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    • 单茂钛催化剂的丙烯无规聚合反应及其动力学研究

    • STUDIES ON ATACTIC SPECIFIC POLYMERIZATION OF PROPENE WITH MONONUCLEAR TITANOCENE CATALYSTS

    • 祝方明

      ,  

      林尚安

      ,  
    • 高分子学报   1998年第1期 页码:83-89
    • 纸质出版日期:1998-2-20

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  • 祝方明, 林尚安. 单茂钛催化剂的丙烯无规聚合反应及其动力学研究[J]. 高分子学报, 1998,(1):83-89. DOI:

    ZHU Fangming, LIN Shangan. STUDIES ON ATACTIC SPECIFIC POLYMERIZATION OF PROPENE WITH MONONUCLEAR TITANOCENE CATALYSTS[J]. Acta Polymerica Sinica, 1998,(1):83-89. DOI:

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    摘要

    比较了不同钛化合物/甲基铝氧烷(MAO)催化体系的丙烯无规聚合,催化活性次序为CpTi(OR)3>CpTi(OPh)3>CpTiCl3>Cp2TiCl2>Ti(OBu)4>TiCl4>Ti(OBu)2Cl2,所得聚丙烯用沸庚烷抽提8h,溶解95%以上,可溶部分经13C-NMR、WADX、FTIR等分析证明为无规聚丙烯(aPP),是没有结晶性的弹性体.GPC测出其分子量Mw=8.0~10.0×104,Mw/Mn≈2.0.探索了催化体系CpTi(O-n-Pr)3/MAO中钛的浓度、[Al]/[Ti]摩尔比,丙烯聚合压力,聚合温度和时间对丙烯聚合反应的影响.研究了该催化体系丙烯聚合反应动力学规律,表观聚合反应速率对催化剂浓度和单体压力(浓度)都呈一级反应关系,表观聚合速率常数KP=2.92×105mol/L·h(40℃).活化能ΔE=-7.88×103J·mol-1,碰撞因子A=1.41×10-4mol/L·h.

    Abstract

    Atactic polypropene was synthsised with homogeneous catalytic systems of varios titanium compounds activated by methylaluminoxane(MAO).The titanium ligands affect both catalytic activity and stereoregularity of polypropene obtained.For novel η 5 cyclopentadienyltri n propyloxy titanium CpTi(O n Pr) 3 /MAO catalytic system,the influencing factors of polymerization temperature,Al/Ti molar ratio and propene pressure on propene polymerization have been studied.The catalytic activity at polymerization temperature 40℃ and Al/Ti molar ratio 200 was 220kgPP/molTi-h.The kinetics of early state propene polymerization with CpTi(O-n-Pr)3/MAO has been inverstigated.The polymer yield increases almost linearly with increasing the titamium or monomer concentration.The apparent rate of polymerization (Rp)versus titanium and monomer concentration appears the first order reaction rule,and the apparent rate constant(Kp)is 2.92×105mol·L-1·h-1 at 40℃.The calculated polymerization activation energy (△E)is 7.88×103J·mol-1,while the impact fractor(A) is 1.41×104mol·L-1·h-1. After boiling heptane extraction of the polypropene for 8h.The soluble fraction with more than 95% by weight was isolated and characterized as atactic polypropene by 13CNMR,WAXD and FTIR.The molecular weight (Mw)and its distribution (Mw/Mn) determined by GPC were 8.0~10.0×104 and 2.0 respectively.

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    无规聚丙烯; 茂钛催化剂; 聚合反应动力学

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