星形支化卤化丁基橡胶的合成及研究
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摘要
研究了星形支化溴化丁基橡胶的合成方法,采用活性负离子聚合法制备端基锂聚苯乙烯-异戊二烯共聚物、端基锂聚异戊二烯聚合物并与溴化丁基橡胶胶液反应合成出星形支化卤化丁基橡胶,以期提高丁基橡胶的某些性能,拓宽丁基橡胶的应用领域。采用红外(IR)、核磁(~1H-NMR)等方法对产物进行表征,并采用示差折光指数(RI)/多角激光光散射(LS)/在线粘度(Vis)三台联用测定产物分子量及接枝状况,采用差示扫描量热法(DSC)测定产物的玻璃化转变温度(Tg),采用氧燃烧.电位滴定法对产物进行溴含量测定并探讨合成反应机理,将产物硫化测定硫化胶硬度、拉伸应力、比重等性能,结果表明,硫化胶的扯断伸长率、拉伸强度值比溴化丁基橡胶(BIIR2222)的测得值要高,而这些性能的提升对橡胶制品的应用是非常有益的。
Star-branched brominated butyl rubber(BSBBR) was synthesized by brominated butyl rubber reacted with Li-capped PSt-PIp copolymer or Li-capped PIp, which was prepared by anion polymerization method. The star-branched brominated butyl rubber was expected to improve some properties of butyl rubber,and broaden butyl rubber's application fields. And star-branched brominated butyl rubber were analysed by IR, ~1H-NMR, etc. Besides,using RI/LS/VIS measured the Mn and the arm numbers of star-brominated butyl rubber,using DSC measured the Tg of star-brominated butyl rubber,using oxygen burnt-potentiometer measured the content of bromine in star-branched brominated butyl rubber and then concluded the mechanism of the reaction. Then vulcanized the product and tested its hardness, tensile stress, density,etc.The results showed that the elongation and tensile strength value of star-branched brominated butyl rubber was higher than BIIR,and it was benefit to be used by rubber produce.
Star-branched brominated butyl rubber(BSBBR) was synthesized by brominated butyl rubber reacted with Li-capped PSt-PIp copolymer or Li-capped PIp, which was prepared by anion polymerization method. The star-branched brominated butyl rubber was expected to improve some properties of butyl rubber,and broaden butyl rubber's application fields. And star-branched brominated butyl rubber were analysed by IR, ~1H-NMR, etc. Besides,using RI/LS/VIS measured the Mn and the arm numbers of star-brominated butyl rubber,using DSC measured the Tg of star-brominated butyl rubber,using oxygen burnt-potentiometer measured the content of bromine in star-branched brominated butyl rubber and then concluded the mechanism of the reaction. Then vulcanized the product and tested its hardness, tensile stress, density,etc.The results showed that the elongation and tensile strength value of star-branched brominated butyl rubber was higher than BIIR,and it was benefit to be used by rubber produce.
引文
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[2]Bruzzone,Mario.New process forIIR production[P].WO:21241,1993.
[3]郑艳华.丁基橡胶发展现状及市场分析[J].化学工程师.2003(5):38-39
[4]崔小明.丁基橡胶生产技术及国内外市场分析[J].化工科技市场,2005,10:13-21;
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[9]王桂贤,张威.丁基橡胶的开发与应用[J]辽宁化工,1990(6):34-38
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[20]周伊云.星形接枝卤化丁基橡胶性能初步研究[J].轮胎工业,1999,2(19):86-93
[21]朱琳.异丁烯类橡胶(丁基橡胶和其他橡胶)的开发[J]橡胶参考资料.2006,36(1):26-27
[22]付岩,张威.性能独特的丁基橡胶[J]吉林石油化工.1990(4):30-9
[23]武冠英.合成橡胶科学技术进展评述[J]合成橡胶工业.1988,11(2):98-110
[24]中国科学院山西煤化所505所.合成丁基橡胶的研究[J]合成橡胶工业.1980,3(3):162-166
[25]申红.国内外丁基橡胶制备技术进展[J].化工科技.2002,10(3):54-60
[26]Baade,Wolfgang.Preparation byaslurryprocess[P].DE:4426765,1996.
