WO2010089264A1 - Verfahren zur herstellung von biscarbonaten - Google Patents

Verfahren zur herstellung von biscarbonaten Download PDF

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Publication number
WO2010089264A1
WO2010089264A1 PCT/EP2010/051141 EP2010051141W WO2010089264A1 WO 2010089264 A1 WO2010089264 A1 WO 2010089264A1 EP 2010051141 W EP2010051141 W EP 2010051141W WO 2010089264 A1 WO2010089264 A1 WO 2010089264A1
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WO
WIPO (PCT)
Prior art keywords
carbonate
alkylene
compound
groups
alkylene carbonate
Prior art date
Application number
PCT/EP2010/051141
Other languages
German (de)
English (en)
French (fr)
Inventor
Rainer Klopsch
Jan Philipp Weyrauch
Kai Gumlich
Joaquim Henrique Teles
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2010089264A1 publication Critical patent/WO2010089264A1/de

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen

Definitions

  • the invention relates to a process for preparing compounds having at least two alkylene carbonate groups (abbreviated to alkylene carbonate) by reacting a compound having at least two alkylene oxide groups (abbreviated to alkylene oxide) with carbon dioxide, in which the reaction is carried out at a pressure of 12 to 40 bar.
  • Bisalkylencarbonates such as the biscarbonate of bisphenol A bisglycidyl ether, are important as starting materials for the preparation of polyurethanes. In particular, they can be used after reaction with an excess of amine compounds as amine hardeners for epoxides, as described in EP-A 661 363.
  • WO 84/03701, DE-A 3 529 263, DE-A 3600602 and DE-A 26 11 087 may be mentioned as state of the art for the production.
  • DE-A 3 529 263 and DE-A 3600602 describe the preparation of biscarbonates. According to DE-A 3529 263, the reaction of the alkylene oxide, e.g. carried out with carbon dioxide at atmospheric pressure or slightly elevated pressure.
  • DE-A 36 00 602 discloses a pressure of 1 to 98 bar, preferably a pressure of 1 to 10, in particular 1 to 3, bar.
  • WO 84/03701 and DE-A 26 11 087 describe the preparation of monoalkylene carbonates, such as ethylene carbonate or propylene carbonate. In the examples of WO 84/03701 takes place at 21 bar, DE-A 26 11 087 discloses a preferred range of 1 to 30 atmospheres.
  • the object of the present invention was to provide such a method.
  • a compound having at least two alkylene oxide groups is reacted with carbon dioxide to form a compound having at least two alkylene carbonate groups.
  • the carbon dioxide is added to the alkylene oxide group to form the cyclic alkylene carbonate group.
  • compounds having 2 to 4 alkylene oxide groups are suitable.
  • Particularly preferred is a compound having two Glyidylethergrup- pen, which to the corresponding Bisalkylencarbonat of formula I.
  • the radical R in formula I stands for any organic group having 2 to 30 C atoms, preferably 6 to 30 C atoms and in particular 12 to 24 C atoms.
  • the radical R can also contain heteroatoms such as oxygen, nitrogen and sulfur.
  • the radical R is a hydrocarbon group which contains no heteroatoms.
  • R is a hydrocarbon group which contains at least one, preferably one or two, more preferably two aromatic ring systems.
  • the aromatic ring system may be mentioned in particular the phenyl ring.
  • the bisalkylene carbonate is the
  • Bisphenol A bisglycerol carbonyl ethers of the formula II (4,4 '- ((1-methylethylidenes) bis (4,1-phenyleneoxymethylene)) bis (1,3-dioxolan-2-ones):
  • the starting compound is the bisphenol A bisglycidyl ether.
  • the reaction is carried out according to the invention at a pressure of 12 to 40 bar, preferably at a pressure of 12 to 35 bar and more preferably from 15 to 30 bar, in particular 20 to 30 bar.
  • the reaction is preferably carried out at a temperature of 50 to 150 0 C, more preferably at 60 to 100 0 C and most preferably at 70 to 90 ° C.
  • the reaction preferably takes place in the presence of a solvent.
  • the solvent is chosen so that the product of the reaction, for example the bisalkylene carbonate in the solvent is not or only slightly soluble and therefore can be separated as a solid from the reaction solution.
  • the alkylene carbonate is preferably at 20 0 C a solubility in the solvent used of not more than 20 parts by weight alkylene carbonate, especially a maximum of 10 parts by weight, more preferably at most 5 parts by weight of alkylene carbonate in 100 parts by weight of solvent.
  • Suitable solvents are, in particular, polar, aprotic solvents, for example tetrahydrofuran or dialkyl carbonates. Particularly preferred solvents are dialkyl carbonates, most preferably dimethyl carbonate.
  • the reaction is carried out in the presence of a catalyst.
  • catalysts are e.g. Phosphorus compounds having a trivalent phosphorus atom, e.g. tertiary phosphines such as trialkyl or triarylphosphine, or salts of quaternary ammonium compounds into consideration.
  • Phosphorus compounds having a trivalent phosphorus atom e.g. tertiary phosphines such as trialkyl or triarylphosphine, or salts of quaternary ammonium compounds into consideration.
  • Preferred salts of the quaternary ammonium compounds are those of the formula
