Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl<sub>6</sub>-based Catalyst System

Yi-Ran Zhang; Ji-Xing Yang; Li Pan; Yue-Sheng Li

doi:10.1007/s10118-018-2055-5

Your Location：

Home >

Browse articles >

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

Articles | Updated：2021-02-18

- Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl₆-based Catalyst System
- Synthesis of High Performance Cyclic Olefin Polymers Using Highly Efficient WCl₆-based Catalyst System
- Chinese Journal of Polymer Science 2018年36卷第2期页码：214-221
- Affiliations：
  
  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
- Author bio：
  
  Li Pan, E-mail lilypan@tju.edu.cn
- Funds：
- DOI：10.1007/s10118-018-2055-5
  中图分类号：
- 收稿：2017-09-15，
  
  录用：2017-10-2，
  
  网络首发：2017-11-21，
  
  纸质出版：2018-02-05
- Accepted：
Scan QR Code
Yi-Ran Zhang, Ji-Xing Yang, Li Pan, 等. 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.

Yi-Ran Zhang, Ji-Xing Yang, Li Pan, et al. 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.
Yi-Ran Zhang, Ji-Xing Yang, Li Pan, 等. 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. DOI：

Yi-Ran Zhang, Ji-Xing Yang, Li Pan, et al. 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. DOI：

摘要

Abstract

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

10-hexahydr

-9

10(1'

2')-benzen

-l

4-methanoanthracene (HBM) and dicyclopentadiene (DCPD) or norbornene (NBE) using WCl

/i-Bu

Al/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 (

) of P-HBM from 5.8×10

to 41.1×10

. 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 (

) around 340℃ and glass transition temperatures (

) 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.

关键词

Keywords

references

G. Khanarian . Optical properties of cyclic olefin copolymers . Opt. Eng. , 2001 . 40 ( 6 ): 1024 - 1029 . DOI: 10.1117/1.1369411 http://doi.org/10.1117/1.1369411 .

J. Y. Shin , J. Y. Park , C. Y. Liu , J.S. He , S. C. Kim . Chemical structure and physical properties of cyclic olefin copolymers (IUPAC technical report) . Pure Appl. Chem. , 2005 . 77 ( 5 ): 801 - 814 . http://www.iupac.org/publications/pac/2005/pdf/7705x0801.pdf http://www.iupac.org/publications/pac/2005/pdf/7705x0801.pdf , .

J. C. Mol . Industrial applications of olefin metathesis . J. Mol. Catal. A:Chem. , 2004 . 213 ( 1 ): 39 - 45 . DOI: 10.1016/j.molcata.2003.10.049 http://doi.org/10.1016/j.molcata.2003.10.049 .

P. Nunes , P. Ohlsson , O. Ordeig , J. Kutter . Cyclic olefin polymers:Emerging materials for lab-on-a-chip applications . Microfluid. Nanofluid. , 2010 . 9 ( 2-3 ): 145 - 161 . DOI: 10.1007/s10404-010-0605-4 http://doi.org/10.1007/s10404-010-0605-4 .

L. Pan , J. Y. Liu , W. P. Ye , M. Hong , Y.S. Li . Efficient, regioselective copolymerization of ethylene with cyclopentadiene by the titanium complexes bearing two β-enaminoketonato ligands . Macromolecules , 2008 . 41 ( 9 ): 2981 - 2983 . DOI: 10.1021/ma800459r http://doi.org/10.1021/ma800459r .

Y. L. Li , J. X. Yang , B. Wang , Y. S. Li . Efficient copolymerization of ethylene with norbornene or its derivatives using half-metallocene zirconium(Ⅳ) catalysts . RSC Adv. , 2016 . 6 ( 64 ): 59590 - 59599 . DOI: 10.1039/C6RA11501B http://doi.org/10.1039/C6RA11501B .

X. F. Li , Z. M. Hou . Organometallic catalysts for copolymerization of cyclic olefins . Coord. Chem. Rev. , 2008 . 252 ( 15-17 ): 1842 - 1869 . DOI: 10.1016/j.ccr.2007.11.027 http://doi.org/10.1016/j.ccr.2007.11.027 .

T. Shiono , M. Sugimoto , T. Hasan , Z. G. Cai , T. Ikeda . Random copolymerization of norbornene with higher 1-alkene with ansa-fluorenylamidodimethyltitanium catalyst . Macromolecules , 2008 . 41 ( 22 ): 8292 - 8294 . DOI: 10.1021/ma802119d http://doi.org/10.1021/ma802119d .

