Effect of different catalyst ratios on the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene

Document Type : Original research

Authors

1 Shanghai Key Laboratory of Multiphase Material Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

2 Sinopec Shanghai Petrochemical Co., Ltd

Abstract

In this paper, the polymerization process of polydicyclopentadiene (PDCPD) obtained by using dicyclopentadiene (DCPD) and the 2nd generation Grubbs’ catalyst is optimized. The curing reaction kinetics was studied by differential scanning calorimetry (DSC), and the solidification reaction process was obtained. The effects of different ratios of monomer to catalyst on the product performance were investigated. In addition, the current common modification methods of PDCPD have been summarized and improved. The results showed that with the increase of the ratio of monomer to the catalyst, the tensile strength, tensile modulus, bending strength and bending modulus of PDCPD all showed a downward trend, and the impact strength showed an upward trend. When nDCPD: nCat =10000:1, the comprehensive mechanical properties of PDCPD reached the best. The bending modulus, tensile strength and impact strength of PDCPD achieved 2100 MPa, 52.4 MPa and 30 kJ/m2, respectively. The glass transition temperature (Tg) of PDCPD also showed a decreasing trend with the increase of the ratio of monomer to the catalyst, at this ratio, the Tg of the polymer reached 147.6°C. The catalyst concentration had a large effect on the product performance.

