超高相对分子质量乙烯/1-十二烯共聚物的合成

Synthesis of Ultra-High Molecular Weight Ethylene/1-Dodecene Copolymers

选用芴基胺基二甲基钛配合物为主催化剂,在改性烷基铝氧烷(MMAO)和2,6-二异丙基苯酚(BHT)的活化下,进行了乙烯与1-十二烯的共聚。结果表明:芴基上引入叔丁基、胺基上引入金刚烷基的芴基氨基二甲基钛配合物对乙烯/1-十二烯的共聚表现出高活性;共聚活性随着Al与Ti物质的量比的增大逐渐上升,当Al与Ti物质的量比为1000时,达到最高活性,为2600 kg Polymer/(mol Ti·h),所得共聚物的重均分子质量最高达到2.7×10~6g/mol,当1-十二烯添加量为6.8 mmol时,共聚物中1-十二烯的插入率达到0.34%,此时共聚物的熔点为124.6℃。

The results of copolymerization of ethylene and 1-dodecene with fluorineaminodimethyltitanium complexes （1） activated by modified methylaluminoxane（MMAO） and 4-Me-2,6-isopropyl-phenol（BHT） in- dicated that [（1-adamantyl）NSiMe2（2,7-tBu2Flu）]TiMe2 （la） showed higher activity, of which value en- hanced by increasing the A1/Ti molar ratio and reached highest activity of 2 600 kg Polymer/（mol Ti. h） and the highest weight average molecular weight （Mw） of 2.7 million g/tool at A1/Ti molar ratio of 1 000. When the additive amount of 1-dodecene was 6.8 mmol, 1-dodecene insertion ratio of the copolymer reached 0.34%, while the melting point of the copolymer was 126.4℃.