2,4-二苯基-4-甲基-1-戊烯在丙烯酸酯共聚乳液中的应用研究
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摘要
比较了分子量调节剂αMSD(2,4-二苯基-4-甲基-1-戊烯)与NDDM(正十二硫醇)对MMA-BA共聚乳液聚合物的分子量及其分布、聚合速率、乳液固含量、单体转化率、粒径、黏度、凝胶率等因素的影响,并对αMSD的调节机理进行了分析。研究结果表明:较低αMSD用量即可降低聚合物分子量,使分子量分布变窄,与正十二硫醇的作用结果差别不大;αMSD会引起丙烯酸酯乳液聚合速率的下降,用量超过1%后会导致乳液固含量和单体转化率的明显下降,乳液粒径分布会变宽,乳液黏度也有所增加,但体系凝胶率始终较低;而NDDM则会引起产物乳液粒径小幅增加,凝胶率升高;通过红外分析确定了αMSD按Yasummasa式不可逆加成断裂链转移反应而起调节作用。
Effects of two different chain transfer agents,2,4-diphenyl-4-methyl-1-pentene(αMSD)and n-dodecyl mercaptan(NDDM)were developed on molecular weight and its distribution,polymerization rate,solidcontent,monomer conversion,particle size,viscosity and gel rate of MMA-BA copolymer emulsion. The mechanismof αMSD regulation was also explored. The research results showed that low content of αMSD could reducemolecular weight highly and narrow its distribution,just like NDDM. Meanwhile,αMSD could reduce the polymerization rate of BA emulsion. When αMSD content was more than 1%,the solid content and monomerconversion decreased obviously,particle size distribution tended to widen,and emulsion viscosity increased also,but gel rate always kept in low level. However,in NDDM system,particle size became bigger slightly as the level ofNDDM went up,and gel rate was higher than that in αMSD. In addition,αMSD regulation mechanism wasconfirmed as Yasummasa irreversible addition-fraction chain transfer reaction,which was represented by FT-IR.
Effects of two different chain transfer agents,2,4-diphenyl-4-methyl-1-pentene(αMSD)and n-dodecyl mercaptan(NDDM)were developed on molecular weight and its distribution,polymerization rate,solidcontent,monomer conversion,particle size,viscosity and gel rate of MMA-BA copolymer emulsion. The mechanismof αMSD regulation was also explored. The research results showed that low content of αMSD could reducemolecular weight highly and narrow its distribution,just like NDDM. Meanwhile,αMSD could reduce the polymerization rate of BA emulsion. When αMSD content was more than 1%,the solid content and monomerconversion decreased obviously,particle size distribution tended to widen,and emulsion viscosity increased also,but gel rate always kept in low level. However,in NDDM system,particle size became bigger slightly as the level ofNDDM went up,and gel rate was higher than that in αMSD. In addition,αMSD regulation mechanism wasconfirmed as Yasummasa irreversible addition-fraction chain transfer reaction,which was represented by FT-IR.
引文
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[2]SENYEK M L,KULIG J J,PARKER D K.Dibenzyl trithiocarbonate molecular weight regulator for emulsion polymerization:US,6369158[P].2002.
[3]孙鹏森,惠嘉,李涛,等.几种烯丙基硫类不可逆加成断裂链转移剂在苯乙烯乳液聚合中的应用[J].弹性体,2014,24(1):9-14.
[4]安粒,惠嘉,孙鹏森,等.不可逆加成-断裂链转移剂正丁基-2-苯基烯丙基硫在苯乙烯乳液聚合中的研究[J].北京化工大学学报(自然科学版),2012,39(5):74-78.
[5]AN L,GAO C,YAN X,et al.Emulsion polymerization of styrene using irreversible addition-fragmentation chain transfer agents:effect on the course of the polymerization and molecular weight[J].Colloid&Polymer Science,2012,290(8):719-729.
[6]AN L,DI Z,YU B,et al.The effect of allylic sulfidemediated irreversible addition-fragment chain transfer on the emulsion polymerization kinetics of styrene[J].Polymers,2015,7(10):1918-1938.
[7]惠嘉.氯丁二烯自由基聚合:可逆-休眠自由基聚合、不可逆加成-断裂链转移聚合的研究[D].北京:北京化工大学,2015.
[8]陈涓,彭朴.以2,4-二苯基-4-甲基-1-戊烯为链转移剂的苯乙烯自由基聚合[J].高分子学报,1999,1(2):178-182.
[9]武鹏,冯小平,姜云刚,等.分子质量调节剂对丙烯酸酯乳液压敏胶性能的影响[J].粘接,2014(2):40-43.
[10]杨丰科,李明,李国强.基础有机化学[M].北京:化学工业出版社,2001.
[11]安粒,刘聪,果晨,等.几种不可逆加成-断裂型链转移剂在苯乙烯乳液聚合中的研究[J].弹性体,2012,22(5):7-13.
[12]刘杰.水难溶性链转移剂在乳液聚合中的扩散机理研究[D].北京:北京化工大学,2008.
[13]杨欢.自交联体系丙烯酸乳液及其水性木器清漆的研究[D].杭州:浙江大学,2006.
[14]胡金生.乳液聚合[M].北京:化学工业出版社,1987.
[15]FISCHER J P,LüDERS W.Kinetik der radikalischen copolymerisationα-substituierter styrole mit styrol.3.Teil.Das zusammenwirken von copolymerisation,retardierung und kettenübertragung in abh?ngigkeit von der chemischen struktur[J].Die Makromolekulare Chemie,1972,155(1):239-257.
[16]WATANABE Y,ISHIGAKI H,OKADA H,et al.New method in free radical chemistry using 2,4-diphenyl-4-methyl-1-pentene as radical trapping agent[J].Polymer Journal,1997,29(4):366-369.