Anionic synthesis of polymers functionalized with a terminal anhydride group

被引:26
作者
Cernohous, JJ
Macosko, CW
Hoye, TR
机构
[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455
[2] UNIV MINNESOTA,DEPT CHEM ENGN & MAT SCI,MINNEAPOLIS,MN 55455
关键词
D O I
10.1021/ma9702096
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Polymers bearing a single succinic anhydride at the chain end were synthesized using anionic polymerization techniques. Specifically, the living anions of poly(methyl methacrylate) (PMMA), polystyrene (PS), polyisoprene (PI), and poly(vinylpyridine) (PVP) were found to exclusively undergo a 1,4-conjugate addition reaction with di-tert-butyl maleate. Only a single maleate adds. The gel permeation chromatograms for the synthesized polymers were found to have very narrow molecular weight distributions (M-w/M-n < 1.15) after the end-capping reaction. Pyrolysis (235 degrees C, 2-12 h) of the resulting substituted di-tert-butyl succinate ester efficiently produced the related succinic anhydride functional polymers in the case of PMMA and PS. The functionality of these polymers (f greater than or equal to 0.81) was determined following derivatization reactions with various amines. Nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) of the resulting amides permits quantification of the extent of functionalization. Upon melt blending (200 degrees C) an anhydride terminal PMMA (29 kg/mol) with an amino terminal PS (18.5 kg/mol) all of the monofunctional homopolymers were converted to PS-PMMA diblock within 20 min (GPC and transmission electron microscopy, TEM). A lamellar morphology (TEM) was obtained after further annealing of this sample (72 h).
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页码:5213 / 5219
页数:7
相关论文
共 20 条
[1]   PREPARATION OF HIGH-PURITY, ANIONIC-POLYMERIZATION GRADE ALKYL METHACRYLATE MONOMERS [J].
ALLEN, RD ;
LONG, TE ;
MCGRATH, JE .
POLYMER BULLETIN, 1986, 15 (02) :127-134
[2]  
CERNOHOUS JJ, 1996, ACS POLYM PREPR, V37, P653
[3]  
FAYT R, 1986, MAKROMOL CHEM, V187, P837
[4]  
Goethals E.J., 1989, Telechelic Polymers: Synthesis and Applications
[5]   KINETICS OF CHAIN COUPLING AT MELT INTERFACES [J].
GUEGAN, P ;
MACOSKO, CW ;
ISHIZONE, T ;
HIRAO, A ;
NAKAHAMA, S .
MACROMOLECULES, 1994, 27 (18) :4993-4997
[6]   Anionic synthesis, modification, and characterization of ABC triblock copolymers [J].
Guegan, P ;
Cernohous, JJ ;
Khandpur, AK ;
Hoye, TR ;
Macosko, CW .
MACROMOLECULES, 1996, 29 (13) :4605-4612
[7]  
KNOCHEL P, 1995, SYNLETT, P393
[8]  
Knochel P., 1991, Comprehensive Organic Synthesis
[9]  
MCLOSKEY AL, 1963, ORGANIC SYNTHESES C, V4, P261
[10]  
Morton M., 1983, ANIONIC POLYM PRINCI