Citation: Hang-sheng Zhou, Kang Li, Ya-wei Qin, Jin-yong Dong. Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst[J]. Acta Polymerica Sinica, ;2019, 50(11): 1177-1186. doi: 10.11777/j.issn1000-3304.2019.19078 shu

Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst

Hang-sheng Zhou ^1,2 ,
Kang Li ^1,2 ,
Ya-wei Qin ^1,2,, ,
Jin-yong Dong ^1,2,,

1.
Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Acadamy of Sciences, Beijing 100190
2.
University of Chinese Acadamy of Sciences, Beijing 100049

Corresponding author: Ya-wei Qin, ywqin@iccas.ac.cn Jin-yong Dong, jydong@iccas.ac.cn
Received Date: 17 April 2019
Revised Date: 28 April 2019
Available Online: 11 June 2019

This study discusses a new strategy for synthesis of long chain-branched polypropylene (LCB-PP) with Ziegler-Natta catalysts, which, on the basis of conventional nonconjugated α,ω-diolefin/propylene copolymerization incapable of affording LCB, utilizes a dichlorosilane-functionalized α,ω-diolefin instead to carry out the copolymerization. Such a copolymerization with Ziegler-Natta catalysts will give PP bearing pending dichlorosilane functional groups, and it will undergo facile interchain condensations, leading to long chain-branched formation under methanol treatment and water vapor treatment. A MgCl₂/TiCl₄ catalyst containing a diether-type internal electron donor, 9,9-bis(methoxymethyl)fluorine (BMMF), was employed to catalyze di(5-hexenyl)dichlorosilane/propylene copolymerization in slurry conditions. It was found that di(5-hexenyl)dichlorosilane neither did harm to catalyst activity, nor changed the chain transfer/chain termination reaction of the original propylene polymerization. Incorporations of the mono-polymerized di(5-hexenyl)dichlorosilane were found to be between 0.02 mol% and 0.1 mol%. After the copolymerization completed, the obtained copolymers were treated with methanol or water vapor, respectively. Both the treatments could effectively transform the polymer chains-pending dichlorosilane groups into siloxane groups. The condensation degrees were distributed, which were centralized between 2 and 3 with methanol treatment. Water vapor treatment showed higher efficiency for dichlorosilane condensation than methanol treatment did. It could be found that water-treated samples exhibited systematically higher degrees of long chain-branched than their methanol-treated counterparts did with multiple evidences. Gel permeation chromatography measurement showed that the molecular weights of the copolymerized samples treated by both water vapor and methanol were improved, and the copolymers treated by water vapor in the Mark-Houwink equation curve were more deviated from the linear polypropylene than those of methanol treatment. The linear viscoelasticity of copolymers with different di(5-hexenyl)dichlorosilane concentrations after water vapor treatment and methanol treatment was investigated by means of small amplitude oscillatory shear (SAOS) to verify the existence of long chain-branched structure. According to extensional rheometry measurement, the strain hardening phenomena of the copolymers treated with water vapor were more obvious than those treated with methanol.
- Long chain-branched polypropylene,
- Nonconjugated α,ω-diolefin,
- Dichlorosilane,
- Ziegler-Natta catalyst,
- Condensation
1. [1]
  Wang Hongying(王红英), Hu Xuteng(胡徐腾), Li Zhenyu(李振宇), Yi Jianjun(义建军), Dong Jinyong(董金勇). Prog Chem(化学进展), 2007, 19(6): 932 − 958
2. [2]
  Borsig E, van Duin M, Gotsis A D, Picchioni F. Eur Polym J, 2008, 44(1): 200 − 212 doi: 10.1016/j.eurpolymj.2007.10.008
3. [3]
  Shamiri A, Chakrabarti M H, Jahan S, Hussain M A, Kaminsky W, Aravind P V, Yehye W A. Materials (Basel), 2014, 7(7): 5069 − 5108 doi: 10.3390/ma7075069
4. [4]
  Yoshii F, Makuuchi K, Kikukawa S, Tanaka T, Saitoh J, Koyama K. J Appl Polym Sci, 1996, 60(4): 617 − 623 doi: 10.1002/(ISSN)1097-4628
5. [5]
  Ratzsch M, Arnold M, Borsig E, Bucka H, Reichelt N. Prog Polym Sci, 2002, 27(7): 1195 − 1282 doi: 10.1016/S0079-6700(02)00006-0
6. [6]
  Hamielec A E, Soares J B P. Prog Polym Sci, 1996, 21(4): 651 − 706 doi: 10.1016/0079-6700(96)00001-9
7. [7]
  Braunschweig H, Breitling F M. Coord Chem Rev, 2006, 250(21-22): 2691 − 2720 doi: 10.1016/j.ccr.2005.10.022
8. [8]
