Ethene/norbornene copolymerization with palladium(II) alpha-diimine catalysts: from ligand screening to discrete catalyst species.
Ethene/norbornene copolymerization with palladium(II) alpha-diimine catalysts: from ligand screening to discrete catalyst species.
复制标题
使用钯 (II) α-二亚胺催化剂进行乙烯/降冰片烯共聚：从配体筛选到离散催化剂种类。
DOI：
10.1002/chem.200390201
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发表时间：
2003
期刊：
影响因子：
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通讯作者：
["J. Kiesewetter
中科院分区：
文献类型：
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作者：
["J. Kiesewetter
研究了十六种钯(II) -二亚胺催化剂在乙烯与降冰片烯共聚过程中的催化作用。用（13）C NMR谱、差示扫描量热法、凝胶渗透色谱法和粘度法对所得共聚物进行了表征。对于大多数催化剂来说，降冰片烯在聚合物链中的掺入程度非常高。为了验证筛选结果，合成了两种催化剂[[ArN=CHCH=NAr]Pd(Me)(CH(3)CN)]BAr(f) (4) (1 b'; Ar=2,6-Me(2)C(6)H(3), BAr(f) (4)= b [3,5-C(6)H(3)(CF(3))（2)](4)）和[[ArN=C(CH(3)))=NAr]Pd(Me)(CH(3)CN)]BAr(f) (4) (2 C '; Ar=2,6- ipr (2)C(6)H(3))]，并对它们的共聚行为进行了详细的研究。与筛选结果一致的是，1b '在聚合物链中比乙烯更好地结合降冰片烯，这种性质在茂金属催化剂中没有类似物。
Sixteen palladium(II) alpha-diimine catalysts were investigated in a screening-like procedure for the copolymerization of ethene with norbornene. The resulting copolymers were characterized by (13)C NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and viscosimetry. The degree of incorporation of norbornene in the polymer chain is very high for most of the catalysts. To validate the results achieved in the screening, two catalysts, [[ArN=CHCH=NAr]Pd(Me)(CH(3)CN)]BAr(f) (4) (1 b'; Ar=2,6-Me(2)C(6)H(3), BAr(f) (4)=B[3,5-C(6)H(3)(CF(3))(2)](4)) and [[ArN=C(CH(3))C(CH(3))=NAr]Pd(Me)(CH(3)CN)]BAr(f) (4) (2 c'; Ar=2,6-iPr(2)C(6)H(3)), were synthesized as discrete catalytically active species, and their copolymerization behavior was investigated in detail. In agreement with the screening results, 1 b' incorporates norbornene much better in the polymer chain than ethene, a property that has no analogue in metallocene catalysts.