PREPARATION OF ALTERNATING COPOLYMERS FROM THE RING-OPENING METATHESIS POLYMERIZATION OF 3-METHYLCYCLOBUTENE AND 3,3-DIMETHYLCYCLOBUTENE

被引:72
作者
WU, Z [1 ]
GRUBBS, RH [1 ]
机构
[1] CALTECH,ARNOLD & MABEL BECKMAN LABS CHEM SYNTHESIS,PASADENA,CA 91125
关键词
D O I
10.1021/ma00114a002
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Monomers 3-methylcyclobutene (1) and 3,3-dimethylcyclobutene (2) can be polymerized by well-defined alkylidene complexes of the type M(CHC(CH3)(3))(NAr)(OC(CH3)(n)(CF3)(3-n))(2) (where Ar = 2,6-diisopropylphenyl; M = Mo or W; n = 2 or 3) to give polymers, which upon hydrogenation are equivalent to alternating copolymers of poly(ethylene-alt-propylene) and poly(ethylene-alt-isobutylene), respectively. Monomer 2 can be polymerized in a highly regioselective fashion to give polymers with exclusively trans and head-to-tail configuration. The high regioselectivity of the polymerization is attributed to the steric directing effect of the bulky substituent on the 3-position of the cyclobutene as the monomer approaches the propagating alkylidenes. In the presence of PPhMe(2) narrowly dispersed poly(3-methylcyclobutene) can be obtained.
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页码:3502 / 3508
页数:7
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共 54 条
  • [41] RABJOHN N, 1962, ORG SYNTH, V4, P288
  • [42] BLOCK AND GRAFT-COPOLYMERS BY LIVING RING-OPENING OLEFIN METATHESIS POLYMERIZATION
    RISSE, W
    GRUBBS, RH
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1991, 65 (1-2): : 211 - 217
  • [43] THIN-FILMS OF N-SI/POLY-(CH3)3SI-CYCLOOCTATETRAENE - CONDUCTING-POLYMER SOLAR-CELLS AND LAYERED STRUCTURES
    SAILOR, MJ
    GINSBURG, EJ
    GORMAN, CB
    KUMAR, A
    GRUBBS, RH
    LEWIS, NS
    [J]. SCIENCE, 1990, 249 (4973) : 1146 - 1149
  • [44] Salaun J., 1986, ORG SYNTH, V64, P50
  • [45] LIVING RING-OPENING METATHESIS POLYMERIZATION CATALYZED BY WELL-CHARACTERIZED TRANSITION-METAL ALKYLIDENE COMPLEXES
    SCHROCK, RR
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1990, 23 (05) : 158 - 165
  • [46] SYNTHESIS OF MOLYBDENUM IMIDO ALKYLIDENE COMPLEXES AND SOME REACTIONS INVOLVING ACYCLIC OLEFINS
    SCHROCK, RR
    MURDZEK, JS
    BAZAN, GC
    ROBBINS, J
    DIMARE, M
    OREGAN, M
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (10) : 3875 - 3886
  • [47] RING-OPENING POLYMERIZATION OF NORBORNENE BY A LIVING TUNGSTEN ALKYLIDENE COMPLEX
    SCHROCK, RR
    FELDMAN, J
    CANNIZZO, LF
    GRUBBS, RH
    [J]. MACROMOLECULES, 1987, 20 (05) : 1169 - 1172
  • [48] MONOADDUCTS OF IMIDO ALKYLIDENE COMPLEXES, SYN AND ANTI ROTAMERS, AND ALKYLIDENE LIGAND ROTATION
    SCHROCK, RR
    CROWE, WE
    BAZAN, GC
    DIMARE, M
    OREGAN, MB
    SCHOFIELD, MH
    [J]. ORGANOMETALLICS, 1991, 10 (06) : 1832 - 1843
  • [49] SEN A, 1986, ADV POLYM SCI, V73-4, P125