Ethylene–Norbornene Copolymers
Abstract
Ethylene–norbornene copolymers are a significant kind of cyclic olefin copolymer (COC) produced by vinyl-type coordination copolymerization of ethylene and norbornene catalyzed by transition metal catalysts. These totally amorphous copolymers are strong, stiff, highly transparent, and colorless. They have a very high moisture barrier and interesting electrical properties. The copolymers became commercially available in 2001, and products can be obtained from manufacturers such as Polyplastics. This article describes the microstructures, properties, manufacturing, processing, and applications of this kind of polymeric materials. A basic background on the general COC materials is provided in the introduction. Then the dependency relationship between the microstructure and property is mainly discussed. The diversified copolymerization systems, including metallocene catalysts and post-metallocene catalysts, for E–NBE copolymers manufacturing have been revealed. The processing and applications of selected commercially available copolymer products are also summarized.
Bibliography
- 1R. Ma, Y. Hou, J. Gao, and F. Bao, J. Macromol. Sci. C: Polym. Rev. 49, 249–287 (2009), DOI: 10.1080/15583720903048276.
- 2F. Blank and C. Janiak, Coordin. Chem. Rev. 253, 827–861 (2009), DOI: 10.1016/j.ccr.2008.05.010.
- 3M. V. Bermeshev and P. P. Chapala, Prog. Polym. Sci. 84, 1–46 (2018), DOI: 10.1016/j.progpolymsci.2018.06.003.
- 4D. S. Suslova, M. V. Bykova, and O. V. Kravchenkoa, Polym. Sci. Ser. C 61, 145–173 (2019), DOI: 10.1134/S181123821901017X.
10.1134/S181123821901017X Google Scholar
- 5I. Tritto, L. Boggioni, and D. R. Ferro, Coord. Chem. Rev. 250, 212–241 (2006), DOI: 10.1016/j.ccr.2005.06.019.
- 6W. Wang, S. Qu, X. Li, J. Chen, Z. Guo, and W.-H. Sun, Coord. Chem. Rev. 494, 215351 (2023), DOI: 10.1016/j.ccr.2023.215351.
- 7M. Li, Y. Fang, Z. Cai, and M. S. Eisen, ChemCatChem (2024), DOI: 10.1002/cctc.202301731.
10.1002/cctc.202301731 Google Scholar
- 8 U.S. Pat. 2721189 (Oct. 18, 1955), A. W. Anderson and N. G. Merckling ( to E. I. du Pont de Nemours & Co., Inc.).
- 9 G.B. Pat. 951022 (Apr. 24, 1962) ( to Montecatini Societa Generale per L'Industria Mineraria e Chimica).
- 10 D.D.R. Pat. 109224 (Jul. 10, 1973), J.-P. Koinzer, U. Langbein, and E. Taeger (to VEB Leuna).
- 11 Eur. Pat. 0156464 (Feb. 1, 1985), H. Kajiura, H. Oda, and S. Minami ( to Mitsui Petrochemical Industries, Ltd.).
- 12 Eur. Pat. 0283164 (Mar. 1, 1988), N. Ishimaru and co-workers ( to Mitsui Petrochemical Industries, Ltd.).
- 13 Eur. Pat. 0407870A2 (Jul. 4, 1990), M.-J. Brekner and co-workers ( to Hoechst Aktiengesellschaft).
- 14Web information. Available at https://us.mitsuichemicals.com. Accessed April 15, 2024.
- 15Web information. Available at https://www.topas.com. Accessed April 15, 2024.
- 16M. Arndt-Rosenau and I. Beulich, Macromolecules 32, 7335–7343 (1999), DOI: 10.1021/ma981813z.
- 17R. A. Wendt and G. Fink, Macromol. Chem. Phys. 202, 3490–3501 (2001), DOI: 10.1002/1521-3935(20011201)202:18<3490::AID-MACP3490>3.0.CO;2-6.
- 18M. Amdt and I. Beulich, Macromol. Chem. Phys. 199, 1221–1232 (1998), DOI: 10.1002/(SICI)1521-3935(19980601)199:6<1221::AID-MACP1221>3.0.CO;2-2.
