【摘要】： 本文首先合成了含保護(hù)性基團(tuán)的新型引發(fā)劑3-(叔丁基二甲基硅氧烷基)-1-丙基鋰,以該有機(jī)鋰化合物為引發(fā)劑引發(fā)丁二烯聚合并制備了端羥基聚丁二烯。與常用的雙鋰引發(fā)劑相比,可以有效的避免在封端時(shí)出現(xiàn)的假凝膠現(xiàn)象。具體方法包括：用環(huán)氧乙烷封端、二溴乙烷偶聯(lián),酸化水解處理制備線型端羥基聚丁二烯；用四氯化硅、二乙烯基苯(DVB)偶聯(lián),酸化水解制備多端羥基聚丁二烯。 在丁二烯合成過程中,通過添加四氫呋喃為結(jié)構(gòu)調(diào)節(jié)劑,研究了此體系對(duì)聚丁二烯的微觀結(jié)構(gòu)的控制。通過GPC、1H-NMR測(cè)試結(jié)果表明：丁二烯聚合在30℃下,不加入調(diào)節(jié)劑時(shí),反應(yīng)20小時(shí)左右,1,4-結(jié)構(gòu)含量較高,可達(dá)92.1%,調(diào)節(jié)劑的加入可使1,4-結(jié)構(gòu)含量顯著下降。同時(shí)聚合物的分子量大小與設(shè)計(jì)分子量接近、分子量分布較窄。對(duì)環(huán)氧乙烷封端及二溴乙烷偶聯(lián)制備線型端羥基聚丁二烯羥值分析,平均官能度接近2；四氯化硅及DVB偶聯(lián)反應(yīng)制備多端羥基聚丁二烯,偶聯(lián)劑的加入量增加偶聯(lián)效率增大。在2L反應(yīng)釜聚合與250ml聚合瓶中相比,偶聯(lián)劑采用分兩次加入方式偶聯(lián)效率較高,單臂分子量設(shè)計(jì)15000,偶聯(lián)劑四氯化硅用量是計(jì)量1.2倍時(shí),偶聯(lián)效率可達(dá)95%,官能度達(dá)3.8,[DVB]/[Li]=5,偶聯(lián)效率達(dá)到了88.7%,平均臂數(shù)為6.1。 對(duì)TDI作為交聯(lián)劑與星型丁羥膠反應(yīng)進(jìn)行了初步研究,并對(duì)制得的羥丁型聚氨酯材料進(jìn)行了DMTA及物理力學(xué)性能測(cè)試,結(jié)果表明星型丁羥膠([DVB]/[Li]=5)單臂分子量為15000時(shí)制得的羥丁型聚氨酯,拉伸強(qiáng)度可達(dá)0.8MPa,斷裂伸長(zhǎng)率為830%,0℃的Tgδ值可達(dá)0.243,60℃的Tgδ值可達(dá)0.235。
[Abstract]:In this paper, a new initiator 3- (tertiary Ding Ji dimethylsiloxane) -1-propyl lithium with protective group was synthesized. The organic lithium compound was used as initiator to initiate the polymerization of butadiene and to prepare hydroxy-terminated polybutadiene. Compared with the commonly used bislithium initiator, the pseudogel phenomenon can be avoided effectively. The specific methods include: synthesis of linear hydroxyl terminated polybutadiene by ethylene oxide sealing, coupling of dibromoethane and acidizing hydrolysis, coupling with silicon tetrachloride and divinylbenzene (DVB), and preparation of multihydroxyl polybutadiene by acidizing hydrolysis. The control of the microstructure of polybutadiene was studied by adding tetrahydrofuran as structure regulator during the synthesis of butadiene. The results of GPC-1H-NMR showed that when butadiene was polymerized at 30 鈩，

本文編號(hào)：2121766