WO2011069746A1 - Compositions réactives sur la base de la transestérification - Google Patents

Compositions réactives sur la base de la transestérification Download PDF

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Publication number
WO2011069746A1
WO2011069746A1 PCT/EP2010/066608 EP2010066608W WO2011069746A1 WO 2011069746 A1 WO2011069746 A1 WO 2011069746A1 EP 2010066608 W EP2010066608 W EP 2010066608W WO 2011069746 A1 WO2011069746 A1 WO 2011069746A1
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Prior art keywords
diisocyanate
component
acid
groups
acrylate
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PCT/EP2010/066608
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German (de)
English (en)
Inventor
Emmanouil Spyrou
Claudia Torre
Marina Grammenos
Elke Gollan
Andrea Diesveld
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Evonik Degussa Gmbh
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Application filed by Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Priority to JP2012542420A priority Critical patent/JP2013513673A/ja
Priority to DE112010004731T priority patent/DE112010004731A5/de
Priority to US13/515,004 priority patent/US20120289648A1/en
Publication of WO2011069746A1 publication Critical patent/WO2011069746A1/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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers

Definitions

  • the invention relates to reactive compositions based on transesterification.
  • Adhesive components eg polyester resins
  • Adhesive components eg polyester resins
  • B carboxylic acid ester.
  • the reaction between polycarboxylic acid esters and polyols (transesterification) has already been described in US Pat
  • Zinc acetate, lead silicate, or zinc octoate used.
  • these catalysts were rather less reactive, so that more active substances were researched, especially for catalysts which have a favorable reactivity / storage stability ratio.
  • Triflates of different metals Li, Na, K, Ba, Mg, Ca, Al, In, Sn, Sc, Y, Ti, Zr, Fe, Cu, Ag, or Zn have also been reported as
  • Transesterification catalysts described EP21 13499. However, it lacks the use in reactive compositions for paint and adhesive applications. For this purpose, for example, diphenylammonium triflate
  • Catalysts for transesterification reactions which have a more favorable ratio of reactivity and storage stability, than conventional catalysts.
  • the task was to find catalysts that make both reactive and storage-stable compositions of polycarboxylic acid esters and polyols accessible.
  • the invention relates to a reactive composition containing
  • A1 at least one di- or polycarboxylic acid ester component having at least two or more ester groups, containing at least one monofunctional
  • the invention accordingly provides reactive compositions of two components A1) and A2, or A1) and B, or A2) and B), or of the three components A1), A2) and B).
  • Both the carboxylic acid ester groups and the alcohol groups can be located anywhere on the molecule. However, the end positions in the reactive starting molecules are preferred. Suitable components A1, A2) and / or B) are z. In US 4,489,182, US 4,362,847, US 4,332,711, US 437848 and US 4,459,393.
  • Suitable components A1), A2) and / or B) are all monomers, oligomers or polymers which contain either ester groups or hydroxyl groups or both
  • Suitable skeletons for the oligomers and polymers are polyesters, polyacrylates, polyethers, polyurethanes, polycarbonates, polyamides, and polyepoxides.
  • Suitable monomeric ester groups A1) are, for example
  • monofunctional alcohols having an average molecular weight Mn of less than or equal to 200 g / mol, preferably with alcohols having 1 -12 C atoms and aromatic
  • component A1 Also preferably used as component A1) are (meth) acrylates and
  • Acrylates are prepared by polymerization of monomers bearing methacrylate or acrylate groups and by copolymerization with other ethylenically unsaturated monomers, wherein peroxides or azo components initiate the radical polymerization of the double bonds.
  • (Meth) acrylate-containing monomers for the preparation of A1) include alkyl esters of acrylic acid or methacrylic acid esterified with monofunctional alcohols having an average molecular weight Mn of less than or equal to 200 g / mol, preferably with alcohols having 1-12 carbon atoms, and aromatic compounds, such as z. Methanol, ethanol,
  • Aromatics such as B phenol, or benzyl alcohol. Preference is given to methanol, ethanol or n-butanol.
