WO2019202038A3 - Synthesis and polymerization of isosorbide-based monomethacrylates - Google Patents

Synthesis and polymerization of isosorbide-based monomethacrylates Download PDF

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Publication number
WO2019202038A3
WO2019202038A3 PCT/EP2019/060005 EP2019060005W WO2019202038A3 WO 2019202038 A3 WO2019202038 A3 WO 2019202038A3 EP 2019060005 W EP2019060005 W EP 2019060005W WO 2019202038 A3 WO2019202038 A3 WO 2019202038A3
Authority
WO
WIPO (PCT)
Prior art keywords
isosorbide
methacrylate
methacrylic
synthesis
derivatives
Prior art date
Application number
PCT/EP2019/060005
Other languages
French (fr)
Other versions
WO2019202038A2 (en
Inventor
Jaan PARVE
Lauri VARES
Tõnis PEHK
Nicholas Gathergood
Omar PARVE
Patric Jannasch
Livia MATT
Original Assignee
University Of Tartu
Tallinn University Of Technology
National Institute of Chemical Physics and Biophysics
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB1806402.2A external-priority patent/GB201806402D0/en
Priority claimed from GBGB1807794.1A external-priority patent/GB201807794D0/en
Application filed by University Of Tartu, Tallinn University Of Technology, National Institute of Chemical Physics and Biophysics filed Critical University Of Tartu
Priority to EP19722803.4A priority Critical patent/EP3781698A2/en
Publication of WO2019202038A2 publication Critical patent/WO2019202038A2/en
Publication of WO2019202038A3 publication Critical patent/WO2019202038A3/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/18—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms containing at least two hetero rings condensed among themselves or condensed with a common carbocyclic ring system, e.g. rifamycin
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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.
PCT/EP2019/060005 2018-04-19 2019-04-17 Synthesis and polymerization of isosorbide-based monomethacrylates WO2019202038A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19722803.4A EP3781698A2 (en) 2018-04-19 2019-04-17 Synthesis and polymerization of isosorbide-based monomethacrylates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB1806402.2 2018-04-19
GBGB1806402.2A GB201806402D0 (en) 2018-04-19 2018-04-19 Synthesis and polymerization of isosorbide-based monomethacrylates
GB1807794.1 2018-05-14
GBGB1807794.1A GB201807794D0 (en) 2018-05-14 2018-05-14 Synthesis and polymerization of isosorbide-based monomethacrylates

Publications (2)

Publication Number Publication Date
WO2019202038A2 WO2019202038A2 (en) 2019-10-24
WO2019202038A3 true WO2019202038A3 (en) 2019-12-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/060005 WO2019202038A2 (en) 2018-04-19 2019-04-17 Synthesis and polymerization of isosorbide-based monomethacrylates

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EP (1) EP3781698A2 (en)
WO (1) WO2019202038A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395075B (en) * 2022-01-20 2023-02-28 上海交通大学医学院附属第九人民医院 Dental zero-filler permeable resin and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530671A2 (en) * 1991-09-02 1993-03-10 Roche Diagnostics GmbH Process for the enzymatic preparation of pure isosorbide-2 or 5-monoester-isomers and conversion to isosorbide-2- and 5-nitrate
US5538891A (en) * 1991-09-02 1996-07-23 Boehringer Mannheim Gmbh Process for enzymatic production of isomerically pure isosorbide-2 and 5-monoesters and their conversion to isosorbide-2 and -5 nitrate
US20160229863A1 (en) * 2015-02-09 2016-08-11 Marc A. Hillmyer Isosorbide-based polymethacrylates
US20170082936A1 (en) * 2014-11-14 2017-03-23 Xerox Corporation Bio-Based Acrylate And Methacrylate Resins
WO2018031373A1 (en) * 2016-08-12 2018-02-15 Iowa State University Research Foundation, Inc. Acrylated and acylated or acetalized polyol as a biobased substitute for hard, rigid thermoplastic and thermoplastic and thermoset materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530671A2 (en) * 1991-09-02 1993-03-10 Roche Diagnostics GmbH Process for the enzymatic preparation of pure isosorbide-2 or 5-monoester-isomers and conversion to isosorbide-2- and 5-nitrate
US5538891A (en) * 1991-09-02 1996-07-23 Boehringer Mannheim Gmbh Process for enzymatic production of isomerically pure isosorbide-2 and 5-monoesters and their conversion to isosorbide-2 and -5 nitrate
US20170082936A1 (en) * 2014-11-14 2017-03-23 Xerox Corporation Bio-Based Acrylate And Methacrylate Resins
US20160229863A1 (en) * 2015-02-09 2016-08-11 Marc A. Hillmyer Isosorbide-based polymethacrylates
WO2018031373A1 (en) * 2016-08-12 2018-02-15 Iowa State University Research Foundation, Inc. Acrylated and acylated or acetalized polyol as a biobased substitute for hard, rigid thermoplastic and thermoplastic and thermoset materials

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
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 *
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 *
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 *
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 *

Also Published As

Publication number Publication date
EP3781698A2 (en) 2021-02-24
WO2019202038A2 (en) 2019-10-24

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