WO2005123797A1 - Amines d'urethane - Google Patents

Amines d'urethane Download PDF

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Publication number
WO2005123797A1
WO2005123797A1 PCT/EP2005/052852 EP2005052852W WO2005123797A1 WO 2005123797 A1 WO2005123797 A1 WO 2005123797A1 EP 2005052852 W EP2005052852 W EP 2005052852W WO 2005123797 A1 WO2005123797 A1 WO 2005123797A1
Authority
WO
WIPO (PCT)
Prior art keywords
urethane
amine
epoxide
carbon atoms
aliphatic
Prior art date
Application number
PCT/EP2005/052852
Other languages
English (en)
Other versions
WO2005123797A8 (fr
Inventor
Jörg Volle
Original Assignee
Huntsman Advanced Materials (Switzerland) Gmbh
Huntsman Advanced Materials (Deutschland) Gmbh & 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 Huntsman Advanced Materials (Switzerland) Gmbh, Huntsman Advanced Materials (Deutschland) Gmbh & Co. Kg filed Critical Huntsman Advanced Materials (Switzerland) Gmbh
Publication of WO2005123797A1 publication Critical patent/WO2005123797A1/fr
Publication of WO2005123797A8 publication Critical patent/WO2005123797A8/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
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/2845—Monohydroxy epoxy compounds
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • 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
    • C08G59/3227—Compounds containing acyclic nitrogen atoms

