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Melt-stable poly(1,4-dioxan-2-one) (co)polymers by ring-opening polymerization via continuous reactive extrusion

2005; Wiley; Volume: 45; Issue: 4 Linguagem: Inglês

10.1002/pen.20312

1548-2634

Jean‐Marie Raquez, Philippe Degée, Philippe Dúbois, Sunder Balakrishnan, Ramáni Narayan,

Advanced Polymer Synthesis and Characterization

Polymer Engineering & ScienceVolume 45, Issue 4 p. 622-629 Article Melt-stable poly(1,4-dioxan-2-one) (co)polymers by ring-opening polymerization via continuous reactive extrusion Jean-Marie Raquez, Jean-Marie Raquez Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, BelgiumSearch for more papers by this authorPhilippe Degee, Philippe Degee Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, BelgiumSearch for more papers by this authorPhilippe Dubois, Corresponding Author Philippe Dubois [email protected] Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Philippe Dubois, Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Ramani Narayan, Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this authorSunder Balakrishnan, Sunder Balakrishnan Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this authorRamani Narayan, Corresponding Author Ramani Narayan [email protected] Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USA Philippe Dubois, Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Ramani Narayan, Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this author Jean-Marie Raquez, Jean-Marie Raquez Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, BelgiumSearch for more papers by this authorPhilippe Degee, Philippe Degee Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, BelgiumSearch for more papers by this authorPhilippe Dubois, Corresponding Author Philippe Dubois [email protected] Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Philippe Dubois, Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Ramani Narayan, Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this authorSunder Balakrishnan, Sunder Balakrishnan Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this authorRamani Narayan, Corresponding Author Ramani Narayan [email protected] Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USA Philippe Dubois, Laboratory of Polymeric and Composite Materials, University of Mons-Hainaut, Place du Parc 20, B-7000 Mons, Belgium Ramani Narayan, Department of Chemical Engineering, Michigan State University, East Lansing, MI 48823, USASearch for more papers by this author First published: 04 March 2005 https://doi.org/10.1002/pen.20312Citations: 19AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Bulk polymerization of ϵ-caprolactone (CL), 1,4-dioxan-2-one (PDX), and mixtures of PDX and CL was carried out by initiation with Al(OsecBu)3 in a co-rotating twin-screw extruder through a fast single-step process. Both homopolymerizations and copolymerization of PDX and CL proceed very rapidly and reach almost complete (co)- monomer(s) conversion as soon as 8 mol% of CL are added in the feed. Even though poly(1,4-dioxan-2-one) (PPDX) is known to thermally degrade mainly through unzipping depolymerization promoted from the hydroxyl end-groups and yielding PDX monomer, it turns out that the thermal stability of PPDX chains is substantially improved by the copolymerization of PDX with limited amounts of CL. Interestingly, DSC analysis of the so-obtained P(PDX-co-CL) copolymers has demonstrated that a CL molar fraction as high as 11 mol% does not prevent the crystallization of the resulting copolymer, which retains a melting temperature close to 95°C. This last observation has been explained by the formation of a blocky-like copolymer structure, in which short PPDX and PCL sequences are randomly distributed. POLYM. ENG. SCI., 45:622–629, 2005. © 2005 Society of Plastics Engineers. REFERENCES 1 K. Yang, X. Wang, and W. Yu-Zhong, J. Macromol. Sci., C42, 373 (2002). 2 N. Doddi, CC. Versfelt, and D. Wasserman, U.S. Patent 4,032,988 (1977). 3 J-M. Raquez, P. Degée, R. Narayan, and P. Dubois, Macromolecules, 34, 8419 (2001). 4 J-M. Raquez, P. Degée, R. Narayan, and P. Dubois, Macromol. Rapid Commun., 21, 1063 (2000). 5 H. Nishida, M. Yamashita, N. Hattori, T. Endo, and Y. Tokiwa, Poly. Degrad. Stab., 70, 485 (2000). 6 H. Nishida, M. Yamashita, and T. Endo, Poly. Degrad. 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