Title:
SYNTHESIS AND POLYMERIZATION OF ISOSORBIDE-BASED MONOMETHACRYLATES
Document Type and Number:
WIPO Patent Application WO/2019/202038
Kind Code:
A3
Abstract:
Isosorbide-5-methacrylate was obtained by enzymatic catalysis with Lipozyme RM IM in a highly regioselective manner in up to 87% yield. The process uses readily available acyl donors (methacrylic anydride or vinyl methacrylate), is easily scalable and chromatography free. Simple extractive workup followed by decoloration and filtration affords the monomer with up to > 99% purity. In addition, the developed enzymatic strategy was applied for the synthesis of a series of isosorbide 5- and 2-methacrylate derivatives. All the sythesized isosorbide monomethacrylates were radically polymerized with AIBN. The properties of these polymers with different side groups in either endo or exo configuration in the isosorbide structure was examined. The methacrylic isosorbide derivatives with OH-group were found to have very high glass transition temperature (Tg = 167 °C) and good thermal stability (at 5% weight loss under N2, Td,95 = 240 °C). The highest molecular weight (Mn = 80.6 kg/mol) was determined for the polymethacrylate with Ac-substitute.
Inventors:
PARVE JAAN (EE)
VARES LAURI (EE)
PEHK TÕNIS (EE)
GATHERGOOD NICHOLAS (EE)
PARVE OMAR (EE)
JANNASCH PATRIC (EE)
MATT LIVIA (EE)
VARES LAURI (EE)
PEHK TÕNIS (EE)
GATHERGOOD NICHOLAS (EE)
PARVE OMAR (EE)
JANNASCH PATRIC (EE)
MATT LIVIA (EE)
Application Number:
PCT/EP2019/060005
Publication Date:
December 12, 2019
Filing Date:
April 17, 2019
Export Citation:
Assignee:
UNIV TARTU (EE)
TALLINN UNIV OF TECHNOLOGY (EE)
NAT INSTITUTE OF CHEMICAL PHYSICS AND BIOPHYSICS (EE)
TALLINN UNIV OF TECHNOLOGY (EE)
NAT INSTITUTE OF CHEMICAL PHYSICS AND BIOPHYSICS (EE)
International Classes:
C12P41/00; C07D493/04; C08F124/00; C12P7/62; C12P17/18
Domestic Patent References:
| WO2018031373A1 | 2018-02-15 |
Foreign References:
| US20170082936A1 | 2017-03-23 | |||
| US5538891A | 1996-07-23 | |||
| US20160229863A1 | 2016-08-11 | |||
| EP0530671A2 | 1993-03-10 |
Other References:
MING-HUA XU ET AL: "Development of a New Reaction System for the Synthesis of Highly Optically Active [alpha],[gamma]-Substituted [gamma]-Butyrolactones", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 66, no. 11, June 2001 (2001-06-01), pages 3953 - 3962, XP055165565, ISSN: 0022-3263, DOI: 10.1021/jo0155153
CAIXIA CUI ET AL: "Insight into the synthesis of isosorbide diester plasticizer using immobilized lipases", RSC ADVANCES, vol. 6, no. 110, 7 November 2016 (2016-11-07), pages 108180 - 108186, XP055596969, DOI: 10.1039/C6RA23984F
JAMES J. GALLAGHER ET AL: "Isosorbide-based Polymethacrylates", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 3, no. 4, 6 April 2015 (2015-04-06), US, pages 662 - 667, XP055383877, ISSN: 2168-0485, DOI: 10.1021/sc5008362
YAGHOUB MANSOORI ET AL: "Nanocomposite materials based on isosorbide methacrylate/Closite 20A", POLYMER INTERNATIONAL, vol. 62, no. 2, 22 June 2012 (2012-06-22), GB, pages 280 - 288, XP055596967, ISSN: 0959-8103, DOI: 10.1002/pi.4297
R. SEEMAYER ET AL: "Enzymatic Preparation of Isomerically Pure 1,4:3,6-Dianhydro-D-glucitol Monoacetates -Precursors for Isoglucitol 2- and 5-mononitrates", TETRAHEDRON ASYMMETRY, vol. 3, no. 9, 1992, pages 1123 - 1126, XP055639662
CAIXIA CUI ET AL: "Insight into the synthesis of isosorbide diester plasticizer using immobilized lipases", RSC ADVANCES, vol. 6, no. 110, 7 November 2016 (2016-11-07), pages 108180 - 108186, XP055596969, DOI: 10.1039/C6RA23984F
JAMES J. GALLAGHER ET AL: "Isosorbide-based Polymethacrylates", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 3, no. 4, 6 April 2015 (2015-04-06), US, pages 662 - 667, XP055383877, ISSN: 2168-0485, DOI: 10.1021/sc5008362
YAGHOUB MANSOORI ET AL: "Nanocomposite materials based on isosorbide methacrylate/Closite 20A", POLYMER INTERNATIONAL, vol. 62, no. 2, 22 June 2012 (2012-06-22), GB, pages 280 - 288, XP055596967, ISSN: 0959-8103, DOI: 10.1002/pi.4297
R. SEEMAYER ET AL: "Enzymatic Preparation of Isomerically Pure 1,4:3,6-Dianhydro-D-glucitol Monoacetates -Precursors for Isoglucitol 2- and 5-mononitrates", TETRAHEDRON ASYMMETRY, vol. 3, no. 9, 1992, pages 1123 - 1126, XP055639662
Attorney, Agent or Firm:
TOLLETT, Ian (GB)
Download PDF: