Citation: Yi-Ran Zhang, Ji-Xing Yang, Li Pan, Yue-Sheng Li. Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl₆-based Catalyst System[J]. Chinese Journal of Polymer Science, ;2018, 36(2): 214-221. doi: 10.1007/s10118-018-2055-5 shu

Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl₆-based Catalyst System

Yi-Ran Zhang ^a ,
Ji-Xing Yang ^a ,
Li Pan ^a,, ,
Yue-Sheng Li ^a,b

a.
Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
b.
Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China

Corresponding author: Li Pan, lilypan@tju.edu.cn
Received Date: 15 September 2017
Accepted Date: 2 October 2017
Available Online: 21 November 2017

Cyclic olefin polymers (COPs) with high glass transition temperature, high transparency (higher than 80%) in the visible light range, excellent thermal stability and outstanding mechanical properties have been synthesized by effective ring opening metathesis polymerization (ROMP) of exo-1, 4, 4a, 9, 9a, 10-hexahydro-9, 10(1', 2')-benzeno-l, 4-methanoanthracene (HBM) and dicyclopentadiene (DCPD) or norbornene (NBE) using WCl₆/i-Bu₃Al/ethanol/1-hexene catalyst system, followed by hydrogenation of double bonds. 1-Hexene acted as a molecular weight controller in the polymerization reaction, tuning the number-average molecular weight (M_n) of P-HBM from 5.8×10⁴ to 41.1×10⁴. The monomer composition and thermal properties of the copolymers were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The saturated polymers exhibited high decomposition temperatures (T_d) around 340℃ and glass transition temperatures (T_g) in the range from 117.5℃ to 219.7℃. What is more, tensile tests indicated that the mechanical properties of the COPs could be effectively tuned in a wide range by introducing varying amount of small cyclic olefin such as DCPD or NBE.
- Ring-opening metathesis polymerization,
- Hydrogenation,
- Cyclic olefin polymers,
- Glass transition temperature,
- Mechanical properties
1. [1]
  Khanarian G.. Optical properties of cyclic olefin copolymers[J]. Opt. Eng., 2001,40(6):1024-1029. doi: 10.1117/1.1369411
2. [2]
  Shin J. Y., Park J. Y., Liu C. Y., He J.S., Kim S. C.. Chemical structure and physical properties of cyclic olefin copolymers (IUPAC technical report)[J]. Pure Appl. Chem., 2005,77(5):801-814.
3. [3]
  Mol J. C.. Industrial applications of olefin metathesis[J]. J. Mol. Catal. A:Chem., 2004,213(1):39-45. doi: 10.1016/j.molcata.2003.10.049
4. [4]
  Nunes P., Ohlsson P., Ordeig O., Kutter J.. Cyclic olefin polymers:Emerging materials for lab-on-a-chip applications[J]. Microfluid. Nanofluid., 2010,9(2-3):145-161. doi: 10.1007/s10404-010-0605-4
5. [5]
  Pan L., Liu J. Y., Ye W. P., Hong M., Li Y.S.. Efficient, regioselective copolymerization of ethylene with cyclopentadiene by the titanium complexes bearing two β-enaminoketonato ligands[J]. Macromolecules, 2008,41(9):2981-2983. doi: 10.1021/ma800459r
6. [6]
  Li Y. L., Yang J. X., Wang B., Li Y. S.. Efficient copolymerization of ethylene with norbornene or its derivatives using half-metallocene zirconium(Ⅳ) catalysts[J]. RSC Adv., 2016,6(64):59590-59599. doi: 10.1039/C6RA11501B
7. [7]
  Li X. F., Hou Z. M.. Organometallic catalysts for copolymerization of cyclic olefins[J]. Coord. Chem. Rev., 2008,252(15-17):1842-1869. doi: 10.1016/j.ccr.2007.11.027
8. [8]
