EP2914643A1 - Polymere von [4-(methylether)-1,3-dioxolan-2-on von polyetherpolyol] - Google Patents

Polymere von [4-(methylether)-1,3-dioxolan-2-on von polyetherpolyol]

Info

Publication number
EP2914643A1
EP2914643A1 EP13801629.0A EP13801629A EP2914643A1 EP 2914643 A1 EP2914643 A1 EP 2914643A1 EP 13801629 A EP13801629 A EP 13801629A EP 2914643 A1 EP2914643 A1 EP 2914643A1
Authority
EP
European Patent Office
Prior art keywords
polymer
formula
radical
och
chosen
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.)
Withdrawn
Application number
EP13801629.0A
Other languages
English (en)
French (fr)
Inventor
Guillaume Michaud
Frédéric Simon
Stéphane Fouquay
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.)
Bostik SA
Original Assignee
Bostik SA
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 Bostik SA filed Critical Bostik SA
Publication of EP2914643A1 publication Critical patent/EP2914643A1/de
Withdrawn legal-status Critical Current

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • C08G65/3245—Carbondioxide
    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences

Definitions

  • the subject of the present invention is polymers comprising at each of their ends a 1,3-dioxolan-2-one (or cyclocarbonate) end group linked to a polymeric chain by an alpha (a) substituted methylether (CH 2 -O) function.
  • These polyurethanes once formulated, are intended for use in coatings, mastics or adhesives, as additives and / or as resins.
  • diisocyanates are toxic compounds as such, and are generally obtained from phosgene, itself very toxic by inhalation or contact.
  • the manufacturing process used in industry generally involves the reaction of an amine with an excess of phosgene to form an isocyanate.
  • Patent Application EP1088021 discloses oligomeric compounds of 1,3-dioxolan-2-one, including oligomeric compounds of 4-methylether-1,3-dioxolan-2-one polypropylene glycol.
  • the oligomeric compounds are synthesized by carbonation in a high pressure reactor, from the corresponding compounds comprising terminal groups with oxirane (or epoxide) terminations: by carbonation, the oxirane groups are converted into 1,3-dioxolan-2-one groups.
  • the oligomeric compounds of 1,3-dioxolan-2-one are then mixed with amine oligomers so as to synthesize, by crosslinking, polyurethanes.
  • the oligomeric 4-methylether-1,3-dioxolan-2-one polypropylene glycol compounds described herein have a low molecular weight, typically 350 to 3200 g / mol, and a star-shaped structure comprising from 2 to 8 branches, each branch comprising a 4-methylether-1,3-dioxolan-2-one polypropylene glycol and all the branches being interconnected by a hydrocarbon group.
  • the 4-methylether-1,3-dioxolan-2-one group terminates the terminal group of each branch, the hydrocarbon group being at the other end of the branch.
  • No example of synthesis of a polypropylene glycol 4-methyl ether-1,3-dioxolane oligomeric compound is described. However, the carbonation reaction is not complete, since the oligomers comprise from 4 to 12% by weight of the starting oligomers, which is problematic during the formation of the polyurethanes.
  • the patent application WO 03/028644 of Eurotech Ltd describes oligomeric compounds of 4-methylether-1,3-dioxolan-2-one which are almost pure, and in particular oligomeric compounds of 4-methylether-1,3-dioxolane.
  • Polypropylene glycol 2-one low molecular weight, typically from 600 to 1600 g / mol.
  • the structure of these oligomers is star-shaped comprising from 3 to 6 branches, each branch comprising a 4-methylether-1,3-dioxolan-2-one of polypropylene glycol, and all the branches being connected together by a group hydrocarbon.
  • the 4-methylether-1,3-dioxolan-2-one group terminates the terminal group of each branch, the hydrocarbon group being at the other end of the branch.
  • No example of synthesis of an oligomeric compound of polypropylene glycol 4-methylether-1,3-dioxolane is described.
  • the present invention aims to provide new intermediates for the synthesis of polyurethanes without using isocyanate.
  • the present invention relates to a polymer of formula (I) comprising at least one terminal group 4-methylether-1,3-dioxolan-2-one:
  • R is a hydrogen or an alkyl which comprises from 1 to 4 carbon atoms, preferably R is hydrogen and / or a methyl radical;
  • n is a number from 1 to 6, preferably m is chosen from 2 and 3, even more preferably m is equal to 2;
  • B is a monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent radical, said radical generally comprising from 1 to 44 carbon atoms per molecule;
  • n is such that the number-average molar mass Mn of the polymer of formula (I) is in the range of 4000 to 18000 g / mol, and such that the polydispersity (Pd) of the polymer of formula (I) is included in a range of 1.0 to 1.4.
  • the polydispersity Pd is defined as the ratio Mw / Mn, that is to say the ratio of the molar mass by weight to the molar mass by number of the polymer.
  • the two molar masses Mn and Mw are measured according to the invention by Size Exclusion Chromatography (SEC), usually with PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration.
  • SEC Size Exclusion Chromatography
  • terminal group means a group located at the end of the chain (or end) of the polymer.
  • the radical B may be linear or branched, may comprise at least one saturated and / or unsaturated bond, and may comprise at least one cyclic and / or alicyclic group.
  • the radical B is preferably chosen from the group formed by the radicals formed from methanol, ethylene glycol, propylene glycol, neopentyl glycol, dimeric fatty alcohol, trimethylolpropane, pentaerythritol, glycerol, arabinol and sorbitol compounds, starting from at least a hydroxyl group.
  • the polymeric divalent radical - (- OCH 2 -CH (R) -) n - generally has a number-average molecular weight in the range of about 667 to 18000 g / mol.
