期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 55, 期 26, 页码 7505-7509出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201600819
关键词
homogeneous catalysis; isospecificity; palladium; polymerization; propylene
资金
- CREST of JST
- MEXT, Japan [12024046]
- Japan Society for the Promotion of Science (JSPS)
- TonenGeneral Sekiyu Foundation
- Grants-in-Aid for Scientific Research [15J10619] Funding Source: KAKEN
Moderately isospecific homopolymerization of propylene and the copolymerization of propylene and polar monomers have been achieved with palladium complexes bearing a phosphine-sulfonate ligand. Optimization of substituents on the phosphorus atom of the ligand revealed that the presence of bulky alkyl groups (e.g. menthyl) is crucial for the generation of high-molecular-weight polypropylenes (M-w approximate to 10(4)), and the substituent at the ortho-position relative to the sulfonate group influences the molecular weight and isotactic regularity of the obtained polypropylenes. Statistical analysis suggested that the introduction of substituents at the ortho-position relative to the sulfonate group favors enantiomorphic site control over chain end control in the chain propagation step. The triad isotacticity could be increased to mm=0.55-0.59, with formation of crystalline polar polypropylenes, as supported by the presence of melting points and sharp peaks in the corresponding X-ray diffraction patterns.
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