Synthesis of cyclic olefin polymers with high glass transition temperature and high transparency using tungsten-based catalyst system

Document Type: Original research

Authors

1 State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

2 School of Material Science and Engineering, Tianjin University, Tianjin 300350, China

Abstract

Novel cyclic olefin polymers (COPs) derived from bulky cyclic olefins, tricyclodipentadiene (TCPD) and tricyclo[6.4.0.19,12]-tridec-10-ene (TTE), with high glass transition temperature (Tg), excellent thermal stability, and high transparency, have been synthesized by ring-opening metathesis polymerization (ROMP) and subsequent hydrogenation. ROMP of TCPD and TTE was carried out successfully without gel formation using a WCl6/i-Bu3Al/Et-OH/hexene catalyst system at room temperature. By changing the TCPD/TTE molar ratio, the optimized catalyst component ratio for the polymerization varied. Chemical structures of the unsaturated and hydrogenated polymers were characterized by 1H NMR technique. Thermal properties of these newly synthesized polymers were determined using TGA and DSC measurements. The degradation temperatures (Td) were all above 420°C in N2, indicating that all these copolymers had excellent thermal stability. After hydrogenation, Tg of ROMP polymers was decreased by 30-60°C. The Tg of h-pTCPD reached as high as about 230°C. The light transmittances of these polymer films were also analyzed using UV-Vis absorption spectroscopy. A high light transmittance of up to 92% was found by UV-Vis absorption spectra for these polymer films.

Keywords

Main Subjects


  1. Shin JY, Park JY, Liu CY, He JS, Kim SC (2005) Chemical structure and physical properties of cyclic olefin copolymers - (IUPAC technical re­port). Pure Appl Chem 77: 801-814
  2. Khanarian G (2001) Optical properties of cyclic olefin copolymers. Opt Eng 40: 1024-1029
  3. Nunes P, Ohlsson P, Ordeig O, Kutter J (2010) Cyclic olefin polymers: Emerging materials for lab-on-a-chip applications. Microfluid Nanofluid 9: 145-161
  4. Yamazaki M (2004) Industrialization and application development of cyclo-olefin polymer. J Mol Catal A-Chem 213: 81-87
  5. Hong M, Cui L, Liu S, Li Y (2012) Synthesis of novel cyclic olefin copolymer (COC) with high performance via effective copolymerization of ethylene with bulky cyclic olefin. Macromolecules 45: 5397-5402
  6. Widyaya VT, Vo HT, Putra RDD, Hwang WS, Ahn BS, Lee H (2013) Preparation and characterization of cycloolefin polymer based on dicyclopentadiene (DCPD) and dimethanooc­tahydronaphthalene (DMON). Eur Polym J 49: 2680-2688
  7. Shiotsuki M, Endo T (2014) Synthesis of hydro­carbon polymers containing bulky dibenzobicy­clic moiety by ROMP and their characteristic optical properties. J Polym Sci Pol Chem 52: 1392-1400
  8. Paddon-Row MN, Hartcher R (1980) 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 102: 671-678
  9. Yang JX, Cui J, Long YY, Li YG, Li YS (2014) Synthesis of cyclic olefin polymers with high glass transition temperature by ring-opening me­tathesis copolymerization and subsequent hydro­genation. J Polym Sci Pol Chem 52: 2654-2661
  10. Yang JX, Cui J, Long YY, Li YG, Li YS (2014) 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 Pol Chem 52: 3240-3249
  11. Park HC, Kim A, Lee BY (2011) Preparation of cycloolefin copolymers of a bulky tricyclopenta­diene. J Polym Sci Pol Chem 49: 938-944
  12. Park E-S, Park J-H, Jeon J, Sung J-U, Hwang W-S, Lee B-Y (2013) Ring-opening metathesis polymerization of dicyclopentadiene and tricy­clopentadiene. Macromol Res 21: 114-117
  13. Yu ST, Na SJ, Lim TS, Lee BY (2010) Prepara­tion of a bulky cycloolefin/ethylene copolymer and its tensile properties. Macromolecules 43: 725-730
  14. Hong M, Yang G-F, Long Y-Y, Yu S, Li Y-S (2013) Preparation of novel cyclic olefin copo­lymer with high glass transition temperature. J Polym Sci Pol Chem 51: 3144-3152
  15. Kim J, Wu CJ, Kim W-J, Kim J, Lee H, Kim J-D (2010) Ring-opening metathesis polymerization of tetracyclododecene using various catalyst systems. J Appl Polym Sci 116: 479-485
  16. Kwon OJ, Huyen Thanh V, Lee SB, Kim TK, Kim HS, Lee H (2011) Ring-opening metath­esis polymerization and hydrogenation of ethyl-substituted tetracyclododecene. Bull Korean Chem Soc 32: 2737-2742
  17. Bielawski CW, Grubbs RH (2007) Living ring-opening metathesis polymerization. Prog Polym Sci 32: 1-29
  18. Calderon N, Ofstead EA, Judy WA (1967) Ring-opening polymerization of unsaturated alicyclic compounds. J Polym Sci Pol Chem 5: 2209-2217
  19. Walker R, Conrad RM, Grubbs RH (2009) The living ROMP of trans-cyclooctene. Macromol­ecules 42: 599-605
  20. Alley WM, Hamdemir IK, Wang Q, Frenkel AI, Li L, Yang JC, Menard LD, Nuzzo RG, Özkar S, Yih K-H, Johnson KA, Finke RG (2011) 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. Langmuir 27: 6279-6294
  21. Louie J, Grubbs RH (2002) Metathesis of elec­tron-rich olefins: Structure and reactivity of elec­tron-rich carbene complexes. Organometallics 21: 2153-2164