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]
  Lingyun Shen , Shenxiang Yin , Qingshu Zheng , Zheming Sun , Wei Wang , Tao Tu . A rechargeable and portable hydrogen storage system grounded on soda water. Chinese Chemical Letters, 2025, 36(3): 110580-. doi: 10.1016/j.cclet.2024.110580
2. [2]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
3. [3]
  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
4. [4]
  Rong-Nan Yi , Wei-Min He . Visible light/copper catalysis enabled radial type ring-opening of sulfonium salts. Chinese Chemical Letters, 2025, 36(4): 110787-. doi: 10.1016/j.cclet.2024.110787
5. [5]
  Dongmei Yao , Junsheng Zheng , Liming Jin , Xiaomin Meng , Zize Zhan , Runlin Fan , Cong Feng , Pingwen Ming . Effect of surface oxidation on the interfacial and mechanical properties in graphite/epoxy composites composite bipolar plates. Chinese Chemical Letters, 2024, 35(11): 109382-. doi: 10.1016/j.cclet.2023.109382
6. [6]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
7. [7]
  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
8. [8]
  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
9. [9]
  Rui HUANG , Shengjie LIU , Qingyuan WU , Nanfeng ZHENG . Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356
10. [10]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
11. [11]
  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
12. [12]
  Xiaxia LIU , Xiaofang MA , Luxia GUO , Xianda HAN , Sisi FENG . Structure and magnetic properties of Mn(Ⅱ) coordination polymers regulated by N-auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 587-596. doi: 10.11862/CJIC.20240269
13. [13]
  Yu-Yao Li , Xiao-Hui Li , Zhi-Xuan An , Yang Chu , Xiu-Li Wang . Room-temperature olefin epoxidation reaction by two 2D cobalt metal-organic complexes under O₂ atmosphere: Coordination and structural regulation. Chinese Chemical Letters, 2025, 36(4): 109716-. doi: 10.1016/j.cclet.2024.109716
14. [14]
  Peipei CUI , Xin LI , Yilin CHEN , Zhilin CHENG , Feiyan GAO , Xu GUO , Wenning YAN , Yuchen DENG . Transition metal coordination polymers with flexible dicarboxylate ligand: Synthesis, characterization, and photoluminescence property. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2221-2231. doi: 10.11862/CJIC.20240234
15. [15]
  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
16. [16]
  Shaoming Dong , Yiming Niu , Yinghui Pu , Yongzhao Wang , Bingsen Zhang . Subsurface carbon modification of Ni-Ga for improved selectivity in acetylene hydrogenation reaction. Chinese Chemical Letters, 2024, 35(12): 109525-. doi: 10.1016/j.cclet.2024.109525
17. [17]
  Jinyuan Cui , Tingting Yang , Teng Xu , Jin Lin , Kunlong Liu , Pengxin Liu . Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu-O-Ce interface. Chinese Journal of Structural Chemistry, 2025, 44(1): 100438-100438. doi: 10.1016/j.cjsc.2024.100438
18. [18]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
19. [19]
  Ying-Yu Zhang , Jia-Qi Luo , Yan Han , Wan-Ying Zhang , Yi Zhang , Hai-Feng Lu , Da-Wei Fu . Bistable switch molecule DPACdCl₄ showing four physical channels and high phase transition temperature. Chinese Chemical Letters, 2025, 36(1): 109530-. doi: 10.1016/j.cclet.2024.109530
20. [20]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(854)
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