,A Herold.Domain model of graphite intercalation compounds in higher stage.C.R.Acad.Sci.Ser.C.1969,268:272-378
16 Hawrylak P,Subbaswamy K R.Kinetic model of stage transformation and intercalation in graphite.Phys Rev Lett,1984,53(22):2098-2101
17 吴翠玲,翁文桂等.膨胀石墨的多层次结构.华侨大学学报(自然科学版),2003,24(2):147-150
18 陈宇飞.可膨胀石墨生产中的技术问题探讨.炭素,1996,2:38-40
19 于仁光.乔小晶等.低硫可膨胀石墨制备新工艺.精细石油化工进展,2003,4(10):8-10
20 Reinheimer Arne,Wenzel Antje.Expandable graphite intercalation compounds,method for synthesizing them and their use.US 7118725,2006
21 Kaschak David M,Robert A,et al.Graphite intercalation and exfoliation process.US 7105108,2006
22 Barsukov Igor V,Zaleski Peter L.Method of preparing graphite intercalation compounds and resultant products.US 6756027,2004
23 Greinke Ronald Alfred,Intercalated graphite flakes exhibiting improved expansion characteristics and process therefore.US 6669919,2003
24 Greinke Ronald Alfred,Robert Anderson.Expandable graphite and method.US 6416815,2002
25 M Inagaki.Applications of graphite intercalation compounds.J.Mater.Res,1989,4(6):1560-1568
26 M Posternak,A Baldereschi,et al.Prediction of Electronic Interlayer States in Graphite and Reinterpretation of Alkali Bands in Graphite Intercalation Compounds.Phys.Rev.Lett.,1983,50(10):761-764
27 Tsutomu Ohzuku,Yasunobu Iwakoshi,Keijiro Sawai.Formation of Lithium-Graphite Intercalation Compounds in Nonaqueous Electrolytes and Their Application as a Negative Electrode for a Lithium Ion(Shuttlecock) Cell.J.Electrochem.Soc.,1993,140(9):2490-2498
28 Chung D.D.L.Flexible Graphite for Gasketing,Adsorption,Electromagnetic Interference Shielding,Vibration Damping,Electrochemical Applications,and Stress Sensing.Journal of Materials Engineering and Performance,2000,9(2):161-163
29 Robert Angelo Mercuri,Jeffrey John Gough.Flexible graphite composite for use in the form of a fuel cell flow field plate.US 6037074,1998
30 Yang L,Jialin G,Wenquan C,Zhang T.Influences of density and flake size on the mechanical properties of flexible graphite.Carbon,1998,36(7):875-881
31 Robert Schlogl,Harald Werner,Michael Wohlers.Metal-fullerene intercalation compounds,process for their preparation and use as catalysts.US 5523438,1996
32 M S.Dresselhaus,G Dresselhaus.Intercalation compounds of graphite.Advances in Physics,2002,51(1):1-186
33 Emmanuelle Alain,Dominique Begin,et al.Pyrolysis of coal tar pitch mixed in the presence of a graphite intercalation compound:A kinetic study.Fuel,1998,77(6):533-541
34 中岛刚,杨学元.石墨层间化合物的功能和应用.新型碳材料,1993,(3):26-29
35 方守狮,董远达.高容量贮氢材料的最新进展.自然杂志,2001,23(5):259-261
36 边福利,陈栋梁等.无卤膨胀型防火密封胶的研究.消防科学与技术,2004,23(4):379-381
37 时虎,赵华伟.石墨插层化合物的合成及在塑料阻燃中的应用.消防技术与产品信息,2001,(10):27-31
38 康飞宇.石墨层间化合物和膨胀石墨.新型碳材料,2000,15(4):80
39 于仁光,乔小晶等.新型环保材料膨胀石墨的电化学法制备及性能.化工生产与技术,2003,10(6):6-8
40 Xie Hai-ming,Yan Xue-dong,et al.A New Tin Graphite Intercalation Compound for Lithium Ion Batteries.Chemical Research in Chinese University,2006,10(5):639-642
41 M Noel,R Santhanam.Electrochemistry of graphite intercalation compounds.Journal of Power Sources,1998,72(1):53-65
42 M Endo,C Kim,K Nishimura,et al.Recent development of carbon materials for Li ion batteries.Carbon,2000,38:183-197
43 田金星,杨华.柔性石墨功能材料的应用研究.矿产保护与利用,1999,(5):14-17
44 于德胜.柔性石墨—新型的发热材料.建材工业信息,1998,(4):40-41
45 于仁光,乔小晶.纳米复合材料——可膨胀石墨的合成及应用.材料导报,2003,17(9):125-126
46 任京成,沈万慈.柔性石墨材料和膨胀石墨材料的现状及发展趋势.非金属矿,1999,22(5):5-7.
