Selectivity of polyamide-supported rhodium catalysts in the addition of hydrosilanes to vinyl compounds

Reactive Polymers Pub Date : 1994-10-01 DOI:10.1016/0923-1137(94)90005-1

Z.M. Michalska , B. Ostaszewski , K. Strzelec , R. Kwiatkowski , A. Włochowicz

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引用次数: 14

Abstract

A series of polyamides containing aromatic or heteroaromatic and aliphatic fragments in their repeat unit were synthesized and used as supports to immobilize a catalyst based on a [RhCl(CO)₂]₂ precursor. The polymeric materials were characterized by differential scanning spectroscopy (DSC), wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), specific surface area and porosity measurements. The catalytic properties of polyamide-supported Rh(I) catalysts were studied in hydrosilylation of vinyl-type olefins. The selectivity of this reaction towards formation of the linear adducts over the branched ones was found to be greatly influenced by the matrix supramolecular structure when compared with that in the homogeneous phase. Based on SAXS measurements, the high selectivity of the polymer-immobilized rhodium catalysts was attributed to the matrix microporous structure displaying a narrow distribution of pores mostly in the range from r = 1.0 to 3.0 nm.

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聚酰胺负载铑催化剂在乙烯基化合物加成氢硅烷中的选择性

合成了一系列在重复单元中含有芳香族或杂芳香族和脂肪族片段的聚酰胺，并以[RhCl(CO)2]2前驱体为载体固定化催化剂。采用差示扫描光谱(DSC)、广角x射线散射(WAXS)、小角x射线散射(SAXS)、比表面积和孔隙度测量对聚合物材料进行了表征。研究了聚酰胺负载Rh(I)催化剂在乙烯基烯烃硅氢化反应中的催化性能。与均相反应相比，该反应对支链加合物的选择性受基质超分子结构的影响较大。基于SAXS测试，聚合物固定化铑催化剂的高选择性归因于基质微孔结构，其孔分布窄，主要分布在r = 1.0 ~ 3.0 nm范围内。

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