摘要
对Ni(naph)_2-(i-Bu)_2AlOAr-BF_3·OEt_2(Ni-AlOAr-B)体系催化丁二烯(Bd)聚合合成BR进行了研究,发现该体系中的Ni(Ⅰ)含量比国内已工业化的Ni-Al-B体系高。对8种AlOAr的研究表明,当—OAr_1为2,6-二叔丁基-4-甲苯氧基时,体系活性最高;且AlOAr_1/Ni=5-10(mol比)、AlOAr_1/B=0.3-1.0(mol比)时,可制得[η]为2.6dL/g左右、顺式-1,4含量大于96％、凝胶含量低于0.15％的BR;该体系的动力学方程为-d[Bd]/dt=αk_p[Bd][Cat],催化剂利用率为3.0％左右,链增长速度常数随聚合温度的升高而迅速增加,但活性中心寿命却缩短。
The synthesis of cis-1,4- polybutadiene was studied by using Ni (naph)2- (i-Bu)2-AlOAr-BF3OEt2 (Ni-AlOAr-B) catalyst system .The results showed that the contentof Ni(Ⅰ) in theis catalyst system was higher than that in Ni -Al -B catalst system. When the-OAr group in the system was 2,6 -di -tert -butyl-4 -cresoxy ,the activityof the catalyst was the highest . When AlOAri1/Ni = 5 -10 (mol ratio) and AlOAr1/B =0.3-l.0(mol ratio), cis-1,4- polybutudiene with [η] =2.6 dL/g , cis-1,4 - unit content >96% , gel content < 0.15% could be obtained . The kinetic equation of the system was -d[Bd]/dt = αkp[Bd][Cat] , the utilization ratio of catalyst was about 3.0% .The rate constant of chain propogation increased rapidly with the increase of polymerization temperature , and the life period of active centers shortened .
出处
《合成橡胶工业》
CAS
CSCD
北大核心
1990年第6期402-405,共4页
China Synthetic Rubber Industry
基金
国家自然科学基金
关键词
丁二烯
聚丁二烯
催化剂
助催化剂
Ziegler-Nattaca talyst
co-catalyst
2,6-di-tert-butyl-4-cresoxy diisobutyl aluminium
cis - polybutadiene rubber
homogeneous polymerization reaction kinetics