  Shiono T., Sugimoto M., Hasan T., Cai Z. G., Ikeda T.. Random copolymerization of norbornene with higher 1-alkene with ansa-fluorenylamidodimethyltitanium catalyst[J]. Macromolecules, 2008,41(22):8292-8294. doi: 10.1021/ma802119d
9. [9]
  Liu J. Y., Nomura K.. Highly efficient ethylene/cyclopentene copolymerization with exclusive 1, 2-cyclopentene incorporation by (cyclopentadienyl)-(ketimide)titanium(Ⅳ) complex-MAO catalysts[J]. Adv. Synth. Catal., 2007,349(14-15):2235-2240. doi: 10.1002/(ISSN)1615-4169
10. [10]
  Li X. F., Baldamus J., Hou Z. M.. Alternating ethylene-norbornene copolymerization catalyzed by cationic half-sandwich scandium complexes[J]. Angew. Chem. Int. Ed., 2005,44(6):962-965. doi: 10.1002/(ISSN)1521-3773
11. [11]
  Okaniwa M., Kawashima N., Kaizu M., Mutsuga Y.. Birefringence control by hydrogen bonding on compatible polymer pair composed of hydrogenated ring-opening polymer and modified polystyrene[J]. J. Polym. Sci., Part A:Polym. Chem., 2013,51(15):3132-3143. doi: 10.1002/pola.26697
12. [12]
  Cui J., Yang J. X., Li Y. G., Li Y. S.. Synthesis of high performance cyclic olefin polymers (COPs) with ester group via ring-opening metathesis polymerization[J]. Polymers, 2015,7(8):1389-1409. doi: 10.3390/polym7081389
13. [13]
  Park E. S., Park J. H., Jeon J., Sung J. U., Hwang W. S., Lee B. Y.. Ring-opening metathesis polymerization of dicyclopentadiene and tricyclopentadiene[J]. Macromol. Res., 2013,21(1):114-117. doi: 10.1007/s13233-012-0190-3
14. [14]
  Cui J., Yang J. X., Pan L., Li Y. S.. Synthesis of novel cyclic olefin polymer with high glass transition temperature via ring-opening metathesis polymerization[J]. Macromol. Chem. Phys., 2016,217(24):2708-2716. doi: 10.1002/macp.v217.24
15. [15]
  Yu S. T., Na S. J., Lim T. S., Lee B. Y.. Preparation of a bulky cycloolefin/ethylene copolymer and its tensile properties[J]. Macromolecules, 2010,43(2):725-730. doi: 10.1021/ma902334d
16. [16]
  Cai Z. G., Harada R., Nakayama Y., Shiono T.. Highly active living random copolymerization of norbornene and 1-alkene with ansa-fluorenylamidodimethyltitanium derivative:substituent effects on fluorenyl ligand[J]. Macromolecules, 2010,43(10):4527-4531. doi: 10.1021/ma1006107
17. [17]
  Liu M. O., Lin H. F., Yang M. C., Lai M. J., Chang C. C., Shiao P. L., Chen I. M., Chen J.Y.. Thermal, dynamic mechanical and rheological properties of metallocene-catalyzed cycloolefin copolymers (mCOCs) with high glass transition temperature[J]. Mater. Lett., 2007,61(2):457-462. doi: 10.1016/j.matlet.2006.04.085
18. [18]
  Rische T., Waddon A. J., Dickinson L. C., MacKnight W. J.. Microstructure and morphology of cycloolefin copolymers[J]. Macromolecules, 1998,31(6):1871-1874. doi: 10.1021/ma971067i
19. [19]
  Park H. C., Kim A., Lee B. Y.. Preparation of cycloolefin copolymers of a bulky tricyclopentadiene[J]. J. Polym. Sci., Part A:Polym. Chem., 2011,49(4):938-944. doi: 10.1002/pola.24506
20. [20]
  Hong M., Yang G. F., Long Y. Y., Yu S. J., Li Y. S.. Preparation of novel cyclic olefin copolymer with high glass transition temperature[J]. J. Polym. Sci., Part A:Polym. Chem., 2013,51(15):3144-3152. doi: 10.1002/pola.26699
21. [21]
  Kaminsky W., Engehausen R., Kopf J.. A tailor-made metallocene for the copolymerization of ethene with bulky cycloalkenes[J]. Angew. Chem. Int. Ed., 1995,34(20):2273-2275. doi: 10.1002/(ISSN)1521-3773
22. [22]
