聚丙烯固相多单体接枝改性技术研究
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摘要
本研究用固相接枝法对PP进行双单体接枝改性。通过接枝丙烯酸乙酯(EA)和马来酸酐(MAH)考察接枝反应温度、时间、引发剂用量、聚丙烯粒径、单体配比、单体用量对接枝率的影响进行研究,通过测定不同条件下产物的接枝率,对接枝工艺条件进行了优化。本研究对单一单体接枝、双单体接枝进行了研究,并通过润湿角、熔体流动速率(MFR)和力学性能测试、以及傅里叶变换红外光谱(FTIR)和差示扫描量热仪(DSC)等分析手段,对接枝产物进行了表征。结果表明:
单一单体接枝的最佳反应条件为:PP10.00g,单体0.70g,引发剂0.03g,界面剂二甲苯1mL,分散剂乙醚1mL,在85℃(引发剂1)和100℃(引发剂2)下反应2h。双单体接枝的最佳反应条件为:PP10.00g,单体0.60g,引发剂0.03g,复配双单体质量比WEA:WMAH=7:3,界面剂二甲苯1mL,分散剂乙醚1mL,在85℃(引发剂1)下反应2h。
表征测试结果表明:双单体被成功地接枝到PP上;接枝产物的热性能得到明显改善;接枝产物的水润湿角比原料降低,极性提高;接枝产物的MFR和力学性能与纯PP性能接近。
The binary monomer grafting technology by solid-grafting method of PP was researched in this research. By studying reaction temperature, time, initiator, polypropylene particle size, monomer ratio and the amount of grafting monomer to measure grafting rate of product under the different conditions and identify the main factors of impaction of graft, the last optimizing graft process. The structure and thermal property of grafted polymers were characterized through FTIR, DSC, contact-angle and melting flow rate (MFR).The results show that:
The optimum single monomer grafting condition is that, PP 10.00g, monomer 0.70g and initiator 0.03g, interfacial agent xylene 1mL, dispersant agent ether 1mL, reaction 2h at 85℃(initiator 1) and 100℃(initiator 2).
The optimum binary monomer grafting condition is that, PP 10.00g, monomer 0.60g and initiator 0.03g, WEA:WMAH=7:3 of binary-monomer, interfacial agent xylene 1mL, dispersant agent ether 1mL, reaction 2h at 85℃(initiator 1).
Characterization test results of grafted products indicate that the monomer were indeed grafted onto PP chains. Its thermal properties had been improved obviously. Its contact-angle was lower than pure PP ,which proved that hydrophilicity had been significantly improved. And the grafting products remain its versatile physical properties.
单一单体接枝的最佳反应条件为:PP10.00g,单体0.70g,引发剂0.03g,界面剂二甲苯1mL,分散剂乙醚1mL,在85℃(引发剂1)和100℃(引发剂2)下反应2h。双单体接枝的最佳反应条件为:PP10.00g,单体0.60g,引发剂0.03g,复配双单体质量比WEA:WMAH=7:3,界面剂二甲苯1mL,分散剂乙醚1mL,在85℃(引发剂1)下反应2h。
表征测试结果表明:双单体被成功地接枝到PP上;接枝产物的热性能得到明显改善;接枝产物的水润湿角比原料降低,极性提高;接枝产物的MFR和力学性能与纯PP性能接近。
The binary monomer grafting technology by solid-grafting method of PP was researched in this research. By studying reaction temperature, time, initiator, polypropylene particle size, monomer ratio and the amount of grafting monomer to measure grafting rate of product under the different conditions and identify the main factors of impaction of graft, the last optimizing graft process. The structure and thermal property of grafted polymers were characterized through FTIR, DSC, contact-angle and melting flow rate (MFR).The results show that:
The optimum single monomer grafting condition is that, PP 10.00g, monomer 0.70g and initiator 0.03g, interfacial agent xylene 1mL, dispersant agent ether 1mL, reaction 2h at 85℃(initiator 1) and 100℃(initiator 2).
The optimum binary monomer grafting condition is that, PP 10.00g, monomer 0.60g and initiator 0.03g, WEA:WMAH=7:3 of binary-monomer, interfacial agent xylene 1mL, dispersant agent ether 1mL, reaction 2h at 85℃(initiator 1).
Characterization test results of grafted products indicate that the monomer were indeed grafted onto PP chains. Its thermal properties had been improved obviously. Its contact-angle was lower than pure PP ,which proved that hydrophilicity had been significantly improved. And the grafting products remain its versatile physical properties.
引文
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[2]张春吉,唐跃.塑料挤出成型工艺[J].塑料加工,2005,40(6):38-41.
[3]冯树铭.双向拉伸聚酯薄膜生产线技术——培训讲义[J].塑料包装,2010,20(3):42-43.
[4]蔡兵,李瑞霞,等.等离子体处理对非织造布表面润湿性的效应[J].四川大学学报(自然科学版),2001,38(1):91-94.
[5]马利福,黄启谷,宋怀河,等.茂金属化合物/Zn/BDGE/MAO催化体系合成aPS-b-P(S- co-E)-b-PE嵌段共聚物的研究[J].高分子学报,2009,0(7):689-694.
[6]吴自强,唐四丁,等.废旧聚丙烯回收利用技术的现状及发展趋势[J].中国再生资源, 2002(1):25-27.