47 沈万慈,祝力.石墨层间化合物(GICs)材料的研究动向与展望.炭素技术,1993,(6):26-32
48 邢玉梅,田军.稀土—石墨层间化合物的合成和应用前景.稀土,2000,21(6):52-57
49 薛恩钰.曾敏修.阻燃科学及应用.北京:国防工业出版社,1988.264
50 Schilling B.Expandierbarer graphit:Ein physikalisch wirkender D(a|¨)mmschichtbildner als Brandschutz.Kunststoffe,1997,87(8):1004-1006
51 欧育湘.阻燃剂——制造、性能及应用.北京:兵器工业出版社,1997.169
52 张旭东.张玉军等.无机非金属材料学.济南:山东大学出版社,2000.309
53 J BEYER,HG von REICHENBACH.An extended revision of the interlayer structures of one-and two-layer hydrates of Na-vermiculite.Clay minerals,2002,37(1):157-168
54 M Roulia,K Chassapis,et al.Dispersion and Sorption of Oil Spills by Emulsifier-Modified Expanded Perlite.Spill science and technology bulletin,2003,8(5-6):425-431
55 倪文.李建平等.矿物材料学导论.北京:科学出版社,1998.223
56 时虎,赵华伟.可膨胀石墨的合成及其阻燃应用.阻燃材料与技术,2002,(3):6-15
57 Heitmann U,Rossel H.Process for preparing a flame-resistant,elastic soft polyurethane foam.US 5192811,1993
58 Terao M,Tsujimoto M.Flame-retardant polyethylene compositon.JP 09059439,1997
59 Okisaki F,Hamada A.Fire-retardant polymer composition.US 5760115,1998
60 Okisaki F.Hamada A,et al.Fire-retardant polymer composition.US 5942561,1999
61 Modesti M.Lorenzetti A.Expandable graphite as an intumescent flame retardant in polyisocyanurate-polyurethane foams,polymer degradation and stability,2002,77(2):195-202
62 Okisaki F.Hamada A.Obasa M.Flame-retardant engineering plastic composition.US 5810914,1998
63 Knox C L.Intumescent nonhalogenated flame retardant polystyrene composition.US 5414031,1995
64 Shen K.Schilling B.RECENT ADVANCES WITH EXPANDABLE GRAPHITE IN INTUMESCENT FLAME RETARDANT TECHNOLOGY.www.nyacol.com
65 Li Z.Qu B.Flammability characterization and synergistic effects of expandable graphite with magnesium hydroxide in halogen-free flame-retardant EVA blends.Polymer degradation and stability,2003,81(3):401-408
66 Dietzen Franz-Josef,Gluck Guiscard.Flame-proofed polystyrene foamed materials.US 6420442,2002
67 Burgun Sandrine,Kammerer Jonathan,et al.Fire resistance acoustic foam.US 7144925,2006
68 Wallace W R.Baumforth R J,et al.Flame retardant flexible foam.US 5719199,1998
69 Wallace W R.Baumforth R J.Flame retardant flexible foam.US 5650448,1996
70 Xie R C.Expandable Graphite Systems for Halogen-Free Flame-Retarding of Polyolefins.I.Flammability Characterization and Synergistic Effect.Journal of Applied Polymer Science,2001,80:1181-1189
71 Duquesne S,Bourbigot S,Bourbigot S.Expandable Graphite:a Fire Retardant Additive for Polyurethane Coatings.Fire and Materials,2003,27(3):103-117
72 Chuang T H,Guo W J,Guo W J.Application of Expandable Graphite as a Flame Retardant and Smoke-Suppressing Additive for Ethylene-Propylene-Dieneterpolymer.Journal of Polymer Research,1997,4(3): 153-158
73 王建祺等.无卤阻燃聚合物基础与应用.北京:科学出版社,2005
74 Reinheimer A.Wenzel A.Expandable graphite intercalation compounds,method for synthesizing them and their use.US 20030157015,2003
75 Wang J Q.Han Z D.In:M Le Bras et al.Fire retardancy of polymer.American Chemical Society,2004:161-176
76 Wang J Q.Han Z D.TGA-FTIR Study on Thermal Degradation and Flammability of Polymer Layered Graphite Oxide(PLGO) Composites.Presented at 228th ACS meeting,2004
77 朱继平.硫酸石墨插层化合物的物性研究.合肥工业大学学报:自然科学版,2001,24(6):1158-1162
78 勒通收,马艳然.可膨胀石墨的制备.无机化学学报,1997,13(2):231-233
79 Herold A,Petitjean D,et al.Exfoliation of graphite intercalation compounds:classification and discussion of the processes from new experimental data relative to graphite-acid compounds.Materials science forum,1994,152-153:281
80 Camino G,Delobel R,Delobel R.Mechanism of Expandable Graphite Fire Retardant Action in Polyurethanes.Fires and Polymers:Materials and Solutions for Hazard Prevention(Symposium Seres No.797)
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