2,3-二羟基苯甲醛缩亚胺镍催化剂的合成及催化降冰片烯聚合

Synthesis of 2,3-dihydroxy-benzalde hydiminato nickel catalysts and polymerization of norbornene

设计合成了3种结构新颖的2,3-二羟基苯甲醛缩亚胺镍配合物,并将其作为催化剂,以甲基铝氧烷（MAO）为助催化剂,催化降冰片烯聚合.考察了催化剂结构、聚合温度、铝镍比等不同聚合条件对聚合活性及聚合物结构的影响.研究表明,配体结构中含有苯二胺结构的催化剂活性较高,在40℃下,铝镍比为1 000时,催化剂活性可以达到5.70×10~5g/（mol·h）.配体结构中含有乙二胺结构的热稳定性较好,在80℃下,铝镍比为1 500,反应时间为10 min时,催化剂活性可以达到3.26×10~5g/（mol·h）.通过IR、NMR对所得聚合物进行结构表征,研究发现聚降冰片烯为加成结构聚合物.

Three new structure 2,3-dihydroxy-benzaldehydiminato nickel catalysts were designed and synthesized. Norbornene polymerization was carried out with synthesized catalysts and MAO as cocatalyst. The polymerization conditions, such as the structure of catalysts and polymerization temperature and n（Al） / n（Ni） have influence on the polymerization activity and the structure of polymer. The results indicate that the structure of the catalyst contain phenylenediamine have high activity. At 40 ℃, n（A1） / n（Ni） of 1 000, when the reaction time was 10 min, polymerization activity reached 5.70 × 10^5 g/（mol.h）. The structure of the catalyst contain ethylenediamine have supreme thermal stability. At 80 ℃, n（A1） / n（Ni） of 1 500, when the reaction time was 10 rain, polymerization activity reached 3.26 × 10^5g/（mol.h）. IR, NMR analysis shows that addition-type polynorbomene was obtained.