Triphenylphosphane-functionalised amphiphilic copolymers:: Tailor-made support materials for the efficient and selective aqueous two-phase hydroformylation of 1-octene
Triphenylphosphane-functionalised amphiphilic copolymers:: Tailor-made support materials for the efficient and selective aqueous two-phase hydroformylation of 1-octene
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DOI：
10.1002/chem.200600718
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Weberskirch, Ralf
中科院分区：
文献类型：
--
作者：
Bortenschlager, Martin;Schoellhorn, Nicole;Weberskirch, Ralf
通过无金属合成路线，用与聚合物共价连接的三苯基膦配体合成了基于 2-恶唑啉的两亲性共聚物（无规 P1 和嵌段 P2）。所得大配体用于1-辛烯的水相两相加氢甲酰化。研究了聚合物结构（无规和嵌段共聚物）对加氢甲酰化反应活性和选择性的影响，并与非官能化共聚物（无规 P3 和嵌段 P4）和作为水溶性催化剂的 Rh-I/三苯基膦三磺酸盐进行了比较。无规共聚物 P1 (p = 50 bar, T = 100 ℃, c = 8 x 10(-4) mol L-1) 的活性最高，周转频率 (TOF) 为 3700 h(-1)，而相应的嵌段共聚物 P2 的 TOF 数为 1630 h(-1)。此外，两种大配体均表现出对异构化的有效抑制，并在底物完全转化后导致几乎恒定的正/异选择性约为3。在相同的反应条件下，共聚物 P3 和 P4 在 40 - 60% 转化率（n/iso 接近 0.7）后表现出强烈的异构化，并且在浓度为 5 x 10(-3) mol L-1 时最大活性为 1560 h(-1) (P3) 和 1330 h(-1) (P4)。
Amphiphilic copolymers (random P1 and block P2) based on 2-oxazolines were synthesised with triphenylphosphane ligands covalently linked to the polymers by means of a metal-free synthesis route. The resulting macroligands were used in the aqueous two-phase hydroformylation of 1-octene. The influence of the polymer architecture (random and block copolymers) on activity and selectivity of the hydroformylation reaction was investigated and compared with that of nonfunctionalised copolymers (random P3 and block P4) and Rh-I/triphenylphosphane trisulfonate as a water-soluble catalyst. The highest activities were observed for the random copolymer P1 (p = 50 bar, T = 100 degrees C, c = 8 x 10(-4) mol L-1) with a turnover frequency (TOF) of 3700 h(-1), whereas the corresponding block copolymer P2 reached TOF numbers of 1630 h(-1). Additionally, both macroligands indicated efficient suppression of isomerisation and led to almost constant n/iso selectivities of about 3 after complete substrate conversion. Copolymers P3 and P4 showed, under identical reaction conditions, strong isomerisation after 40 - 60% conversion (n/iso approximate to 0.7) and maximum activities of 1560 h(-1) (P3) and 1330 h(-1) (P4) at a concentration of 5 x 10(-3) mol L-1.