序列分布导向的CGC催化乙烯与1-辛烯共聚过程建模

田洲; 焦栋; 王金强; 刘柏平

doi:10.11949/0438-1157.20190930

您当前的位置：

首页 >

文章列表页 >

序列分布导向的CGC催化乙烯与1-辛烯共聚过程建模

催化、动力学与反应器 | 更新时间：2026-07-24

- 序列分布导向的CGC催化乙烯与1-辛烯共聚过程建模
- Sequence distribution oriented modeling of ethylene and 1-octene copolymerization process catalyzed by CGC
- 化工学报 2020年71卷第2期页码：651-659
- 作者机构：
  
  1. 华东理工大学化工过程先进控制和优化技术教育部重点实验室，上海 200237
  2. 华东理工大学化工学院，上海 200237
  3. 华南农业大学材料与能源学院，广州 510642
- 作者简介：
  
  田洲（1984—），男，博士，副教授，tianzhou@ecust.edu.cn
- 基金信息：
  
  中央高校基本科研业务费(222201714054)
- DOI：10.11949/0438-1157.20190930
  中图分类号： TQ 316.3
- 收稿：2019-08-13，
  
  修回：2019-09-29，
  
  网络首发：2020-08-14，
  
  纸质出版：2020-02-05
- 稿件说明：
移动端阅览
田洲, 焦栋, 王金强, 刘柏平. 序列分布导向的CGC催化乙烯与1-辛烯共聚过程建模[J]. 化工学报, 2020, 71(2): 651-659

TIAN Zhou, JIAO Dong, WANG Jinqiang, LIU Boping. Sequence distribution oriented modeling of ethylene and 1-octene copolymerization process catalyzed by CGC[J]. CIESC Journal, 2020, 71(2): 651-659
田洲, 焦栋, 王金强, 刘柏平. 序列分布导向的CGC催化乙烯与1-辛烯共聚过程建模[J]. 化工学报, 2020, 71(2): 651-659 DOI： 10.11949/0438-1157.20190930.

TIAN Zhou, JIAO Dong, WANG Jinqiang, LIU Boping. Sequence distribution oriented modeling of ethylene and 1-octene copolymerization process catalyzed by CGC[J]. CIESC Journal, 2020, 71(2): 651-659 DOI： 10.11949/0438-1157.20190930.

摘要

限制几何构型催化剂(constrained geometry catalyst，CGC)特别适用于乙烯与α-烯烃溶液聚合法制备高性能聚烯烃弹性体POE(polyolefin elastomer)。基于CGC催化乙烯与1-辛烯共聚反应机理，建立了乙烯与1-辛烯共聚反应动力学模型并确定了动力学参数。采用前期实验获得的乙烯消耗速率曲线与催化剂平均活性验证了动力学模型的准确性。基于动力学模型和面向序列结构的共聚机理，建立了乙烯与1-辛烯共聚过程序列分布模型。模型可准确预测序列分布与短支链含量及其随反应条件的变化趋势。结果表明，随着1-辛烯浓度的增加，乙烯序列长度逐渐减小，其平均序列长度线性降低，而1-辛烯平均序列平均长度呈线性增加的趋势。所建模型可为从聚合过程角度调控POE链结构提供理论参考。

Abstract

Constrained geometry catalyst (CGC) is particularly suitable for the preparation of high performance polyolefin elastomer (POE) using ethylene and α-olefin solution polymerization process. Based on the reaction mechanism of ethylene copolymerization with 1-octene catalyzed by CGC

a kinetic model was established and its kinetic parameters were determined. The kinetic model was validated by the consumption rate of ethylene and catalyst activity. Based on the kinetic model and sequence structure oriented copolymerization mechanism

a sequence distribution model of ethylene and 1-octene copolymerization was established. The model can accurately predict the sequence distribution

the content of short branch chains and their changing trend with reaction conditions. The results show that with the increase of 1-octene concentration

the average sequence length of ethylene decreases gradually and linearly

while the average sequence length of 1-octene increases linearly. The model can provide a theoretical reference for regulating the structure of the POE chain from the perspective of polymerization process.