  • the polymeric divalent radical - (- OCH 2 --CH (R) -) n - may be formed from a block or random copolymer of at least two divalent radicals of polymers of formulas - (- OCH 2 - CH (R1) -) n i- and - (- OCH 2 -CH (R2) -) n2 -, where n1 and n2 are such that the molar mass by number Mn of the polymer of formula (I) is within a range from 4000 to 18000 g / mol, and such that the polydispersity (Pd) of the polymer of formula (I) is in the range of 1.0 to 1.4.
  • the polymeric divalent radical - (- OCH 2 -CH (R) -) n - comprises a plurality of oxyalkylene repeating units, preferably oxyethylenes, oxypropylenes, oxybutylenes and / or oxyhexylenes.
  • the polymeric divalent radical - (- OCH 2 -CH (R) -) n - is chosen from the group formed by the polyoxyethylene, polyoxypropylene, polyoxybutylene and polyoxyhexylene radicals, and their copolymers.
  • the copolymers are generally sequenced or statistical.
  • the divalent radical - (- OCH 2 -CH (R) -) n - is formed from a polyether polyol selected from the group consisting of copolymers formed from ethylene oxide and oxide of propylene.
  • the copolymers are generally sequenced or statistical.
  • these polyether polyols can be prepared by cyclic ring-opening polymerization. comprising oxygen such as a compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, often in the presence of an initiator such as a monomeric diol.
  • the invention also relates to a process for the preparation of at least one polymer of formula (I) according to the invention, comprising a step of carbonation of at least one polymer of formula (III) below in which B, R, m and n have the same meanings as those of formula (I):
  • the carbonation step is generally carried out as is known to those skilled in the art, at the pressure and temperature indicated above.
  • the carbonation step is generally carried out in the presence of CO2 in any form, for example in the liquid, gaseous or supercritical state (depending on the reaction pressure), and a reagent generally chosen from tetrabutylammonium bromide, tetrabutylammonium hydroxide, the mixtures comprising tin tetrachloride (SnCl 4 : 5H 2 O).
  • the carbonation step is preferably carried out in the presence of supercritical CO2 and tetrabutylammonium bromide.
  • the carbonation step is for example carried out according to the procedure described in the patent application WO 03/028644 or in the patent application FR 2952933.
  • the polymer of formula (III) is obtained by reaction of at least one polymer of formula (II), in which B, R, m and n have the same meanings as those of formula (I). ):
  • This reaction which makes it possible to substitute the terminal hydroxyl groups with oxirane (or epoxidic) groups, can be carried out for example according to the procedure described in US Pat. No. 2,888,426, or else according to the procedure described in patent application JP 2007009158. It can be done in one or more stages.
  • the invention finally relates to a process for preparing polyurethanes comprising reacting at least one polymer of formula (I) according to the invention with at least one compound comprising at least one, preferably at least two, amino groups, for example chosen from amines, diamines, triamines and polyamines, as well as polyurethanes obtainable by this preparation process.
  • the amines are preferably such that at least one amino group, preferably all the amino groups, are primary amino groups.
  • polyurethanes once formulated (i.e. formulated with other optional additives), are intended for use in coatings, putties or adhesives, as fillers and / or as resins. It is also possible to independently formulate the polymer of formula (I) and the compound comprising at least one amino group, before mixing.
  • the starting material PPG polypropylene glycol
  • the starting material PPG was either the commercial product Acclaim ® Polyol 4200 (molar mass Mn of 4000 g / mol) or the commercial product Acclaim ® Polyol 18200 (having a molecular weight Mn of 18000 g / mol), both products being marketed by Bayer Material Science.
  • Each PPG was of formula:
  • n being a function of the molar mass of the PPG.
  • the starting compound is a Acclaim ® Polyol 4200 or Acclaim ® Polyol 18200:
  • the total yield of all the two steps a) and b) in each case was about 93% calculated on the initial polypropylene glycol, whether the Acclaim ® 4200 or 18200 Acclaim ®.
  • the starting compound is a Acclaim ® Polyol 4200 or Acclaim ® Polyol 18200:
  • This carbonation step was carried out in the presence of supercritical CO2 and tetrabutylammonium bromide at a temperature of about 120 ° C, and the carbon dioxide was introduced at a pressure of about 20 MPa.
  • a mixture of one of the propylene glycol di [4- (methyl ether) -1,3-dioxolan-2-one] from the example was separately reacted at 80 ° C and in a stoichiometric ratio. 2 and primary diamine type polyether diamine (JEFFAMINE EDR 176, Huntsman) and this, until complete disappearance of the infrared band characteristic of groups 1, 3-dioxolan-2-one (at 1800 cm "1 ) and appearance of bands characteristic of the carbamate bond (band at 1700 cm -1 ).
  • the reaction time was about 72 hours.
  • the product thus synthesized resulted in the formation of a polyhydroxyurethane, which suitably formulated two-component blend provided the desired adhesive properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP13801629.0A 2012-11-05 2013-10-30 Polymere von [4-(methylether)-1,3-dioxolan-2-on von polyetherpolyol] Withdrawn EP2914643A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1260484A FR2997700B1 (fr) 2012-11-05 2012-11-05 Polymeres de [4-(methylether)-1,3-dioxolane-2-one de polyether polyol]
PCT/FR2013/052596 WO2014068251A1 (fr) 2012-11-05 2013-10-30 Polymères de [4-(méthyléther)-1,3-dioxolane-2-one de polyéther polyol]

