WO2010091975A1 - Procédé de production d'esters d'acide cyanoacrylique - Google Patents

Procédé de production d'esters d'acide cyanoacrylique Download PDF

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Publication number
WO2010091975A1
WO2010091975A1 PCT/EP2010/051225 EP2010051225W WO2010091975A1 WO 2010091975 A1 WO2010091975 A1 WO 2010091975A1 EP 2010051225 W EP2010051225 W EP 2010051225W WO 2010091975 A1 WO2010091975 A1 WO 2010091975A1
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WO
WIPO (PCT)
Prior art keywords
formula
general formula
acid
acid ester
cyanoacrylic
Prior art date
Application number
PCT/EP2010/051225
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German (de)
English (en)
Inventor
Carsten Friese
Lars Zander
Original Assignee
Henkel Ag & Co. Kgaa
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Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2010091975A1 publication Critical patent/WO2010091975A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to a process for the preparation of cyanoacrylic acid esters.
  • the process is essentially based on a transesterification reaction, wherein the transesterification reaction is carried out in the presence of a transesterification catalyst which comprises at least one acid having a pks value ⁇ 5 and at least one metal catalyst.
  • Cyanacrylic acid ester polymerizable adhesive compositions have found wide use in both industrial and medical applications because of their ease of use, as well as the high rate of cure and strength of the resulting adhesive bond. It is known that monomeric forms of cyanoacrylates are extremely reactive and rapidly polymise in the presence of even minute amounts of a polymerization initiator, including airborne or surface moisture. The polymerization is initiated by anions, free radicals, zwitterions or ion pairs. Once the polymerization has been started, the cure speed can be very high. Polymeric adhesive compositions based on cyanoacrylic acid esters have therefore proved to be attractive solutions, for example, in the bonding of plastics, rubbers, glass, metals, wood and also biological tissues.
  • Stabilizers that prevent anionic repolymerization are usually, but not exclusively, Lewis acids, such as sulfur dioxide, nitric oxide or boron trifluoride or inorganic or organic Br ⁇ nsted acids, especially those having a pKa ⁇ 5, such as sulfuric acid, phosphoric acid or organic sulfonic acids ,
  • the very high concentration of stabilizers used in the process results in the removal of some of the stabilizer by the removal of the monomer from the reaction solution by distillation.
  • the resulting sometimes very high residual concentration of the stabilizer in the distilled Cyanacrylatmonomer leads to overstabilization, especially in low-demanding cyanoacrylic acid esters, whereby the rate of polymerization is reduced.
  • the biscyanoacrylates are obtained by reaction of 2-cyanoacrylic acid or its alkyl ester with diols, the reaction preferably being carried out in the presence of sulfonic acids as catalyst in solution.
  • the biscyanoacrylates are then isolated by fractional crystallization.
  • the aim of the present invention was therefore the development of an effective process for the preparation of mono-, bis- and / or Multicyanacyrlklaestern in high purity using as small amounts of anionic polymerization inhibitors.
  • the solution according to the invention can be found in the claims. It consists essentially in the transesterification of mono-cyanoacrylic acid esters with monohydric and / or polyhydric alcohols in the presence of a transesterification catalyst comprising at least one acid having a pks value ⁇ 5 and additionally at least one metal catalyst.
  • a transesterification catalyst comprising at least one acid having a pks value ⁇ 5 and additionally at least one metal catalyst.
  • the present invention therefore provides a process for preparing at least one cyanoacrylic acid ester of the general formula (I), comprising the steps: Formula (I) a) transesterification of at least one 2-cyanoacrylic acid ester of the general formula (II),
  • R 1 is a branched or unbranched alkyl radical having 1 to 6 C atoms, with at least one alcohol of the general formula (III)
  • Hn R formula (III) in the presence of a transesterification catalyst comprising at least one acid having a pks value ⁇ 5 and at least one metal catalyst and b) isolating the cyanoacrylic acid ester of the general formula (I) obtained in step a), where n is a is integer from 1 to 6 and R is an n-valent radical comprising 1 to 100 carbon atoms.
  • an n-valent radical R is an n-valent organic radical having 1 to 100 carbon atoms which, starting from the cyanoacrylic acid ester of the general formula (I) or alcohol of the general formula (III), is replaced by the homolytic one Cleavage of n carbon-oxygen bonds is formally formed.
