烯烃易位法降解顺丁橡胶及制备遥爪低聚物的研究

发布时间：2018-11-19 12:39

【摘要】：采用烯烃交叉易位反应,在Grubbs二代催化剂和含有功能基团的链转移剂作用下,研究了工业级高分子量顺丁橡胶的降解以及高附加值遥爪型丁二烯低聚物的制备.涉及的链转移剂主要是轴对称的顺丁烯类衍生物:顺-1,4-二氯-2-丁烯(DCB)、顺-1,4-二乙酰氧基-2-丁烯(DAB)、马来酸二甲酯(DMM)、马来酸二乙酯(DEM).产物的分子量(Mn)和分子量分布指数(PDI)通过凝胶渗透色谱仪(GPC)测定,产物的分子链段结构和组分通过红外光谱(FTIR)、核磁共振氢谱(1H-NMR)以及高效液相色谱-质谱联用(LC-MS)表征.实验结果表明,通过引入不同的链转移剂,控制顺丁橡胶/链转移剂、顺丁橡胶/催化剂的摩尔投料比以及反应时间,可以有效控制低聚物的Mn和PDI,其Mn变化范围为230~4800,PDI变化范围为1.09~2.82.进一步研究发现,在一定反应条件引入DAB,可以逐一断裂顺丁橡胶的主链,获得丁二烯重复单元仅为1的小分子新结构.
[Abstract]:The degradation of high molecular weight cis-butadiene rubber and the preparation of high value-added tele-clawed butadiene oligomer were studied by using Grubbs second generation catalyst and chain transfer agent containing functional groups. The main chain transfer agents involved are axisymmetric maleic derivatives: cis-1- 4- dichloro-2-butene (DCB),-cis-1- (4-diacetyl-2-butene) -dimethyl maleate (DMM),) diethyl maleate (DEM). (diethyl maleate) The molecular weight (Mn) and molecular weight distribution index (PDI) of the product were determined by gel permeation chromatography (GPC). The molecular chain structure and components of the product were determined by IR (FTIR),. Nuclear magnetic resonance (1H-NMR) and high performance liquid chromatography-mass spectrometry (LC-MS) characterization. The experimental results show that by introducing different chain transfer agents, controlling the mole ratio of cis-butadiene rubber / chain transfer agent, the molar ratio of cis-butadiene rubber / catalyst and the reaction time, the Mn range of Mn and PDI, of oligomers can be effectively controlled in the range of 230? 4800? The range of PDI was 1.09 and 2.82. It was found that the main chain of cis-butadiene rubber could be broken one by one with the addition of DAB, under certain reaction conditions, and a new structure of butadiene repeat unit with only 1 was obtained.
【作者单位】：苏州大学材料与化学化工学部绿色高分子工程与催化技术实验室;
【基金】：国家自然科学基金项目(基金号21176163,21576174) 苏州工业园区、江苏高校优势学科建设工程资助项目苏州大学创新研究小组计划
【分类号】：O631.3;TQ333.2

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