Citation: Peng Wei, Qi Peiyao, Dong Kaixuan, He Aihua. Oligomerization and Polymerization of Isoprene Catalyzed by Alkylaluminium with Different Structures[J]. Acta Chimica Sinica, ;2020, 78(12): 1418-1425. doi: 10.6023/A20070336 shu

Oligomerization and Polymerization of Isoprene Catalyzed by Alkylaluminium with Different Structures

Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization, Key Laboratory of Rubber-Plastics (Ministry of Education), School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Shandong Provincial Key Laboratory of Olefin Catalysis and Polymerization, Key Laboratory of Rubber-Plastics (Ministry of Education), School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Corresponding author: He Aihua, ahhe@qust.edu.cn; aihuahe@iccas.ac.cn
Received Date: 30 July 2020
Available Online: 9 October 2020
Fund Project: Project supported by the Major Scientific and Technological lnnovation Project of Shandong Province(No.2019JZZY010352) and Taishan Scholar Programthe Major Scientific and Technological lnnovation Project of Shandong Province 2019JZZY010352

Figures(8)

Alkylaluminium (AlR₃), as co-catalyst component in Ziegler-Natta catalytic system, plays important roles in the alkylation, forming and changing the structure and concentration of active centers through the reduction and reversible adsorption-desorption reactions with the metal compound of the catalyst, acting as chain transfer agent, etc. However, the alkylaluminium itself do have the catalytic effect on the conjugated diene monomers. In this article, alkylaluminium with different structures such as triethylaluminium (AlEt₃), triisobutylaluminium (Al(i-Bu)₃), diisobutylaluminium hydride (AlH(i-Bu)₂), diethylaluminium chloride (AlEt₂Cl), ethylaluminium dichloride (AlEtCl₂) were used to catalyze isoprene oligomerization and polymerization. The effects of the structure and concentration of alkylaluminiums (n(Al)/n(M)=7×10^-5, 35×10^-5, 350×10^-5, 1050×10^-5) on the catalytic behaviors of isoprene were studied. The microstructure (trans-1, 4 and cis-1, 4), molecular weight and molecular weight distribution of the products were characterized by ¹H nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC) and gas chromatography-mass spectrometry (GC-MS). It was found that alkylaluminium could initiate oligomerization and cationic polymerization of isoprene under the minor incorporation of H₂O, which were affected greatly by the structure and concentration of alkylaluminium. Using AlEtCl₂ led to the highest catalytic activity and produced products containing more linear polymers with mixed cis-1, 4/trans-1, 4 structures when n(Al)/n(M)=1050×10^-5. The Al(i-Bu)₃ and AlH(i-Bu)₂ didn't have basically cation initiation ability, which led to isoprene oligomerization. The alkylaluminium with n(Al)/n(M) ≤ 350×10^-5 had negligible influence on the isoprene polymerization and oligomerization. And lower or higher alkylaluminium concentration were not beneficial to obtain polyisoprene with high molecular weight. The catalytic mechanism of alkylaluminium on isoprene was discussed, which provided a further understanding on the catalytic behavior of alkylaluminium components in Ziegler-Natta catalyst and the effect of alkylaluminium on polymers.
- alkylaluminium,
- isoprene,
- catalysis,
- oligomerization,
- polymerization behavior
1. [1]
  Mori, H.; Hasebe, K.; Terano, M. Polymer 1999, 40, 1389.
2. [2]
  Yang, H. R.; Zhang, L. T.; Zang, D. D.; Fu, Z. S.; Fan, Z. Q. Catal. Commun. 2015, 62, 104.
3. [3]
  Bahri-Laleh, N.; Correa, A.; Mehdipour-Ataei, S.; Arabi, H.; Haghighi, M. N.; Zohuri, G.; Cavallo, L. Macromolecules 2011, 44, 778.
4. [4]
  Liu, B. P.; Nitta, T.; Nakatani, H.; Terano, M. Macromol. Chem. Phys. 2002, 203, 2412.
5. [5]
  Liu, B. P.; Nitta, T.; Nakatani, H.; Terano, M. Macromol. Chem. Phys. 2003, 204, 395.
6. [6]
  Liu, B. P.; Nitta, T.; Nakatani, H.; Terano, M. Macromol. Symp. 2004, 213, 7.
7. [7]
  Potapov, A. G.; Terskikh, V. V.; Zakharov, V. A.; Bukatov, G. D. J. Mol. Catal. A:Chem. 1999, 145, 147.
8. [8]