Definitions

  • the invention relates to specific urethane amines as curing agents for epoxy resins, to a curable composition comprising these products, and to the use of these curable compositions for producing mouldings and coatings.
  • Epoxy resins have long been in widespread use for the production of corrosion control coatings, abrasion-resistant coatings, casting compositions and adhesives which possess outstanding mechanical strength and have good chemical resistance. Owing to their high crosslinking density, amine-cured epoxy resins, especially those based on diphenyl propane and epichlorohydrin, are brittle and hard with glass transition ranges above 20°C.
  • the degree of elasticization can be increased internally by lowering the crosslinking density and externally by adding plasticizer.
  • External elasticizers are not reactive and not incorporated into the thermoset network. They produce a widening of the network only by means of space-filling.
  • the external plasticizers include tar, phthalates, high-boiling alcohols, glycols, ketone resins, vinyl polymers, and similar products that are not reactive with epoxy resins and amine hardeners. This type of modification is suitable only for specific applications. With regard to elasticization it makes virtually no contribution, since the glass softening range is not substantially affected but the thermoset structure is highly disrupted. Internal elasticization of epoxy resins can be achieved by reducing the functionality of the hardener, as described for example in DE-A 2200 717.
  • the present invention accordingly provides new urethane amines.
  • These urethane amines are obtainable by reacting A) urethane epoxides of the general formula (I) (I),
  • Ri is a straight-chain or branched, saturated or unsaturated, aliphatic or cycloaliphatic hydrocarbon radical having 2 to 40, preferably 4 to 10, carbon atoms;
  • R 2 is an aromatic, aliphatic, cycloaliphatic, araliphatic, unbranched or branched hydrocarbon _. •. radical having 1 to 30, preferably 6 to 20, carbon atoms; and
  • R 3 independently at each occurrence H or
  • the urethane epoxides A) used for reaction of the amine compounds are obtainable by partially glyddylizing polyalcohols with epichlorohydrin and subsequently linking the products with di- or polyisocyanates via the remaining hydroxyl groups of the partially glycidylized polyols.
  • polyols here are meant polyhydric alcohols, containing at least two hydroxyl groups in the molecule.
  • the polyols are glycidylized by processes which are known per se, by reaction of the polyalcohols with epichlorohydrin in the presence of a catalyst and subsequent treatment with sodium hydroxide solution.
  • the molar ratio of polyol to epichlorohydrin is preferably chosen such that after the reaction there remains on average at least one free hydroxyl group per molecule for further reaction with the di- or polyisocyanate.
  • the reaction of the partially glycidylized polyols with the isocyanate compound takes place by addition of the polyisocyanate in the presence of a catalyst (e.g. dibutyltin laurate) to the initial charge of dewatered, partially glycidylized polyol at about 60°C with subsequent stirring for one hour.
  • a catalyst e.g. dibutyltin laurate
  • the reaction ratio of the partially glycidylized polyols to the isocyanate compound is preferably chosen stoichiometrically, i.e. such that for each hydroxyl group still present in the partially glycidylized polyols use is made of one isocyanate group of the diisocyanate or isocyanate of higher functionality for the reaction.
  • the reaction ratio of the partially glycidylized polyols to the isocyanate compound is preferably chosen stoichiometrically, i.e. such that for each hydroxyl group still present in the partially glycidylized polyols use is made of one isocyanate group of the diisocyanate or isocyanate of higher functionality for the reaction.
  • the alcohol and of the isocyanate compound it is possible to adjust certain properties, such as the flexibility in particular.
  • the use of polyols and/or polyisocyanates of higher functionality tends to produce brittle properties while the use of polyol
  • any alcoholic compounds which have at least two hydroxyl groups per molecule. Possible examples would include diols, such as ethanediol, propandiol, hexanediol, dimer diol, etc.; triols, such as glycerol, trimethylolethane, trimethylolpropane, etc.; and tetrahydric alcohols, such as erythritol, pentaerythritol.
  • diols such as ethanediol, propandiol, hexanediol, dimer diol, etc.
  • triols such as glycerol, trimethylolethane, trimethylolpropane, etc.
  • tetrahydric alcohols such as erythritol, pentaerythritol.
  • the isocyanates used in accordance with the invention for reaction of the partially glycidylized diols or polyols are the commercially customary aliphatic, araliphatic, cycloaliphatic or aromatic diisocyanates or polyfunctional isocyanates and also the trimerization products thereof.
  • Preferred examples would include the following: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methy1enedi(phenyl isocyanate) and tetramethylene diisocyanate.
  • amine compounds B) which can be used additionally for the reaction of the urethane epoxides A) it is possible in principle to use all amines which have at least two reactive amine hydrogen atoms, examples being heterocyclic amines such as piperazine and N- aminoethylpiperazine; cycloaliphatic amines such as isophoronediamine, 1,2-(1,3; 1,4)diaminocyclohexane, aminopropylcydohexylamine and tricyclododecanediamine (TCD); araliphatic amines such as xylylenediamine; aliphatic unsubstituted or substituted amines such as ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-(2,4,4)trimethyl- hexamethylenediamine and 2-methylpentamethylenediamine; ether amines such as 1,7- diamino-4-oxaheptane,
  • Use may also be made of relatively high molecular weight ether diamines based on propoxylated diols, triols and polyols ("Jeffamines" from the company Huntsman) with an average molar weight of above about 150.
  • polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine and also high molecular weight amines or adducts or condensates that contain free amine hydrogen.
  • polyethylene polyamines such as, for example, ethylenediamine, diethylenetriamine and N- aminoethylpiperazine and cycloaliphatic amines such as, for example, isophoronediamine or aminopropylcyclohexvlamine.
  • the reaction of the urethane epoxides A) with the amine compounds B) takes place such that the amine compound is introduced as an initial charge and the urethane epoxide is added over the course of about an hour with stirring at 60°C to 90°C, and the mixture is subsequently stirred for 1 hour until reaction is complete. Any excess amine can be removed under reduced pressure.
  • the molar ratios are chosen such that, following the reaction, there are on average at least two reactive amine hydrogens per molecule present in the reaction product. In order to set specific properties it is possible for the compounds of the invention to be subsequently adducted with epoxide compounds.