  • the acid used is preferably acrylic acid and / or methacrylic acid.
  • Cresyl glycidyl ether reacted with acrylic acid and methacrylic acid.
  • Polymerizable double bonds containing co-monomers include
  • vinyl chloride, vinyl fluoride, and vinylidene chlorides styrene, methylstyrene and alkylstyrenes, chlorostyrene, vinyltoluene, vinylnaphthalene, Vivinylbenzoat and cyclohexene.
  • alpha-olefins such. Ethylene, propylene, isobutylene, and cyclohexene, and butadienes, methyl-2-butadiene,
  • Ester-containing polyurethanes can also be used as component A1).
  • Such polyurethanes are prepared by the reaction of mono-, di-or polyols as the alcohol component which simultaneously contain ester moiety with di- or polyisocyanates.
  • Suitable alcohol components are all (for example in this document under B) described, monomeric, oligomeric or polymeric alcohols, provided they contain at least one ester group esterified with
  • monofunctional alcohols having an average molecular weight Mn of less than or equal to 200 g / mol, preferably with alcohols having 1 -12 C atoms and aromatic
  • Benzyl alcohol In question come z. B. glycolic acid esters, hydroxypropionic acid esters and Hydroxybutanklareester. Also preferred are reaction products of lactones (eg epsilon-caprolactone) with low molecular weight monoalcohols, eg. For example, methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, or 2-butanol. The formation of polylactones is z. In Kowalski, A. et al.
  • Monoalcohols as starter molecules form monoalcohols, which additionally carry a carboxylic acid ester with a low molecular weight alcohol. Such molecules are particularly suitable in the reaction with isocyanate-containing components
  • aromatic di- or polyisocyanates are suitable as aromatic di- or polyisocyanates. Particularly suitable are 1, 3 and 1, 4-phenylene diisocyanate,
  • MDI monomeric diphenylmethane diisocyanates
  • polymeric MDI oligomeric diphenylmethane diisocyanates
  • Suitable aliphatic di- or polyisocyanates advantageously have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z.
  • B. isophorone diisocyanate is the case.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • Nonane triisocyanate such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediol and triisocyanate, dodecanedi and triisocyanates.
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediol and triisocyanate
  • dodecanedi and triisocyanates dodecanedi and triisocyanates.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • IPDI, HDI, TMDI and / or H12MDI the isocyanurates and uretdiones preferably being used as well.
  • Component A1) can be carried out in suitable units, stirred tanks, static mixers, tubular reactors, kneaders, extruders or other reaction spaces with or without mixing function.
  • the reaction is carried out at temperatures between room temperature and 220 ° C, preferably between 40 ° C and 120 ° C and takes depending on the temperature and reaction components between a few seconds and several weeks. A reaction time between 30 minutes and 24 hours is preferred.
  • the final product has no significant free NCO groups
  • the catalysts customary in PU chemistry can be used. They are used in a concentration of 0.001 to 2 wt .-%, preferably from 0.01 to 0.5 wt .-%, based on the reaction components used. Catalysts are for example tert. Amines such as triethylamine, pyridine or ⁇ , ⁇ -dimethylaminocyclohexane or metal salts such as iron (III) chloride, molybdenum glycolate and zinc chloride. Particularly suitable proved tin-Il and -IV compounds. Dibutyltin dilaurate (DBTL) and tin octoate may be mentioned here in particular.
  • DBTL dibutyltin dilaurate
  • tin octoate may be mentioned here in particular.
  • the polyurethanes may be solid, viscous, liquid and also in powder form.
  • Particularly preferred as A2) are 1, 4-butanediol, 1, 3-propanediol,
  • Hydroxypivalate They are used alone or in mixtures. 1, 4-butanediol is used only in mixtures.
  • Suitable compounds A2) are also diols and polyols which contain further functional groups.
  • hydroxyl-containing polymers A2 preference is given to using polyesters, polyethers, polyacrylates, polyurethanes, polyvinyl alcohols and / or polycarbonates having an OH number of 5 to 500 mg KOH / gram.