  Potapov, A. G.; Terskikh, V. V.; Bukatov, G. D.; Zakharov, V. A. J. Mol. Catal. A:Chem. 2000, 158, 457.
9. [9]
  Hu, J.; Han, B.; Shen, X. R.; Fu, Z. S.; Fan, Z. Q. Chin. J. Polym. Sci. 2013, 31, 583.
10. [10]
  Franceschini, F. C.; Tavares, T. T. D. R.; Greco, P. P.; Galland, G. B.; dos Santos, J. H.; Soares, J. B. J. Appl. Polym. Sci. 2005, 95, 1050.
11. [11]
  Rocha, T. C. J.; Coutinho, F. M. B.; Soares, B. G. Polym. Bull. 2009, 62, 1.
12. [12]
  Gao, H.; Liu, X.; Tang, Y.; Pan, J.; Wu, Q. Polym. Chem. 2011, 2, 1398.
13. [13]
  Huang, W. Q.; Yang, L.; Zhao, X.; Man, Y.; Li, B. Y.; Zhang, Y.; Yang, W. T. Chem. Ind. & Eng. Pro. 2011, 30, 1231(in Chinese).
14. [14]
  Blaakmeer, E. S. M.; van Eck, E. R. H.; Kentgens, A. P. M. Phys. Chem. Chem. Phys. 2018, 20, 7974.
15. [15]
  Niu, Q. T.; Zhang, J. Y.; Peng, W.; Fan, Z. Q.; He, A. H. Mol. Catal. 2019, 471, 1.
16. [16]
  Richardson, W. S. J. Polym. Sci. 1954, 13, 325.
17. [17]
  Ferington, T. E.; Tobolsky, A. V. J. Polym. Sci. 1958, 31, 25.
18. [18]
  Dolgoplosk, B.; Belonovskaia, G. P.; Boldyreva, I. I.; Nelson, K. V.; Kropacheva, E. N.; Rosinoer, J. M.; Chernova, J. D. J. Polym. Sci. 1961, 53, 209.
19. [19]
  Kennedy, J. P.; Squires, R. G. Polymer 1965, 6, 579.
20. [20]
  Binder, J. L. J. Polym. Sci. Part A:Gen. Pap. 1963, 1, 37.
21. [21]
  Kössler, I.; Vodehnal, J.; Štolka, M. J. Polym. Sci. Part A:Gen. Pap. 1965, 3, 2081.
22. [22]
  Pétiaud, R.; Taärit, Y. B. J. Chem. Soc. 1980, 10, 1385.
23. [23]
  Peng, Y. X.; Deng, Y. G.; Liu, J. L.; Dai, H. S.; Cun, L. F. Polym. Mater. Sci. Eng. 1997, 13, 95(in Chinese).
24. [24]
  Gaylord, N. G.; Matyska, B.; Mach, K.; Vodehnal, J. J. Polym. Sci. Pol. Chem. 1966, 4, 2493.
25. [25]
  Gaylord, N. G.; Kössler, I.; Matyska, B.; Mach, K. J. Polym. Sci. Pol. Chem. 1968, 6, 125.
26. [26]
  Matyska, B.; Doležal, I.; Kössler, I. Collect. Czech. Chem. C 1971, 36, 2924.
27. [27]
  Uchida, Y.; Furuhata, K. I.; Ishiwata, H. Bull. Chem. Soc. Jpn. 1971, 44, 1118.
28. [28]
  Akutagawa, S.; Taketomi, T.; Otsuka, S. Chem. Lett. 1976, 5, 485.
29. [29]
  Shen, G. L. Journal of Liaoyang Petrochemical College 1996, 12, 1(in Chinese).
30. [30]
  Yu, S. J. Speciality Petrochemicals 2000, (2), 20(in Chinese).
31. [31]
  Shen, G. L.; Tang, L. H. Speciality Petrochemicals 2004, (1), 17(in Chinese).
32. [32]
  Xia, S. W.; Xia, S. W.; Ma, S. X. Acta Polym. Sinica 1998, (3), 262(in Chinese).
1. [1]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
2. [2]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
3. [3]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
4. [4]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
5. [5]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
6. [6]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
7. [7]
  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-. doi: 10.3866/PKU.WHXB202406029
8. [8]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
9. [9]
  Fang Niu , Rong Li , Qiaolan Zhang . Analysis of Gas-Solid Adsorption Behavior in Resistive Gas Sensing Process. University Chemistry, 2024, 39(8): 142-148. doi: 10.3866/PKU.DXHX202311102
10. [10]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
11. [11]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
12. [12]
  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
13. [13]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
14. [14]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
15. [15]
  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
16. [16]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
17. [17]
  Minna Ma , Yujin Ouyang , Yuan Wu , Mingwei Yuan , Lijuan Yang . Green Synthesis of Medical Chemiluminescence Reagents by Photocatalytic Oxidation. University Chemistry, 2024, 39(5): 134-143. doi: 10.3866/PKU.DXHX202310093
18. [18]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
19. [19]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
20. [20]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084

Get Citation

PDF

XML

Metrics

PDF Downloads(35)
Abstract views(3217)
HTML views(419)

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