HM型高效催化剂的乙烯聚合应用研究

Study on application of HM-type high efficiency catalyst in ethylene polymerization

研究组分为TiCl_4/MgCl_2-ZnCl_2-SiO_2/AlR_3的HM型高效催化剂的乙烯聚合,发现催化剂组分SiCl_4有促进乙烯聚合的作用,并可以通过调节SiCl_4用量控制催化剂Ti含量ZnCl_2有调节分子量的作用,由MgCl_2ZnCl_2-SiO复合载体组成的Ti系催化剂乙烯均聚催化效率为7.4～14.0kg/g,聚合产物表观密度为0.23～0.30g/cm^2.20～200日颗粒质量为90％～95％,乙烯与1-丁烯共聚时催化效率大大提高,当1-丁烯的体积分数为10％时,效率高达26.0kg/g,共聚产物熔点、结晶度随1-丁烯的体积分数增加而下降,而支化度则随之上升,HM催化剂1m^2反应釜工业试生产的试验结果表明,在0.5MPa下催化效率达152～241kg/g,聚合产物表观密度为0.33～0.34g cm,20～200日颗粒质量为60.6％～84.3％,小于200日颗粒占1％以下,工业试生产的HM催化剂具有催化效率高,颗粒度均匀,极少细粉,表观密度大等优点,达到或超过了实验室研制的技术指标,具有优良有聚合性能。

Through the study on ethylene homo- and copolymerization with HM -type high efficiency catalyst composedof TiCl4/ MgCl2 - ZnCl2 - SiO2 AIR3, it was found out that the catalytic component SiCl4 possessed a function for promoting ethylene polymerization, and the content of catalytic component Ti could be controlled by adjusting the dosage of SiCl4. ZnCl2 showed a function for regulating molecular weight. The ethylene homopolymerization efficiency of the catalyst reached 7.1 - 14.0 kg/ g under the pressure of 106.7 kPa. The bulk density of the polymer powder was 0.23 - 0. 30 g/ cm3. The content of the 20 - 200 mesh particles accounted for 90% - 95% . The catalytic efficiency was significantly raised in the eopolymerization of ethylene and 1-butene; the efficiency could reach up to 26.0 kg/ g when 1 - butene content was 10% . The melting point and crystallinity of the copolymer was decreased while its branching degree was increased as the 1- butene content in the feed went up. In the trial operation of the HM - type catalyst in a reactor with capacity of 1 m3 . the catalytic efficiency reached 152-241 kg/ g under the pressure of 0.5 MPa. The bulk density of the polymer powder so prepared attained 0.33 - 0.34 g/ cm3 and the content of the 20 - 200 mesh particles accounted for 60.6% - 84.3% . The data confirm that the HM - type catalyst prepared in the trial industrial production possesses the advantages of high catalytic efficiency, homogeneous particle size, less fine powder and high bulk density, and reaches or exceeds the technical index of the catalyst made in laboratory.