  • Preferred as A2) are linear or slightly branched hydroxyl-containing polyester-polyesterpolyols - or mixtures of such polyesters. They are z. Example by reacting diols with minor amounts of dicarboxylic acids, corresponding dicarboxylic anhydrides, corresponding dicarboxylic acid esters of lower alcohols, lactones or hydroxycarboxylic acids produced. Preference is given to 1,4-butanediol, 1,2-propanediol, cyclohexanedimethanol, hexanediol, neopentyl glycol, decanediol, dodecanediol, trimethylolpropane, ethylene glycol,
  • Triethylene glycol pentanediol-1, 5, hexanediol-1, 6, 3-methylpentanediol-1, 5,
  • Diols and polyols which are suitable for the preparation of the preferred polyester polyols are, in addition to the abovementioned diols and polyols, 2-methylpropanediol,
  • Suitable dicarboxylic acids or derivatives for the preparation of the polyester polyols may be aliphatic, cycloaliphatic, aromatic and / or heteroaromatic nature and optionally, for. B. by halogen atoms, substituted and / or unsaturated.
  • Preferred dicarboxylic acids or derivatives include succinic, adipic, corkic, azelaic and sebacic acids, 2,2,4 (2,4,4) -thmethyl-adipic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
  • Suitable polyester polyols are also those which in a known manner by ring opening from lactones, such as ⁇ -caprolactone, and simple diols as
  • Polyester of phosphoric acid eg. From methane, ethane, ⁇ -chloroethane, benzene or styrene phosphoric acid or their derivatives, such as, for example, phosphoric acid chlorides or phosphoric acid esters and polyhydric alcohols or polyphenols of the abovementioned type; Polyester of boric acid; Polysiloxanes, such as. B. by hydrolysis of
  • Dialkyldichlorosilanes with water and subsequent treatment with polyalcohols the products obtainable by addition of polysiloxane dihydrides to olefins, such as allyl alcohol or acrylic acid, are suitable as starting materials for the
  • the polyesters can be obtained in a manner known per se by condensation in an inert gas atmosphere at temperatures of 100 to 260 ° C, preferably 130 to 220 ° C, in the melt or in azeotropic procedure, as described, for.
  • in methods of organic chemistry Houben-Weyl; Volume 14/2, pages 1 to 5, 21 to 23, 40 to 44, Georg Thieme Verlag, Stuttgart, 1963, or by C. R.
  • the diols and dicarboxylic acids or derivatives thereof used for the preparation of the polyesterpolyols can be used in any desired mixtures.
  • Suitable compounds A2) are also the reaction products of
  • glycidyl compounds which can be used are esters of 2,3-epoxy-1-propanol with monobasic acids having 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate, alkylene oxides of 4 to 18 carbon atoms, such as butylene oxide, and Glycidyl ethers, such as octyl glycidyl ether.
  • glycidic compounds are those which, in addition to an epoxide group, still carry at least one further functional group, such as, for example, For example, carboxyl, hydroxyl, mercapto or amino groups that react with a
  • Hydroxyl-containing polyurethanes can also be used as component A2).
  • Such polyurethanes are prepared by the reaction of polyols and di- or polyisocyanates.
  • Suitable polyol components are all monomeric, oligomeric or polymeric polyols already described in this document.
  • Triethylene glycol pentanediol-1, 5, hexanediol-1, 6, 3-methylpentanediol-1, 5,
  • Hydroxypivalate They are used alone or in mixtures. 1, 4-butanediol is used only in mixtures.
  • aromatic di- or polyisocyanates are particularly suitable. Particularly suitable are 1, 3 and 1, 4 phenylene diisocyanate,
  • MDI Diphenylmethane diisocyanates
  • polymeric MDI oligomeric diphenylmethane diisocyanates
  • xylylene diisocyanate tetramethylxylylene diisocyanate
  • Suitable aliphatic di- or polyisocyanates advantageously have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic Diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z.