  • both mono-cyanoacrylic acid esters and also higher cyanoacrylic acid esters can be prepared by the process according to the invention.
  • the cyanoacrylic acid ester of the general formula (I) is therefore prepared from monocyan cyanoacrylates of the general formula (Ia)
  • the radical R in formula (I), formula (Ia), formula (Ib), formula (Ic) and / or formula (III) comprises a C3 to Cioo chain, preferably a C 5 to C70 chain and in particular a C 10 to C 50 chain, which is interrupted by at least one oxygen atom.
  • the rest R can be linear, branched or cyclic.
  • radicals R which have at least one polyethylene glycol and / or at least one polypropylene glycol unit are preferred.
  • the radical R in formula (I), formula (Ia), formula (Ib), formula (Ic) and / or formula (III) comprises 3 to 18, in particular 4, 8, 10 and / or 12 directly connected C atoms.
  • the remainder R can likewise be linear, branched or cyclic.
  • the radical R may furthermore contain an aromatic group or, in addition to hydrogen and carbon atoms, also comprise at least one heteroatom, for example selected from halogen, oxygen and / or nitrogen atoms.
  • the alcohols used in the process according to the invention are preferably primary or secondary alcohols, primary alcohols being preferred since these have a higher reactivity in the transesterification reaction exhibit. In general, any mixtures of different alcohols can be used.
  • the alcohol of the general formula (III) used in the process according to the invention is selected in a preferred embodiment of the present invention from compounds of the general formula (IIIa) R 2 COO (CH 2 CH 2 O) m H formula (IIIa) in which R 2 CO is a linear or branched acyl radical having 12 to 22 carbon atoms and m is a number from 5 to 30 and preferably 15 to 25.
  • Typical examples are adducts of ethylene oxide with lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, for example in the pressure cracking of natural fats and oils or in the reduction of aldehydes from Roelen's oxosynthesis.
  • addition products of ethylene oxide are used to fatty acids having 16 to 18 carbon atoms.
  • Further preferred alcohols are preferably selected from methylglycol, methyldiglycol, hexanediol, octanediol, decanediol dodecanediol, glycerol and / or trimethylolpropane and / or from any desired mixtures thereof.
  • R 1 Formula (II) wherein R 1 is a branched or un branched AI kylrest having 1 to 6 carbon atoms.
  • methyl-2-cyanoacrylic acid esters or ethyl-cyanoacrylic acid esters are preferred 2-cyanoacrylic acid esters, since the alcohol methanol or ethanol formed in the transesterification reaction can be easily removed. It is also possible to use mixtures of different 2-cyanoacrylic acid esters in the process according to the invention, with mixtures of methyl-2-cyanoacrylic acid ester or ethyl-2-cyanoic acid acrylic ester being preferred.
  • the at least one 2-cyanoacrylic acid ester of the general formula (II) is preferably used in excess in the process according to the invention.
  • the molar ratio of 2-cyanoacrylic acid ester to the alcohol of the general formula (III) is preferably at least 2.0: 1, 0 ..
  • the molar ratio of 2-cyanoacrylic acid ester to the alcohol of the general formula (III) is between 2.0: 1 , 0 and 10.0: 1, 0, preferably between 2.1; : 1, 0 and 2.5: 1, 0, with a ratio of 2.2: 1, 0 being particularly preferred.
  • transesterification is carried out according to the process of the invention in the presence of a transesterification catalyst comprising at least one acid having a pks value ⁇ 5 and at least one metal catalyst.
  • the pks value of the at least one acid is determined in aqueous solution at 25.degree. C., it also being easy for the person skilled in the art to derive the pKa values of acids from the corresponding literature.
  • a compilation of different pKs values can be found, for example, in Holleman-Wiberg, Lehrbuch der anorganischen Chemie, 101st edition, pp. 237-238 and the literature cited therein.
  • Preferred acids are distinguished by a pKs value ⁇ 4, in particular by a pKs value ⁇ 3 or ⁇ 2, and particularly preferably by a pKs value ⁇ 1.
  • the technically appropriate lower limit of the pKs value of At least one acid is present at a value of -20, with particular preference being given to acids which have a pKa value> -16.