关键词

Keywords

references

Stevens J C , Neithamer D R . Metal complex compounds : US 5064802 A [P ] . 1990-07-03 .

Chum P S , Swogger K W . Olefin polymer technologies-history and recent progress at the Dow Chemical Company [J ] . Progress in Polymer Science , 2008 , 33 ( 8 ): 797 - 819 .

李伯耿 , 张明轩 , 刘伟峰 , 等 . 聚烯烃类弹性体—现状与进展 [J ] . 化工进展 , 2017 , 36 ( 9 ): 3135 - 3144 .

Li B G , Zhang M X , Liu W F , et al . Polyolefin elastomers - status and progress [J ] . Chemical Industry and Engineering Progress , 2017 , 36 ( 9 ): 3135 - 3144 .

Braunschweig H , Breitling F M . Constrained geometry complexes—synthesis and applications [J ] . Coordination Chemistry Reviews , 2006 , 250 ( 21/22 ): 2691 - 2720 .

李良杰 . 聚烯烃弹性体及其催化体系研究进展 [J ] . 弹性体 , 2015 , 5 : 88 - 94 .

Li L J . Research progress of polyolefin elastomers and their catalytic systems [J ] . Elastomers , 2015 , 5 : 88 - 94 .

Tian S , Arredondo V M , Stern C L , et al . Constrained geometry organolanthanide catalysts. synthesis, structural characterization, and enhanced aminoalkene hydroamination/cyclization activity [J ] . Organometallics , 1999 , 18 ( 14 ): 2568 - 2570 .

Resconi L , Camurati I , Grandini C , et al . Indenyl-amido titanium and zirconium dimethyl complexes: improved synthesis and use in propylene polymerization [J ] . Journal of Organometallic Chemistry , 2002 , 664 ( 1/2 ): 5 - 26 .

Sakai S , Kojima Y . Theoretical studies on the role of bridging group of CGC type ligands for the Ziegler-Natta catalysis [J ] . Journal of Organometallic Chemistry , 2009 , 694 ( 20 ): 3276 - 3280 .

Young M J , Ma C-C M . Polymerization kinetics and modeling of solution PE process with metallocene catalysts [J ] . Journal of Polymer Engineering , 2002 , 22 ( 2 ): 75 - 94 .

Wang W J , Yan D , Zhu S P , et al . Kinetics of long chain branching in continuous solution polymerization of ethylene using constrained geometry metallocene [J ] . Macromolecules , 1998 , 31 ( 25 ): 8677 - 8683 .

Mehdiabadi S , Soares J B P . Ethylene homopolymerization kinetics with a constrained geometry catalyst in a solution reactor [J ] . Macromolecules , 2012 , 45 ( 4 ): 1777 - 1791 .

Liu W F , Wang W J , Fan , H , et al . Structure analysis of ethylene/1-octene copolymers synthesized from living coordination polymerization [J ] . European Polymer Journal , 2014 , 54 : 160 - 171 .

Liu W F , Zhang K , Fan H , et al . Living copolymerization of ethylene/1‐octene with fluorinated FI-Ti catalyst [J ] . Journal of Polymer Science Part A: Polymer Chemistry , 2013 , 51 ( 2 ): 405 - 414 .

Liu P W , Liu W F , Wang W J , et al . A comprehensive review on controlled synthesis of long‐chain branched polyolefins: Part 1, single catalyst systems [J ] . Macromolecular Reaction Engineering , 2016 , 10 ( 3 ): 156 - 179 .

Liu W F , Liu P W , Wang W J , et al . A comprehensive review on controlled synthesis of long-chain branched polyolefins: Part 2, multiple catalyst systems and prepolymer modification [J ] . Macromolecular Reaction Engineering , 2016 , 10 ( 3 ): 180 - 200 .

Liu P W , Liu W F , Wang W J , et al . A comprehensive review on controlled synthesis of long‐chain branched polyolefins: Part 3, characterization of long‐chain branched polymers [J ] . Macromolecular Reaction Engineering , 2017 , 11 ( 1 ): 1600012 .

