Effect of gegen ion in cationic polymerization and copolymerization of trioxane
Effect of gegen ion in cationic polymerization and copolymerization of trioxane
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葛根离子在阳离子聚合和三恶烷共聚中的作用
DOI：
10.1002/pol.1976.170140113
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发表时间：
1976
期刊：
影响因子：
--
通讯作者：
C. H. Chen
中科院分区：
文献类型：
--
作者：
C. H. Chen
对氯苯基重氮六氟磷酸盐
据报道，与三氟化硼二丁基醚合物 (BF3·Bu2O)1 相比，它是一种用于阳离子聚合和三恶烷共聚的优异催化剂。在本研究中，已确定源自 VA 族元素、AsF 和 SbF 的阴离子的影响。结论是，对氯苯基重氮六氟砷酸盐
也是优于三氟化硼二丁基乙醚 (BF3·Bu2O) 的催化剂，而对氯苯基重氮六氟锑酸盐
是劣等的。
获得具有最高聚合物产率 (>95%) 和分子量（特性粘度 = 4 至 5）的共聚物
据观察，催化剂浓度的简单依赖性适用于较宽的催化剂浓度范围 ([M]/[C]) = (1 至 20) × 105：
对于
同样的关系成立。然而，聚合物产率（75%）和分子量（特性粘度≃1）却相当低，而链转移程度却较高。此外，聚合反应以爆炸性暴力进行。
聚合产生的定量方面在很大程度上可以根据传播离子的解离程度来解释。
p-Chlorophenyldiazonium hexafluorophosphate
has been reported to be a superior catalyst for cationic polymerization and copolymerization of trioxane as compared to boron trifluoride dibutyl etherate (BF3·Bu2O)1. In the present investigation the effect of anions derived from elements in Group VA, AsF and SbF, has been ascertained. It has been concluded that p-chlorophenyldiazonium hexafluoroarsenate
is also a superior catalyst to boron trifluoride dibutyletherate (BF3·Bu2O), while p-chlorophenyl-diazonium hexafluoroantimonate
is inferior.
Copolymers with the highest polymer yield (>95%) and molecular weight (intrinsic viscosity = 4 to 5) were obtained with
Simple dependences on catalyst concentration have been observed to hold for a wide catalyst concentration range ([M]/[C]) = (1 to 20) × 105:
For
the same relationships hold. However, the polymer yield (75%) and molecular weights (intrinsic viscosity ≃1) are considerably lower while the extent of chain transfer is higher. Furthermore, the polymerization proceeds with explosive violence.
The quantitative aspects resulting from polymerization, for the most part, can be interpreted in terms of the extent of dissociation of the propagating ions.