多孔有机聚合物中试制备及其在聚烯烃催化剂中的应用

doi:10.16085/j.issn.1000-6613.2023-0437

摘要/Abstract

摘要：

多孔有机聚合物广泛应用在吸附、分离、催化等领域。本文采用分散聚合工艺，中试制备得到形貌及流动性良好的POP3120T和POP3100载体，POP3120T载体堆密度为0.29g/cm³，比表面积为282m²/g，与无机硅胶载体相当，颗粒粒径23.4μm，粒径分布1.00；POP3100载体堆密度为0.34g/cm³，比表面积约503m²/g，均高于无机硅胶载体，颗粒粒径36.0μm，粒径分布0.93。负载的POP型Z-N聚丙烯催化剂具有良好的丙烯聚合活性，其活性可达到1.0×10⁷g/(mol·h)以上。得到的聚合物堆密度可以达到0.36g/cm³，聚合物细粉含量小于1%，达到商业催化剂的水平，此外负载的POP型Z-N聚丙烯催化剂具有高的立构规整选择性及宽的分子量分布，采用DIBP作为内给电子体制备的催化剂，丙烯聚合制备的聚合物等规度可达97.5%以上，分子量分布可达11以上。

关键词: 多孔有机聚合物, 聚烯烃催化剂, 丙烯聚合, 聚丙烯

Abstract:

Porous organic polymers (POPs) are widely used in many fields such as adsorption, separation and catalysis. In this research, pilot scale POPs (POP3120T and POP3100) were produced by via of dispersion polymerization, which exhibited excellent flowability and surface morphology. High specific surface area (SSA of 282m²/g), bulk density (0.29g/cm³) of POP3120T with average particle size of 23.4µm (PSD: 1.0) were obtained, which was comparable to inorganic silica gel support. POP3100 obtained higher SSA of 503m²/g with average particle size of 36.0µm (PSD: 0.93). The supported Z-N@POP PP catalysts exhibited good polymerization activity above 1.0×10⁷gPP/(mol Ti·h), high bulk density of 0.36g/cm³ and low fine powder content (≥100 mesh, <1%), which was equal to the level of commercial PP catalysts. Furthermore, the supported Z-N@POP PP catalysts showed high stereoregularity with isotacticity index above 97.5% and broad molecular weight distribution above 11.

Key words: porous organic polymers, polyolefin catalysts, propylene polymerization, polypropylene

中图分类号:

TQ32

王雄, 康文倩, 任悦, 乔彤森, 张鹏, 黄安平, 李广全. 多孔有机聚合物中试制备及其在聚烯烃催化剂中的应用[J]. 化工进展, 2024, 43(3): 1412-1417.

WANG Xiong, KANG Wenqian, REN Yue, QIAO Tongsen, ZHANG Peng, HUANG Anping, LI Guangquan. Pilot scale production of porous organic polymers and their application in polyolefin catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1412-1417.

图/表 10

参考文献 17

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催化剂	活性/10⁶ g·mol^-1·h^-1	产率/kg·g^-1·h^-1	堆密度/g·cm^-3	等规度/%	重均均分子量M_w/g·mol^-1	数均分子量M_n/g·mol^-1	分子量分布
Cat-1	8.6	5.8	0.36	97.5	39.40	3.47	11.4
Cat-2	10.3	7.6	0.35	97.8	39.87	3.56	11.2
Cat-3	1.9	1.3	—	92.1	27.49	1.37	20.1

催化剂	活性/10⁶ g·mol^-1·h^-1	产率/kg·g^-1·h^-1	堆密度/g·cm^-3	等规度/%	重均均分子量M_w/g·mol^-1	数均分子量M_n/g·mol^-1	分子量分布
Cat-1	8.6	5.8	0.36	97.5	39.40	3.47	11.4
Cat-2	10.3	7.6	0.35	97.8	39.87	3.56	11.2
Cat-3	1.9	1.3	—	92.1	27.49	1.37	20.1

聚合物	˂20目	20～40目	40～60目	60～80目	80～100目	>100目
PP-1	0.68	14.16	69.80	5.70	8.93	0.73
PP-2	1.23	16.72	71.46	5.20	4.78	0.61

聚合物	˂20目	20～40目	40～60目	60～80目	80～100目	>100目
PP-1	0.68	14.16	69.80	5.70	8.93	0.73
PP-2	1.23	16.72	71.46	5.20	4.78	0.61

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