EFFICIENT PALLADIUM CATALYSTS FOR THE COPOLYMERIZATION OF CARBON-MONOXIDE WITH OLEFINS TO PRODUCE PERFECTLY ALTERNATING POLYKETONES
EFFICIENT PALLADIUM CATALYSTS FOR THE COPOLYMERIZATION OF CARBON-MONOXIDE WITH OLEFINS TO PRODUCE PERFECTLY ALTERNATING POLYKETONES
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DOI：
10.1016/0022-328x(91)80176-k
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发表时间：
1991-10-01
影响因子：
2.3
通讯作者：
DOYLE, MJ
中科院分区：
文献类型：
--
作者：
DRENT, E;VANBROEKHOVEN, JAM;DOYLE, MJ
开发了一类高效的均相钯催化剂体系，用于生产一氧化碳与乙烯的完全交替共聚物。 将一氧化碳、乙烯和丙烯的混合物转化成相应的交替一氧化碳/烯烃三元共聚物，其中C3单元沿链沿着无规地取代乙烯单元。 新的催化剂体系的基本特征是，它们是由等摩尔量的合适的双齿膦配体与钯（II）物种的组合形成的，其中抗衡阴离子是弱配位的。 对于一系列通式为Ph 2 P（CH 2）（m）PPh 2的二苯基膦基烷烃，用于生产高分子量聚酮的最有效的催化剂体系是m = 3的催化剂体系。 获得了每个钯中心超过一百万个一氧化碳和乙烯分子的高转化率。 在甲醇中，产生的大部分共聚物链是通式为H（CH 2CH 2CO）（n）OMe的聚酮酯;甲醇可溶性低聚物馏分的分析表明，还形成了二酯MeOCO（CH 2CH 2CO）（n）OMe和二酮H（CH 2CH 2CO）（n）CH 2CH 3。 两个相互关联的催化循环被调用来解释与酮酯，二酯和二酮端基的聚酮的形成。
A class of highly efficient homogeneous palladium catalyst systems has been developed for the production of perfectly alternating copolymers of carbon monoxide with ethylene. Mixtures of carbon monoxide, ethylene and propene are converted into the corresponding alternating carbon monoxide/olefin terpolymers in which C3 units randomly replace ethylene units along the chain. The essential features of the new catalyst systems are that they are formed by the combination of an equimolar quantity of a suitable bidentate phosphine ligand with a palladium(II) species in which the counter anions are weakly coordinating. For a series of diphenylphosphinoalkanes of general formula Ph2P(CH2)(m)PPh2 the most efficient catalyst system for the production of high-molecular-weight polyketones is that with m = 3. High rates with conversions of more than one million molecules of carbon monoxide and ethylene per palladium center are obtained. In methanol, the majority of the copolymer chains produced are polyketo-esters of general formula H(CH2CH2CO)(n)OMe; analyses of methanol-soluble oligomer fractions shows that diesters MeOCO(CH2CH2CO)(n)OMe and diketones H(CH2CH2CO)(n)CH2CH3 are also formed. Two interlinked catalytic cycles are invoked to account for the formation of polyketones with keto-ester, diester and diketone end groups.