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WO2003031494A1 - Polyester - Google Patents

Polyester Download PDF

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Publication number
WO2003031494A1
WO2003031494A1 PCT/EP2002/010665 EP0210665W WO03031494A1 WO 2003031494 A1 WO2003031494 A1 WO 2003031494A1 EP 0210665 W EP0210665 W EP 0210665W WO 03031494 A1 WO03031494 A1 WO 03031494A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
process according
epoxidized
anhydride
carboxylic acid
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2002/010665
Other languages
German (de)
English (en)
Inventor
Horst Sulzbach
Michael Skwiercz
Ralf Bemmann
Thorsten Roloff
Rainer HÖFER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of WO2003031494A1 publication Critical patent/WO2003031494A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof

Definitions

  • the present invention relates to polyesters obtained by reacting epoxidized triglycerides with suitable anhydrides, a process for the preparation of the polyesters and the use of certain carboxylic anhydrides for the production of polyesters
  • Carboxylic anhydrides have long been known as so-called hot hardeners of petrochemically based epoxides, for example bisphenol A diglycidyl ethers. It is also known that certain anhydrides can be used to cure fat based epoxies. The polyesters formed in such curing reactions are suitable, for example, as a matrix material for the production of composite materials.
  • DD 48 687 describes the reaction of epoxidized soybean oil with valley anhydrides with the simultaneous addition of adipic acid.
  • WO 97/02307 discloses composite materials of a matrix based on polyester, the polyesters being produced from epoxidized fats and oils, carboxylic acid anhydrides and polycarboxylic acids. From the publication by Rösch et. al., Polymer Bulletin 31, 1993, page 679, describes the physical properties of polyester which are obtainable by curing epoxidized soybean oils with carboxylic acid anhydrides.
  • a first subject of the present application therefore relates to a process for the preparation of polyesters, in which epoxidized triglycerides are reacted in the presence of alkyl-substituted carboxylic acid anhydrides which are liquid at 21 ° C. and further catalysts are reacted at elevated temperature.
  • the epoxidized triglycerides used in the process according to the invention are known to the person skilled in the art. It is preferably epoxidized soybean oil, epoxidized cottonseed oil, epoxidized olive oil, epoxidized olive oil-epoxidized linseed oil, epoxidized linola oil], epoxidized sesame oil, epoxidized sunflower oil, epoxidized rapeseed oil and epoxidized castor oil or mixtures of these epoxies. It is preferred if the epoxidized triglycerides have an epoxide content of ind.
  • carboxylic acid anhydrides When selecting suitable carboxylic acid anhydrides, it is essential that the compounds are liquid at 21 ° C, i.e. room temperature.
  • the carboxylic acid anhydrides must be structured so that the anhydride is attached to an aiphatic ring. Furthermore, this cyclic, aromatic compound must be alkyl, and preferably methyl or ethyl substituted. It has also been shown that preference is given to using carboxylic anhydrides in which the two carboxyl groups are conjugated.
  • alkyl- preferably methyl-substituted derivatives of cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, cycloheptane which are liquid at room temperature.
  • Unsaturated derivatives can also be used.
  • isomeric methylcyclohexane carboxylic anhydride is very particularly preferred.
  • Methylcyclohexenecarboxylic anhydride is also preferred.
  • the process according to the invention is carried out at temperatures of 100 to 200 ° C. and preferably 150 to 200 ° C.
  • catalysts are also essential to the invention, it being possible here in particular to use N-methylimidazoles.
  • suitable catalysts are, for example Alumim 'umacetylacetonat, benzyl or 2-ethylimidazole, but other compounds known as Epoxidharzbechan, preferably 2,4,6-tris (dimethylaminoethyl) phenol (Versamine EH 30, Cognis Corp.) and bis-N , N- (dimethylaminopropy ⁇ ) urea (Versamine EH 50, Cognis Corp.).
  • the reaction time is generally between 1 and 80 minutes, preferably between 20 and 60 minutes.
  • the polyesters obtained by the process according to the invention are notable in particular for their high Shore D hardness, which is at least 70, preferably 75 and in particular 80>.
  • the molar ratio between carboxylic acid anhydrides and epoxidized triglycerides is preferably in the range from 1: 1 to 1: 2.
  • the catalysts are also used in amounts which are known to those skilled in the art for such reactions, preferably in amounts of 0.5 to 2% by weight. % based on the mixture of anhydrides and epoxides.
  • the polyesters according to the invention show low fogging and are therefore preferably suitable for use in materials, e.g. fiber-reinforced composite materials, for the interior of automobiles.
  • the present invention further relates to the use of alkyl and preferably methyl-substituted carboxylic anhydrides which are liquid at 21 ° C. for curing fatty acid triglyceride epoxides.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production de polyesters. Ce procédé consiste à faire réagir des triglycérides époxydés en présence d'anhydrides d'acide carboxylique cycliques, substitués par un alkyle et liquides à 21 DEG C et de catalyseurs à des températures élevées.
PCT/EP2002/010665 2001-10-02 2002-09-23 Polyester Ceased WO2003031494A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10148672.3 2001-10-02
DE2001148672 DE10148672A1 (de) 2001-10-02 2001-10-02 Polyester

Publications (1)

Publication Number Publication Date
WO2003031494A1 true WO2003031494A1 (fr) 2003-04-17