Ray W H . On the mathematical modeling of polymerization reactors [J ] . Journal of Macromolecular Science—Reviews in Macromolecular Chemistry , 1972 , 8 ( 1 ): 1 - 56 .

Ye Y , Schork F J . Modeling of sequence length and distribution for the NM-CRP of styrene and 4-methylstyrene in batch and semi-batch reactors [J ] . Macromolecular Reaction Engineering , 2010 , 4 ( 3/4 ): 197 - 209 .

Zargar A , Schork F J . Copolymer sequence distributions in controlled radical polymerization [J ] . Macromolecular Reaction Engineering , 2009 , 3 ( 2/3 ): 118 - 130 .

Zargar A , Schork F J . Design of copolymer molecular architecture via design of continuous reactor systems for controlled radical polymerization [J ] . Industrial & Engineering Chemistry Research , 2009 , 48 ( 9 ): 4245 - 4253 .

邱云霞 . 面向序列结构的乙烯—丙烯共聚过程建模 [D ] . 杭州 : 浙江大学 , 2014 .

Qiu Y X . Modeling of ethylene-propylene copolymerization process oriented to sequence structure [D ] . Hangzhou : Zhejiang University , 2014 .

王金强 , 田洲 , 程瑞华等 . CGC/i-Bu3Al/Ph3C+B(C6F5)4-催化乙烯均聚及乙烯与 1-辛烯共聚行为 [J ] . 合成树脂及塑料 , 2018 , 35 ( 6 ): 15 - 21 .

Wang J Q , Tian Z , Cheng R H , et al . CGC/i-Bu3Al/Ph3C+B(C6F5)4- catalyzed ethylene homopolymerization and copolymerization of ethylene and 1-octene [J ] . Synthetic Resins & Plastics , 2018 , 35 ( 6 ): 15 - 21 .

Soares J B , Mckenna T F . Polyolefin reaction engineering [M ] . Weinheim : WILEY-VCH Verlag GmbH & Co . KGaA , 2012 : 145 - 148 .

Ostrovskii N , Stoiljković D . Evaluation of the effect of reaction and mass transfer on the growth of polymer particles in olefin polymerization [J ] . Theoretical Foundations of Chemical Engineering , 2011 , 45 ( 1 ): 40 - 52 .

Soga K , Yanagihara H , Lee D H . Effect of monomer diffusion in the polymerization of olefins over Ziegler-Natta catalysts [J ] . Die Makromolekulare Chemie: Macromolecular Chemistry and Physics , 1989 , 190 ( 5 ): 995 - 1006 .

Anantawaraskul S , Soares J B P , Wood-Adams P M , et al . Effect of molecular weight and average comonomer content on the crystallization analysis fractionation (Crystaf) of ethylene alpha-olefin copolymers [J ] . Polymer , 2003 , 44 ( 8 ): 2393 - 2401 .

Matsuba G , Shimizu K , Wang H , et al . Kinetics of phase separation and crystallization in poly (ethylene-ran-hexene) and poly (ethylene-ran-octene) [J ] . Polymer , 2003 , 44 ( 24 ): 7459 - 7465 .

Sarzotti D M , Soares J B P , Simon L C , et al . Analysis of the chemical composition distribution of ethylene/alpha-olefin copolymers by solution differential scanning calorimetry: an alternative technique to Crystaf [J ] . Polymer , 2004 , 45 ( 14 ): 4787 - 4799 .

Arndt J H , Brull R , Macko T , et al . Characterization of the chemical composition distribution of polyolefin plastomers/elastomers (ethylene/1-octene copolymers) and comparison to theoretical predictions [J ] . Polymer , 2018 , 156 : 214 - 221 .

刘伟峰 . 乙烯/辛烯溶液共聚及其聚合物链结构的调控 [D ] . 杭州 : 浙江大学 , 2014 .

Liu W F . Ethylene/octene solution copolymerization and regulation of its polymer chain structure [D ] . Hangzhou : Zhejiang University , 2014 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

POE溶液聚合反应器内混合与反应过程的CFD研究

基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型

基于改进Kalman滤波算法的多模型融合建模方法

基于机器学习算法的生物质热解产物产率预测研究

饱和气液相密度关联外推的新通用对比态方程