硅烷交联无卤阻燃LLDPE/LDPE/POE的加工特性研究
|
摘要
针对硅烷交联无卤阻燃聚烯烃电缆料易吸潮,产生预交联导致挤出性差的问题,将氢氧化镁(MH)与氢氧化铝(ATH)阻燃剂复配后硅烷偶联处理,采用熔融共混的方式制备了硅烷交联LLDPE/LDPE/POE无卤阻燃材料。重点研究了阻燃剂硅烷处理前后对其加工性能的影响以及MH与ATH不同配比对其力学性能、氧指数、热延伸性能的影响。结果表明氢氧化物阻燃剂经硅烷偶联处理的比未处理的挤出的复合材料片材表面平整光滑,流变性能好,没有预交联。此时,平衡扭矩下降了24.8%,熔体流动速率提高了23.5%。随着MH/ATH配比的增加,复合材料的氧指数、拉伸强度呈现出先升高后降低的趋势,热延伸率、永久变形率、断裂伸长率呈现出先降低后升高的趋势。当MH/ATH配比为2/1时,经过8d耐水实验,复合材料性能最佳,此时的拉伸强度为17.5MPa、断裂伸长率为349%、氧指数为34.2%、热延伸率为17%和永久变形率为3.3%。
In this paper,the silane cross-linking halogen-free flame-retardant polyolefin cable material was easy to absorb water,resulting in poor cross-linking and extrusion.The silane couple was compounded with magnesium hydroxide(MH)and aluminum hydroxide(ATH)flame retardant.Silane crosslinked LLDPE/LDPE/POE halogen-free flame retardant materials were prepared by melt blending.The effects of flame retardant on the processing properties before and after silane treatment and the effects of different ratios of MH and ATH on its mechanical properties,oxygen index and thermal elongation were investigated.The results showed that the surface of the hydroxide flame retardant treated by silane coupling was smoother than that of the untreated extruded composite sheet,and the rheological property was good.There was no pre-crosslinking.At this time,the balance torque dropped by 24.8%,and the melt flow rate increased by 23.5%.With the increased of MH/ATH ratio,the oxygen index and tensile strength of the composites increased firstly and then decreased,but the thermal elongation,permanent deformation rate and elongation at break showed a trend of decreasing firstly and then increased.When the ratio of MH/ATH was 2/1,the composite had the best performance after 8dof water resistance test.The tensile strength reached to 17.5MPa,the elongation at break reached to 349%,the oxygen index reached to 34.2%,the thermal elongation reached 17%,and the permanent deformation rate reached to 3.3%.
In this paper,the silane cross-linking halogen-free flame-retardant polyolefin cable material was easy to absorb water,resulting in poor cross-linking and extrusion.The silane couple was compounded with magnesium hydroxide(MH)and aluminum hydroxide(ATH)flame retardant.Silane crosslinked LLDPE/LDPE/POE halogen-free flame retardant materials were prepared by melt blending.The effects of flame retardant on the processing properties before and after silane treatment and the effects of different ratios of MH and ATH on its mechanical properties,oxygen index and thermal elongation were investigated.The results showed that the surface of the hydroxide flame retardant treated by silane coupling was smoother than that of the untreated extruded composite sheet,and the rheological property was good.There was no pre-crosslinking.At this time,the balance torque dropped by 24.8%,and the melt flow rate increased by 23.5%.With the increased of MH/ATH ratio,the oxygen index and tensile strength of the composites increased firstly and then decreased,but the thermal elongation,permanent deformation rate and elongation at break showed a trend of decreasing firstly and then increased.When the ratio of MH/ATH was 2/1,the composite had the best performance after 8dof water resistance test.The tensile strength reached to 17.5MPa,the elongation at break reached to 349%,the oxygen index reached to 34.2%,the thermal elongation reached 17%,and the permanent deformation rate reached to 3.3%.
引文
[1]Wang Zhengzhou,Fan weicheng,Zhai Baojun,et al.Silane-crosslinked polyethylenes containing Mg(OH)2flame retardant[J].Journal of Functional Polymers,2000,13(1):78-80(in Chinese).王正洲,范维澄,瞿保钧,等.含氢氧化镁的阻燃硅烷交联聚乙烯[J].功能高分子学报,2000,13(1):78-80.
[2]Ren Xiaobing,Kan Chengyou.Development of polyolefin elastomers and their application in the modification of polyolefin resins[J].China Elastomer,2017,27(04):59-64(in Chinese).任晓兵,阚成友.聚烯烃弹性体及其在树脂改性中的应用[J].弹性体,2017,27(04):59-64.