10.1002/(SICI)1521?3935(19980601)199:6<1221::AID?MACP1221>3.0.CO;2?2 Google Scholar
- 19J. Forsyth, J. M. Peren, R. Benavente, E. Perez, I. Tritto, L. Boggioni, and H.-H. Brintzinger, Macromol. Chem. Phys. 202, 614–620 (2001), DOI: 10.1002/1521-3935(20010301)202:5<614::AID-MACP614>3.0.CO;2-C.
- 20D. McNally, Ethylene-Norbornene Copolymers, Encyclopedia of Polymer Science and Technology (online), October 22, (2001), DOI: 10.1002/0471440264.pst124.
10.1002/0471440264.pst124 Google Scholar
- 21A. M. Bravakis, L. E. Bailey, M. Pigeon, and S. Collins, Macromolecules 31, 1000–1009 (1998), DOI: g/10.1021/ma971325b.
- 22R. R. Lamonte and D. McNally, Plast. Eng. 56 (6), 51 (2000).
- 23H. Wang, H. Cheng, R. Tanaka, T. Shiono, and Z. Cai, Polym. Chem. 9, 4492–4497 (2018).
- 24H. Cheng and Z. Cai, ChemCatChem 9, 1–5 (2017), DOI: 10.1002/cctc.201701418.
10.1002/cctc.201601629 Google Scholar
- 25 W. Kaminsky, A. Dark, I. Dake, T. Keii, and K. Soga, eds, Catalytic Olefin Polymerization, Kodansha Ltd., Tokyo, 1990.
- 26W. Kaminsky and R. Spiehl, Makromol. Chem. 190, 515–526 (1989), DOI: 10.1002/macp.1989.021900308.
- 27A. L. McKnight and R. M. Waymouth, Chem. Rev. 98, 2587–2598 (1998), DOI: 10.1021/cr940442r.
- 28A. L. McKnight and R. M. Waymouth, Macromolecules 32, 2816–2825 (1999), DOI: 10.1021/ma981365v.
- 29K. Thorshaug, R. Mendichi, L. Boggioni, I. Tritto, S. Trinkle, C. Friedrich, and R. Mülhaupt, Macromolecules 35, 2903–2911 (2002), DOI: 10.1021/ma011949o.
- 30T. Hasan, T. Ikeda, and T. Shiono, Macromolecules 37, 8503–8509 (2004), DOI: 10.1021/ma048492d.
- 31Y. Sun, B. Xu, T. Shiono, and Z. Cai, Organometallics 36, 3009–3012 (2017), DOI: 10.1021/acs.organomet.7b00415.
- 32K. Nomura, B. K. Bahuleyan, S. Zhang, P. M. V. Sharma, S. Katao, A. Igarashi, A. Inagaki, and M. Tamm, Inorg. Chem. 53, 607–623 (2014), DOI: 10.1021/ic402747d.
- 33W. Zhao and K. Nomura, Catalysts 6, 175 (2016), DOI: 10.3390/catal6110175.
- 34Y. Yoshida, J. Mohri, S. Ishii, M. Mitani, J. Saito, S. Matsui, H. Makio, T. Nakano, H. Tanaka, M. Onda, Y. Yamamoto, A. Mizuno, and T. Fujita, J. Am. Chem. Soc. 126, 12023–12032 (2004), DOI: 10.1021/ja048357g.
- 35H. Terao, A. Iwashita, S. Ishii, H. Tanaka, Y. Yoshida, M. Mitani, and T. Fujita, Macromolecules 42, 4359–4361 (2009), DOI: 10.1021/ma900890b.
- 36W. Zuo, W.-H. Sun, S. Zhang, P. Hao, and A. Shiga, J. Polym. Sci., Part A: Polym. Chem. 45, 3415–3430 (2007), DOI: 10.1002/pola.22094.
- 37X. F. Li, D. Ke, W. P. Ye, L. Pan, and Y. S. Li, Organometallis 23, 1223–1230 (2004), DOI: 10.1021/om030396y.
- 38A. Ravasio, L. Boggioni, G. Scalcione, F. Bertini, D. Piovani, and I. Tritto, J. Polym. Sci., Part A: Polym. Chem. 50, 3867–3874 (2012), DOI: 10.1002/pola.26182.
- 39L.-P. He, J.-Y. Liu, Y.-G. Li, S.-R. Liu, and Y.-S. Li, Macromolecules 42, 8566–8570 (2009), DOI: 10.1021/ma901285a.
