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纸质出版日期:1963-12-20,
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孙家珍, 高国经. 四氟乙烯和全氟丙烯的幅射共聚合[J]. 高分子学报, 1963,5(3):123-130.
SUN CHIA-TSUNO, KAO KO-CHING. RADIATION COPOLYMERIZATION OF TETRAFLUOROETHYLENE AND HEXAFLUOROPROPYLENE[J]. Acta Polymerica Sinica, 1963,5(3):123-130.
进行了四氟乙烯与全氟丙烯在-78℃的辐射共聚合。辐照是在20
000居里的钴源中进行的。测定了不同组分的单体混合物的共聚反应速率常数(k)
发现k值随单体混合物中全氟丙烯含量增加而递减。这表示全氟丙烯的共聚活性较低。测得的辐射剂率对共聚反应速率关系式(R=KIn)中的n值系随全氟丙烯含量增加(克分子分数为0.1
0.5及0.7)而递增(分别为0.60
0.78及0.85)。这意味着增加全氟丙烯含量降低了双基终止的几率。 研究了共聚反应的后效应。发现后聚合反应的kp/kt值随辐照剂量增加而递增
这是由于辐照剂量增大相应地增加了“在源”聚合的转化率(共聚物不溶于单体)
因而诱陷了较多的游离基
以致降低了kt值的结果。 观察了一些常用的溶剂及阻聚剂对共聚反应速率的影响。大部分的结果支持这一低温液相辐射共聚反应是游离基型反应。但也不排除在某些情况下是阳离子型和游离基型并存或是阳离子型的可能。
The radiation copolymerization of tetrafluoroethylene and hexafluoropropylene was investigated at -78℃ with a 20,000-curie Co60 r-source. Values of the copolymeriza-tion rate constant were found to decrease with the increase of the amount of hexafluoro-propylene in the monomcr mixtures.This indicates that hexafluoropropylene has a lower copobrmerization reactivity. Values of n in the rate equation R=KIn are 0.60
0.78,and 0.85
as the mole fractions of hexafluoropropylene in the monomer mixtures are 0.1,0.5,and 0.7,respectively.This signifies that an increase in hexafluoropropylene concentration lowers the propability of biradical termination.A post-effect of the copolymerization was noticed. It was found that values of kp/kt in post-polymerization increase with the irradiation dosage.This fact is explained as due to the decrease in kt resulting from the enrichment of trapped polymeric radicals as a consequence of increased “in source”conversion on lfigher irradiation dosages.The effect of some common organic solvents and inhibitors on the copolymerization rate was also studied.Most of the results support a free.radical mechanism for this low-temperature liquid—phase radiation copolymerization;possibilities of simultaneous radical- cationic polymerization or of cationic polymerization,however,can not bc ruled out.
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