无卤阻燃改性聚乙烯的研究
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摘要
聚乙烯(PE)是一类生产量大、用途广泛的通用塑料。其制成品从薄膜、日用品、管材到电线电缆护套等等随处可见。但是PE的氧指数仅为17.3,属于易燃材料,且燃烧时产生熔滴,不易熄灭,极易造成火灾,对人们的生命和财产安全形成巨大的威胁。其制品在高层建筑、煤矿、地铁隧道及大型船舶等许多领域的应用受到限制,因此聚乙烯的阻燃改性研究受到广泛关注。由于含卤阻燃剂有诸多不利因素,而无卤阻燃剂有更好的发展前景,于是,本论文采用无卤阻燃技术对PE进行阻燃改性研究。
论文采用氧指数试验、水平燃烧试验作为考查阻燃性能的手段;以试样的拉伸强度和冲击强度评定力学性能;以挤出机的主电机电流及机头压力考查加工性能。以三聚氰胺、纤维、季戊四醇硬脂酸酯为基本组分。
结合各种基本组分单独对聚乙烯阻燃性能、力学性能、加工性能的影响,获得了每种阻燃剂在聚乙烯中的适宜添加量。
研究由基本组分构成的两组复合阻燃体系的综合性能,获得了每组体系中各组分的合适配比。
研究硅烷对聚乙烯/纤维体系阻燃性能的影响,得到了其适宜用量。
研究氧化锌对聚乙烯复合体系的影响,获得了它与其余基本组分的恰当配比。
氧指数试验说明了聚乙烯接枝马来酸酐和三聚氰胺复合对聚乙烯有阻燃作用,并用红外光谱试验证实生成了新基团,两者发生交联反应,促进成炭起到阻燃作用。
Polyethylene(PE) is a kind of general plastic which has been produced in bulk and used widely. Its products include film,daily-appliance,pipe,cable and wire,etc.However PE has only a limiting oxygen index(LOI) value of 17.3 and is flammable and there is a great deal of flux-drop when PE is being burned,which is easy to bring about fire. This is a threat to people and property. PE has been limited in many fields such as high building,coal mineral,subway,great ship,etc.So many reseachers keep a close watch on study on PE modified by flame retardant.As a result of many disadvantages of halogen flame retardant and excellent prospect of non-halogen flame retardant, non-halogen flame retardant methods were used to modify PE in this paper.
LOI and horizontal burning velocity were used as main measures to test the flame retardancy of materials;tensile strength and impact strength were done to estimate mechanical property of materials; main-moter current and mould pressure of the intruder were recorded to test processability.
Melamine,fiber and pentaerythritol stearate are the basic ingredient.
The suitable dosage in PE of each basic ingredient was obtained by combining the influence of them on flame retardancy , mechanical property and processability of PE respectively.
The suitable proportion of components in two sets of complex systems were obtained by studying composite properties.
The effect of silane coupler on flame retardancy of PE/fiber system was studied to obtain its suitable dosage.
The influence of zinc oxide on flame retardancy of PE complex system was studied in order to obtain suitable proportion of components.
The result of LOI showed that the PE-g-MAH combining with melamine had a role of flame retardation on PE.Also infrared spectroscopy bore out that they generated crosslinking reaction,which accelerated char-forming and arised from flame retarded effect.
论文采用氧指数试验、水平燃烧试验作为考查阻燃性能的手段;以试样的拉伸强度和冲击强度评定力学性能;以挤出机的主电机电流及机头压力考查加工性能。以三聚氰胺、纤维、季戊四醇硬脂酸酯为基本组分。
结合各种基本组分单独对聚乙烯阻燃性能、力学性能、加工性能的影响,获得了每种阻燃剂在聚乙烯中的适宜添加量。
研究由基本组分构成的两组复合阻燃体系的综合性能,获得了每组体系中各组分的合适配比。
研究硅烷对聚乙烯/纤维体系阻燃性能的影响,得到了其适宜用量。
研究氧化锌对聚乙烯复合体系的影响,获得了它与其余基本组分的恰当配比。
氧指数试验说明了聚乙烯接枝马来酸酐和三聚氰胺复合对聚乙烯有阻燃作用,并用红外光谱试验证实生成了新基团,两者发生交联反应,促进成炭起到阻燃作用。
Polyethylene(PE) is a kind of general plastic which has been produced in bulk and used widely. Its products include film,daily-appliance,pipe,cable and wire,etc.However PE has only a limiting oxygen index(LOI) value of 17.3 and is flammable and there is a great deal of flux-drop when PE is being burned,which is easy to bring about fire. This is a threat to people and property. PE has been limited in many fields such as high building,coal mineral,subway,great ship,etc.So many reseachers keep a close watch on study on PE modified by flame retardant.As a result of many disadvantages of halogen flame retardant and excellent prospect of non-halogen flame retardant, non-halogen flame retardant methods were used to modify PE in this paper.