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[28]崔小明.丁基橡胶生产技术及国内外市场分析[J].化工科技市场,2005,10:13-21
[29]梁玉蓉.合成橡胶卤化改性的研究进展[J]特种橡胶制品.2005,12(26):55-56
[30]解洪梅,张立红,哀辉志.橡胶氯化工艺发展概况[J].合成橡胶工业,1997,20(2):124-126.
[31]AsvinkumarN.Process for Halogention OF Butadiene Polymer in the Presence of Aluminom-Containing Material.U S,U 54405759,1983.
[32]小仓城,土屋浩,中山睦,等.氯化橡胶的制备方法[J].日本公开特许公报(日文),平04-46905,1992.
[33]Aires F,Perrey H,Heyer K H,et al.Water.Water-Re-sistant Film-Forming Chlorinated Polymer-Prcpd.Ger Offen,DE 3102511.1981.
[34]Frank E.Removeal of Residual Acid from Chlorinated Polymers.U S,US 5137943,1992.
[35]Neff F.Process for the Manufacture of Haloenated Elastomers.U S,U 54486575.1984.
[36]Osman,Akhtar.Processforpreparingbutylpolymerswithal2lylichalidefunctionality[P].USUSP:5473029,1994.
[37]BayerCorparation.MethodofproducingIIR[P].USUSP:5342908,1993.
[38]钱寒东.溴化丁基橡胶性能研究[J]世界橡胶工业.2004,31(12):6-7
[39]梁玉蓉.合成橡胶卤化改性的研究进展[J].特种橡胶制品,2005,26(6):55-56
[40]]宋改云,,蓝林立,李树新,郭文莉.星形支化丁基橡胶的合成及研究[J],高分子材料科学与工程2005,21(2)
[41]Romeo P.F.,Wang H.C.,Wheeler L.M.,"Star" brancbed butyl-Anovel butyi robber for improved processability[J].Polymer Prepare,1988,13(4):460
[42]Gyor M.,Fodor Z.,Wang H.C.,Structure and molecular weight characterization,[J].Polymer Prepare,1988,31(1):460
[43]Puskas J.E.,Gabor K.Catalyst for manufacture of butyl rubber with bimodal molecular weight istribution[P].U S 5,194,538.1993
[44]Duvdevani I.,星型支化型丁基橡胶的合成、表征及其加工性[J]合成橡胶工业.1993,16(6):371
[45]MiTSUO SAWAMOTO.Star-branched functional polymers by living cationic polymerization[J]Macromolecules.43-61
[46]Vairon J P and Charleux B.Ionic Polymerization and Related Process.Boston:Kluwer Academic Publishers,1999:177
[47]陈福泰.高支化聚合物的研究进展及应用前景[J]化工进展.2000(4):33-37
[48]具有卤化丁基橡胶主链结构的梳形聚合物US5342896
[49]Ikeda,Yuko.ChemicalmodificationofIIR.Structurean propertiesofpoly(ethyleneoxide)2grafledIIR[J]Polym.Sci,1995,33(3):387-394.
[50]Roha,Max./living0freeradicalgraftcopolymers.Preparatio andproperties[J].Macromol.Symp.,1995,91:81-89.
[51]具有卤化丁基橡胶主链结构的梳形聚合物US5342896
[52]I.Duvdevani,J.V.Fusco,K.W.Power and H-C.Wang,Star-Branched Butyl: Synthesis,Characterization and Processability IRC-92,Beijing,1992-10
[53]钱梅.异丁烯的化工应用[J]化学推进剂与高分子材料.2000(2):22-24
[54]魏廷贤,杨建森.国产与进口IIR性能对比研究[J]橡胶工业.2002,149(2):87-89
[55]张爱民.我国合成橡胶工业的现状与发展[J]橡胶工业.2000,147(2):107-116
[56]舒朝霞.国内外丁基橡胶市场分析与预测[J]橡胶工业.1994,41(41):242-243
[57]杨迪.凝胶色谱测定聚合物相对分子质量及其分布[J].现代塑料加工应用,2005,17(6):36-39
[58]张锐.现代材料分析方法[M].北京:化学工业出版社,2007.40-41
[59]徐寿昌.有机化学[M].北京:高等教育出版社,294-299
[60]周伊云.星形接枝卤化丁基橡胶性能初步研究[J]轮胎工业,1999,19(2):86-90
[61]王作玲.卤化丁基橡胶的硫化体系[J],世界橡胶工业,1999,26(3):50-62
[62]魏强邦.n-BuLi的浓度对异戊二烯聚合的影响[J],合成橡胶工业,1999,22(6):375
[63]杨性坤.异戊二烯负离子聚合机理探讨[J],信阳师范学院学报(自然科学版)2001,14(4):407-410
[2]Bruzzone,Mario.New process forIIR production[P].WO:21241,1993.
