合成橡胶工业090609-橡胶技术网 www.sto.net.cn

	合成橡胶工业 CHINA SYNTHETIC RUBBER INDUSTRY 2009 Vol.32 No.6 P.480-484

窄分布低乙烯基线型液体聚丁二烯的环氧化反应

张红霞　张春庆　陈畅　王玉荣　李杨　

摘　要：采用负离子聚合法设计合成了分子量分布(MWD)窄、乙烯基含量低的线型液体聚丁二烯(NDLPB),然后用过氧甲酸原位法制备了不同环氧度的环氧化线型液体聚丁二烯(ENDLPB),并以其为偶联剂合成了梳状聚丁二烯,通过核磁共振法对ENDLPB的环氧度和结构进行了表征,考察了ENDLPB环氧度的影响因素.结果表明,随着ENDLPB环氧度的增加,环氧基特征峰逐渐增强,顺式-1,4-结构和反式-1,4-结构含量减小,1,2-结构含量不变;随着NDLPB数均分子量(~￣M_n)的增加,ENDLPB的环氧度减小,且~￣M_n略有增大,MWD约为1.08;以~￣M_n为2 450、MWD为1.07的NDLPB为反应物,在H_2O_2/NDLPB(摩尔比)为0.5、甲酸/NDLPB(摩尔比)为 0.4、反应温度为50 ℃的条件下反应2 h,可获得环氧度约为33%的ENDLPB,且实验的重复性良好;改变ENDLPB用量可获得不同偶联度的梳状聚丁二烯.
关键词：负离子聚合;液体聚丁二烯;环氧化;微观结构;分子量分布;偶联剂
分类号：TQ333.99 　文献标识码：A
文章编号：1000-1255(2009)06-0480-05

Epoxidation of low vinyl linear liquid polybutadiene with narrow molecular weight distribution

Zhang Hongxia（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Zhang Chunqing（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Chen Chang（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Wang Yurong（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Li Yang（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　

Abstract：The linear liquid polybutadiene with narrow molecular weight distribution(MWD)and low vinyl content (NDLPB)were synthesized by anionic polymerization. The epoxidized liquid polybutadiene(ENDLPB) with different epoxidation degree were prepared by formic acid-hydrogen peroxide in-situ method and used as coupling agent for comb polybutadiene. The epoxidation degree and microstructure of ENDLPB were characterized by nuclear magnetic resonance. The effect factors on epoxidation degree of ENDLPB were investigated. The results showed that with the increase of epoxidation degree, the characteristic peaks of epoxy group gradually increased, the contents of cis-1,4-uint and trans-1,4-unit decreased, and the 1,2-unit content almost had no change. With increasing ~￣M_n of NDLPB, epoxidation degree of ENDLPB decreased,~￣M_n of ENDLPB slightly increased, and the MWD of ENDLPB was around 1.08. With NDLPB of ~￣M_n of 2 450,MWD of 1.07 as the reactants, under the conditions of H_2O_2/NDLPB(mole ratio) 0.5, formic acid/NDLPB(mole ratio) 0.4, reaction at 50 ℃ for 2 h, the epoxidation degree of ENDLPB was about 33%, and experimental repeatability was good. The comb polybutadienes with different coupling degree were synthesized by changing amount of ENDLPB .
Keywords：anionic polymerization; liquid polybutadiene; epoxidation;microstructure;molecular weight distribution; coupling agent

基金项目：国家"八六三"计划资助项目(2007 AA 03 Z 532).
作者简介：张红霞(1982-),女,博士研究生.已发表论文6篇.
作者单位：张红霞（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连,116012）　
　　　　　张春庆（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连,116012）　
　　　　　陈畅（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连,116012）　
　　　　　王玉荣（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连,116012）　
　　　　　李杨（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连,116012）　

参考文献：

[1]王维.液体聚丁二烯在橡胶加工、树脂、电子及电力工业中的应用[J].弹性体,2000,10 (1):30-33.
[2]陈勇,赵巍,谢洪泉.顺丁橡胶及环氧化产物作为增容剂的研究[J].弹性体,2007,17(1):28-31.
[3]Zhang Chunqing,Chen Chang,Zhang Hongxia,et al.Coupling agent of epoxidized liquid polybutadiene for anionic polymerization of butadiene[J].合成橡胶工业,2008,31(5):403.
[4]Zuchowska D.Polybutadiene modified by epoxidation(1):Ef-fect of polybutadiene microstructure on the reactivity of double bonds[J].Polymer,1980,21 (5):514-520.
[5]宋西全.特种弹性体的研制[D].大连:大连理工大学,1999.
[6]Wang Xiaosong,Winnik M A,Manners I.Synthesis of the first organometallic miktoarm star polymer[J].Macromol Rapid Commun,2003,24(5/6):403-407.
[7]Liu Shaoyu,Zhang Chunqing,Zeng Fanjun,et al.Anionic homopolymerization of butadiene withepoxidized soybean oilascoupling agent[J].合成橡胶工业,2006,29(3):227.
[8]Gregório J R,Gerbase A E,Mendes Ana N F,et al.Pre-determination of the epoxidation degree of polydienes using methyltrioxorhenium-CH_2Cl_2/H_2O_2 biphasic catalytic system[J].React Funct Polym,2005,64(2):83-91.
[9]Maenz K,Schuetz H,Stadermann D,et al.Structural investigations on low molecular weight polybutadienes and the corresponding epoxides[J].Eur Polym J,1993,29(6):855-861.
[10]Wang Yurong,Qi Shicheng,Song Xiquan,et al.Epoxidation of low vinyl polybutadiene rubbers[J].合成橡胶工业,1998,21(2):1.

收稿日期：2008年12月25日

修稿日期：2009年9月2日

出版日期：2009年11月15日