【摘要】：本文采用本體原位法成功制備了一系列高抗沖聚苯乙烯(HIPS)樹脂。首先在苯乙烯中選擇性聚合二烯烴得到增韌橡膠的苯乙烯溶液,然后直接在自由基引發(fā)劑下進行共聚合制備HIPS。由于省去了傳統(tǒng)工藝中橡膠與惰性溶劑的分離、橡膠的干燥、橡膠在苯乙烯中溶解等步驟,因而它是一種節(jié)約成本、環(huán)境友好的新技術(shù)。主要研究內(nèi)容及結(jié)果如下： 采用稀土催化體系(酸性膦酸酯釹鹽(Nd(P507)3)/氫化二異丁基鋁(AlH(i-Bu)2)/一氯二乙基鋁(AlEt2Cl))在苯乙烯中選擇性聚合丁二烯,制得了適合增韌聚苯乙烯的聚丁二烯膠液。聚合物中苯乙烯鏈節(jié)的摩爾含量低至1.01%,聚丁二烯的順-1,4結(jié)構(gòu)含量高達96.6%。另外,采用催化體系(酸性膦酸酯釹鹽(Nd(P507)3)/氫化二異丁基鋁(AlH(i-Bu)2)/叔丁基氯(t-BuCl))在苯乙烯中選擇性共聚合丁二烯和異戊二烯。考察了聚合溫度和時間、催化劑配比、催化劑用量、陳化條件及單體配比對共聚合反應(yīng)的影響。結(jié)果表明,在Al/Nd(摩爾比)為15.0、Cl/Nd(摩爾比)為3.0、Nd/(Bd+Ip)為0.8 mmol/100g、Ip/Bd(質(zhì)量比)為1.0、70℃下聚合4 h,Bd和Ip的轉(zhuǎn)化率分別達到90%和70%以上,且共聚物中St鏈節(jié)的摩爾含量小于7%。共聚物中丁二烯和異戊二烯鏈節(jié)的1,4結(jié)構(gòu)含量均在96%以上,且其微觀結(jié)構(gòu)幾乎不受聚合條件的影響。 在制得的聚丁二烯膠液中,采用自由基引發(fā)劑3,6,9-三甲基-3,6,9-三乙基-1,4,7-三過氧烷(TETMTPA)直接引發(fā)聚丁二烯與苯乙烯共聚合制備了HIPS�？疾炝瞬煌酆蠗l件對聚合過程以及產(chǎn)品結(jié)構(gòu)和性能的影響。實驗結(jié)果表明,可通過改變聚合溫度、橡膠用量、引發(fā)劑濃度、攪拌速率和乙苯用量等因素調(diào)節(jié)苯乙烯的聚合速率、相轉(zhuǎn)變過程、聚苯乙烯的分子量及其分布、HIPS的表觀接枝率和力學(xué)性能。制得的HIPS中橡膠顆粒呈現(xiàn)較好的"salami"結(jié)構(gòu),HIPS的沖擊強度高達166 J/m。與其它自由基引發(fā)劑過氧化苯甲酰(BPO)、1,1-二(叔丁基過氧基)環(huán)己烷(DP275B)或2,2-二(4,4-二叔丁基過氧環(huán)己基)丙烷(TBPP)相比,TETMTPA引發(fā)制備的HIPS具有最高的沖擊強度。
[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，

本文編號：2490114