  • R a , Rb, Rc and Rd independently represent a hydrocarbon group having 1 to 12 C-atoms, for example an alkyl or aryl group, and Y "is an anion, in particular a halide, particularly preferably a chloride.
  • Preferred salts of the quaternary ammonium compounds are the halides, especially chlorides and bromides.
  • Examples include benzyltrimethylammonium chloride or tetraethylammonium bromide.
  • the above salt of the quaternary ammonium compound may be used in combination with a metal salt.
  • a metal salt for example, metal halides such as alkali metal chlorides, alkali bromides, Alkaliiodi- de, zinc halides considered. Examples include potassium iodide and ZnBr2.
  • the amount of the catalysts used is preferably at least 0.1 part by weight, more preferably at least 0.3 part by weight and most preferably at least 0.5 part by weight per 100 parts by weight of alkylene oxide.
  • the amount of the catalysts used is preferably not more than 20 parts by weight, more preferably not more than 15 parts by weight per 100 parts by weight of alkylene oxide. In general, a content of between 0.5 and 10 parts by weight per 100 parts by weight of alkylene oxide is sufficient.
  • the implementation of the reaction can be carried out in a conventional manner in an autoclave.
  • the starting compounds i. the alkylene oxide, solvent and catalyst can be placed in the autoclave and then the desired pressure is set by introducing the gaseous carbon dioxide.
  • the resulting alkylene carbonate precipitates out of the reaction solution as a solid and can be easily separated after completion of the reaction.
  • the product obtained may optionally contain compounds in which not all alkylene oxide groups have been converted to alkylene carbonate groups.
  • the reaction is very simple and almost complete, so that more than 70 mol%, in particular more than 85 mol%, very particularly preferably more than 90 mol% of all alkylene oxide groups are converted into alkylene carbonate groups.
  • the epoxy number of the product obtained is preferably greater than 2000 and more preferably greater than 3000.
  • the epoxy number is the quotient of the mass of the product in grams and the number of moles of epoxy groups present. The lower the number of remaining epoxy groups, the greater the epoxy number.
  • the resulting alkylene carbonate, in particular bisalkylene carbonate is suitable as part of a two-component (2-K) system.
  • the one component (1st component) is the alkylene carbonate, in particular bisalkylene carbonate, alone or optionally in admixture with other compounds, the other (2.) component is preferably an amino compound or mixture of amino compounds.
  • the 2-component system can be used, for example, as a paint or adhesive system or for the production of composites.
  • amino compounds having at least two amino groups which may be secondary or primary amino groups, are suitable as the second component.
  • Preferred compounds having two secondary amino groups are in particular cyclic compounds such as piperazine.
  • Particularly preferred are amino compounds having at least two primary amino groups.
  • the two components are usually combined just before use. For amino compounds having more than two primary amino groups and a bisalkylene carbonate, crosslinked polymer systems are obtained.
  • Such a 2-component system represents an alternative to epoxy or PU systems.
  • the alkylene carbonate in particular bisalkylene carbonate
  • an amino compound having at least two primary or secondary amino groups Preferred compounds having two secondary amino groups are in turn cyclic compounds such as piperazine. Particularly preferred are amino compounds having at least two primary amino groups.
  • the amino groups are preferably present in excess in relation to the carbonate groups.
  • the molar ratio of the primary amino groups to the carbonate groups is 2: 1; e.g. Two moles of diamine are used per mole of bisalkylene carbonate.
  • the resulting reaction product then has the corresponding number of free, reactive amino groups and is suitable as an amine hardener for epoxy resins.
  • BGE carbonate is obtained as a colorless solid (melting point 148 to 150 ° C.), if appropriate mixed with unreacted educt.
  • a measure of the conversion of glycidyl groups into carbonate groups is the epoxy number (mass of products / mole of epoxy groups); the higher the epoxy number, the lower the content of epoxy groups. The epoxy number was determined according to DIN standard ASTM D 1652.
  • the examples marked V are comparative examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP2010/051141 2009-02-05 2010-02-01 Verfahren zur herstellung von biscarbonaten WO2010089264A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09152139.3 2009-02-05
EP09152139 2009-02-05

Publications (1)

Publication Number Publication Date
WO2010089264A1 true WO2010089264A1 (de) 2010-08-12

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WO (1) WO2010089264A1 (ru)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013050311A1 (de) * 2011-10-04 2013-04-11 Basf Se Epoxidharz-zusammensetzungen, enthaltend ein 2-oxo-[1,3]dioxolanderivat
WO2017156132A1 (en) * 2016-03-08 2017-09-14 3D Systems, Incorporated Non-isocyanate polyurethane inks for 3d printing
US10501572B2 (en) 2015-12-22 2019-12-10 Carbon, Inc. Cyclic ester dual cure resins for additive manufacturing

