导　　师： 戚国荣

学科专业： 070305

授予学位： 博士

作　　者： ;

机构地区： 浙江大学

摘　　要： 首次使用以Zn/_3/[Co/(CN/)/_6/]/_2/(ZHCC/)为基础的双金属氰化络合物/(DMC/)催化剂成功地进行了环氧丙烷/(PO/)与CO/_2的共聚反应,得到的脂肪族聚碳酸酯中CO/_2摩尔分数/(f/_/(CO2/)/)达到0.32以上,同时生成碳酸亚丙酯副产物,表观催化剂效率高达2000g聚合物//g催化剂以上。催化效率是Fe-Zn DMC,羧酸锌催化剂效率的约20倍,ZnEt/_2-多质子化合物催化剂的约50倍。系统地研究了聚合反应条件对催化效率和产物组成的影响,结果表明,在80-130℃范围内催化剂效率随温度升高而增加;压力增大,催化剂效率下降,一次加料呈现的催化效率低于逐步加料方式。多数聚合物的f/_/(CO2/)在0.1～0.32之间,并且f/_/(CO2/)随温度下降,压力升高而增加,而碳酸亚丙酯的含量依条件变化在10～30/%之间,较高的反应温度,较高的体系压力有利于碳酸亚丙酯的生成。 系统研究了催化剂制备方法对其催化效率的影响。结果表明,使用不同有机配体的催化剂活性有明显差异,以叔丁醇为有机配体的催化剂活性最好,使用这些催化剂制备的共聚物的f/_/(CO2/)差异不大;使用多种锌盐制备的催化剂中,已证明Lewis酸ZnX/_w/(X=Cl、Br、I、F/)是催化剂催化活性的关键组分:通过对掺杂其它金属卤盐的实验表明,除AlCl/_3、SnCl/_2不影响催化效率外,多数金属卤盐的加入降低催化效率,达不到预期提高催化效率的目的。 将该催化剂用于催化氧化环己烯/(CHO/)与CO/_2的共聚反应,得到了重均分子量在40,000～50,000,接近交替的共聚物/(f/_/(CO2/)=0.45～0.47/)。在催化剂浓度为1.2×10~/(-4/)下可有效催化CHO与CO/_2的共聚合,催化效率最高达到10,000g聚合物//g ZHCC以上。该DMC催化剂催化效率是二乙基锌,羧酸锌等传统催化剂的20-50倍,是最新的二亚胺合锌催化剂的10倍左右,是目前各文献报道的催化剂中催化效率最高的催化剂。 The DMC catalyst based on Zn3/[Co/(CN/)6/]2 /(ZHCC/) was employed successfully in copolymerization of propylene oxide /(PO/) and CO2, the highest molar fraction of CO2 in PO- CO2 copolymer/(f CO2/) was 0.32, at the same time, propylene carbonate/(PC/) was also obtained as by-product. The efficiency of catalyst was up to 2,000 g copolymer//g ZHCC, which was about 20 times and 50 times over efficiency of Fe-Zn DMC, zinc carboxylate and ZnEt2-multiprotic compounds respectively. The effect of reaction conditions on efficiency and composition of products was investigated. The results revealed that catalytic efficiency increased with ascending temperature and descending pressure. The efficiency demonstrated in stepwise feed was lower than that in one-pot feed. The f CO2 was at the range of 0.1-0.32, and it ascended with increased pressure and decreased temperature. The content of PC varied between 10~30/% under different reaction conditions. The results showed that higher temperature and pressure were favored for production of PC.The effect of preparative method on catalytic efficiency was systematically studied. The results showed that catalyst exhibited different efficiency when various organic solvents were employed in preparation of catalyst, the catalyst exhibited highest efficiency when tert-butyl alcohol was used. These catalysts showed no difference on f CO2- Lewis acid zinc halide was testified as important composition when various zinc salts were used in preparation of catalysts. When other halide salts were used combining with zinc chloride in preparation, the efficiency of resulted catalysts decreased sharply except for AlCl3, SnCl2.When the catalyst was used in copolymerization of cyclohexene oxide /(CHO/) and CO2 , the nearly alternative copolymer /(f CO2=0.45~0.47/) with Mw = 40,000~50,000 was obtained. The efficiency for CHO- CO2 copolymerization was up to 10,000 copolymer// g ZHCC at concentration of 120 ppm. To sum up, the catalyst exhibited highest efficiency for epoxide-CO2 copolymerization among co

关 键 词： 环氧化物 二氧化碳 聚碳酸酯 共聚 氰化络合物催化剂

领　　域： [理学] [理学]