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纸质出版日期:1965-6-20,
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郑国栋, 刘鑫业. 聚乙烯醇与苯乙烯的辐射接枝共聚[J]. 高分子学报, 1965,7(3):178-184.
CHENG KUO-DUNG, LIU HSIN-YEH. THE RADIATION-INDUCED GRAFT COPOLYMERIZATION OF STYRENE TO POLYVINYL ALCOHOL[J]. Acta Polymerica Sinica, 1965,7(3):178-184.
本文研究了若干因素对聚乙烯醇与苯乙烯辐射接枝共聚反应的影响
并对接枝产品的性能作了初步鉴定。 在体系里加入适量的水
接枝即甚易发生
此后接枝率先随着聚合物膜片的水含量而急剧增加
然后趋于平坦
而均聚反应速度增加较慢
且在较低的水含量时就不再上升。研究了剂率对接枝过程的影响
发现在常温当所用剂率大于100伦/分时
接枝反应完全受单体扩散控制
此时
接枝速率与剂率的依赖关系式V=KI~n中的n值趋近于零。 在10~80℃范围内
接枝与温度关系的曲线在60℃通过一极大值
然后下降。但均聚反应在整个温度范围内一直随温度而不断地增加
并在温度高于60℃时出现自动加速现象
这大概是凝胶效应的缘故。氧的存在对接枝反应起抑制作用。发现适量氧或空气 的存在可以使均聚反应受到显著抑制
而接枝反应仅略为减慢。接枝产品在沸水或沸苯中的溶胀比与接枝量成线性关系
膜片的抗酸碱性能因接枝而有明显改善。
The effect of some factors on the graft copolymerization of styrene tO polyvinyl alcohol induced by γ-irradiation has been studied,and a preliminary estimation was made on the properties of the graft products.The grafting occured very readily if a proper amount of water was added to the system. It was shown that the rate of grafting in-creased sharply with the increase of water content in the polymer film and then levelled off.while the rate of homopolymerization increased more slowJY and levelled off rapidly at a lower water content.The effect of dose rate on the grafting process at room tem-perature was studied,and it was found that the grafting was entirely diffusion—controlled with the dose rate larger than 100 r/min.at which the dose rate exponent of the relation V=KP approached zero.The plot of the amount of grafting with temperature in the range of 10—80℃ passed through a maximum at 60℃ and then fell off,while the homo-polymerization increased steadily all over the temperature range and showed an auto-acceleration at temperatures above 60℃ presumably owing tO the gel effect.The presence of oxygen has an inhibiting effect on the grafting.It was found that the homopolymeriza-tion could be remarkably inhibited,with only slight reduction in the grafting,by the pre-sence of a proper amount of oxygen or air.The graft product is soluble in dimethylformamide at 150℃.The swelling ratio of the product in boiling water or in boiling benzene was found to change linearly with the grafting.It was also found that the resistance of the film to acid or alkali was signifi.candy improved by the grafting.
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