  • the acid having a pks value ⁇ 5 is a sulfonic acid of the general formula (IV)
  • R 2 is a presumptive substituted aryl group or a fluoro-substituted alkyl group.
  • R 2 in formula (IV) is a trifluoromethane group or a group of general formula (V), Formula (V) wherein R 3 represents a methyl, methoxy, ethyl, ethoxy, n-propyl, / propyl or n-butyl group, and especially a methyl group.
  • the at least one acid having a pKa value ⁇ 5 has a stabilizing effect on the cyanoacrylic acid ester produced in the process according to the invention, since the acid prevents anionic polymerization of the cyanoacrylic acid ester. If large amounts of the corresponding acid are used in the transesterification reaction, overstabilization of just less reactive cyanoacrylic acid esters can occur since complete removal of the acid from the product obtained is often difficult.
  • the at least one acid having a pks value ⁇ 5 in an amount of 0.0001 to 0, 75% by weight, preferably from 0.001 to 0.5 wt .-% and in particular from 0.01 to 0.2 wt .-%, each based on the total amount of the 2-cyanoacrylic acid ester of the general formula (II), is present.
  • the proportion of the at least one acid having a pKa value ⁇ 5, based on the total amount of the 2-cyanoacrylic acid ester of the general formula (II), should be below 0.25% by weight, in order to overstabilize the product produced in the process according to the invention avoid.
  • the transesterification catalyst used in the process according to the invention comprises, in addition to the at least one acid having a pKa ⁇ 5, at least one metal catalyst which is suitable for catalyzing the transesterification reaction.
  • Preferred metal catalysts are, for example, metal alkoxides and / or metal acetylacetonates.
  • tin catalysts In general, tin catalysts, chromium catalysts, titanium catalysts, zirconium catalysts and / or lithium catalysts and / or any desired mixtures thereof are also preferred metal catalysts in the context of the process according to the invention.
  • Suitable metal catalysts from the group of tin catalysts are dialkyltin dicarboxylates, such as dibutyltin dicarboxylates, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diisoctoate, dibutyltin maleate and mixed dibutyltin dicarboxylates, especially with longer-chain fatty acid residues, dioctyltin dicarboxylates, in particular dioctyltin dilaurate, trialkyltin alkoxides, such as.
  • dialkyltin dicarboxylates such as dibutyltin dicarboxylates, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diisoctoate, dibutyltin maleate and mixed dibutyltin dicarboxylates, especially with longer-chain fatty acid
  • tributyltin oxide For example, tributyltin oxide, monoalkyltin compounds such as Monobutylzinndihydroxychlorid and monobutyltin dioxide, tin salts such as tin acetate, tin oxalate, and tin chloride, tin oxides such.
  • monoalkyltin compounds such as Monobutylzinndihydroxychlorid and monobutyltin dioxide
  • tin salts such as tin acetate, tin oxalate, and tin chloride
  • tin oxides such.
  • titanium catalysts are monomeric and polymeric titanates and titanium chelates such as tetraisopropyl orthotitanate, tetrapropyl orthotitanate, tetraethyl orthotitanate, tetrabutyl orthotitanate, tetraisobutyl orthotitanate, 2-ethylhexyl titanate, Stearyltitanat, Kresyltitanat, titanium acetylacetonate, triethanolamine titanate, octylene glycol titanate, Isostearyltitanat, Zitronenklathylestertitanat and from the group of zirconium catalysts, zirconates and zirconium chelates such as tetrapropyl zirconate, tetraisopropyl zirconate, tetrabutyl zirconate, Triethanolaminzirkonat, Zitronen GmbH
  • dibutyltin diacetate mixed dibutyltin dicarboxylates with longer-chain fatty acid esters, dioctyltin dilaurate,
  • dibutyltin diacetate tetraisopropyl orthotitanate and / or tetraethyl orthotitanate.
  • the at least one metal catalyst is preferably present in amounts of from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight and in particular from 1 to 3% by weight, depending on the reactivity of the individual reactants and the reaction conditions selected .-%, in each case based on the total amount of the 2-cyanoacrylic acid ester of the general formula (II) used.
