Citation: Hong-ran Fu, Yun-yun Song, Xiao-rui Ren, Fang Guo. Copolymerization of Myrcene and Butadiene Catalyzed by Half-sandwich Scandium Complexes[J]. Acta Polymerica Sinica, ;2018, 0(11): 1416-1421. doi: 10.11777/j.issn1000-3304.2018.18088 shu

Copolymerization of Myrcene and Butadiene Catalyzed by Half-sandwich Scandium Complexes

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024

Corresponding author: Fang Guo, guofang@dlut.edu.cn
Received Date: 21 March 2018
Revised Date: 8 April 2018
Available Online: 19 July 2018

Polymerization of myrcene and its copolymerization with butadiene by half-sandwich scandium complexes, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (1) and Cp′Sc(CH₂C₆H₄NMe₂-o)₂ (2: Cp′ = C₅Me₄SiMe₃; 3: Cp′ = C₅H₅), have been examined. The microstructures and thermal properties of the obtained polymers were characterized by ¹H-NMR, ¹³C-NMR, GPC and DSC. Significant ligand influence on the catalytic activity, selectivity, and polymer molecular weight has been observed in the homopolymerization of myrcene. The scandium complexes 1 and 2 bearing large C₅Me₄SiMe₃ ligand showed relatively low activity (10⁴ g polymer mol_Sc⁻¹ h⁻¹) and preferred 3,4-selectivity (74% for 1 and 61% for 2). The myrcene homopolymers prepared by complexes 1 and 2 have low molecular weight (M_n = 1.7 × 10⁴ − 5.6 × 10⁴) and relatively high glass transition temperature (−48 and −45 °C). The complex 3 bearing small C₅H₅ ligand showed high activity (10⁵ g polymer mol_Sc⁻¹ h⁻¹) and high cis-1,4-selectivity (95%). The myrcene homopolymers prepared by complex 3 have high molecular weight (M_n = 7.0 × 10⁴ − 2.31 × 10⁵) and low glass transition temperature (T_g = −70 °C). By use of complex 3, the copolymerization of myrcene with butadiene was also achieved for the first time to afford a novel family of rubber materials. The copolymerization reaction was completed within 5 min, irrespective of the monomer feed ratio, and the copolymerization activity was raised to as high as 10⁵ g polymer mol_Sc⁻¹ h⁻¹. The copolymer composition was in agreement with the co-monomer feed ratio, suggesting that both monomers were completely incorporated into their copolymers. The obtained myrcene-butadiene copolymers showed a random monomer sequence distribution, and the cis-1,4 contents of both monomers in the copolymers were more than 92%. All of these copolymers showed a single T_g varing with the myrcene/butadiene ratio. The T_gs of the copolymers with myrcene content of 19 mol% − 75 mol% fell in a range of −95 °C to −71 °C, which are between those of homopolymyrcene (−70 °C) and homopolybutadiene (−107 °C). The T_g of the copolymers decreased with increasing butadiene content. The molecular weight of the myrcene-butadiene copolymers can be controlled simply by changing the monomer/catalyst ratio.
- Scandium,
- Myrcene,
- Butadiene,
- Copolymerization
1. [1]
  Wilbon P A, Chu F, Tang C. Macromol Rapid Commun, 2013, 34(1): 8 − 37
2. [2]
  Zhao J, Schlaad H. Adv Polym Sci, 2013, 253(19): 151 − 190
3. [3]
  Nishiura M, Hou Z. Nat Chem, 2010, 2(4): 257 − 268
4. [4]
  Nishiura M, Guo F, Hou Z. Acc Chem Res, 2015, 48(8): 2209 − 2220
5. [5]
  Huang J, Liu Z, Cui D, Liu X. Chemcatchem, 2018, 10(1): 42 − 61
6. [6]
  Loughmari S, Hafid A, Bouazza A, Bouadili A E, Zinck P, Visseaux M. J Polym Sci, Part A: Polym Chem, 2012, 50(14): 2898 − 2905
7. [7]
  Loughmari S, Hafid A, Bouazza A, Bouadili A E, Zinck P, Visseaux M. J Polym Sci, Part A: Polym Chem, 2014, 52(11): 1642
8. [8]
  Georges S, Toure A O, Visseaux M, Zinck P. Macromolecules, 2014, 47(14): 4538 − 4547
9. [9]
  Liu B, Han B, Zhang C, Li S, Sun G, Cui D. Chinese J Polym Sci, 2015, 33(5): 792 − 796
10. [10]
  Liu B, Li L, Sun G, Liu D, Li S, Cui D. Chem Commun, 2015, 51(6): 1039 − 1041
11. [11]
  Liu B, Liu D, Li S, Sun G, Cui D. Chinese J Polym Sci, 2016, 34(1): 104 − 110
12. [12]
  Luo Y, Baldamus J, Hou Z. J Am Chem Soc, 2004, 126(43): 13910 − 13911
13. [13]
  Li X, Nishiura M, Mori K, Mashiko T, Hou Z. Chem Commun, 2007, (40): 4137 − 4139
14. [14]
  Guo F, Nishiura M, Koshino H, Hou Z. Macromolecules, 2011, 44(16): 6335 − 6344
15. [15]
  Chiem J C W, Tsai W M, Rausch M D. J Am Chem Soc, 1991, 113(22): 8570 − 8571
