超高分子量聚丙烯的制备

doi:10.16085/j.issn.1000-6613.2017-2040

化工进展 ›› 2018, Vol. 37 ›› Issue (09): 3534-3539.DOI: 10.16085/j.issn.1000-6613.2017-2040

超高分子量聚丙烯的制备

王帆¹, 刘小燕², 赵文康³, 朱博超², 张平生²

1 兰州交通大学化学与生物工程学院, 甘肃兰州 730070;
2 中国石油天然气股份有限公司兰州化工研究中心, 甘肃兰州 730060;
3 兰州理工大学材料科学与工程学院, 甘肃兰州 730050

收稿日期:2017-09-30 修回日期:2017-11-22 出版日期:2018-09-05 发布日期:2018-09-05
通讯作者: 刘小燕,硕士,工程师,研究方向为聚丙烯。
作者简介:王帆(1992-),男,硕士研究生。E-mail:m15612772022@126.com。
基金资助:
中国石油天然气集团公司项目（2013E-3706）。

Preparation of ultra-high molecular weight polyprolene

WANG Fan¹, LIU Xiaoyan², ZHAO Wenkang³, ZHU Bochao², ZHANG Pingsheng²

1 Institute of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, Gansu, China;
2 Lanzhou Petrochemical Research Center, PetroChina, Lanzhou 730060, Gansu, China;
3 School of Material Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China

Received:2017-09-30 Revised:2017-11-22 Online:2018-09-05 Published:2018-09-05

摘要/Abstract

摘要： 超高分子量聚丙烯（UHMWPP）是一种黏均分子量百万以上，具有超高的强度、超高的耐磨性、较强的抗氧化能力的热塑性工程塑料，可用于制备高强度、高模量、耐腐蚀、抗冲击、耐应力开裂的聚丙烯产品。本工作的目的在于制备出分子量超过200万的聚丙烯，将其用作3D打印材料来解决由于分子链较长引起高熔体黏度和低流动性而导致加工难成型问题。本工作基于传统的Ziegler-Natta催化剂，对主催化剂进行金属离子和有机物的负载，通过控制丙烯的链转移来控制聚丙烯的分子量，并且在聚合反应过程中不加入氢气（带有活性氢的物质），以防止其成为聚合反应的终止剂。研究了聚合反应温度、聚合反应时间、助催化剂和外给电子体对聚丙烯分子量的影响。采用黏度法、升温淋洗分级法等表征了制备的聚丙烯分子量。通过聚合工艺优化，在聚合反应温度70℃、聚合反应时间60min、助催化剂三异丁基铝、外给电子体P Donor下，最终制备出了黏均分子量超过204万的超高分子量聚丙烯。

关键词: 超高分子量聚丙烯, Ziegler-Natta催化剂, 助催化剂, 外给电子体, 升温淋洗分级

Abstract: Ultra-high molecular weight polypropylene (UHWMPP) is a kind of thermoplastic engineering plastics which has viscosity-averaged molecular weight of more than 1 million, along with incredible strength, high wear resistance, strong antioxidant abilities, and thus it can be used to prepare the polypropylene products with high strength and modulus, as well as high resistance to corrosion, impact and stress crack. The main purpose of the study is to produce the polypropylene with molecular weight over 2 million, which can be used as a 3D printing material to avoid the problems of high melt viscosity and low fluidity caused by long molecular chain. Based on the traditional Ziegler-Natta catalyst, the main catalyst was loaded with metal ions and organics. The molecular weight of the polypropylene was controlled by controlling the chain transfer of propylene and hydrogen (active hydrogen-containing substance) was not added during the polymerization to prevent the termination of the reaction. The effects of the polymerization action temperature, polymerization action time, promoters and external electron donors on the molecular weight of polypropylene were investigated. The molecular weight of the prepared polypropylene was characterized by viscometry and temperature rising elution fractionation method. Finally, the ultra-high molecular weight polypropylene with molecular weight of more than 2.04 million was successfully prepared at polymerization reaction temperature of 70℃, polymerization time of 60min, with triisobutylaluminum as the promoters and P Donor as the external donor.

Key words: ultra high molecular weight polypropylene, catalyst of Ziegler-Natta, promoters, external electron donors, temperature rising elution fractionation

中图分类号:

TQ325.1⁺4

王帆, 刘小燕, 赵文康, 朱博超, 张平生. 超高分子量聚丙烯的制备[J]. 化工进展, 2018, 37(09): 3534-3539.

WANG Fan, LIU Xiaoyan, ZHAO Wenkang, ZHU Bochao, ZHANG Pingsheng. Preparation of ultra-high molecular weight polyprolene[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3534-3539.

