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Internal functionalization in hyperbranched polyesters

1998; Wiley; Volume: 36; Issue: 17 Linguagem: Inglês

10.1002/(sici)1099-0518(199812)36

1099-0518

M. Trolls�s, James L. Hedrick, David Mecerreyes, R. J�r�me, Philippe Dúbois,

Synthetic Organic Chemistry Methods

Journal of Polymer Science Part A: Polymer ChemistryVolume 36, Issue 17 p. 3187-3192 Communication Internal functionalization in hyperbranched polyesters M. Trollsås, M. Trollsås IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099Search for more papers by this authorJ. Hedrick, Corresponding Author J. Hedrick IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099Search for more papers by this authorD. Mecerreyes, D. Mecerreyes Center for Education and Research on Macromolecules (CERM), University of Liege, Sart-Tilman, B6, 4000 Liege, BelgiumSearch for more papers by this authorR. Jérôme, R. Jérôme Center for Education and Research on Macromolecules (CERM), University of Liege, Sart-Tilman, B6, 4000 Liege, BelgiumSearch for more papers by this authorPh. Dubois, Ph. Dubois Laboratory of Polymer and Composite Materials, University of Mons-Hainaut, Place du Parc, 20, 7000 Mons, BelgiumSearch for more papers by this author M. Trollsås, M. Trollsås IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099Search for more papers by this authorJ. Hedrick, Corresponding Author J. Hedrick IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099IBM Research Division, Almaden Research Center, 650 Harry Road, San Jose, California 95120-6099Search for more papers by this authorD. Mecerreyes, D. Mecerreyes Center for Education and Research on Macromolecules (CERM), University of Liege, Sart-Tilman, B6, 4000 Liege, BelgiumSearch for more papers by this authorR. Jérôme, R. Jérôme Center for Education and Research on Macromolecules (CERM), University of Liege, Sart-Tilman, B6, 4000 Liege, BelgiumSearch for more papers by this authorPh. Dubois, Ph. Dubois Laboratory of Polymer and Composite Materials, University of Mons-Hainaut, Place du Parc, 20, 7000 Mons, BelgiumSearch for more papers by this author First published: 21 January 2000 https://doi.org/10.1002/(SICI)1099-0518(199812)36:17 3.0.CO;2-ACitations: 26AboutPDF 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 References and Notes 1(a) P. J. Flory, J. Am. Chem. Soc., 75, 2718 (1952); (b) Y. H. Kim and O. W. Webster, J. Am. Chem. Soc., 112, 4592 (1990); (c) H. R. Kricheldorf, Q. Z. Zhang, and G. 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Hedrick, Macromolecules, 31, 3439 (1998). 6 M. Trollsås, J. L. Hedrick, D. Mecerreyes, Ph. Dubois, R. Jéröme, H. Ihre, and A. Hult, Macromolecues, 30, 8508 (1997). 7 M. Trollsås, J. L. Hedrick, D. Mecerreyes, Ph. Dubois, R. Jéröme, H. Ihre, and A. Hult, Macromolecules, 31, 2756 (1998). 8 M. Trollsås, J. L. Hedrick, Ph. Dubois, R. Jéröme, J. Polym. Sci.: Polym. Chem. Ed., Part A, 36, 1345 (1998). 9 J. S. Moore and S. I. Stupp, Macromolecules, 23, 65 (1990). 10(a) D. Tian, P. Dubois, C. Grandfils, and R. Jéröme, Macromolecules, 30, 406 (1997); (b) D. Tian, Ph.D. Thesis, University of Liege, Belgium, 1997; (c) D. Tian, O. Halleux, Ph. Dubois, R. Jéröme, R. Sobry, and G. Van den Bossche, Macromolecules, 31, 924 (1998). 11 The polymerization of ϵ-caprolactone (and/or TOSUO) was initiated with bis-MPA or its derivatives using a catalytic amount of Sn(Oct)2. The polymerizations were carried out in the melt at 100°C (20 h). The polymers were then dissolved in THF and precipitated in cold methanol. 12 1H-NMR spectra were recorded with a Bruker AM 250 (250 MHz) spectrometer. The number average molecular weights were calculated from the intenity ratios of the OCHOOCH2 methylene proton signals (δ = 3.65) in the 1H-NMR spectra. Sizeexclusion chromatography was carried out on a Waters chromatograph connected to a Waters 410 differential refractometer. Four 5 μm Waters columns (300 3 7.7 mm) connected in series in order of increasing pore size (100, 1000, 105, and 106 Å) were used with THF as solvent. Glass transition temperatures (Tg) were recorded on a PerkinElmer DSC 7. 13 A general procedure for the preparation of AB2 functional alpha;-carboxylic-ω-dihydroxy poly(ϵ-caprolactone) (3-n). Pd/C (0.40 g) was added to a solution of 1–20 (4.00 g) in THF (10 mL) and EtOAc (40 mL). The flask was evacuated and put under H2(g) atmosphere. The reaction was stopped after 24 h, the Pd/C was filtered off and the clear solution was precipitated into cold methanol. The obtained macromonomer was a white crystalline powder. Yield: 3.00 g. 14 Polymerization of α-carboxylic-ω-dihydroxy poly(ϵcaprolactone) (1–20). The macromonomer 1–20(1.00 g, 0.33 mmol) was dissolved in CH2Cl2 (3 mL) in a previously flamed flask, into which a solution of DPTS (16.0 mg, 0.05 mmol) in THF and then DCC (0.10 g, 0.50 mmol) was added. After 48 h the reaction mixture was precipitated into methanol and then filtered to yield 0.87 g (87%) of hyperbranched polymer 4-c. 15 Deacetalization of TOSUO containing copolymers: ϵ-CL/TOSUO block copolymer (2.4 mmol of TOSUO) and triphenylcarbenium tetrafluoroborate (2.5 mmol) were dissolved under stirring for 30 min in 100 mL of dichloromethane (3 wt % copolymer). The copolyester was recovered by precipitation in cold methanol. Reduction of ketone pendent groups into hydroxyl groups: Copolyester A (1.2 mmol of ketone) and sodium borohydride (1.45 mmol) were dissolved under stirring in a CH2Cl2/ethanol (5/2 v/v) mixture (ca). 1.0 wt % copolymer for min. The polymer was isolated by precipitation in cold methanol. Citing Literature Volume36, Issue17December 1998Pages 3187-3192 ReferencesRelatedInformation