J. Y. Liu , K. Nomura . Highly efficient ethylene/cyclopentene copolymerization with exclusive 1, 2-cyclopentene incorporation by (cyclopentadienyl)-(ketimide)titanium(Ⅳ) complex-MAO catalysts . Adv. Synth. Catal. , 2007 . 349 ( 14-15 ): 2235 - 2240 . DOI: 10.1002/(ISSN)1615-4169 http://doi.org/10.1002/(ISSN)1615-4169 .

X. F. Li , J. Baldamus , Z. M. Hou . Alternating ethylene-norbornene copolymerization catalyzed by cationic half-sandwich scandium complexes . Angew. Chem. Int. Ed. , 2005 . 44 ( 6 ): 962 - 965 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

M. Okaniwa , N. Kawashima , M. Kaizu , Y. Mutsuga . Birefringence control by hydrogen bonding on compatible polymer pair composed of hydrogenated ring-opening polymer and modified polystyrene . J. Polym. Sci., Part A:Polym. Chem. , 2013 . 51 ( 15 ): 3132 - 3143 . DOI: 10.1002/pola.26697 http://doi.org/10.1002/pola.26697 .

J. Cui , J. X. Yang , Y. G. Li , Y. S. Li . Synthesis of high performance cyclic olefin polymers (COPs) with ester group via ring-opening metathesis polymerization . Polymers , 2015 . 7 ( 8 ): 1389 - 1409 . DOI: 10.3390/polym7081389 http://doi.org/10.3390/polym7081389 .

E. S. Park , J. H. Park , J. Jeon , J. U. Sung , W. S. Hwang , B. Y. Lee . Ring-opening metathesis polymerization of dicyclopentadiene and tricyclopentadiene . Macromol. Res. , 2013 . 21 ( 1 ): 114 - 117 . DOI: 10.1007/s13233-012-0190-3 http://doi.org/10.1007/s13233-012-0190-3 .

J. Cui , J. X. Yang , L. Pan , Y. S. Li . Synthesis of novel cyclic olefin polymer with high glass transition temperature via ring-opening metathesis polymerization . Macromol. Chem. Phys. , 2016 . 217 ( 24 ): 2708 - 2716 . DOI: 10.1002/macp.v217.24 http://doi.org/10.1002/macp.v217.24 .

S. T. Yu , S. J. Na , T. S. Lim , B. Y. Lee . Preparation of a bulky cycloolefin/ethylene copolymer and its tensile properties . Macromolecules , 2010 . 43 ( 2 ): 725 - 730 . DOI: 10.1021/ma902334d http://doi.org/10.1021/ma902334d .

Z. G. Cai , R. Harada , Y. Nakayama , T. Shiono . Highly active living random copolymerization of norbornene and 1-alkene with ansa-fluorenylamidodimethyltitanium derivative:substituent effects on fluorenyl ligand . Macromolecules , 2010 . 43 ( 10 ): 4527 - 4531 . DOI: 10.1021/ma1006107 http://doi.org/10.1021/ma1006107 .

M. O. Liu , H. F. Lin , M. C. Yang , M. J. Lai , C. C. Chang , P. L. Shiao , I. M. Chen , J.Y. Chen . Thermal, dynamic mechanical and rheological properties of metallocene-catalyzed cycloolefin copolymers (mCOCs) with high glass transition temperature . Mater. Lett. , 2007 . 61 ( 2 ): 457 - 462 . DOI: 10.1016/j.matlet.2006.04.085 http://doi.org/10.1016/j.matlet.2006.04.085 .

T. Rische , A. J. Waddon , L. C. Dickinson , W. J. MacKnight . Microstructure and morphology of cycloolefin copolymers . Macromolecules , 1998 . 31 ( 6 ): 1871 - 1874 . DOI: 10.1021/ma971067i http://doi.org/10.1021/ma971067i .

H. C. Park , A. Kim , B. Y. Lee . Preparation of cycloolefin copolymers of a bulky tricyclopentadiene . J. Polym. Sci., Part A:Polym. Chem. , 2011 . 49 ( 4 ): 938 - 944 . DOI: 10.1002/pola.24506 http://doi.org/10.1002/pola.24506 .

M. Hong , G. F. Yang , Y. Y. Long , S. J. Yu , Y. S. Li . Preparation of novel cyclic olefin copolymer with high glass transition temperature . J. Polym. Sci., Part A:Polym. Chem. , 2013 . 51 ( 15 ): 3144 - 3152 . DOI: 10.1002/pola.26699 http://doi.org/10.1002/pola.26699 .