  • the urethane amines of the invention can be used in particular - alone or in a mixture with other amine hardeners customary in this field - as curing agents in curable epoxy resin compositions for producing elastic coatings, mouldings and adhesive bonds having improved adhesion.
  • the present invention therefore additionally provides a curable composition
  • a curable composition comprising a) a urethane amine of the invention, b) an epoxy resin having on average more than one epoxide group in the molecule, c) if desired a further aminic curing agent other than a), and d) optionally customary additives.
  • customary curing agents c) include the following: aliphatic amines, e.g. polyethylene polyamines and polypropylene polyamines, examples being diethylenetriamine and dipropylenetriamine, and 2,4,4-(2,2,4)trimethylhexamethylenediamine; cycloaliphatic diamines, such as 1-amino-3-aminomethyl-3,5,5-trimethylcydohexane, also called isophoronediamine, and 3,3 ' -dimethyl-4,4'-diaminodicydohexylmethane; heterocyclic amines, such as piperazine; long-chain polyether amines, such as 1,12-diamino-4,8- dioxadodecane; aromatic amines, such as phenylenediamine and diaminodiphenylmethane; polyamido amines formed from natural or synthetic fatty acids and polyamines; amine adducts; and
  • the epoxy resins b) that are used additionally can be cured hot and cold with the hardeners or hardener mixtures of the invention.
  • They contain on average more than one epoxide group in the molecule and may be glycidyl ethers of monohydric or polyhydric alcohols, such as glycerol or hydrogenated diphenylolpropane, for example, or of polyhydric phenols, such as resorcinol, diphenylolpropane or phenol-aldehyde condensates, for example.
  • glycidyl esters of polybasic carboxylic acids such as hexahydrophthalic acid or dimerized fatty acids.
  • liquid epoxy resins based on epichlorohydrin and diphenylolpropane having epoxide values of 0.4-0.6 epoxide groups/100 g of resin.
  • reactive diluents it is also possible as reactive diluents to use monofunctional aliphatic and aromatic glycidyl ethers, such as butyl glycidyl ether and phenyl glycidyl ether, or glycidyl esters, such as glycidyl acrylate, or epoxides, such as styrene oxide, or polyfunctional diglycidyl or triglycidyl ethers, particularly those of low molecular weight.
  • monofunctional aliphatic and aromatic glycidyl ethers such as butyl glycidyl ether and phenyl glycidyl ether
  • glycidyl esters such as glycidyl acrylate
  • epoxides such as styrene oxide
  • polyfunctional diglycidyl or triglycidyl ethers particularly those of low molecular weight.
  • the combination of the long-chain polyether urethane amines, with a low degree of crosslinking, with high-crosslinking amine formulations allows the properties of the reactive resin composition to be adjusted within a wide range in respect of viscosity, reactivity and the like and allows the properties of the thermoset to be adjusted within a wide range in respect of the elasticity, crosslinking density, mechanical strength and chemical resistance.
  • Suitable components for formulating a reactive resin composition for coating, adhesive bonding or casting include the customary organic- and mineral-based additives d), pigments, plasticizers, accelerators, solvents and other adjuvants.
  • the blowing agents that are customary in this field particularly the silane compounds that give off hydrogen.
  • the urethane amines of the invention themselves but also the curable compositions exhibit, surprisingly, a comparatively low viscosity, and the cured thermosets exhibit outstanding adhesion properties, particularly to metal sheets.
  • compositions of the invention can be employed with particular advantage where there is a need for effective adhesion to the substrate and elasticity in order to bridge cracks in the substrate, and for reducing internal stress, induding such applications at relatively low temperatures, and also as adhesives.
  • compositions of the invention are additionally suitable as casting compositions for joints, adhesives, and crack-bridging membranes that are impervious to liquids.
  • the low- shrink and low-stress curing also allows the production of shaped articles and mouldings in large format.
  • the present invention accordingly further provides a process for producing mouldings, coatings, adhesive bonds and foam materials, characterized in that they are produced using a curable composition of the invention. Examples:
  • reaction product from A) (about 1 equivalent of A) are admixed by a known method over the course of 60 minutes with 111 g (1 equivalent) of isophorone diisocyanate in the presence of 0.1 g of dibutyltin laurate at approximately 60°C. This is followed by stirring for 60 minutes until reaction is complete. This gives 281 g of a urethane epoxide.
  • 281 g (about 1 equivalent) of the urethane epoxide from B) are metered into 136 g (1 mol) of xylylenediamine over the course of about 60 minutes at 60 C C to 90 ⁇ C. This is followed by stirring for an hour until reaction is complete.
  • the resulting urethane amine is homogenized with 278 g of benzyl alcohol (40% based on the total amount).
  • Viscosity/25°C 1500 mPa « s, theoretical amine hydrogen equivalent: about 230.
  • Example 1 In the same way as in Example 1 the urethane amines listed in Table 1 below were prepared from the hydroxyalkyl glycidyl ether of Example 1 A).
  • IPDI isophorone diisocyanate
  • TDI tolylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • Example 5 Comparative example with Aradur 45 (commercial, fiexibilized polyamine from
  • Viscosity 5.4 Pa » s/25 ⁇ C;
  • Example 6 Comparative example with Aradur 145 (commercial polyamino amide from
  • Viscosity 3.5 Pa « s/25°C;
  • the adhesion was measured manually after 7 days' curing at room temperature with the epoxy resin Araldite GY 783 (reactively diluted base resin, epoxide equivalent: about 190).
  • the curable composition is applied at a film thickness of approximately 0.5 mm to an unpretreated metal sheet and is cured at room temperature for 7 days. Subsequently the film is removed.
  • the adhesion to the metal sheet is evaluated as follows:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une amine d'uréthane pouvant être obtenue en faisant réagir, d'une part, A) un époxyde d'uréthane représenté par la formule générale (I), dans laquelle R1 désigne un radical hydrocarboné aliphatique ou cycloaliphatique, saturé ou insaturé, linéaire ou ramifié, comportant 2 à 40 atomes de carbone ; R2 désigne un radical hydrocarboné aromatique, aliphatique, cycloaliphatique, araliphatique, non ramifié ou ramifié ; et R3 désigne indépendamment à chaque occurrence H ou (Ia), avec d'autre part, B) un composé aminé contenant au moins deux atomes d'hydrogène réactifs par molécule. L'invention concerne également l'utilisation de ces amines d'uréthane comme agents de traitement dans des compositions de résine époxyde polymérisables, destinées en particulier à la production de moulages, de liens adhésifs, de revêtements et de matériaux alvéolaires.
PCT/EP2005/052852 2004-06-21 2005-06-20 Amines d'urethane WO2005123797A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004029919 2004-06-21
DE102004029919.6 2004-06-21

