张书华,刘波,李洪森,张娅娅,朱晓鹰,唐家玲,陈砾

• 1:哈尔滨理工大学化学与环境工程学院
• 2:上海工程技术大学化学化工学院

摘要(Abstract)：

采用混合溶剂法和相转移催化剂合成酯基锡(甲酯)。结果表明,反应时间为5～6 h,反应温度为53～58℃,Na2CO3水溶液浓度为20%是最佳合成条件。所合成产物存放120 d以上依然澄清透明,解决了NaHCO3法合成酯基锡(甲酯)放置不超过7 d就出现沉淀和臭味重的问题。用IR、1H-NMR对产物进行结构表征。结果表明,新方法合成产物红外吸收峰归属和主要官能团化学位移与NaHCO3法合成的产物一致。在50～650℃,空气氛围,用TG/DTG研究了酯基锡(甲酯)/PVC复合体系的热降解过程,并与甲基硫醇锡/PVC复合体系进行对比。结果表明,酯基锡(甲酯)对PVC的初期稳定性好于甲基硫醇锡,抑制PVC着色性能不及甲基硫醇锡。当T>300℃时,酯基锡(甲酯)/PVC复合体系的降解速度相对变慢,热失重率更小。用塑炼机和比色测色仪测试两个复合体系的动态热稳定性,从测试结果可见,在180～183℃,塑炼15 min,酯基锡(甲酯)/PVC复合体系的透光率仅从86.76%下降到84.18%,黄度值从7.54上升到8.95。透光率好于甲基硫醇锡/PVC复合体系,黄度值变化相差不大,说明酯基锡(甲酯)能使PVC保持良好的透明性和加工稳定性。研究提出的合成方法解决了酯基锡合成中存在的瓶颈问题,所合成的产品适合应用于制备PVC透明制品。

关键词(KeyWords)： 聚氯乙烯;酯基锡;合成;热稳定性

Abstract:

Keywords:

基金项目(Foundation): 上海市教育委员会科研创新项目(09YZ369);; 上海工程技术大学大学生科研训练项目(A-0500-08-E793)