W. Kaminsky , R. Engehausen , J. Kopf . A tailor-made metallocene for the copolymerization of ethene with bulky cycloalkenes . Angew. Chem. Int. Ed. , 1995 . 34 ( 20 ): 2273 - 2275 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

M. Hong , L. Cui , S. R. Liu , Y. S. Li . Synthesis of novel cyclic olefin copolymer (COC) with high performance via eff ective copolymerization of ethylene with bulky cyclic olefin . Macromolecules , 2012 . 45 ( 13 ): 5397 - 5402 . DOI: 10.1021/ma300730y http://doi.org/10.1021/ma300730y .

J. X. Yang , J. Cui , Y. Y. Long , Y. G. Li , Y. S. Li . 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. Polym. Sci., Part A:Polym. Chem. , 2014 . 52 ( 22 ): 3240 - 3249 . DOI: 10.1002/pola.v52.22 http://doi.org/10.1002/pola.v52.22 .

J. X. Yang , J. Cui , Y. Y. Long , Y. G. Li , Y. S. Li . Synthesis of cyclic olefin polymers with high glass transition temperature by ring-opening metathesis copolymerization and subsequent hydrogenation . J. Polym. Sci., Part A:Polym. Chem. , 2014 . 52 ( 18 ): 2654 - 2661 . DOI: 10.1002/pola.v52.18 http://doi.org/10.1002/pola.v52.18 .

J. Kim , C. J. Wu , W. J. Kim , J. Kim , H. Lee , J. D. Kim . Ring-opening metathesis polymerization of tetracyclododecene using various catalyst systems . J. Appl. Polym. Sci. , 2010 . 116 ( 1 ): 479 - 485 . DOI: 10.1002/app.v116:1 http://doi.org/10.1002/app.v116:1 .

V. T. Widyaya , H. T. Vo , R. D. D. Putra , W. S. Hwang , B. S. Ahn , H. Lee . Preparation and characterization of cycloolefin polymer based on dicyclopentadiene (DCPD) and dimethanoocta hydronaphthalene (DMON) . Eur. Polym. J. , 2013 . 49 ( 9 ): 2680 - 2688 . DOI: 10.1016/j.eurpolymj.2013.05.022 http://doi.org/10.1016/j.eurpolymj.2013.05.022 .

O. J. Kwon , H. T. Vo , S. B. Lee , T. K. Kim , H. S. Kim , H. Lee . Ring-opening metathesis polymerization and hydrogenation of ethyl-substituted tetracyclododecene . Bull. Korean. Chem. Soc. , 2011 . 32 ( 8 ): 2737 - 2742 . DOI: 10.5012/bkcs.2011.32.8.2737 http://doi.org/10.5012/bkcs.2011.32.8.2737 .

M. N. Paddon-Row , R. Hartcher . Orbital interactions. 7. The birch reduction as a tool for exploring orbital interactions through bonds. Through-four-, -five-, and -six-bond interactions . J. Am. Chem. Soc. , 1980 . 102 ( 2 ): 671 - 678 . http://www.wiley.com/WileyCDA/WileyTitle/productCd-047108039X.html http://www.wiley.com/WileyCDA/WileyTitle/productCd-047108039X.html , .

C. W. Bielawski , R. H. Grubbs . Living ring-opening metathesis polymerization . Prog. Polym. Sci. , 2007 . 32 ( 1 ): 1 - 29 . DOI: 10.1016/j.progpolymsci.2006.08.006 http://doi.org/10.1016/j.progpolymsci.2006.08.006 .

W. M. Alley , I. K. Hamdemir , Q. Wang , A. I. Frenkel , L. Li , J. C. Yang , L. D. Menard , R. G. Nuzzo , S. Ozkar , K. H. Yih , K. A. Johnson , R. G. Finke . Industrial Ziegler-type hydrogenation catalysts made from Co(neodecanoate) 2 or Ni(2-ethylhexanoate) 2 and AlEt 3 :evidence for nanoclusters and sub-nanocluster or larger Ziegler-nanocluster based catalysis . Langmuir , 2011 . 27 ( 10 ): 6279 - 6294 . DOI: 10.1021/la200053f http://doi.org/10.1021/la200053f .

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Physical Properties of Polymers under Soft and Hard Nanoconfinement: A Review

Research on the Glass Transition Temperature and Mechanical Properties of Poly(vinyl chloride)/Dioctyl Phthalate (PVC/DOP) Blends by Molecular Dynamics Simulations

Alternating Poly(ether-alt-ester)s with High Glass Transition Temperature Enabled by Rotationally Constrained Biaryl Units

Highly Regio- and trans-Selective Ring-opening Metathesis Polymerization of Chiral Aza-norbornene with a Simple Phenylimido-Tungsten Catalyst

Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

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

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

DOI：10.1007/s10118-018-2055-5

摘要

Abstract

关键词

Keywords

references

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

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