本体原位法制备高抗冲聚苯乙烯树脂
发布时间：2019-06-01 08:04
【摘要】：本文采用本体原位法成功制备了一系列高抗冲聚苯乙烯(HIPS)树脂。首先在苯乙烯中选择性聚合二烯烃得到增韧橡胶的苯乙烯溶液,然后直接在自由基引发剂下进行共聚合制备HIPS。由于省去了传统工艺中橡胶与惰性溶剂的分离、橡胶的干燥、橡胶在苯乙烯中溶解等步骤,因而它是一种节约成本、环境友好的新技术。主要研究内容及结果如下： 采用稀土催化体系(酸性膦酸酯钕盐(Nd(P507)3)/氢化二异丁基铝(AlH(i-Bu)2)/一氯二乙基铝(AlEt2Cl))在苯乙烯中选择性聚合丁二烯,制得了适合增韧聚苯乙烯的聚丁二烯胶液。聚合物中苯乙烯链节的摩尔含量低至1.01%,聚丁二烯的顺-1,4结构含量高达96.6%。另外,采用催化体系(酸性膦酸酯钕盐(Nd(P507)3)/氢化二异丁基铝(AlH(i-Bu)2)/叔丁基氯(t-BuCl))在苯乙烯中选择性共聚合丁二烯和异戊二烯。考察了聚合温度和时间、催化剂配比、催化剂用量、陈化条件及单体配比对共聚合反应的影响。结果表明,在Al/Nd(摩尔比)为15.0、Cl/Nd(摩尔比)为3.0、Nd/(Bd+Ip)为0.8 mmol/100g、Ip/Bd(质量比)为1.0、70℃下聚合4 h,Bd和Ip的转化率分别达到90%和70%以上,且共聚物中St链节的摩尔含量小于7%。共聚物中丁二烯和异戊二烯链节的1,4结构含量均在96%以上,且其微观结构几乎不受聚合条件的影响。 在制得的聚丁二烯胶液中,采用自由基引发剂3,6,9-三甲基-3,6,9-三乙基-1,4,7-三过氧烷(TETMTPA)直接引发聚丁二烯与苯乙烯共聚合制备了HIPS。考察了不同聚合条件对聚合过程以及产品结构和性能的影响。实验结果表明,可通过改变聚合温度、橡胶用量、引发剂浓度、搅拌速率和乙苯用量等因素调节苯乙烯的聚合速率、相转变过程、聚苯乙烯的分子量及其分布、HIPS的表观接枝率和力学性能。制得的HIPS中橡胶颗粒呈现较好的"salami"结构,HIPS的冲击强度高达166 J/m。与其它自由基引发剂过氧化苯甲酰(BPO)、1,1-二(叔丁基过氧基)环己烷(DP275B)或2,2-二(4,4-二叔丁基过氧环己基)丙烷(TBPP)相比,TETMTPA引发制备的HIPS具有最高的冲击强度。
[Abstract]:In this paper, a series of high impact polystyrene (HIPS) resins were successfully prepared by bulk in situ method. The styrene solution of toughened rubber was obtained by selective polymerization of diolefins in styrene, and then HIPS. was prepared by direct polymerization under free radical initiator. Because the separation of rubber and lazy solvent, the drying of rubber and the dissolution of rubber in styrene are eliminated, it is a cost-saving and environmentally friendly new technology. The main research contents and results are as follows: rare earth catalytic system (acid phosphonic acid ester neodymium salt (Nd (P507) 3) / diisobutylaluminum hydrogenated (AlH (i-Bu) 2) / monochlorodiethyl aluminum (AlEt2Cl) in phenylethyl Selective polymerization of Butadiene in alkene, PolyButadiene glue suitable for toughening polystyrene was prepared. The molar content of styrene in the polymer is as low as 1.01%, and the content of cis-1 and 4 structure of polyButadiene is as high as 96.6%. In addition, catalytic system (acid phosphonic acid ester neodymium salt (Nd (P507) 3) / diisobutylaluminum (AlH (i-Bu) 2) / tert-butylchloride (t-BuCl) was used for selective polymerization of Butadiene and Isoprene in styrene. The effects of polymerization temperature and time, catalyst ratio, catalyst dosage, aging condition and monomer ratio on the polymerization were investigated. The results show that when Al/Nd (molar ratio) is 15.0, Cl 鈮，
本文编号：2490114
[Abstract]:In this paper, a series of high impact polystyrene (HIPS) resins were successfully prepared by bulk in situ method. The styrene solution of toughened rubber was obtained by selective polymerization of diolefins in styrene, and then HIPS. was prepared by direct polymerization under free radical initiator. Because the separation of rubber and lazy solvent, the drying of rubber and the dissolution of rubber in styrene are eliminated, it is a cost-saving and environmentally friendly new technology. The main research contents and results are as follows: rare earth catalytic system (acid phosphonic acid ester neodymium salt (Nd (P507) 3) / diisobutylaluminum hydrogenated (AlH (i-Bu) 2) / monochlorodiethyl aluminum (AlEt2Cl) in phenylethyl Selective polymerization of Butadiene in alkene, PolyButadiene glue suitable for toughening polystyrene was prepared. The molar content of styrene in the polymer is as low as 1.01%, and the content of cis-1 and 4 structure of polyButadiene is as high as 96.6%. In addition, catalytic system (acid phosphonic acid ester neodymium salt (Nd (P507) 3) / diisobutylaluminum (AlH (i-Bu) 2) / tert-butylchloride (t-BuCl) was used for selective polymerization of Butadiene and Isoprene in styrene. The effects of polymerization temperature and time, catalyst ratio, catalyst dosage, aging condition and monomer ratio on the polymerization were investigated. The results show that when Al/Nd (molar ratio) is 15.0, Cl 鈮，
本文编号：2490114
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