作者(Author): 张书华,刘波,李洪森,张娅娅,朱晓鹰,唐家玲,陈砾

参考文献(References)：

• [1]Jindra P,Kim F D,Wendy V Z,et al.New insight into the formation of structural defects in poly(vinyl chloride)[J].Macromolecules,2005,38(15):6352-6366.
• [2]ZHAN Xiao-qiang(占晓强),YIN Jian-ping(尹建平),WEI Jia-fu(魏家福),et al.Effects of agitation speed on the average diameter ofPVC suspension resin(搅拌速度对悬浮PVC树脂平均粒径的影响)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2009,23(6):962-966.
• [3]Tran V H,Nguyen T P,Molinie P.Thermal stabilization of PVC via the polaron mechanism,PartⅢ:Stabilization with organotincompounds[J].Polymer Degradation and Stability,1996,53(2):279-288.
• [4]Madoka O,Takaomi A,Sayaka M,et al.Distribution and fate of organotin compounds in Japanese coastal waters[J].Water,Air,Soil Pollut,2007,178(6):255-265.
• [5]Choi Mink-yu,Choi Hee-gu,Moon Hyo-bang,et al.Spatial and temporal distribution of tributyltin(TBT)in seawater,sediments andbivalves from coastal areas of Korea during 2001-2005[J].Environ Monit Access,2009,151(8):301-310.
• [6]Karin B.Organotin compounds in sediments from the G?TA ALV ESTUARY[J].Water,Air,and Soil Pollution,2002,135(1):131-140.
• [7]OU Q R,WHANG C W.Determination of butyltin and octyltin stabilizers in poly(vinyl chloride)products by headspace solid-phasemicroextraction and gas chromatography with flame-photometric detection[J].Anal Bioanal Chem,2006,386(6):376-381.
• [8]Pablo R G,Jorge R E J,Ignacio G A.Monitoring the degradation and solubilisation of butyltin compounds during in vitrogastrointestinal digestion using‘‘triple spike’’isotope dilution GC-ICP-MS[J].Anal Bioanal Chem,2005,381(4):3801-3807.
• [9]FANG Zhi-yong(方志永),WU Bin(吴斌),YONG Xiao-jia(雍晓嘉),et al.An investigation analysis of a toxicosis event byorganotin(一起有机锡中毒事件调查分析)[J].Zhejiang Prev Med(浙江预防医学),2008,6(2):36-37.
• [10]WANG Tao-feng(汪涛峰),YE Bei(叶焙),JIANG Shi-lu(江世履),et al.The toxicosis of trimethytin chloride and some suggestionsto the development of methyltin mercaptide(三甲基氯化锡的毒性及对甲基硫醇锡开发工作的几点建议)[J].PlasticsAdditives(塑料助剂),2003,39(3):25-30.
• [11]YU Li-hong(于立红),WANG Meng-xue(王梦雪),ZHANG You-li(张有利).Contamination of organotin compounds to environmentand its toxicity(有机锡化合物对环境的污染及其毒性)[J].Heilongjiang Agricultural Science(黑龙江农业科学),2008,23(2):91-92.
• [12]AKZO N V Company.Process for making organotin dihalides and trihalides and stabilizers prepared:Holand,7,790,176[P].1976-12-24.
• [13]Ronald E H,Burley J W,Vincento O.β-substituted alkyltin halides(Ⅰ)[J].Journal of Organometallic Chemmistry,1978,156(4):369-382.
• [14]Burley J W,Peter H,Ronald E H.β-substituted alkyltin halides(Ⅱ)[J].Journal of Organometallic Chemmistry,1979,170(1):21-37.
• [15]WEI Rong-bao(魏荣宝),LIANG Ya(梁娅),LU Shi-rong(卢士荣),et al.Synthesis and properties of organotin carboxylates(双β-烷氧羰烷基)锡羧酸酯的合成及性质)[J].Chemical Industry and Engineering(化学工业与工程),1997,14(1):46-51.
• [16]ZHANG Shu-hua(张书华),WANG Hong(王虹),ZHAO Chun-shan(赵春山),et al.Study on industrial production process ofbis(β-methoxycarbonylethyl)tin dichlorides(二-β甲氧甲酰乙基二氯化锡工业化生产工艺路线研究)[J].Journal of HarbinUniversity of Science and Technology(哈尔滨理工大学学报),2004,9(4):127-129.
• [17]National Plastics Standardization Technology Committee.GB2917-2002 National Standard of Peoples Republic of China[S].Beijing:National Standard General Bureau,2002.
• [18]ZHANG Qiang(张强),LüJie-bin(吕杰斌).Thermal stability and fluid properties of poly(vinyl chloride)filled with hydrotalcite(水滑石填充PVC材料的热稳定性能及流动性能)[J].Journal of Beijing University of Chemical Technology(北京化工大学学报),2002,29(1):36-38.
• [19]LI Sheng-xing(李盛兴),BAO Yong-zhong(包永忠),HUANG Zhi-ming(黄志明).Influence of nano-hydrotalcite on thermalstability and smoke density of poly(vinyl chloride)(纳米水滑石对PVC热稳定性和烟密度的影响)[J].Plastics Additives(塑料助剂),2007,62(2):20-21.
• [20]Joseph W B,Ronald E H.A study of mercaptoester/chlorine exchange equlibria exhibited byβ-carboalkoxyethyltin compounds[J].Journal of Organometallic Chemistry,1985,284(2):171-180.
• [21]ZHANG Shu-hua(张书华),LIU Bo(刘波),CAO Jian(曹俭),et al.Synthesis of ester-tin(butyl acrylate)and processing stability forPVC(酯基锡(丁酯)的合成及其对PVC的热稳定性)[J].J Chem Ind and Eng(China)(化工学报),2009,60(8):2112-2117.
• [22]Vrandecic N S,Klaric I,Kovicic I.Thermooxidative degradation of poly(vinyl chloride)and chlorinated polyethylene with differentCa/Zn carboxylates[J].Journal of Thermal Analysis and Calorimetry,2003,74(3):171-180.
• [23]TANG Ai-dong(唐爱东),HUANG Ke-long(黄可龙),TANG You-gen(唐有根).Developing status and prospect of estertin as PVCheat stabilizer(PVC热稳定剂酯基锡的研究现状与展望)[J].Modern Plastics Processing and Application(现代塑料加工应用).1998,10(4):28-31.
• [24]TIAN Lai-jin(田来进),ZHUO Run-sheng(卓润生).Synthesis of ester-tin-new organotin stabilizer middle substance for PVC(新型PVC有机锡类稳定剂中间体_酯基锡的合成)[J].Shandong Chemical Engineering(山东化工),1996,2(1):18-20.
• [25]CHEN Shen-qing(陈深情).Studies on Effect of Additives on Photo Aging and Smoke Suppression Property(改性剂对聚氯乙烯紫外光老化性能和抑烟性能的研究)[D].Chengdu(成都):Sichuan University(四川大学),2007.