- 40L. K. Johnson, C. M. Killian, and M. Brookhart, J. Am. Chem. Soc. 117, 6414–6415 (1995), DOI: 10.1021/ja00128a054.
- 41L. K. Johnson, S. Mecking, and M. Brookhart, J. Am. Chem. Soc. 118, 267–268 (1996), DOI: 10.1021/ja953247i.
- 42S. Mecking, L. K. Johnson, L. Wang, and M. Brookhart, J. Am. Chem. Soc. 120, 888–899 (1998), DOI: 10.1021/ja964144i.
- 43C. Wang, S. Friedrich, T. R. Younkin, R. T. Li, R. H. Grubbs, D. A. Bansleben, and M. W. Day, Organometallics 17, 3149–3151 (1998), DOI: 10.1021/om980176y.
- 44T. R. Younkin, E. F. Connor, J. I. Henderson, S. K. Friedrich, R. H. Grubbs, and D. A. Bansleben, Science 287, 460–462 (2000), DOI: 10.1126/science.287.5452.460.
- 45M. Chen, W. Zou, Z. Cai, and C. Chen, Polym. Chem. 6, 2669–2676 (2015), DOI: 10.1039/c5py00010f.
- 46P. Xiang and Z. Ye, J. Polym. Sci., Part A: Polym. Chem. 51, 672–686 (2013), DOI: 10.1002/pola.26419.
- 47H. Gao, Y. Liu, G. Li, Z. Xiao, G. Liang, and Q. Wu, Polym. Chem. 5, 6012–6018 (2014), DOI: 10.1039/C4PY00701H.
- 48N. M. Franssen, J. N. Reek, and B. de Bruin, Chem. Soc. Rev. 42, 5809–5832 (2013), DOI: 10.1039/C3CS60032G.
- 49A. Keyes, H. E. Basbug Alhan, E. Ordonez, U. Ha, D. B. Beezer, H. Dau, Y. S. Liu, E. Tsogtgerel, G. R. Jones, and E. Harth, Angew. Chem. Int. Ed. 58, 12370–12391 (2019), DOI: 10.1002/anie.201900650.
- 50G. Menendez Rodriguez, M. M. Díaz-Requejo, and P. J. Pérez, Macromolecules 54, 4971–4985 (2021), DOI: 10.1021/acs.macromol.1c00374.
- 51E. Beer and W. Hatke, Plastics Special 6, (1999).
- 52E. Beer and K. Trombley, in Blister-Pack 2000 Conference, Jamesburg, NJ, May 17, 2000.
- 53F. Guo, C. Li, W. Wang, and A. Yang, Mod. Plast. Process. Appl. 28, 60–63 (2016).
- 54R. R. Lamonte, in 10th Worldwide Flexible Packaging Conference, Amsterdam, Nov. 2000.
- 55T. Weller, in New Plastics '98 Conference, London, Jan. 22, 1998.
- 56Schott Pharmaceutical Packaging, American Association of Pharmaceutical Scientists Conference and Exhibition, Philadelphia, Nov. 15, 1999.
- 57U.S. Pat. 5910287 (Jun. 8, 1999), P. J. Cassin and co-workers (to Aurora Biosciences Corp.).
- 58U.S. Pat. 6063338 (May 16, 2000), A. A. Pham and co-workers (to Aurora Biosciences Corp.).
- 59H. T. Land, F. Osan, and T. Wehrmeister, Polym. Mater. Sci. Eng. 76, 22 (1997).
- 60J. Ji, W. Fan, D. Kong, and L. Wang, Infrared Laser Eng. 42, 1212–1217 (2013).
- 61J. Ji, D. Kong, T. Ma, X. He, Q. Chen, and L. Wang, Infrared Laser Eng. 43, 1909–1913 (2014).
- 62G. Emiliyanov, J. B. Jensen, O. Bang, P. E. Hoiby, L. H. Pedersen, E. M. Kjær, and L. Lindvold, Opt. Lett. 32, 460–462 (2007), DOI: 10.1364/OL.32.000460.
This article is based on the article ‘Ethylene-Norbornene Copolymers’ by D. McNally, published in EPST (online), posting date: October 22, 2001, DOI 10.1002/0471440264.pst124.