WO2010006702A1 - Procédé de fabrication de copolyesters, copolyesters et corps moulés de copolyesters - Google Patents

Procédé de fabrication de copolyesters, copolyesters et corps moulés de copolyesters Download PDF

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Publication number
WO2010006702A1
WO2010006702A1 PCT/EP2009/004761 EP2009004761W WO2010006702A1 WO 2010006702 A1 WO2010006702 A1 WO 2010006702A1 EP 2009004761 W EP2009004761 W EP 2009004761W WO 2010006702 A1 WO2010006702 A1 WO 2010006702A1
Authority
WO
WIPO (PCT)
Prior art keywords
dicarboxylic acid
group
copolyester
copolyesters
diol
Prior art date
Application number
PCT/EP2009/004761
Other languages
German (de)
English (en)
Inventor
Michael Schweizer
Christopher Hess
Erich Biermann
Rainer Schaller
Original Assignee
Uhde Inventa-Fischer Gmbh
Deutsche Institute für Textil- und Faserforschung
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 Uhde Inventa-Fischer Gmbh, Deutsche Institute für Textil- und Faserforschung filed Critical Uhde Inventa-Fischer Gmbh
Priority to EP09776912A priority Critical patent/EP2334713A1/fr
Publication of WO2010006702A1 publication Critical patent/WO2010006702A1/fr

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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters

Definitions

  • the invention describes a process for the preparation of copolyesters, in particular based on a polycondensation product of terephthalic acid with ethylene glycol and propylene oxide. These copolyesters have a comparatively low melting point. A sufficiently high intrinsic viscosity for further processing can be achieved, for example, by a postcondensation.
  • Propylene oxide is not yet used as a comonomer in connection with the production of polyesters based on terephthalic acid and ethylene glycol.
  • the object of the present invention is to develop a process for the production of specifically structurally-influenced polyesters of the abovementioned type, in which sufficiently high viscosities are achieved for further processing steps.
  • the polymerization reaction is thus to be referred to as polycondensation, wherein in the event that dicarboxylic acid esters are used, is to speak of transesterification.
  • polycondensation wherein in the event that dicarboxylic acid esters are used, is to speak of transesterification.
  • mixed forms of the reaction types are also possible when both free acids and esters of dicarboxylic acids are used.
  • the amounts of the diol and of the alkylene oxide used are matched to one another such that, based on the sum of the at least one diol and the at least one alkylene oxide, between 70 and 99.9 mol%, preferably 80 to 99.5 mol -% of the at least one diol and 30 to 0.01 mol%, preferably 20 to 0.5 mol% of the at least one alkylene oxide are used.
  • the numbers thus indicate the preferred mixing ratios of diol to alkylene oxide.
  • dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid and / or mixtures thereof, while the preferred dicarboxylic acid are selected from the group consisting of aliphatic diesters of terephthalic acid and / or isophthalic with aliphatic alcohols having 1 to 6 carbon atoms, preferably Dimethyl terephthalate and / or dimethyl isophthalate.
  • Preferred diols to be used are selected from the group consisting of 1, 2-ethylene glycol, 1,3-propylene glycol, 1, 4-butylene glycol, cyclohexane-1, 4-diemthanol and / or mixtures thereof.
  • Advantageous alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and / or mixtures thereof.
  • the present invention relates to a process for the preparation of a polyester based on a polycondensation product of terephthalic acid with ethylene glycol and propylene oxide, and the reaction products prepared in this way.
  • reaction mixture before, during and / or after the cocondensation or transesterification further additives selected from the group consisting of catalysts, pigments, dyes, fillers, stabilizers, in particular phosphorus compounds, flame retardants, lubricants, antioxidants , nano-scale fillers, silver-containing additives, in particular silver salts for antibacterial action, scavengers for acetaldehyde reduction and / or combinations thereof, whereby the can respectively control specifically desired properties of the copolyester.
  • catalysts selected from the group consisting of catalysts, pigments, dyes, fillers, stabilizers, in particular phosphorus compounds, flame retardants, lubricants, antioxidants , nano-scale fillers, silver-containing additives, in particular silver salts for antibacterial action, scavengers for acetaldehyde reduction and / or combinations thereof, whereby the can respectively control specifically desired properties of the copolyester.
  • the esterification reaction can be carried out in two alternative ways, depending on whether carboxylic acid diesters or free carboxylic acids are used as starting materials.
  • the individual reaction stages can be carried out successively in a reactor (batch process) or divided into continuous units in corresponding reaction stages / plant parts (such as paste mixer, pre-esterification, esterification, precondensation, polycondensation, post-condensation, etc.) ,
  • suitable catalysts are those which are selected from the group consisting of Ti salts, Ti organyls, in particular titanium tetravutylate, Ge compounds, Sb compounds, in particular antimony oxide, antimony acetate, antimony glycolate, Co compounds and / or co-salts, in particular co-acetate, tin compounds, alkylamines, especially primary, secondary and / or tertiary amines, such as Triethylamine, tributylamine, pyridine, quaternary ammonium salts, salts of amines or amides and / or combinations thereof.
  • Preferred temperature ranges of the polycondensation or transesterification reaction are at temperatures between 190 ° C. and 290 ° C., preferably between 200 and 280 ° C., particularly preferably between 230 and 240 ° C.
  • the process can be carried out in one stage, wherein the intrinsic viscosity of the copolyester is adjusted to 0.91 dL / g, preferably between 0.78 and 0.91 dL / g
  • the process can be carried out in two stages, wherein initially in a precondensation stage the copolyester is copolymerized or transesterified up to an intrinsic viscosity of between 0.46 and 0.7 dL / g, preferably between 0.55 and 0.7 dL / g, and subsequently in a postcondensation stage intrinsic viscosity of the copolyester in the post-condensation stage up to 0.91 dL / g, preferably 0.78 to 0.91 dL / g is increased.
  • the precondensation step is carried out at pressures between 1 and 20 bar, preferably between 5 and 12 bar and / or the postcondensation step at pressures between 0.1 mbar and 0.1 bar, preferably between 0.1 mbar and 10 mbar is performed.
  • a copolyester is also provided which can be prepared according to the process of the invention described above.
  • the polyesters according to the invention are distinguished by a comparatively low melting point of about 200 ° C. to about 260 ° C., preferably 230 ° C. to 260 ° C. As a result of the lowered melting point, undesired side reactions and degradation reactions occur to a lesser extent during further processing. In addition, energy costs are reduced.
  • Polyesters of the type described above have an intrinsic viscosity of 0.46 to 0.7 dL / g.
  • moldings are likewise provided which contain a copolyester according to the invention.
  • the moldings are in particular selected from films, bottles, filaments, film-molded parts, injection-molded parts and deep-drawn moldings.

