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纸质出版日期:1963-10-20,
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唐学明, 杨超雄, 赵善康. 用可溶性催化剂合成顺式聚丁二烯的研究——Ⅰ.用CoCl2·4C5H5N-(C2H5)2AlCl作催化剂[J]. 高分子学报, 1963,5(2):49-59.
TONG HSUEN-MING, YANG CHAO-HSIUNG, CHAO SHAN-KONG. SYNTHESIS OF C/5-l,4-POLYBUTADIENE WITH SOLUBLE CATALYSTSⅠ. CoCl2·C5H5N-(C2H5)2AlCl CATALYST[J]. Acta Polymerica Sinica, 1963,5(2):49-59.
本文研究了催化剂的用量、单体的浓度、聚合温度等聚合条件对聚丁二烯的转化率、分子量以及链结构的影响。试验结果表明:这个催化剂的特点是催化剂用量极少
1
4-顺式含量高而且稳定
聚合速度太快
高聚物的分子量过大
因此进一步研究了聚合速度的控制和高聚物分子量的调节。已得到的结果是:(1)在不同溶剂中聚合的速度相差甚大。其快慢的顺序是
苯>甲苯>二甲苯>三甲苯。(2)添加一些如苯基-β-萘胺、N
N′-二苯基对苯二胺等胺类
既可减慢聚合速度
又能降低高聚物的分子量。(3)调节体系中水分的含量
控制高聚物的分子量。(4)利用二种溶剂混合的不同比例
调节高聚物的分子量。(5)加入少量的萘、蒽等稠环芳烃于庚烷溶剂中
则大大提高高聚物的分子量。对上述结果进行了讨论。
The effects of the catalyst concentration,the monomer concentration and the poly-merization temperature on the conversion,average molecular weight and microstructure of the polybutadienes obtained have been studied. Results showed that the characteris-tics of this catalyst system are the extremely low requirement of catalyst and the high and rather constant cis一1,4-content of the polymer.The rate of polymerization is,how-ever,too fast and the molecular weight of the polymer too high. Further studies aimed at controlling the polymerization rate and regulating the molecular weight of the poly-mers showed:(1) The rate of polymerization varies greatly with the solvents,the order of which being benzene> toluene > xylene > mesitylene.(2) Addition of phenyl一β-naphthylamine or N,N’-diphenyl-p-phenylene diamine lowers both the rate of polymerisa-tion and the molecular weight of the polymer.(3) The molecular weight of the poly- met can be regulated by controlling the water content in the system.(4) The molecular weight of the polymer can also be regulated by varying the ratio of the two components of a mixed solvent.(5) Addition of small amount of polynuclear hydrocarbons,such as naphthalene or anthracene to the heptane polymerization solution raised the molecular weight of the polymer to a considerable extent.The above results were discussed.
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