[3]郑艳华.丁基橡胶发展现状及市场分析[J].化学工程师.2003(5):38-39
[4]崔小明.丁基橡胶生产技术及国内外市场分析[J].化工科技市场,2005,10:13-21;
[5]戴长华.世界丁基橡胶供需现状[J].中国橡胶,2000,12:30-31
[6]梁玉蓉.合成橡胶卤化改性的研究进展[J].特种橡胶制品,2005,26(6):55-56
[7]Vukov.R.,Rubb.Chem Technol[J],1984,57(2):275
[8]Gardner,Irwin J,Process for preparing improved halogenated butyl rubber[P],US4681 921.1987-07-21
[9]王桂贤,张威.丁基橡胶的开发与应用[J]辽宁化工,1990(6):34-38
[10]Huang K.J.,Zsuga M.J.P.Kennedy Living carbocationie polymerization(ⅩⅨ):Synthesis of four-arm star polyisobutylenes capped by t-chlorine and isopropylidene groups,[J].Polymer Bull,1988,19(1):43
[11]Storey R.F.,Lee Y.,Sulfonation of tert-alkyl chlorides:Application to the tert-chloride terminated polyisobutene system[J].Polymer Science,Part A:Polymer Chemstry,1991,29(3):317
[12]Omura N.,Lubnin A.V.,J.P.Kennedy,Multiarm star polyisobutylenes,[A].In Faust R.,Shaffer T.D.Cationic Polymerization Fundamentals & Applications,ACS Series 665,Washington D.C.,1998:178
[13]Fuseo J.V.,Young D.G.,Isobutylene-based polymers in tires-status and future,[J].Rubber World,1992,206(2):34
[14]Faust R.,Shaffer T.D.,Cationic polymerization fundamentals & applications [A].ACS Series 665,Washington D.C.,1997
[15]Ivan B.,J.P.Kennedy,Maeromolecular engineering by Carbocationic polymerization,[M].In:Macromolecular design of polymeric materials.New York:Marcel Dekker Inc,1997:51
[16]林振国.星形分支的丁基橡胶[J]橡胶译丛.1995(1):1-10
[17]林振国.星形分支的丁基橡胶[J].橡胶译丛,1995(1):1-5
[18]Gursky L.et al.136~(th)Meeting Rubber Division Acs[R],1989-10:55
[19]韩秀山.丁基橡胶功能化品种[J].四川化工与腐蚀控制,2002.5(3):53-55
[20]周伊云.星形接枝卤化丁基橡胶性能初步研究[J].轮胎工业,1999,2(19):86-93
[21]朱琳.异丁烯类橡胶(丁基橡胶和其他橡胶)的开发[J]橡胶参考资料.2006,36(1):26-27
[22]付岩,张威.性能独特的丁基橡胶[J]吉林石油化工.1990(4):30-9
[23]武冠英.合成橡胶科学技术进展评述[J]合成橡胶工业.1988,11(2):98-110
[24]中国科学院山西煤化所505所.合成丁基橡胶的研究[J]合成橡胶工业.1980,3(3):162-166
[25]申红.国内外丁基橡胶制备技术进展[J].化工科技.2002,10(3):54-60
[26]Baade,Wolfgang.Preparation byaslurryprocess[P].DE:4426765,1996.
[27]Bruzzone,Mario.NewproccssforIIRproduction[P].WO:21241,1993.
[28]崔小明.丁基橡胶生产技术及国内外市场分析[J].化工科技市场,2005,10:13-21
[29]梁玉蓉.合成橡胶卤化改性的研究进展[J]特种橡胶制品.2005,12(26):55-56
[30]解洪梅,张立红,哀辉志.橡胶氯化工艺发展概况[J].合成橡胶工业,1997,20(2):124-126.
[31]AsvinkumarN.Process for Halogention OF Butadiene Polymer in the Presence of Aluminom-Containing Material.U S,U 54405759,1983.