  Hong M., Cui L., Liu S. R., Li Y. S.. Synthesis of novel cyclic olefin copolymer (COC) with high performance via eff ective copolymerization of ethylene with bulky cyclic olefin[J]. Macromolecules, 2012,45(13):5397-5402. doi: 10.1021/ma300730y
23. [23]
  Yang J. X., Cui J., Long Y. Y., Li Y. G., Li Y. S.. Synthesis of novel cyclic olefin polymers with excellent transparency and high glass-transition temperature via gradient copolymerization of bulky cyclic olefin and cis-cyclooctene[J]. J. Polym. Sci., Part A:Polym. Chem., 2014,52(22):3240-3249. doi: 10.1002/pola.v52.22
24. [24]
  Yang J. X., Cui J., Long Y. Y., Li Y. G., Li Y. S.. Synthesis of cyclic olefin polymers with high glass transition temperature by ring-opening metathesis copolymerization and subsequent hydrogenation[J]. J. Polym. Sci., Part A:Polym. Chem., 2014,52(18):2654-2661. doi: 10.1002/pola.v52.18
25. [25]
  Kim J., Wu C. J., Kim W. J., Kim J., Lee H., Kim J. D.. Ring-opening metathesis polymerization of tetracyclododecene using various catalyst systems[J]. J. Appl. Polym. Sci., 2010,116(1):479-485. doi: 10.1002/app.v116:1
26. [26]
  Widyaya V. T., Vo H. T., Putra R. D. D., Hwang W. S., Ahn B. S., Lee H.. Preparation and characterization of cycloolefin polymer based on dicyclopentadiene (DCPD) and dimethanoocta hydronaphthalene (DMON)[J]. Eur. Polym. J., 2013,49(9):2680-2688. doi: 10.1016/j.eurpolymj.2013.05.022
27. [27]
  Kwon O. J., Vo H. T., Lee S. B., Kim T. K., Kim H. S., Lee H.. Ring-opening metathesis polymerization and hydrogenation of ethyl-substituted tetracyclododecene[J]. Bull. Korean. Chem. Soc., 2011,32(8):2737-2742. doi: 10.5012/bkcs.2011.32.8.2737
28. [28]
  Paddon-Row M. N., Hartcher R.. Orbital interactions. 7. The birch reduction as a tool for exploring orbital interactions through bonds. Through-four-, -five-, and -six-bond interactions[J]. J. Am. Chem. Soc., 1980,102(2):671-678.
29. [29]
  Bielawski C. W., Grubbs R. H.. Living ring-opening metathesis polymerization[J]. Prog. Polym. Sci., 2007,32(1):1-29. doi: 10.1016/j.progpolymsci.2006.08.006
30. [30]
  Alley W. M., Hamdemir I. K., Wang Q., Frenkel A. I., Li L., Yang J. C., Menard L. D., Nuzzo R. G., Ozkar S., Yih K. H., Johnson K. A., Finke R. G.. Industrial Ziegler-type hydrogenation catalysts made from Co(neodecanoate)₂ or Ni(2-ethylhexanoate)₂ and AlEt₃:evidence for nanoclusters and sub-nanocluster or larger Ziegler-nanocluster based catalysis[J]. Langmuir, 2011,27(10):6279-6294. doi: 10.1021/la200053f
1. [1]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
2. [2]
  Ming Huang , Xiuju Cai , Yan Liu , Zhuofeng Ke . Base-controlled NHC-Ru-catalyzed transfer hydrogenation and α-methylation/transfer hydrogenation of ketones using methanol. Chinese Chemical Letters, 2024, 35(7): 109323-. doi: 10.1016/j.cclet.2023.109323
3. [3]
  Yi Liu , Peng Lei , Yang Feng , Shiwei Fu , Xiaoqing Liu , Siqi Zhang , Bin Tu , Chen Chen , Yifan Li , Lei Wang , Qing-Dao Zeng . Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers. Chinese Chemical Letters, 2024, 35(10): 109571-. doi: 10.1016/j.cclet.2024.109571
4. [4]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
5. [5]
  Shuwen SUN , Gaofeng WANG . Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 613-620. doi: 10.11862/CJIC.20230368
6. [6]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
7. [7]