Publications (2)

Publication Number Publication Date
WO2005123797A1 true WO2005123797A1 (fr) 2005-12-29
WO2005123797A8 WO2005123797A8 (fr) 2006-03-02

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PCT/EP2005/052852 WO2005123797A1 (fr) 2004-06-21 2005-06-20 Amines d'urethane

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533983A (en) * 1966-06-01 1970-10-13 Furane Plastics Thermosetting phenyl glycidyl ether derivatives of isocyanate-terminated organic compounds
US3624178A (en) * 1966-07-19 1971-11-30 Ciba Ltd Epoxy terminated polyurethanes
WO2004003050A1 (fr) * 2002-07-01 2004-01-08 Huntsman Advanced Materials (Switzerland) Gmbh Amines de polyether-urethane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533983A (en) * 1966-06-01 1970-10-13 Furane Plastics Thermosetting phenyl glycidyl ether derivatives of isocyanate-terminated organic compounds
US3624178A (en) * 1966-07-19 1971-11-30 Ciba Ltd Epoxy terminated polyurethanes
WO2004003050A1 (fr) * 2002-07-01 2004-01-08 Huntsman Advanced Materials (Switzerland) Gmbh Amines de polyether-urethane

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Publication number Publication date
WO2005123797A8 (fr) 2006-03-02

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