16. [16]
  Kang X, Zhou G, Wang X, Qu J, Hou Z, Luo Y. Organometallics, 2016, 35(6): 913 − 920
17. [17]
  Wang Yurong(王玉荣). Acta Polymerica Sinica(高分子学报), 2014, (10): 1420 − 1427
18. [18]
  Li X, Nishiura M, Hu L, Mori K, Hou Z. J Am Chem Soc, 2009, 131(38): 13870 − 13882
1. [1]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
2. [2]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
3. [3]
  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
4. [4]
  Yunting Shang , Yue Dai , Jianxin Zhang , Nan Zhu , Yan Su . Something about RGO (Reduced Graphene Oxide). University Chemistry, 2024, 39(9): 273-278. doi: 10.3866/PKU.DXHX202306050
5. [5]
  Anbang Du , Yuanfan Wang , Zhihong Wei , Dongxu Zhang , Li Li , Weiqing Yang , Qianlu Sun , Lili Zhao , Weigao Xu , Yuxi Tian . Photothermal Microscopy of Graphene Flakes with Different Thicknesses. Acta Physico-Chimica Sinica, 2024, 40(5): 2304027-0. doi: 10.3866/PKU.WHXB202304027
6. [6]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
7. [7]
  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
8. [8]
  Zhenlin Zhou , Siyuan Chen , Yi Liu , Chengguo Hu , Faqiong Zhao . A New Program of Voltammetry Experiment Teaching Based on Laser-Scribed Graphene Electrode. University Chemistry, 2024, 39(2): 358-370. doi: 10.3866/PKU.DXHX202308049
9. [9]
  Rui Gao , Ying Zhou , Yifan Hu , Siyuan Chen , Shouhong Xu , Qianfu Luo , Wenqing Zhang . Design, Synthesis and Performance Experiment of Novel Photoswitchable Hybrid Tetraarylethenes. University Chemistry, 2024, 39(5): 125-133. doi: 10.3866/PKU.DXHX202310050
10. [10]
  Jiahao Lu , Xin Ming , Yingjun Liu , Yuanyuan Hao , Peijuan Zhang , Songhan Shi , Yi Mao , Yue Yu , Shengying Cai , Zhen Xu , Chao Gao . High-Precision and Reliable Thermal Conductivity Measurement for Graphene Films Based on an Improved Steady-State Electric Heating Method. Acta Physico-Chimica Sinica, 2025, 41(5): 100045-0. doi: 10.1016/j.actphy.2025.100045
11. [11]
  Tianqi Bai , Kun Huang , Fachen Liu , Ruochen Shi , Wencai Ren , Songfeng Pei , Peng Gao , Zhongfan Liu . Nanoscale Mechanism of Microstructure-Dependent Thermal Diffusivity in Thick Graphene Sheets. Acta Physico-Chimica Sinica, 2025, 41(3): 100025-0. doi: 10.3866/PKU.WHXB202404024
12. [12]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
13. [13]
  Hao BAI , Weizhi JI , Jinyan CHEN , Hongji LI , Mingji LI . Preparation of Cu₂O/Cu-vertical graphene microelectrode and detection of uric acid/electroencephalogram. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1309-1319. doi: 10.11862/CJIC.20240001
14. [14]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
15. [15]
  Jiamin Li , Wenyue Zhong , Kin Shing Chan . “烯”君入瓮又入学——据元素周期表与酸碱理论谈烯烃教学. University Chemistry, 2025, 40(6): 177-182. doi: 10.12461/PKU.DXHX202408040
16. [16]
  Yawen Guo , Dawei Li , Yang Gao , Cuihong Li . Recent Progress on Stability of Organic Solar Cells Based on Non-Fullerene Acceptors. Acta Physico-Chimica Sinica, 2024, 40(6): 2306050-0. doi: 10.3866/PKU.WHXB202306050
17. [17]
  Yue Zhang , Bao Li , Lixin Wu . GO-Assisted Supramolecular Framework Membrane for High-Performance Separation of Nanosized Oil-in-Water Emulsions. Acta Physico-Chimica Sinica, 2024, 40(5): 2305038-0. doi: 10.3866/PKU.WHXB202305038
18. [18]
  Dafa Chen , Haiping Xia . From Pollutant to Metal-Centred Annulene: The Transformation Journey of a Little Osmium Atom. University Chemistry, 2025, 40(10): 156-160. doi: 10.12461/PKU.DXHX202508094
19. [19]
  Hailang JIA , Yujie LU , Pengcheng JI . Preparation and properties of nitrogen and phosphorus co-doped graphene carbon aerogel supported ruthenium electrocatalyst for hydrogen evolution reaction. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2327-2336. doi: 10.11862/CJIC.20250021
20. [20]
  Yuanchun Pan , Xinyun Lin , Leyi Yang , Wenya Hu , Dekui Song , Nan Liu . Artificial Intelligence Science Practice: Preparation of Electronic Skin by Chemical Vapor Deposition of Graphene. University Chemistry, 2025, 40(11): 272-280. doi: 10.12461/PKU.DXHX202412052

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(260)
HTML views(8)

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