Keywords

References

  1. Kovacˇic S, Slugovc C (2020) Ring-opening metathesis polymerisation derived poly(dicyclo-pentadiene) based materials. Mater Chem Front 4: 2235-2255
  2. Jeong W, Kessler MR (2008) Toughness enhance­ment in ROMP functionalized carbon nanotube/ polydicyclopentadiene composites. Chem Mater 20: 7060-7068
  3. Toohey KS, Sottos NR, White SR (2009) char­acterization of microvascular-based self-healing coatings. Exp Mech 49: 707-717
  4. Hu F, Jie D, Tao O, Zheng Y (2014) Preparation and properties of high performance phthalide-containing bismaleimide reinforced polydicyclo­pentadiene. J Appl Polym Sci 131: 40474-40480
  5. Martina AD, Hilborn JG, Mühlebach A (2000) Macroporous cross-linked poly(dicyclopentadiene). Macromolecules 33: 2916-2921
  6. Kim HG, Son HJ, Lee DK, Kim DW, Park HJ, Cho DH (2017) Optimization and analysis of reaction injection molding of polydicyclopentadiene using response surface methodology. Korean J Chem Eng 34: 2099-2109
  7. Hu YH, Lang AW, Li XC, Nutt SR (2014) Hygrothermal aging effects on fatigue of glass fiber/polydicyclopentadiene composites. Polym Degrad Stabil 110: 464-472
  8. Mol JC (2004) Industrial applications of olefin metathesis. J Mol Catal A- Chem 213: 39-45
  9. Yao Z, Zhou LW, Dai BB, Cao K (2012) Ring-opening metathesis copolymerization of dicyclo­pentadiene and cyclopentene through reaction injection molding process. J Appl Polym Sci 125: 2489-2493
  10. Kim HG, Son HJ, Lee DK, Kim DW, Park HJ, Cho DH (2017) Optimization and analysis of reaction injection molding of polydicyclopentadiene using response surface methodology. Korean J Chem Eng 34: 2099-2109
  11. Steese ND, Barvaliya D, Poole XD, McLemore DE, DiCesare JC, Schanz HJ (2018) Synthesis and thermal properties of linear polydicyclo-pentadiene via ring-opening metathesis polymerization with a third generation grubbs-type ruthenium-alkylidene complex. Polym Chem 56: 359-364
  12. Wang B, Mireles K, Rock M, Li Y, Thakur VK, Gao D, Kessler MR (2016) Synthesis and preparation of bio-based ROMP thermosets from functionalized renewable isosorbide derivative. Macromol Chem Phys 217: 871-879
  13. Cao K, Fu Q, Zhou L, Yao Z (2012) Reaction injection molding of dicyclopentadiene. Prog Chem 24: 1368-1377
  14. Schaubroeck D, Brughmans S, Vercaemst C, Schaubroeck J, Verpoort F (2006) Verpoort. Qualitative FT-Raman investigation of the ring opening metathesis polymerization of dicyclo­pentadiene. J Mol Catal A - Chem 254: 180-185
  15. Drozdzak R, Nishioka N, Recher G, Verpoort F (2010) Latent olefin metathesis catalysts for polymerization of DCPD. Macromol Symp 293: 1-4
  16. Grubbs RH, Chang S (1998) Recent advances in olefin metathesis and its application in organic synthesis. Tetrahedron 54: 4413-4450
  17. Bielawski CW, Grubbs RH (2000) Highly efficient ring-opening metathesis polymerization (ROMP) using new ruthenium catalysts containing N-heterocyclic carbine ligands. Angew Chem Int Ed 39: 2903-2906
  18. Scholl M, Ding S, Lee CW, Grubbs RH (1999) Synthesis and activity of a new generation of ruthenium-based olefin metathesis catalysts coordinated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligands. Org Lett 1: 953-956
  19. Schrock R, Murdzek J, Bazan G (1990) Synthesis of molybdenum imido alkylidene complexes and Some Reactions Involving Acyclic Olefins. J Am Chem Soc 112: 3875-3886
  20. Schrock RR (1999) Olefin metathesis by molyb­denum imido alkylidene catalysts. Tetrahedron 55: 8141-8153
  21. Schrock R (2002) High Oxidation state multiple metal/carbon bonds. Chem Rev 102: 145-180
  22. Schrock RR, Hoveyda AH (2003) Molybdenum and tungsten imido alkylidene complexes as efficient olefin-metathesis catalysts. Angew Chem Int Ed 42: 4592-4633
  23. Kuang J, Zheng N, Liu C, Zheng Y (2018) Mani-pulating the thermal and dynamic mechanical properties of polydicyclo pentadiene via tuning the stiffness of the incorporated monomers. e-Polymers 19: 355-364
  24. Nguyen SBT, Johnson LK, Grubbs RH (1992) Ring-opening metathesis polymerization (ROMP) of norbornene by a group VIII carbene complex in protic media. J Am Chem Soc 114: 3974-3975
  25. Arduengo AJ (1999) Looking for stable carbenes: The difficulty in starting anew. Acc Chem Res 32: 913-921
  26. Scholl M, Trnka TM, Morgan JP (1999) Increased ring closing metathesis activity of ruthenium-based olefin metathesis catalysts coordinated with imidazolin-2-ylidene ligands. Tetrahedron Lett 40: 2247-2250
  27. Vidavsky Y, Navon Y, Ginzburg Y, Gottlieb M, Lemcoff NG (2015) Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene. Beilstein J Org Chem 11: 1469-1474
  28. White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, Brown EN, Viswana­than S (2001) Autonomic healing of polymer composites. Nature 409: 794-797
  29. Kessler MR, Sottos NR, White SR (2003) Self-healing structural composite materials. Compos Part A-Appl S 34: 743-753
  30. Kessler MR, White SR (2002) Cure kinetics of the ring-opening metathesis polymerization of dicyclopentadiene. J Polym Sci Pol Chem 40: 2373-2383
  31. Yang G, Lee JK (2013) Effect of Grubbs’ cata­lysts on cure kinetics of endo-dicyclopentadiene. Thermochim Acta 566: 105-111
  32. Xia Y, Larock RC (2010) Castor oil-based ther­mosets with varied crosslink densities prepared by ring-opening metathesis polymerization (ROMP). Polymer 51: 2508-2514
  33. Sun Q, Ma S, Ge Z, Luo Y (2017) Preparation and curing behavior of high-stress solid propel­lant binder based on polydicyclopentadiene. High Perform Polym 29: 931-936
  34. Kissinger HE (1957) Reaction kinetics in dif­ferential thermal analysis. Anal Chem 29: 1702- 1706
  35. Zhao F, Bi W, Zhao S (2011) Influence of cross­link density on mechanical properties of natural rubber vulcanizates. J Macromol Sci Phys 50: 1460-1469

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History

  • Receive Date: 30 March 2022
  • Revise Date: 02 May 2022
  • Accept Date: 21 May 2022
  • First Publish Date: 26 May 2022

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