[3]Mai Jianzhang.Study on graft copolymerization of vinyl monomers from polyolefin elastomers and toughening effect of its product on SAN resin[D].Guangzhou:South China University of Technology,2014:1-2(in Chinese).麦剑章.聚烯烃弹性体与乙烯基单体接枝反应及其接枝产物对SAN树脂增韧作用的研究[D].广州:华南理工大学,2014:1-2.
[4]Peng Hui,Hao Jianwei,Li Zhuoshi,et al.Characteristic on halogen-free flame retardant synergism and suppressing smoke for LLDPE[J].Polymer Materials Science and Engineering,2014,30(07):56-59(in Chinese).彭辉,郝建薇,李茁实,等.线性低密度聚乙烯的无卤协同阻燃及抑烟性能表征[J].高分子材料科学与工程,2014,30(07):56-59.
[5]Shieh Y T,Liu C M.Silane grafting reactions of LDPE,HDPE,and LLDPE[J].Journal of Applied Polymer Science,1999,74:3404-3411.
[6]Zuo Ruilin,Zhang Guangcheng,He Hongwei,et al.Recent advances of silane crosslinking technology for PE[J].Plastic,2000,6(29):41-46(in Chinese).左瑞霖,张广成,何宏伟,等.聚乙烯的硅烷交联技术进展[J].塑料,2000,6(29):41-46.
[7]Song Xiaohui,Bi Tingting,Wang Renjie,et al.Preparation and properties of silane cross-linked POE/PE-LLDhose material[J].Engineering Plastics Application,2014,42(10):28-32(in Chinese).宋小辉,毕婷婷,王仁杰,等.硅烷交联POE/PE-LLD软管材料的制备[J].工程塑料应用,2014,42(10):28-32.
[8]Zhengzhou W,Yuan H,Zhou G,et al.Halogen-free flame retardation and silane ccross-linking of polyethylenes[J].Material Properties,2002,22(2003):533-538.
[9]Guan Wenwu,Zhang Ermei,Zhu Jun.Preparation and properties of silane crosslinked and low smoke halogen free-flame retardant cable matrix[C]//2014China Flame Retardant Academic Annual Conference Paper.Beijing:Tongfang Zhiwang Digital Publishing House,2014:293-299(in Chinese).管文武,张尔梅,朱俊.低烟无卤阻燃硅烷交联电缆料的制备和性能研究[C]//2014年中国阻燃学术年会论文集.北京:同方知网数字出版社,2014:293-299.
[10]Zhang Jianyao,Wu Lihao.Preparation and properties of silane crosslinked halogen-free flame retardant ethyleneoctene copolymer[J].China Plastic,2017,31(12):56-61(in Chinese).张建耀,邬立灏.硅烷交联无卤阻燃乙烯-辛烯共聚物的制备与性能[J].中国塑料,2017,31(12):56-61.
[11]Jiao Chuanmei.The preparation,properties of halogenfree flame retardant EVA,POE and their cross-linking modification composites[D].Hefei:University of Science&Technology of China,2007:31-36(in Chinese).焦传梅.无卤阻燃EVA、POE及其交联改性复合材料的制备和性能研究[D].合肥:中国科学技术大学,2007:31-36.
[12]Zhang Jianyao.Preparation and properties of silanecrosslinked halogen-free flame retardant polypropylene/poly(ethylene-1-octene)compounds[J].China Plastic,2018,32(1):59-66(in Chinese).张建耀.硅烷交联无卤阻燃PP/POE复合材料的制备和性能[J].中国塑料,2018,32(1):59-66.
[13]Zhang Jianyao,Wu Lihao.Preparation and properties of silane crosslinked halogen-free flame-retardant polyethylene-octene elastomer[J].China Plastic,2017,31(12):56-61(in Chinese).张建耀,邬立灏.硅烷交联无卤阻燃乙烯-辛烯共聚物的制备与性能[J].中国塑料,2017,31(12):56-61.
[14]Zhang Guoqiang.Investigation of silane-crosslinked and flame retardant polyolefin elastomer composites[D].Shanghai:Shanghai Jiao Tong University,2007:28-31(in Chinese).张国强.硅烷交联聚烯烃弹性体无卤阻燃复合材料的研究[D].上海:上海交通大学,2007:28-31.
[15]Dai Yajie,Shan Yuling,Zhang Wenlong,et al.Effects of zinc oxide on silane crosslinked polyethylene[J].Plastic,2018,47(2):4-7(in Chinese).戴亚杰,单毓玲,张文龙,等.氧化锌对硅烷交联聚乙烯的影响[J].塑料,2018,47(2):4-7.
[2]Ren Xiaobing,Kan Chengyou.Development of polyolefin elastomers and their application in the modification of polyolefin resins[J].China Elastomer,2017,27(04):59-64(in Chinese).任晓兵,阚成友.聚烯烃弹性体及其在树脂改性中的应用[J].弹性体,2017,27(04):59-64.