参考文献

[1] THENEPALLI T, JUN A Y, HAN C, et al. A strategy of precipitated calcium carbonate (CaCO₃) fillers for enhancing the mechanical properties of polypropylene polymers[J]. Korean Journal of Chemical Engineering, 2015, 32(6):1009-1022.
[2] HOFMANN M. 3D printing gets a boost and opportunities with polymer materials[J]. ACS Macro Letters, 2014, 3(4):382-386.
[3] 苏桂明, 姜海健, 马宇良. 3D打印材料技术及其趋势[J]. 中国科技博览, 2015(18):101. SU Guiming, JIANG Haijian, MA Yuliang. 3D printing materials technology and trends[J]. China Science and Technology Expo, 2015(18):101.
[4] CECCHIN G, MORINI G, PELLICONI A. Polypropene product innovation by reactor granule technology[C]//Macromolecular symposia. WILEY-VCH Verlag GmbH, 2001, 173(1):195-210.
[5] 刘小燕, 陈旭, 谢克锋, 等. 一种球形卤化镁载体的制备方法及其应用:CN₂ 01310552108.7[P]. 2013-11-08. LIU Xiaoyan, CHEN Xu, XIE Kefeng, et al. A method for preparing a spherical support of magnesium halide and its Application:CN₂ 01310552108.7[P]. 2013-11-08.
[6] GALLI P, HAYLOCK J C, SIMONAZZI T. Manufacturing and properties of polypropylene copolymers[M]//Polypropylene structure, blends and composites. Springer Netherlands, 1995:1-24.
[7] 马尔帕斯. 工业聚丙烯导论[M]. 宁夏:宁夏人民教育出版社, 2015:101. MALPASS Dennis B. Introduction to industrial polypropylene[M]. Ningxia:Ningxia People's Education Press, 2015:101.
[8] 塑料聚丙烯(PP)和丙烯共聚物热塑性塑料等规指数的测定:GB/T2412-2008[S]. Determination of the isotactic index of polypropylene plastic(PP)and propylene copolymers and other thermoplastics:GB/T2412-2008[S].
[9] WILD L, GLÖCKNER G. Temperature rising elution fractionation[C]//Separation techniques thermodynamics liquid crystal polymers, 1991:1-47.
[10] 王重, 李旭日, 王良诗, 等. TREF在抗冲共聚聚丙烯研究中的应用[J]. 高分子材料科学与工程, 2008, 24(6):5-8. WANG Chong, LI Xuri, WANG Liangshi, et al. Application of polypropylene impact copolymer in TREF[J]. Polymer Materials Science and Engineering, 2008, 24(6):5-8.
[11] 潘祖仁. 高分子化学[M]. 北京:化学工业出版社, 2011:204-206. PAN Zuren. Polymer chemistry[M]. Beijing:Chemical Industry Press, 2011:204-206.
[12] MÜLLER A J, ARNAL M L. Thermal fractionation of polymers[J]. Progress in Polymer Science, 2005, 30(5):465-603.
[13] ARNAL M L, SANCHEZ J J, MÜLLER A J. Miscibility of linear and branched polyethylene blends by thermal fractionation:use of the successive self-nucleation and annealing (SSA) technique[J]. Polymer, 2001, 42(16):6877-6890.
[14] 白雪, 高明智, 李天益. 外给电子体对N催化剂丙烯聚合性能的影响[J]. 石油化工, 2004, 33(7):615-618. BAI Xue, GAO Mingzhi, LI Tianyi. Effect of external donors on performance of N-catalyst in propylene polymerization[J]. Petrochemical Technology, 2004, 33(7):615-618.
[15] 雷华, 徐宏彬, 冯连芳, 等. 丙烯聚合ZN催化剂中的给电子体及其作用机理[J]. 高分子材料科学与工程, 2004, 20(6):51-54. LEI Hua, XU Hongbin, FENG Lianfang, et al. Propylene polymerization mechanism to the electron donor and ZN catalyst[J]. Polymer Materials Science and Engineering, 2004, 20(6):51-54.

超高分子量聚丙烯的制备

Preparation of ultra-high molecular weight polyprolene

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 10

编辑推荐

Metrics

本文评价

[1]	符淑瑢, 王丽娜, 王东伟, 刘蕊, 张晓慧, 马占伟. 析氧助催化剂增强光阳极光电催化分解水性能研究进展[J]. 化工进展, 2023, 42(5): 2353-2370.
[2]	孙珍珍, 刘化章, 叶攀, 韩文锋. Fe_1-_x O基氨合成催化剂助催化剂的优选[J]. 化工进展, 2022, 41(4): 1886-1893.
[3]	李林辉,刘化章,韩文锋,黎志,李蕾,王志昆. SrO助催化剂对Fe_1- _x O基熔铁氨合成催化剂性能的影响[J]. 化工进展, 2019, 38(03): 1371-1376.
[4]	刘润雪, 刘任杰, 徐艳, 吕静, 李振花. 铁基费托合成催化剂研究进展[J]. 化工进展, 2016, 35(10): 3169-3179.
[5]	黄文氢1，2，杨岭2，赵曦2，满毅2，李秉毅2，张颖2，杨万泰1. 烷基铝对TiClx/MgCl2/THF催化剂化学结构及性能的影响 [J]. 化工进展, 2011, 30(6): 1231-.
[6]	谭忠1，徐秀东1，2，严立安1，周奇龙1. Ziegler-Natta型丙烯聚合催化剂内给电子体复配的研究进展[J]. 化工进展, 2011, 30(12): 2628-.
[7]	徐秀东1，2，毛炳权2，谭忠2，夏先知2. 镁醇体系聚丙烯催化剂制备技术进展 [J]. 化工进展, 2011, 30(1): 155-.
[8]	黄文氢1，2，张颖2，杨万泰1. Ziegler-Natta催化剂的表征研究进展 [J]. 化工进展, 2010, 29(7): 1224-.
[9]	宁英男，丁万友，殷喜丰，李小辉，薛秋梅，姜　涛. Unipol工艺聚乙烯Ziegler-Natta催化剂研究及应用进展 [J]. 化工进展, 2010, 29(4): 649-.
[10]	李昌秀，李现忠，李季禹，王军，张晓帆. Ziegler-Natta聚丙烯催化剂体系给电子体的研究进展 [J]. 化工进展, 2009, 28(5): 793-.