Family

ID=7701176

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/010665 Ceased WO2003031494A1 (fr) 2001-10-02 2002-09-23 Polyester

Country Status (2)

Country Link
DE (1) DE10148672A1 (fr)
WO (1) WO2003031494A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007138529A3 (fr) * 2006-05-31 2008-02-14 Luca Toncelli Procédé de fabrication de dalles ou de blocs d'aggloméré de pierre et de résine polyester
CN108558523A (zh) * 2018-06-07 2018-09-21 中国林业科学研究院林产化学工业研究所 一种植物油基聚合物包膜材料与包膜肥及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006003762A1 (de) * 2006-01-25 2007-07-26 Dracowo Forschungs- Und Entwicklungs Gmbh Leinölepoxid-basierte Faserverbundwerkstoffe

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD48687A (fr) *
US3006936A (en) * 1956-11-30 1961-10-31 Swift & Co Polyesters from epoxy-containing oleaginous materials and process of making same
US3296202A (en) * 1962-05-11 1967-01-03 Bayer Ag Process for curing polyepoxides
JPS54125299A (en) * 1978-03-23 1979-09-28 Hitachi Cable Ltd Epoxy resin composition
US4371688A (en) * 1980-08-22 1983-02-01 Milliken Research Corporation Substituted cyclohexane-1,2-dicarboxylic anhydrides and epoxy resins containing same
EP0257512A2 (fr) * 1986-08-21 1988-03-02 Ppg Industries, Inc. Composition de revêtement thermodurcissable à haute teneur en matière sèche à base d'époxydes contenant des groupes hydroxyliques et d'anhydrides
DE19627165A1 (de) * 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
US6194490B1 (en) * 1998-02-27 2001-02-27 Vantico, Inc. Curable composition comprising epoxidized natural oils
WO2001032755A1 (fr) * 1999-10-30 2001-05-10 Cognis Deutschland Gmbh & Co. Kg Feuille preimpregnee stable au stockage a base de matrices lipochimiques thermodurcissables

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD48687A (fr) *
US3006936A (en) * 1956-11-30 1961-10-31 Swift & Co Polyesters from epoxy-containing oleaginous materials and process of making same
US3296202A (en) * 1962-05-11 1967-01-03 Bayer Ag Process for curing polyepoxides
JPS54125299A (en) * 1978-03-23 1979-09-28 Hitachi Cable Ltd Epoxy resin composition
US4371688A (en) * 1980-08-22 1983-02-01 Milliken Research Corporation Substituted cyclohexane-1,2-dicarboxylic anhydrides and epoxy resins containing same
EP0257512A2 (fr) * 1986-08-21 1988-03-02 Ppg Industries, Inc. Composition de revêtement thermodurcissable à haute teneur en matière sèche à base d'époxydes contenant des groupes hydroxyliques et d'anhydrides
DE19627165A1 (de) * 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
US6194490B1 (en) * 1998-02-27 2001-02-27 Vantico, Inc. Curable composition comprising epoxidized natural oils
WO2001032755A1 (fr) * 1999-10-30 2001-05-10 Cognis Deutschland Gmbh & Co. Kg Feuille preimpregnee stable au stockage a base de matrices lipochimiques thermodurcissables

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BOQUILLON N ET AL: "Polymer networks derived from curing of epoxidised linseed oil: influence of different catalysts and anhydride hardeners", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 41, no. 24, November 2000 (2000-11-01), pages 8603 - 8613, XP004228784, ISSN: 0032-3861 *
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; 1975, MITCH E.L. & AL: "Novel catalysts for rapid acid/anhydride cure of epoxy resins and epoxidized oils", XP002225070, Database accession no. EIX75120001923 *
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; 1992, KOMATA K. & AL.: "Curing reaction of internal and external epoxide with various acid anhydrides", XP002225069, Database accession no. EIX93021418166 *
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; KOMATA M. & AL.: "Reactivity and the ring-opening reaction mechniasm for various substituted acid anhydrides of epoxide-anhydride reaction", XP002225078, Database accession no. EIX93021418167 *
DATABASE WPI Week 7945, Derwent World Patents Index; AN 1979-81461b, XP002225071 *
ROSCH J ET AL: "POLYMERS FROM RENEWABLE RESOURECES: POLYESTER RESINS AND BLENDS BASED UPON ANHYDRIDE-CURED EPOXIDIZED SOYBEAN OIL", POLYMER BULLETIN, SPRINGER VERLAG. HEIDELBERG, DE, vol. 31, no. 6, 1 December 1993 (1993-12-01), pages 679 - 685, XP000412408, ISSN: 0170-0839 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007138529A3 (fr) * 2006-05-31 2008-02-14 Luca Toncelli Procédé de fabrication de dalles ou de blocs d'aggloméré de pierre et de résine polyester
US9199415B2 (en) 2006-05-31 2015-12-01 Luca Toncelli Process for the manufacturing of slabs or blocks of conglomerate of stone granulate and polyester resin
US20160002109A1 (en) * 2006-05-31 2016-01-07 Luca Toncelli Process for the manufacturing of slabs or blocks of conglomerate of stone granulate and polyester resin
CN108558523A (zh) * 2018-06-07 2018-09-21 中国林业科学研究院林产化学工业研究所 一种植物油基聚合物包膜材料与包膜肥及其制备方法

Also Published As

Publication number Publication date
DE10148672A1 (de) 2003-04-24

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