  • B. isophorone diisocyanate is the case.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediisocyanate, triisocyanate, dodecanediand triisocyanates.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • IPDI, HDI, TMDI and / or H12MDI the isocyanurates and uretdiones preferably being used as well.
  • mixtures of di- and polyisocyanates can be used.
  • the reaction of the polyol component and isocyanate component for component A2) can be carried out in suitable units, stirred tanks, static mixers, tubular reactors, kneaders, extruders or other reaction spaces with or without mixing function.
  • the reaction takes place at temperatures between
  • Room temperature and 220 ° C preferably carried out between 40 ° C and 120 ° C. and lasts between a few seconds and several weeks, depending on the temperature and reaction components. A reaction time between 30 minutes and 24 hours is preferred.
  • the final product has no significant free NCO groups
  • the catalysts customary in PU chemistry can be used. They are used in a concentration of 0.001 to 2 wt .-%, preferably from 0.01 to 0.5 wt .-%, based on the reaction components used. Catalysts are for example tert. Amines such as triethylamine, pyridine or ⁇ , ⁇ -dimethylaminocyclohexane or metal salts such as iron (III) chloride, molybdenum glycolate and zinc chloride. Particularly suitable proved tin-Il and -IV compounds. Dibutyltin dilaurate (DBTL) and tin octoate may be mentioned here in particular.
  • DBTL dibutyltin dilaurate
  • tin octoate may be mentioned here in particular.
  • the polyurethanes may be solid, viscous, liquid and also in powder form.
  • component B) are OH-containing ester group-containing compounds in which the ester-forming alcohol has a molecular weight of not more than 200 g / mol. In question come here low molecular weight molecules such. Glycolic acid esters, hydroxypropionic acid esters and hydroxybutanoic acid esters,
  • Lactic acid esters citric acid esters and or tartaric acid esters in which the
  • Poly (meth) acrylates Be prepared by the co-polymerization of (meth) acrylates, with individual feeds OH groups, however, do not carry others. Thus, a randomly distributed OH-containing polymer is produced. Such polymers are described below:
  • Acrylates are prepared by polymerization of monomers bearing methacrylate or acrylate groups and optionally by copolymerization with other ethylenically unsaturated monomers, wherein peroxides or azo components initiate the radical polymerization of the double bonds.
  • Preferred (meth) acrylate-containing monomers include alkyl esters of acrylic acid or methacrylic acid esterified with monofunctional alcohols having an average molecular weight Mn of less than or equal to 200 g / mol, preferably alcohols having 1-12
  • C atoms and aromatic compounds such as.
  • B phenol or benzyl alcohol Preferred are methanol, ethanol and n-butanol.
  • the acid used is preferably acrylic acid and / or methacrylic acid.
  • Polymerizable double bonds containing co-monomers include vinyl group-containing monomers, allyl-containing monomers and
  • Vinylester such as vinyl chloride, vinyl fluoride, and vinylidene chlorides, styrene, methylstyrene and alkylstyrenes, chlorostyrene, vinyltoluene, vinylnaphthalene, Vivinylbenzoat and cyclohexene.
  • alpha-olefins such as Ethylene, propylene, isobutylene, and cyclohexene, and butadienes, methyl-2-butadiene,
  • Dicyclopentadiene Dicyclopentadiene.
  • methyl vinyl ether isopropyl vinyl ether, butyl vinyl ether, and isobutyl vinyl ether.
  • the methacrylate or acrylate groups bearing hydroxy-functional component B) is prepared by copolymerization of special hydroxylated monomers such. 2-hydroxyethyl acrylates and 2-hydroxyethyl methacrylates, 2-hydroxypropyl acrylates and 2-hydroxypropyl methacrylates, hydroxybutyl acrylates and 2-hydroxybutyl methacrylates, and similar hydroxyalkyl acrylates with the above (meth) acrylates and
  • Hydroxyl-containing polyacrylates bearing methacrylate or acrylate groups are preferably used as component B). They are commercially available for. B. at the company. NUPLEX under the trade name
  • Designation JONCRYL for example the JONCRYL 587), BASF (SCX 804) and Anderson (ALMATEX 2001).