[32]小仓城,土屋浩,中山睦,等.氯化橡胶的制备方法[J].日本公开特许公报(日文),平04-46905,1992.
[33]Aires F,Perrey H,Heyer K H,et al.Water.Water-Re-sistant Film-Forming Chlorinated Polymer-Prcpd.Ger Offen,DE 3102511.1981.
[34]Frank E.Removeal of Residual Acid from Chlorinated Polymers.U S,US 5137943,1992.
[35]Neff F.Process for the Manufacture of Haloenated Elastomers.U S,U 54486575.1984.
[36]Osman,Akhtar.Processforpreparingbutylpolymerswithal2lylichalidefunctionality[P].USUSP:5473029,1994.
[37]BayerCorparation.MethodofproducingIIR[P].USUSP:5342908,1993.
[38]钱寒东.溴化丁基橡胶性能研究[J]世界橡胶工业.2004,31(12):6-7
[39]梁玉蓉.合成橡胶卤化改性的研究进展[J].特种橡胶制品,2005,26(6):55-56
[40]]宋改云,,蓝林立,李树新,郭文莉.星形支化丁基橡胶的合成及研究[J],高分子材料科学与工程2005,21(2)
[41]Romeo P.F.,Wang H.C.,Wheeler L.M.,"Star" brancbed butyl-Anovel butyi robber for improved processability[J].Polymer Prepare,1988,13(4):460
[42]Gyor M.,Fodor Z.,Wang H.C.,Structure and molecular weight characterization,[J].Polymer Prepare,1988,31(1):460
[43]Puskas J.E.,Gabor K.Catalyst for manufacture of butyl rubber with bimodal molecular weight istribution[P].U S 5,194,538.1993
[44]Duvdevani I.,星型支化型丁基橡胶的合成、表征及其加工性[J]合成橡胶工业.1993,16(6):371
[45]MiTSUO SAWAMOTO.Star-branched functional polymers by living cationic polymerization[J]Macromolecules.43-61
[46]Vairon J P and Charleux B.Ionic Polymerization and Related Process.Boston:Kluwer Academic Publishers,1999:177
[47]陈福泰.高支化聚合物的研究进展及应用前景[J]化工进展.2000(4):33-37
[48]具有卤化丁基橡胶主链结构的梳形聚合物US5342896
[49]Ikeda,Yuko.ChemicalmodificationofIIR.Structurean propertiesofpoly(ethyleneoxide)2grafledIIR[J]Polym.Sci,1995,33(3):387-394.
[50]Roha,Max./living0freeradicalgraftcopolymers.Preparatio andproperties[J].Macromol.Symp.,1995,91:81-89.
[51]具有卤化丁基橡胶主链结构的梳形聚合物US5342896
[52]I.Duvdevani,J.V.Fusco,K.W.Power and H-C.Wang,Star-Branched Butyl: Synthesis,Characterization and Processability IRC-92,Beijing,1992-10
[53]钱梅.异丁烯的化工应用[J]化学推进剂与高分子材料.2000(2):22-24
[54]魏廷贤,杨建森.国产与进口IIR性能对比研究[J]橡胶工业.2002,149(2):87-89
[55]张爱民.我国合成橡胶工业的现状与发展[J]橡胶工业.2000,147(2):107-116
[56]舒朝霞.国内外丁基橡胶市场分析与预测[J]橡胶工业.1994,41(41):242-243
[57]杨迪.凝胶色谱测定聚合物相对分子质量及其分布[J].现代塑料加工应用,2005,17(6):36-39
[58]张锐.现代材料分析方法[M].北京:化学工业出版社,2007.40-41
[59]徐寿昌.有机化学[M].北京:高等教育出版社,294-299
[60]周伊云.星形接枝卤化丁基橡胶性能初步研究[J]轮胎工业,1999,19(2):86-90
[61]王作玲.卤化丁基橡胶的硫化体系[J],世界橡胶工业,1999,26(3):50-62
[62]魏强邦.n-BuLi的浓度对异戊二烯聚合的影响[J],合成橡胶工业,1999,22(6):375
[63]杨性坤.异戊二烯负离子聚合机理探讨[J],信阳师范学院学报(自然科学版)2001,14(4):407-410