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2611087A1 (de) 1975-03-17 1976-09-23 Anic Spa Verfahren zur herstellung von alkylencarbonaten
EP0069494A1 (en) * 1981-06-29 1983-01-12 The Standard Oil Company Catalytic synthesis of cyclic carbonates
WO1984003701A1 (en) 1983-03-18 1984-09-27 Bp Chem Int Ltd Preparation of carbonates
DE3529263A1 (de) 1985-08-16 1987-02-19 Hoechst Ag Verfahren zur herstellung von 2-oxo-1,3-dioxolanen
DE3600602A1 (de) 1986-01-11 1987-07-16 Hoechst Ag Verfahren zur herstellung von 2-oxo-1,3-dioxolanen
DE4344510A1 (de) * 1993-12-24 1995-06-29 Hoechst Ag Flüssige Zweikomponenten-Überzugsmittel
GB2432160A (en) * 2005-11-14 2007-05-16 Sun Chemical Ltd Energy curable cyclic carbonate compositions
WO2008139315A2 (en) * 2007-05-11 2008-11-20 Sun Chemical Limited Sensitizer for cationic photoinitiators

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2611087A1 (de) 1975-03-17 1976-09-23 Anic Spa Verfahren zur herstellung von alkylencarbonaten
EP0069494A1 (en) * 1981-06-29 1983-01-12 The Standard Oil Company Catalytic synthesis of cyclic carbonates
WO1984003701A1 (en) 1983-03-18 1984-09-27 Bp Chem Int Ltd Preparation of carbonates
DE3529263A1 (de) 1985-08-16 1987-02-19 Hoechst Ag Verfahren zur herstellung von 2-oxo-1,3-dioxolanen
DE3600602A1 (de) 1986-01-11 1987-07-16 Hoechst Ag Verfahren zur herstellung von 2-oxo-1,3-dioxolanen
DE4344510A1 (de) * 1993-12-24 1995-06-29 Hoechst Ag Flüssige Zweikomponenten-Überzugsmittel
EP0661363A1 (de) 1993-12-24 1995-07-05 Hoechst Aktiengesellschaft Flüssige Zweikomponenten-Überzugsmittel
GB2432160A (en) * 2005-11-14 2007-05-16 Sun Chemical Ltd Energy curable cyclic carbonate compositions
WO2008139315A2 (en) * 2007-05-11 2008-11-20 Sun Chemical Limited Sensitizer for cationic photoinitiators

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BOBYLEVA L I ET AL: "Condensation of olefin oxides with carbon dioxide in the presence of metal chloride-dimethylformamide catalyst", NEFTEHIMIA, MOSCOW, RU, vol. 36, no. 3, 1 January 1996 (1996-01-01), pages 209 - 213, XP009132962, ISSN: 0028-2421 *
GABRIEL ROKICKI, CZAJKOWSKA J: "Studies on the synthesis of poly(hydroxyurethanes)s from diepoxides carbon dioxide and diamines", POLIMERY, INSTYTUT CHEMII PRZEMYSOWEJ, WARSAW, PL, vol. 34, no. 4, 1 January 1989 (1989-01-01), pages 140/141 - 147, XP009132957, ISSN: 0032-2725 *
ONDRUSCHKA B ET AL: "Incorporation of CO2 into various terminal and internal Epoxides", COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, vol. 73, no. 1, 2008, pages 88 - 96, XP002581705 *
ROKICKI G, KURAN W: "Cyclic Carbonates Obtained by Reactions of Alkali Metal Carbonates with Epihalohydrins", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 57, no. 6, 1984, pages 1662 - 1666, XP002581706 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013050311A1 (de) * 2011-10-04 2013-04-11 Basf Se Epoxidharz-zusammensetzungen, enthaltend ein 2-oxo-[1,3]dioxolanderivat
US10501572B2 (en) 2015-12-22 2019-12-10 Carbon, Inc. Cyclic ester dual cure resins for additive manufacturing
US10774177B2 (en) 2015-12-22 2020-09-15 Carbon, Inc. Cyclic ester dual cure resins for additive manufacturing
WO2017156132A1 (en) * 2016-03-08 2017-09-14 3D Systems, Incorporated Non-isocyanate polyurethane inks for 3d printing
US20170260418A1 (en) * 2016-03-08 2017-09-14 3D Systems, Incorporated Non-Isocyanate Polyurethane Inks for 3D Printing
US10316214B2 (en) 2016-03-08 2019-06-11 3D Systems, Incorporated Non-isocyanate polyurethane inks for 3D printing
US10487238B2 (en) * 2016-03-08 2019-11-26 3D Systems, Inc. Non-isocyanate polyurethane inks for 3D printing
EP3426737B1 (en) 2016-03-08 2021-11-24 3D Systems, Incorporated Non-isocyanate polyurethane inks for 3d printing
EP3950855A1 (en) * 2016-03-08 2022-02-09 3D Systems, Incorporated Non-isocyanate polyurethane inks for 3d printing

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