  Zhenghua ZHAO , Qin ZHANG , Yufeng LIU , Zifa SHI , Jinzhong GU . Syntheses, crystal structures, catalytic and anti-wear properties of nickel(Ⅱ) and zinc(Ⅱ) coordination polymers based on 5-(2-carboxyphenyl)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 621-628. doi: 10.11862/CJIC.20230342
8. [8]
  Gaofeng WANG , Shuwen SUN , Yanfei ZHAO , Lixin MENG , Bohui WEI . Structural diversity and luminescence properties of three zinc coordination polymers based on bis(4-(1H-imidazol-1-yl)phenyl)methanone. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 849-856. doi: 10.11862/CJIC.20230479
9. [9]
  Weizhong LING , Xiangyun CHEN , Wenjing LIU , Yingkai HUANG , Yu LI . Syntheses, crystal structures, and catalytic properties of three zinc(Ⅱ), cobalt(Ⅱ) and nickel(Ⅱ) coordination polymers constructed from 5-(4-carboxyphenoxy)nicotinic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1803-1810. doi: 10.11862/CJIC.20240068
10. [10]
  Long TANG , Yaxin BIAN , Luyuan CHEN , Xiangyang HOU , Xiao WANG , Jijiang WANG . Syntheses, structures, and properties of three coordination polymers based on 5-ethylpyridine-2,3-dicarboxylic acid and N-containing ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1975-1985. doi: 10.11862/CJIC.20240180
11. [11]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
12. [12]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
13. [13]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
14. [14]
  Xinyu You , Xin Zhang , Shican Jiang , Yiru Ye , Lin Gu , Hexun Zhou , Pandong Ma , Jamal Ftouni , Abhishek Dutta Chowdhury . Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process. Chinese Journal of Structural Chemistry, 2024, 43(4): 100265-100265. doi: 10.1016/j.cjsc.2024.100265
15. [15]
  Zixu Xie , Pengfei Zhang , Ziyao Zhang , Chen Chen , Xing Wang . The choice of antimicrobial polymers: Hydrophilic or hydrophobic?. Chinese Chemical Letters, 2024, 35(9): 109768-. doi: 10.1016/j.cclet.2024.109768
16. [16]
  Zhihao Gu , Jiabo Le , Hehe Wei , Zehui Sun , Mahmoud Elsayed Hafez , Wei Ma . Unveiling the intrinsic properties of single NiZnFeO_x entity for promoting electrocatalytic oxygen evolution. Chinese Chemical Letters, 2024, 35(4): 108849-. doi: 10.1016/j.cclet.2023.108849
17. [17]
  Wenzhong Zhang , Zirui Yan , Lingcheng Chen , Yi Xiao . Sn-fused perylene diimides: Synthesis, mechanism, and properties. Chinese Chemical Letters, 2024, 35(10): 109582-. doi: 10.1016/j.cclet.2024.109582
18. [18]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
19. [19]
  Yanbing Shen , Yuan Yuan , Yaxin Wang , Xiaonan Ma , Wensheng Yang , Yulan Chen . Dihydroanthracene bridged bis-naphthopyrans: A multimodal chromophore with mechano- and photo-chromic properties. Chinese Chemical Letters, 2024, 35(5): 108949-. doi: 10.1016/j.cclet.2023.108949
20. [20]
  Zhengzheng LIU , Pengyun ZHANG , Chengri WANG , Shengli HUANG , Guoyu YANG . Synthesis, structure, and electrochemical properties of a sandwich-type {Co₆}-cluster-added germanotungstate. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1173-1179. doi: 10.11862/CJIC.20240039

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(727)
HTML views(27)

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

Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl6-based Catalyst System

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl₆-based Catalyst System