  • Ester-containing and hydroxyl-containing polyurethanes can also be used as component B).
  • the isocyanate component is prepared by the reaction of mono, di and / or polyols with di- or polyisocyanates.
  • Suitable alcohol components are the monomeric, oligomeric or polymeric alcohols already described in this document for the formation of
  • Polyurethane group-containing component A1) and the monomeric, oligomeric or polymeric alcohols for the formation of component A2) containing polyurethane groups are examples of polyurethane groups.
  • Triethylene glycol pentanediol-1, 5, hexanediol-1, 6, 3-methylpentanediol-1, 5,
  • Hydroxypivalate They are used alone or in mixtures. 1, 4-butanediol is used only in mixtures.
  • aromatic di- or polyisocyanates are particularly suitable. Particularly suitable are 1, 3 and 1, 4 phenylene diisocyanate,
  • MDI Diphenylmethane diisocyanates
  • polymeric MDI oligomeric diphenylmethane diisocyanates
  • xylylene diisocyanate tetramethylxylylene diisocyanate
  • Suitable aliphatic di- or polyisocyanates advantageously have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. isophorone diisocyanate is the case.
  • cycloaliphatic diisocyanates are understood as meaning those which are only directly on the cycloaliphatic ring bonded NCO groups have, for. Eg H12MDI.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • Non-isocyanate such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediand thisocyanate, dodecanediisocyanate and isocyanate.
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediand thisocyanate
  • dodecanediisocyanate dodecanediisocyanate and isocyanate.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-methylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • IPDI, HDI, TMDI and / or H12MDI the isocyanurates and uretdiones preferably being used as well.
  • mixtures of di- and polyisocyanates can be used.
  • the isocyanate component is containing at least one ester group
  • Alcohol component is reacted, which is esterified with monofunctional alcohols having an average molecular weight Mn of less than or equal to 200 g / mol, preferably with
  • Alcohols having 1 -12 C atoms and aromatic compounds such as Methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, or 2-butanol, aromatics such as. B phenol or benzyl alcohol. Preferred are methanol, ethanol and n-butanol.
  • the isocyanate component can additionally be reacted with at least one ester group-free alcohol component.
  • the reaction of the alcohol components and the isocyanate component to component B) can be carried out in suitable units, stirred tanks, static mixers, tubular reactors, kneaders, extruders or other reaction spaces with or without mixing function.
  • the ratio between alcohols containing ester groups and ester-free alcohols may be between 1:20 and 20: 1, preferably a ratio between 1: 5 and 5: 1, more preferably between 1: 2 and 2: 1.
  • the reaction is carried out at temperatures between room temperature and 220 ° C, preferably between 40 ° C and 120 ° C and takes depending on the temperature and reaction components between a few seconds and several weeks. A reaction time between 30 minutes and 24 hours is preferred.
  • the ratio between the NCO component and the alcohol components, calculated as NCO / OH 0.3: 1 to 1, 05: 1, preferably 0.5: 1 to 1: 1.
  • the final product has no significant free NCO groups ( ⁇ 0.5 wt .-%).
  • the catalysts customary in PU chemistry can be used. They are used in a concentration of 0.001 to 2 wt .-%, preferably from 0.01 to 0.5 wt .-%, based on the reaction components used. Catalysts are for example tert. Amines such as triethylamine, pyridine or ⁇ , ⁇ -dimethylaminocyclohexane or metal salts such as iron (III) chloride, molybdenum glycolate and zinc chloride. Particularly suitable proved tin-Il and -IV compounds. Dibutyltin dilaurate (DBTL) and tin octoate may be mentioned here in particular.
  • DBTL dibutyltin dilaurate
  • tin octoate may be mentioned here in particular.
  • the polyurethanes may be solid, viscous, liquid and also in powder form.
  • the reactive compositions contain bismuth triflate.
