POLYMERIZATION OF MONOMERS CONTAINING FUNCTIONAL SILYL GROUPS .11. ANIONIC LIVING POLYMERIZATION OF 3-(TRI-2-PROPOXYSILYL)PROPYL METHACRYLATE

被引:48
作者
OZAKI, H [1 ]
HIRAO, A [1 ]
NAKAHAMA, S [1 ]
机构
[1] TOKYO INST TECHNOL,FAC ENGN,DEPT POLYMER CHEM,2-12-1 OHOKAYAMA,MEGURO KU,TOKYO 152,JAPAN
关键词
D O I
10.1021/ma00031a005
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Anionic polymerizations of 3-(trimethoxysilyl)propyl (3a), 3-(triethoxysilyl)propyl (3b), and 3-(tri-2-propoxysilyl)propyl methacrylates (3c) were investigated in THF at -78-degrees-C with a variety of initiators. They included butyllithium, 1,1-diphenylhexyllithium, 1,1-diphenylhexyllithium-LiCl, cumylpotassium capped with 1,1-diphenylethylene (DPE), 1,4-dipotassio-1,1,4,4-tetraphenylbutane from potassium naphthalenide and DPE, benzylmagnesium chloride, potassium tert-butoxide, and LiAlH4. The polymerization of 3c proceeded well to give poly(3c) quantitatively with each of all the initiators except for LiAlH4. Among these, the combination of 1,1-diphenylhexyllithium and LiCl is particularly an excellent initiator system which produces polymers of predictable molecular weights and of very narrow molecular weight distributions (M(w)BAR/M(n)BAR < 1.05). Thus, the living character of the polymerization of 3c with this system has been demonstrated. A novel well-defined block copolymer, poly(3c-b-methyl methacrylate), could be synthesized by the sequential anionic living polymerization of 3c with methyl methacrylate. Similarly, block copolymers of poly(methyl methacrylate-b-3c) and poly(styrene-b-3c) were also synthesized quantitatively. The hydrolytic behavior of poly(3c) was studied in detail in water, 2 N HCl, or 1 N NaOH.
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页码:1391 / 1395
页数:5
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