SYNTHESIS AND PROPERTIES OF NOVEL LINEAR DENDRITIC BLOCK-COPOLYMERS - REACTIVITY OF DENDRITIC MACROMOLECULES TOWARD LINEAR-POLYMERS

被引：173

作者：

GITSOV, I ^{[1
]}

WOOLEY, KL ^{[1
]}

HAWKER, CJ ^{[1
]}

IVANOVA, PT ^{[1
]}

FRECHET, JMJ ^{[1
]}

机构：

[1] CORNELL UNIV,DEPT CHEM,BAKER LAB,ITHACA,NY 14853

来源：

MACROMOLECULES | 1993年 / 26卷 / 21期

关键词：

D O I：

10.1021/ma00073a014

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The reactivity of benzylic dendritic polyethers toward linear polymers was investigated using coupling reactions of preformed dendritic and linear blocks in solution and in the melt. It was found that the rate constants for the Williamson reaction of poly(ethylene oxide)s (PEO) or poly(ethylene glycol)s (PEG) with dendritic bromides of various sizes increased with the length of the linear block and the generation of the dendrimer. This anomalous behavior is attributed to the increased reactivity of the PEO and PEG alcoholate anions due to the solvation of the counterion by the linear block and to the conformation changes occurring after attachment of the first dendritic block to PEG. It was shown that the functional group at the ''focal point'' of the dendrimer preserves its accessibility and reactivity even in highly restrictive medium and is able to participate in transesterification reactions with PEO and PEG in the melt. Thus, block copolymers that differ by a single linking bond between the linear and dendritic blocks were formed.

引用

页码：5621 / 5627

页数：7

共 28 条

[1]

ALLEN G, 1985, COMPREHENSIVE POLYM, V5, P275

[2]

BARTL H, 1987, METHODEN ORG CHEM E, V20, P1405

[3]

BENDER ML, 1960, CHEM REV, V53, P60

[4]

BERLINOVA IV, 1989, MAKROMOL CHEM, V190, P1515

[5]

BUHLEIER E, 1978, SYNTHESIS-STUTTGART, P155

[6]

EREMIN EN, 1976, BASICS CHEM KINETICS, V2, P540

[7]

Flory P. J., 1953, PRINCIPLES POLYM CHE, P75

[8]

Fox TG, 1956, B AM PHYS SOC, V1, P123

[9] NOVEL POLYETHER COPOLYMERS CONSISTING OF LINEAR AND DENDRITIC BLOCKS [J].

GITSOV, I ;

WOOLEY, KL ;

FRECHET, JMJ .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1992, 31 (09) :1200-1202

[10]

GITSOV L, 1991, J POLYM PREPR, V32, P631

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