  • Triflate is the common abbreviation for salts of trifluoromethylsulfonic acid.
  • the reactive compositions may also include adjuvants D) selected from inhibitors, organic solvents optionally containing unsaturated moieties, surfactants, oxygen and / or radical scavengers, catalysts, sunscreens, color brighteners,
  • Photoinitiators photosensitizers, thixotropic agents,
  • Anti-skinning agents defoamers, dyes, pigments, fillers and matting agents.
  • the amount varies greatly from the field of application and type of auxiliary and additive.
  • Suitable organic solvents are all liquid substances which do not react with other ingredients, eg. Acetone, xylene, Solvesso 100, Solvesso 150, dioxane, DMF.
  • additives D such as leveling agents, for.
  • leveling agents for.
  • Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.
  • Ester groups in the reactive composition of at least two or even three components can be between 1:20 and 20: 1, preferably a ratio between 1: 5 and 5: 1, more preferably between 1: 2 and 2: 1.
  • the components of the reactive composition of the invention may be dissolved in suitable aggregates solvent-free or in inert solvents (e.g.
  • the reactive compositions according to the invention are storage-stable.
  • a stable composition is considered to be a reactive composition if the viscosity does not increase more than twice as high as originally within 4 weeks at 40 ° C. The reactivity is measured comparatively. This must be given
  • the invention also provides a process for transesterification
  • the reactive composition can be used as a coating, as an adhesive or as a
  • Sealant can be used.
  • the curing temperature is between room temperature and 240 ° C, preferably between 80 ° C and 200 ° C.
  • MEK test Methyl ethyl ketone resistance test by rubbing with a cotton pad soaked in MEK with 1 kg of support until the layer is dissolved (double strokes are counted).
  • composition 1 b is fully cured: the flexibility (Erichsentiefung> 5 mm, dir. Ball impact> 80 inch * lbs) is sufficient and the
  • composition 1 is both reactive and storage stable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des compositions réactives sur la base de la transestérification contenant A1) au moins un composant ester d'acide di- ou polycarboxylique avec au moins deux ou plusieurs groupes ester, contenant au moins un alcool monofonctionnel avec une masse molaire moyenne Mn inférieure ou égale à 200 g/mole comme composant d'estérification et A2) au moins un composant diol ou polyol avec au moins deux ou plusieurs groupes OH et/ou B) au moins un composant, qui porte aussi bien des groupes ester d'acide carboxylique, contenant au moins un alcool monofonctionnel avec une masse molaire moyenne Mn inférieure ou égale à 200 g/mol comme composant d'estérification, que des groupes alcool ; et C) du triflate de bismuth comme catalyseur ; D) facultativement d'autres adjuvants.
PCT/EP2010/066608 2009-12-11 2010-11-02 Compositions réactives sur la base de la transestérification WO2011069746A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2012542420A JP2013513673A (ja) 2009-12-11 2010-11-02 トランスエステル化に基づく反応性組成物
DE112010004731T DE112010004731A5 (de) 2009-12-11 2010-11-02 Reaktive zusammensetzungen auf basis der transveresterung
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CN110997619A (zh) * 2017-08-17 2020-04-10 巴斯夫欧洲公司 连续制备丙烯酸正丁酯或丙烯酸异丁酯的方法
WO2021092789A1 (fr) * 2019-11-13 2021-05-20 Rohm And Haas Company Composition adhésive

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Publication number Priority date Publication date Assignee Title
CN110997619A (zh) * 2017-08-17 2020-04-10 巴斯夫欧洲公司 连续制备丙烯酸正丁酯或丙烯酸异丁酯的方法
CN110997619B (zh) * 2017-08-17 2023-06-27 巴斯夫欧洲公司 连续制备丙烯酸正丁酯或丙烯酸异丁酯的方法
WO2021092789A1 (fr) * 2019-11-13 2021-05-20 Rohm And Haas Company Composition adhésive
CN114630878A (zh) * 2019-11-13 2022-06-14 罗门哈斯公司 粘合剂组合物

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