LOI and horizontal burning velocity were used as main measures to test the flame retardancy of materials;tensile strength and impact strength were done to estimate mechanical property of materials; main-moter current and mould pressure of the intruder were recorded to test processability.
Melamine,fiber and pentaerythritol stearate are the basic ingredient.
The suitable dosage in PE of each basic ingredient was obtained by combining the influence of them on flame retardancy , mechanical property and processability of PE respectively.
The suitable proportion of components in two sets of complex systems were obtained by studying composite properties.
The effect of silane coupler on flame retardancy of PE/fiber system was studied to obtain its suitable dosage.
The influence of zinc oxide on flame retardancy of PE complex system was studied in order to obtain suitable proportion of components.
The result of LOI showed that the PE-g-MAH combining with melamine had a role of flame retardation on PE.Also infrared spectroscopy bore out that they generated crosslinking reaction,which accelerated char-forming and arised from flame retarded effect.
引文
[1]徐应麟等.高聚物材料的实用阻燃技术[M].北京:化学工业出版社,1987:199,54.
[2]张军等.聚合物燃烧与阻燃技术[M].北京:化学工业出版社,2005:1,118,41.
[3]欧育湘等.阻燃高分子材料[M].北京:国防工业出版社,2001:56.
[4]陈卫等.阻燃剂的微胶囊化[J].阻燃材料与技术,1998,1:1-3
[5]于永忠等.阻燃材料手册[M].北京:群众出版社,1997:264.
[6] Chang,T.M. ed Norman,N.Li.,Resent Development in Separation Science,The Chemical Rubber Co.USA,1972,1.
[7]葛世成.塑料阻燃实用技术[M].北京:化学工业出版社,2004:205.
[8]鲍治宇等. 阻燃聚乙烯的研究[J].哈尔滨建筑大学学报,1998,31(4):112
[9]Troitzsch J.International Plastics Flammability Handbook.2nd Edition,New York,1991:1435.
[10]Pillai C K S.et Al.Journal of Applied Polymer Science,1997,66(11):2157.
[11]李凤岭.聚烯烃的阻燃技术[J].化工新材料,1999,27(5):14
[12]Yang J P,Brewer D G and Venart J E S.Fire and Materials,1991,15:37.
[13]Yang J P,Brewer D G and Venart J E S.Fire and Materials,1991,15:127.
[14]左建东等.十溴二苯乙烷协同三氧化二锑阻燃 PE 研究[J].现代塑料加工应用,2004,16(3):32-34.
[15]罗筑等.有机溴/氧化锑体系对 PET、PE 类材料阻燃特性研究[J].贵州工业大学学报,2002,31(1):84-87.
[16]欧育湘.阻燃聚烯烃[J].塑料科技,1994(4):17-19.
[17]刘方等.高密度聚乙烯阻燃性能的研究[J].合成树脂及塑料,2001,18(1):18-20.
[18]夏英等.阻燃聚乙烯塑料的阻燃实验[J].大连轻工业学院学报,1998,(17):3-9.
[19]李纠等.溴系阻燃剂的生产和发展前景[J].东莞理工学院学报,2005,12(3):97.
[20]高世双等.无卤阻燃剂在聚乙烯中的应用[J].合成树脂及塑料,2001, 18(2):38-40.
[21]E N Peters.Flame─retardant thermoplastic Polyethylene red phosphorous[J].J. Appi. Polym. Sci,1979,24:1457-1460.
[22]Cullis C F,Hirschler M M and Tao Q M.European Polymer Journal,1991,27:281.
[23]徐闻等.电子束辐照对HDPE及其与Mg(OH)2共混体系力学性能影响的研究[J].高分子材料科学与工程,1997,13(1):103-106.
[24]王秀芬.包覆红磷及其在聚合物材料中的应用[J].阻燃材料与技术,1994(3):4-10.
