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纸质出版日期:1964-8-20,
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江英彦, 林尧昌, 林一. 聚有机硅氧烷的研究——Ⅲ.甲基苯基硅氧烷的平衡化反应[J]. 高分子学报, 1964,6(4):322-329.
CHIANG YIN-YEN, LIN YAO-CHANG, LIN I. STUDIES ON POLYORGANOSILOXANES——Ⅲ. THE EQUILIBRATION OF METHYPHENYLSILOXANES[J]. Acta Polymerica Sinica, 1964,6(4):322-329.
(1)研究了甲基苯基硅氧烷在碱及酸存在下的平衡化反应
得到有机硅氧烷的反应性的顺序如下:在碱的催化下
[(CH3)(C6H5)SiO]3>[(CH3)2SiO]3>[(CH3)(C6H5)2Si]2O (?) 在酸的催化下
[(CH3)2SiO]3>[(CH3)(C6H5)SiO]3 [(CH3)2SiO]4>[(CH3)(C6H5)SiO]4 [(CH3)2SiO]4>[(CH3)(C6H5)2Si]2O (2)由CH3SiCl3与(CH3)2SiCl2共水解及共缩合所得的环状聚合体在平衡化反应中出现了特殊的现象
就是聚合体的粘度低于平衡时的粘度
而且达到平衡的时间很长。其原因系环状聚合体中合有SiOH。这羟基可用大量溶剂在碱催化下加热去掉。这种含有三官能度的环状聚合体与MD2M或MM进行平衡化时容易出现凝胶。改用M″M″可以避免凝胶。
(1) The relative reactivities of various methylphenysiloxanes were studied by the method of equilibration of Kantor using (CH3)4NoH as catalyst.The results are given in Fig.1—5.The reactivities of the cyclic polyphenylsiloxanes and cyclic polymethy-siloxanes were compared by means of copolymerization in the presence of (CH3)4NOH or H2SO4.See Table 1. From these results,methyl and phenyl siloxanes can be arranged in the following order of decreasing reactivity: In basic medium,[(CH3)(C6H5)ao]3>[(CH3)2slo]3>[(CH3)(C6H5)2Si]2O>[CH3)(C6H5)SiO]4>[(CH3)2SiO]4In acid medium, [(CH3)2SiO]3>[(CH3)(C6H5)SiO]3
[(CH3)2SiO]4>[(CH3)(C6H5)SiO]4
[(CH3)2SiO]4>[(CH3)(C6H5)2Si]2O.Increasing phenyl groups increases the reactivity of siloxanes in basic medium with the exception that [(C6H5)3Si]2O being less reactive than [(CH3)(C6H5)2Si]2O.This is prob-ably due to the steric hindrance of the large number of bulky phenyl groups.On the other hand,phenyl group lowers the reactivity of siloxanes in acid medium.(2) Cyclic low polymers of polysiloxane containing small amount of trifunctional groups were prepared by cohydrolysis of (CH3)2SiCl2 and CH3SiCl3.When incor-porated with [(CH3)3SiOSi(CH3)2]2O and equilibrated in the presence of (CH3)4 NOH,the equilibrium was reached only after long time of heating,and there was a lowering of the viscosity below that of the equilibrium level (Fig.6,curve 1).This phenomenon is traced to the presence of OH groups in the cyclic low polymers. Gel formation which is observed when [(CH3)3SiOSi(CH3)2]2O is used in small amount as chain terminating agent can be avoided when [(CH3)(C6H5)2Si]2O is used in its place(Fig.6,7).
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