[3]Mai Jianzhang.Study on graft copolymerization of vinyl monomers from polyolefin elastomers and toughening effect of its product on SAN resin[D].Guangzhou:South China University of Technology,2014:1-2(in Chinese).麦剑章.聚烯烃弹性体与乙烯基单体接枝反应及其接枝产物对SAN树脂增韧作用的研究[D].广州:华南理工大学,2014:1-2.
[4]Peng Hui,Hao Jianwei,Li Zhuoshi,et al.Characteristic on halogen-free flame retardant synergism and suppressing smoke for LLDPE[J].Polymer Materials Science and Engineering,2014,30(07):56-59(in Chinese).彭辉,郝建薇,李茁实,等.线性低密度聚乙烯的无卤协同阻燃及抑烟性能表征[J].高分子材料科学与工程,2014,30(07):56-59.
[5]Shieh Y T,Liu C M.Silane grafting reactions of LDPE,HDPE,and LLDPE[J].Journal of Applied Polymer Science,1999,74:3404-3411.
[6]Zuo Ruilin,Zhang Guangcheng,He Hongwei,et al.Recent advances of silane crosslinking technology for PE[J].Plastic,2000,6(29):41-46(in Chinese).左瑞霖,张广成,何宏伟,等.聚乙烯的硅烷交联技术进展[J].塑料,2000,6(29):41-46.
[7]Song Xiaohui,Bi Tingting,Wang Renjie,et al.Preparation and properties of silane cross-linked POE/PE-LLDhose material[J].Engineering Plastics Application,2014,42(10):28-32(in Chinese).宋小辉,毕婷婷,王仁杰,等.硅烷交联POE/PE-LLD软管材料的制备[J].工程塑料应用,2014,42(10):28-32.
[8]Zhengzhou W,Yuan H,Zhou G,et al.Halogen-free flame retardation and silane ccross-linking of polyethylenes[J].Material Properties,2002,22(2003):533-538.
[9]Guan Wenwu,Zhang Ermei,Zhu Jun.Preparation and properties of silane crosslinked and low smoke halogen free-flame retardant cable matrix[C]//2014China Flame Retardant Academic Annual Conference Paper.Beijing:Tongfang Zhiwang Digital Publishing House,2014:293-299(in Chinese).管文武,张尔梅,朱俊.低烟无卤阻燃硅烷交联电缆料的制备和性能研究[C]//2014年中国阻燃学术年会论文集.北京:同方知网数字出版社,2014:293-299.
[10]Zhang Jianyao,Wu Lihao.Preparation and properties of silane crosslinked halogen-free flame retardant ethyleneoctene copolymer[J].China Plastic,2017,31(12):56-61(in Chinese).张建耀,邬立灏.硅烷交联无卤阻燃乙烯-辛烯共聚物的制备与性能[J].中国塑料,2017,31(12):56-61.
[11]Jiao Chuanmei.The preparation,properties of halogenfree flame retardant EVA,POE and their cross-linking modification composites[D].Hefei:University of Science&Technology of China,2007:31-36(in Chinese).焦传梅.无卤阻燃EVA、POE及其交联改性复合材料的制备和性能研究[D].合肥:中国科学技术大学,2007:31-36.
[12]Zhang Jianyao.Preparation and properties of silanecrosslinked halogen-free flame retardant polypropylene/poly(ethylene-1-octene)compounds[J].China Plastic,2018,32(1):59-66(in Chinese).张建耀.硅烷交联无卤阻燃PP/POE复合材料的制备和性能[J].中国塑料,2018,32(1):59-66.
[13]Zhang Jianyao,Wu Lihao.Preparation and properties of silane crosslinked halogen-free flame-retardant polyethylene-octene elastomer[J].China Plastic,2017,31(12):56-61(in Chinese).张建耀,邬立灏.硅烷交联无卤阻燃乙烯-辛烯共聚物的制备与性能[J].中国塑料,2017,31(12):56-61.
[14]Zhang Guoqiang.Investigation of silane-crosslinked and flame retardant polyolefin elastomer composites[D].Shanghai:Shanghai Jiao Tong University,2007:28-31(in Chinese).张国强.硅烷交联聚烯烃弹性体无卤阻燃复合材料的研究[D].上海:上海交通大学,2007:28-31.
[15]Dai Yajie,Shan Yuling,Zhang Wenlong,et al.Effects of zinc oxide on silane crosslinked polyethylene[J].Plastic,2018,47(2):4-7(in Chinese).戴亚杰,单毓玲,张文龙,等.氧化锌对硅烷交联聚乙烯的影响[J].塑料,2018,47(2):4-7.