[25]吴勇等.包覆红磷阻燃剂的研究和应用[J].河南化工,1999,(9):14-17.
[26]王勇等.大分子偶联剂对 PE/氢氧化铝阻燃复合材料性能的影响[J].中国塑料,2004,18(1):67-70.
[27]刘敏江等.聚乙烯无卤阻燃体系配方及性能[J].中国塑料,1999,13(10):49-54.
[28]方征平等.高填充聚乙烯/氢氧化铝体系的交联改性[J].中国塑料,1998,12(2):49-51.
[29]时虎等.磷腈阻燃剂的合成及在聚乙烯阻燃中的应用[J].消防技术与产品信息,2001,(9):25-28.
[30] 王心蕊等 . 炭黑在超高分子量聚乙烯阻燃改性中的作用 [J]. 现代化工 ,2001, 21(6):38-40.
[31] 王 志 德 等 . 红 磷 阻 燃 增 效 LDPE─Al(OH)3/Mg(OH)2 体 系 的 研 究 [J]. 塑 料 科技,1992,(5):34-38.
[32]欧育湘.新型磷-氮系膨胀型阻燃剂的性能、合成与应用[J].江苏化工,1998,26(3):6-11.
[33]欧育湘.Exolit 系列新型无卤低烟低毒阻燃剂[J].塑料科技,2001,(1):1-3.
[34]Baillet C,Gandi S,P Breant,L Delfoe.Polym Degrad and Stab,1992,37:149.
[35]张志龙等.膨胀型无卤阻燃聚乙烯材料的研究[J].塑料,2000,29(3):15-21.
[36]李斌等.淀粉对聚乙烯膨胀型阻燃体系热降解和阻燃的影响[J].高分子材料科学与工程,2000,(2):155-157.
[37]师华等.三聚氰胺磷酸类盐在膨胀型阻燃体系中的应用[J]. 高分子材料科学与工程,2000,(2):17-19.
[38]田春明等.膨胀石墨在聚乙烯中阻燃协效作用的研究[J].中国塑料,2003,17(12):49-52.
[39]鲍志素.一种无卤阻燃剂的复配及应用[J].塑料助剂,2003,(3):8-9,13.
[40] 徐 晓 楠 等 . 二 氧 化 硅 对 膨 胀 型 阻 燃 聚 乙 烯 的 性 能 影 响 研 究 [J]. 火 灾 科学,2004,13(3):168-172.
[41]曾祥斌.聚乙烯膨胀体系的研究.硕士学位论文[D].北京:北京化工大学,2000:35-36.
[42]赵彦芝.聚丙烯膨胀型阻燃剂及协同效应的研究. 硕士学位论文[D].广州:华南理工大学,2005:35-41.
[43]Russel,K.E.,Grafting of Maleic Anhydride to Hydrocarbons below the ceiling Temperature,J.Polym.Sci.:Part A:Polymer chemistry,Vol.33,555-561,1995.
[44]张华等.现代有机波谱分析[M].北京:化学工业出版社,2005:250-327.
[2]张军等.聚合物燃烧与阻燃技术[M].北京:化学工业出版社,2005:1,118,41.
[3]欧育湘等.阻燃高分子材料[M].北京:国防工业出版社,2001:56.
[4]陈卫等.阻燃剂的微胶囊化[J].阻燃材料与技术,1998,1:1-3
[5]于永忠等.阻燃材料手册[M].北京:群众出版社,1997:264.
[6] Chang,T.M. ed Norman,N.Li.,Resent Development in Separation Science,The Chemical Rubber Co.USA,1972,1.
[7]葛世成.塑料阻燃实用技术[M].北京:化学工业出版社,2004:205.
[8]鲍治宇等. 阻燃聚乙烯的研究[J].哈尔滨建筑大学学报,1998,31(4):112
[9]Troitzsch J.International Plastics Flammability Handbook.2nd Edition,New York,1991:1435.
[10]Pillai C K S.et Al.Journal of Applied Polymer Science,1997,66(11):2157.
[11]李凤岭.聚烯烃的阻燃技术[J].化工新材料,1999,27(5):14
[12]Yang J P,Brewer D G and Venart J E S.Fire and Materials,1991,15:37.
[13]Yang J P,Brewer D G and Venart J E S.Fire and Materials,1991,15:127.
[14]左建东等.十溴二苯乙烷协同三氧化二锑阻燃 PE 研究[J].现代塑料加工应用,2004,16(3):32-34.