Publications (1)

Publication Number Publication Date
EP2914643A1 true EP2914643A1 (de) 2015-09-09

Family

ID=47624339

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13801629.0A Withdrawn EP2914643A1 (de) 2012-11-05 2013-10-30 Polymere von [4-(methylether)-1,3-dioxolan-2-on von polyetherpolyol]

Country Status (8)

Country Link
US (1) US20150299390A1 (de)
EP (1) EP2914643A1 (de)
KR (1) KR20150082281A (de)
CN (1) CN104918982A (de)
AU (1) AU2013340641A1 (de)
BR (1) BR112015010100A2 (de)
FR (1) FR2997700B1 (de)
WO (1) WO2014068251A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3199569B1 (de) * 2016-01-29 2021-05-19 FAURECIA Sièges d'Automobile Isocyanatfreie polyurethanschäume
WO2019164900A1 (en) 2018-02-21 2019-08-29 Cryovac, Llc Method and formulation for an isocyanate-free foam using isocyanate-free polyurethane chemistry

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239580A (en) * 1962-03-19 1966-03-08 Dow Chemical Co Elastomeric epoxy resins
US5567527A (en) * 1995-02-21 1996-10-22 Eastman Chemical Company Copolymers containing 1,3-dioxolane-2-one-4-yl groups and coatings made therefrom
US6120905A (en) * 1998-06-15 2000-09-19 Eurotech, Ltd. Hybrid nonisocyanate polyurethane network polymers and composites formed therefrom
EP1020457A1 (de) * 1999-01-14 2000-07-19 Polymate Ltd. Verfahren zur Herstellung von polyfunktionellen Polycarbonat-oligomern,und ihren enthaltenden Polymeren
AU2002337780A1 (en) * 2001-10-01 2003-04-14 Eurotech, Ltd. Preparation of oligomeric cyclocarbonates and their use in ionisocyanate or hybrid nonisocyanate polyurethanes
GB2432160A (en) * 2005-11-14 2007-05-16 Sun Chemical Ltd Energy curable cyclic carbonate compositions
DE102008013584A1 (de) * 2008-03-11 2009-09-17 Momentive Performance Materials Gmbh Neue Polycarbonat-Polyorganosiloxan- und/oder Polyurethan-Polyorganosiloxan-Verbindungen
JP5277233B2 (ja) * 2010-11-19 2013-08-28 大日精化工業株式会社 熱可塑性ポリヒドロキシウレタンの製造方法
CN102718964A (zh) * 2012-07-09 2012-10-10 广西民族大学 非异氰酸酯聚氨酯的制备及在喷涂聚脲中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014068251A1 *

Also Published As

Publication number Publication date
BR112015010100A2 (pt) 2017-07-11
CN104918982A (zh) 2015-09-16
AU2013340641A1 (en) 2015-05-21
FR2997700A1 (fr) 2014-05-09
KR20150082281A (ko) 2015-07-15
US20150299390A1 (en) 2015-10-22
FR2997700B1 (fr) 2015-01-16
WO2014068251A1 (fr) 2014-05-08

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