  Bernasconi E, Greco F, Longi P, Valvassori A. US patent, C08g, 3658770. 1972
9. [9]
  Shi Jianjun(师建军), Qin Yawei(秦亚伟), Niu Hui(牛慧), Dong Jinyong(董金勇). Petrochem Technol(石油化工), 2014, 43(6): 618 − 624
10. [10]
  Naga N, Shiono T, Ikeda T. Macromolecules, 1999, 32(5): 1348 − 1355 doi: 10.1021/ma9814144
11. [11]
  Yang T T, Qin Y W, Dong J Y. Macromolecules, 2018, 51(22): 9234 − 9249 doi: 10.1021/acs.macromol.8b01958
12. [12]
13. [13]
  Smith A L. Spectrochimica Acta, 1960, 16(1-2): 87 − 105 doi: 10.1016/0371-1951(60)80074-4
14. [14]
  Harris G I. J Chem Soc B, 1970, (3): 492 − 496
15. [15]
  Tian J H, Yu W, Zhou C X. Polymer, 2006, 47(23): 7962 − 7969 doi: 10.1016/j.polymer.2006.09.042
16. [16]
  Larson R G. Macromolecules, 2001, 34(13): 4556 − 4571 doi: 10.1021/ma000700o
17. [17]
  van Ruymbeke E, Keunings R, Stephenne V, Hagenaars A, Bailly C. Macromolecules, 2002, 35(7): 2689 − 2699 doi: 10.1021/ma011271c
18. [18]
  Gabriel C, Munstedt H. Rheol Acta, 2002, 41(3): 232 − 244 doi: 10.1007/s00397-001-0219-6
19. [19]
  Kolodka E, Wang W J, Zhu S P, Hamielec A E. Macromolecules, 2002, 35(27): 10062 − 10070 doi: 10.1021/ma021171m
20. [20]
  El Mabrouk K, Parent J S, Chaudhary B I, Cong R J. Polymer, 2009, 50(23): 5390 − 5397 doi: 10.1016/j.polymer.2009.09.066
1. [1]
  Xunzhang Fan , Yuanjin Zhao , Shufang Luo , Aihua He . Karl Ziegler: A Pioneer in the Polyolefin Industry – Commemorating the 50th Anniversary of the German Chemist’s Passing. University Chemistry, 2024, 39(8): 389-394. doi: 10.3866/PKU.DXHX202312065
2. [2]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
3. [3]
  Qi Wang , Yuqing Liu , Jiefei Wang , Yuan-Yuan Ma , Jing Du , Zhan-Gang Han . Catalysts for electrocatalytic dechlorination of chlorinated aromatic hydrocarbons: synthetic strategies, applications, and challenges. Acta Physico-Chimica Sinica, 2025, 41(10): 100120-0. doi: 10.1016/j.actphy.2025.100120
4. [4]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-0. doi: 10.3866/PKU.WHXB202312024
5. [5]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029
6. [6]
  Hailang JIA , Pengcheng JI , Hongcheng LI . Preparation and performance of nickel doped ruthenium dioxide electrocatalyst for oxygen evolution. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1632-1640. doi: 10.11862/CJIC.20240398
7. [7]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
8. [8]
  Lewang Yuan , Yaoyao Peng , Zong-Jie Guan , Yu Fang . Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis. Acta Physico-Chimica Sinica, 2025, 41(8): 100086-0. doi: 10.1016/j.actphy.2025.100086
9. [9]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
10. [10]
  Yukun Chang , Haoqin Huang , Baolei Wang . Preparation of Trans-Cinnamic Acid via “One-Pot” Protocol of Aldol Condensation-Hydrolysis Reaction: Recommending an Improved Organic Synthesis Experiment. University Chemistry, 2024, 39(4): 322-328. doi: 10.3866/PKU.DXHX202309095
11. [11]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-0. doi: 10.1016/j.actphy.2025.100067
12. [12]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
13. [13]
  Ruonan Li , Shijie Liang , Yunhua Xu , Cuifen Zhang , Zheng Tang , Baiqiao Liu , Weiwei Li . Chlorine-Substituted Double-Cable Conjugated Polymers with Near-Infrared Absorption for Low Energy Loss Single-Component Organic Solar Cells. Acta Physico-Chimica Sinica, 2024, 40(8): 2307037-0. doi: 10.3866/PKU.WHXB202307037
14. [14]
  Fangxuan Liu , Ziyan Liu , Guowei Zhou , Tingting Gao , Wenyu Liu , Bin Sun . 中空结构光催化剂. Acta Physico-Chimica Sinica, 2025, 41(7): 100071-0. doi: 10.1016/j.actphy.2025.100071
15. [15]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
16. [16]
  Ran HUO , Zhaohui ZHANG , Xi SU , Long CHEN . Research progress on multivariate two dimensional conjugated metal organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2063-2074. doi: 10.11862/CJIC.20240195
17. [17]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
18. [18]
  Jianan Zhang , Mengzhen Xu , Jiamin Liu , Yufei He . 面向“双碳”目标的脱氯吸附剂开发研究型综合实验设计. University Chemistry, 2025, 40(6): 248-255. doi: 10.12461/PKU.DXHX202408068
19. [19]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
20. [20]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(324)
HTML views(11)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142