[15]罗筑等.有机溴/氧化锑体系对 PET、PE 类材料阻燃特性研究[J].贵州工业大学学报,2002,31(1):84-87.
[16]欧育湘.阻燃聚烯烃[J].塑料科技,1994(4):17-19.
[17]刘方等.高密度聚乙烯阻燃性能的研究[J].合成树脂及塑料,2001,18(1):18-20.
[18]夏英等.阻燃聚乙烯塑料的阻燃实验[J].大连轻工业学院学报,1998,(17):3-9.
[19]李纠等.溴系阻燃剂的生产和发展前景[J].东莞理工学院学报,2005,12(3):97.
[20]高世双等.无卤阻燃剂在聚乙烯中的应用[J].合成树脂及塑料,2001, 18(2):38-40.
[21]E N Peters.Flame─retardant thermoplastic Polyethylene red phosphorous[J].J. Appi. Polym. Sci,1979,24:1457-1460.
[22]Cullis C F,Hirschler M M and Tao Q M.European Polymer Journal,1991,27:281.
[23]徐闻等.电子束辐照对HDPE及其与Mg(OH)2共混体系力学性能影响的研究[J].高分子材料科学与工程,1997,13(1):103-106.
[24]王秀芬.包覆红磷及其在聚合物材料中的应用[J].阻燃材料与技术,1994(3):4-10.
[25]吴勇等.包覆红磷阻燃剂的研究和应用[J].河南化工,1999,(9):14-17.
[26]王勇等.大分子偶联剂对 PE/氢氧化铝阻燃复合材料性能的影响[J].中国塑料,2004,18(1):67-70.
[27]刘敏江等.聚乙烯无卤阻燃体系配方及性能[J].中国塑料,1999,13(10):49-54.
[28]方征平等.高填充聚乙烯/氢氧化铝体系的交联改性[J].中国塑料,1998,12(2):49-51.
[29]时虎等.磷腈阻燃剂的合成及在聚乙烯阻燃中的应用[J].消防技术与产品信息,2001,(9):25-28.
[30] 王心蕊等 . 炭黑在超高分子量聚乙烯阻燃改性中的作用 [J]. 现代化工 ,2001, 21(6):38-40.
[31] 王 志 德 等 . 红 磷 阻 燃 增 效 LDPE─Al(OH)3/Mg(OH)2 体 系 的 研 究 [J]. 塑 料 科技,1992,(5):34-38.
[32]欧育湘.新型磷-氮系膨胀型阻燃剂的性能、合成与应用[J].江苏化工,1998,26(3):6-11.
[33]欧育湘.Exolit 系列新型无卤低烟低毒阻燃剂[J].塑料科技,2001,(1):1-3.
[34]Baillet C,Gandi S,P Breant,L Delfoe.Polym Degrad and Stab,1992,37:149.
[35]张志龙等.膨胀型无卤阻燃聚乙烯材料的研究[J].塑料,2000,29(3):15-21.
[36]李斌等.淀粉对聚乙烯膨胀型阻燃体系热降解和阻燃的影响[J].高分子材料科学与工程,2000,(2):155-157.
[37]师华等.三聚氰胺磷酸类盐在膨胀型阻燃体系中的应用[J]. 高分子材料科学与工程,2000,(2):17-19.
[38]田春明等.膨胀石墨在聚乙烯中阻燃协效作用的研究[J].中国塑料,2003,17(12):49-52.
[39]鲍志素.一种无卤阻燃剂的复配及应用[J].塑料助剂,2003,(3):8-9,13.
[40] 徐 晓 楠 等 . 二 氧 化 硅 对 膨 胀 型 阻 燃 聚 乙 烯 的 性 能 影 响 研 究 [J]. 火 灾 科学,2004,13(3):168-172.
[41]曾祥斌.聚乙烯膨胀体系的研究.硕士学位论文[D].北京:北京化工大学,2000:35-36.
[42]赵彦芝.聚丙烯膨胀型阻燃剂及协同效应的研究. 硕士学位论文[D].广州:华南理工大学,2005:35-41.
[43]Russel,K.E.,Grafting of Maleic Anhydride to Hydrocarbons below the ceiling Temperature,J.Polym.Sci.:Part A:Polymer chemistry,Vol.33,555-561,1995.
[44]张华等.现代有机波谱分析[M].北京:化学工业出版社,2005:250-327.