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 des diodes électroluminescentes organiques (OLED) et un dispositif permettant de les fabriquer. Les diodes électroluminescentes organiques selon l'invention sont caractérisées par le fait qu'une substance est intégrée dans l'empilement de couches (empilement), dont la conductivité électrique est réduite par apport d'énergie, ce par quoi peut être empêché une détérioration irréversible des diodes électroluminescentes organiques, telle qu'elle peut apparaître par exemple par formation de défauts ou par des particules.
PCT/EP2009/004761 2008-07-15 2009-07-01 Procédé de fabrication de copolyesters, copolyesters et corps moulés de copolyesters WO2010006702A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09776912A EP2334713A1 (fr) 2008-07-15 2009-07-01 Procédé de fabrication de copolyesters, copolyesters et corps moulés de copolyesters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008033188.0 2008-07-15
DE200810033188 DE102008033188A1 (de) 2008-07-15 2008-07-15 Verfahren zur Herstellung von Copolyestern, Copolyester und Formkörper aus Copolyestern

Publications (1)

Publication Number Publication Date
WO2010006702A1 true WO2010006702A1 (fr) 2010-01-21

Family

ID=41111152

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/004761 WO2010006702A1 (fr) 2008-07-15 2009-07-01 Procédé de fabrication de copolyesters, copolyesters et corps moulés de copolyesters

Country Status (3)

Country Link
EP (1) EP2334713A1 (fr)
DE (1) DE102008033188A1 (fr)
WO (1) WO2010006702A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1126915A (en) * 1965-02-25 1968-09-11 Metallgesellschaft Ag A method of after-treating fibre- and film-forming polyesters
EP0089038A1 (fr) * 1982-03-17 1983-09-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Procédé de préparation de composés à haut poids moléculaire
EP0203634A1 (fr) * 1985-05-17 1986-12-03 Akzo N.V. Copolyétherester à base de polyoxyde de propylène bloqué avec de l'oxyde d'éthylène
WO1998008888A1 (fr) * 1996-08-28 1998-03-05 Unichema Chemie B.V. Polyol de polyether et procede de fabrication d'un polyester moulable et contenant de polyol de polyether

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD49055A (fr)
US3746744A (en) 1971-03-25 1973-07-17 Atlantic Richfield Co Process for the manufacture of esters of dicarboxylic acid
CA987832A (en) * 1971-07-19 1976-04-20 Teijin Limited Process for preparation of unsaturated polyester
DE2801422A1 (de) 1978-01-13 1979-07-19 Dow Chemical Co Katalysatorsystem fuer die umsetzung zwischen carbonsaeuren und epoxiden
US4306056A (en) * 1979-05-23 1981-12-15 Mitsubishi Gas Chemical Company, Inc. Process for producing an oligoester and producing unsaturated polyester resin by use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1126915A (en) * 1965-02-25 1968-09-11 Metallgesellschaft Ag A method of after-treating fibre- and film-forming polyesters
EP0089038A1 (fr) * 1982-03-17 1983-09-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Procédé de préparation de composés à haut poids moléculaire
EP0203634A1 (fr) * 1985-05-17 1986-12-03 Akzo N.V. Copolyétherester à base de polyoxyde de propylène bloqué avec de l'oxyde d'éthylène
WO1998008888A1 (fr) * 1996-08-28 1998-03-05 Unichema Chemie B.V. Polyol de polyether et procede de fabrication d'un polyester moulable et contenant de polyol de polyether

Also Published As

Publication number Publication date
DE102008033188A1 (de) 2010-01-21
EP2334713A1 (fr) 2011-06-22

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