[7]林果,黄玉惠,廖兵,等.废旧聚丙烯塑料回收利用的研究[J].广州化学, 1995(1).26-29
[8]林剑英,张华集,张雯.提高聚丙烯熔体强度的研究进展[J].高分子通报,2010(1).11-15
[9]周红军,容敏智,章明秋,等.纳米SiO2/聚丙烯复合材料的反应性增容[J].高分子学报,2007(2):158-164.
[10]麦堪成,张声春,高庆福,等.聚苯硫醚/尼龙6共混物界面对结晶行为的影响[J].高分子学报,2001,74(1):121-123.
[11]杨慧丽张春静.辐射增强PP/BR共混体系的力学性能[J].功能高分子学报,1998, 11(3):392-396.
[12]游长江.SEP对PP/PS共混物的增容作用[J].广州化学,2001,26(3):7-14.
[13]李锦春,俞强.尼龙1010/马来酸酐接枝聚丙烯共混体系的反应增容[J].应用化学, 1996, 13(4):38-40.
[14]张秀芹,朱磊,王笃金,等.PP/PP-g-MAH/PA6共混物结构与可纺性研究[J].高分子学报,2004(1):74-77.
[15]汪月定,张彤,刘婷,等.聚丙烯与聚酯-聚醚多嵌段共聚物共混的研究[J].高分子学报, 1987(1).9-13.
[16]张耀东,马彦龙,卫爱丽.废旧塑料改性再生技术现状及进展[J].资源再生, 2008(9): 44-46.
[17]杜咏梅;应用激光电离质谱在线定性分析卷烟抽吸烟气和烟草裂解气体中的有机化学成分[A];2004年CORESTA会议第58届烟草科学研究会议论文集[C];2004年.
[18] Gebauer K,Brown P,Varigos G.Topical diclofenacin hyaluronan gel for the treatment of solar keratosi[J]. Australas J Dermatol,2003,44(1):40-43.
[19] Sullivan J L. The relaxation and deformation properties of a carbon-black filled elastomer in biaxial tension[J]. Journal of Polymer Science: Polymer Physics Edition, 1986, 24(1): 161-173.
[20] Sullivan J L. A nonlinear viscoelastic model for representing nonfactorizable time-dependent behavior in cured rubber[J]. Journal of Rheology, 1987, 31(3): 271 -295.
[21]龚佰勋,吴学龙.城市生活垃圾蕴含热能的分布及4种回收方法[J].环境卫生工程,2003,11(2):92-93.
[22]宋旭东.浅析塑料废物的处理与再利用[J].气象与环境学报,2006,22(5):56-58.
[23]赵胜利,黄宁生,朱照宇.塑料废弃物污染的综合治理研究进展[J].生态环境, 2008,17(6):14-18.
[24]高建国,陈世山,高玫,等.废旧塑料鉴别方法的初步研究[J].工程塑料应用, 2004,32(2):47-51.
[25]王安鑫,薛平,贾明印.再生聚合物异性混容技术研究[J].中国塑料,2008,22(8):90-95.
[26]徐兆瑜.超临界技术在化学工业中的应用浅析[J].甘肃化工,2006,20(1):11-17.
[27]吕占霞,胡友良,张欣,等.功能化聚烯烃研究进展[J].合成树脂及塑料, 2002, 19(6):51-56.
[28]王鉴,赵洪坤,乔岩,等.聚丙烯接枝改性技术研究进展[J].炼油与化工,2010,(5):1-5.
[29]晋日亚,贺增第.聚丙烯的改性[J].现代塑料加工应用,2001,13(1):62-64.
[30]张立峰,郭宝华,张增民.共单体在固相合成高极性聚丙烯中的应用[J].塑料工业,2000,28(6):7-9.
[31]王雅珍,贾宏葛,菜英慧.聚丙烯双单体接枝体系研究[J].中国塑料,2003,17(11):28-30.
[32] Jia Demin, Luo Yuanfang, Li Yanmei,et al. Synthesis and characterization of solid -phase graft copolymer of polypropylene with styrene and malefic anhydride [J].J Appl Polym Sci, 2000, 78(14): 2482-2487.
[33]贾德民,罗远芳,何慧,等.聚烯烃与三单体周相接枝共聚物的制备方法及其应用[P].中国,ZL 00117390,2004.
[34]李颖,谢续明.马来酸酐-苯乙烯多组分单体熔融接枝聚丙烯的机理研究[J].高等学校化学学报,2000,21(4):637-642.
[35]谢续明,李颖,张景春,等.马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究[J].高分子学报,2002(1):7-12.
[36] Chrastova V, Citovicky P, Foldesova M. The copolymerization of styrene and malefic anhydride initiated by peroxides of isotactic polypropylene[J].Eur Polym J, 1996,32 (2):153-158.
[37] Sun Yinjun, Hu Guohua, Lambla M. Free radical grafting of glycidyl methacrylate onto polypropylene in a co-rotating twin screw extruder[J].J Appl Polym Sci,1995,57(9): l043-1054.
[38]张艳中,范志强,刘钊,等.球形聚丙烯粒子固相接枝苯乙烯的研究[J].高分子学报,2002,(4):432-436.
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