  • the transesterification catalyst used in the process according to the invention comprises a trifluoromethanesulfonic acid as acid with a pks value ⁇ 5 and at least one titanium catalyst as metal catalyst or consists of these components. It is particularly advantageous if the trifluoromethanesulfonic acid in an amount of 0.001 to 0.2 wt .-% and / or the titanium catalyst in an amount of 0.01 up to 3% by weight, based in each case on the total amount of 2-
  • the process according to the invention is preferably carried out in the presence of at least one radical polymerization inhibitor, the required amount of which can easily be determined by a person skilled in the art.
  • Suitable free-radical polymerization inhibitors are, for example, phenol compounds such as hydroquinone, hydroquinone monomethyl ether, butylated hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT), t-butylcatequinone, catechol and p-methoxyphenol. Mixtures of said radical polymerization inhibitors can also be used.
  • a particularly preferred radical polymerization inhibitor in the context of the present invention is butylated hydroxyanisole (BHA) and / or hydroquinone monomethyl ether.
  • the process according to the invention is preferably carried out in the presence of a gaseous acid at 22 ° C., in particular a Lewis acid, the acid being selected, for example, from sulfur dioxide and / or boron trifluoride.
  • a gaseous acid at 22 ° C. in particular a Lewis acid, the acid being selected, for example, from sulfur dioxide and / or boron trifluoride.
  • the transesterification can be carried out at atmospheric pressure, but also at reduced or overpressure from 0.001 to 200 bar.
  • the cleaved in the transesterification alcohol is preferably distilled off continuously or after completion of the reaction, wherein the reaction in a suitable solvent, such as toluene, xylene or toluene / xylene mixtures can be carried out.
  • a suitable solvent such as toluene, xylene or toluene / xylene mixtures can be carried out.
  • the process according to the invention is preferably carried out with the aid of a distillation column having a high separation efficiency.
  • the cyanoacrylic acid ester of the general formula (I) obtained by the process according to the invention can be obtained in a highly pure form, in particular by Distillation or crystallization can be isolated, with product purities of greater than 98% can be achieved.
  • the cyanoacrylate esters prepared by the present process can be used for bonding components, in particular for bonding electrical and / or electronic components, and for producing medical adhesives for treating surgically cut or traumatically torn tissue.
  • the toluene / ethanol mixture is then removed azeotropically slowly (about 17 ml). After cooling, the residue is filtered off and the eluate (about 7 ml) is diluted with the same amount of heptane. At a temperature of -2O 0 C, the biscyanoacrylate slowly precipitates as a white powder in a yield of 50%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'esters d'acide cyanoacrylique qui repose essentiellement sur une réaction de transestérification. Cette réaction de transestérification a lieu en présence d'un catalyseur de transestérification qui comprend au moins un acide de pKa ≤ 5, ainsi qu'au moins un catalyseur métallique.
PCT/EP2010/051225 2009-02-13 2010-02-02 Procédé de production d'esters d'acide cyanoacrylique WO2010091975A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200910000861 DE102009000861A1 (de) 2009-02-13 2009-02-13 Verfahren zur Herstellung von Cyanacrylsäureestern
DE102009000861.6 2009-02-13

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013036347A1 (fr) 2011-09-06 2013-03-14 Henkel Corporation Poudres métalliques revêtues d'oléfines difonctionnelles ou polyfonctionnelles déficientes en électrons pour pâtes à souder
US8486498B2 (en) 2008-11-21 2013-07-16 Henkel Corporation Thermally decomposable polymer coated metal powders
US9416091B1 (en) 2015-02-04 2016-08-16 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US9512058B2 (en) 2011-10-19 2016-12-06 Sirrus Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform
US9567475B1 (en) 2016-06-03 2017-02-14 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9617377B1 (en) 2016-06-03 2017-04-11 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9637564B2 (en) 2014-09-08 2017-05-02 Sirrus, Inc. Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions
US9657120B1 (en) 2011-09-06 2017-05-23 Henkel IP & Holding GmbH Cyanoacrylate compositions
US9790295B2 (en) 2014-09-08 2017-10-17 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US9828324B2 (en) 2010-10-20 2017-11-28 Sirrus, Inc. Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
US10196481B2 (en) 2016-06-03 2019-02-05 Sirrus, Inc. Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof
US10414839B2 (en) 2010-10-20 2019-09-17 Sirrus, Inc. Polymers including a methylene beta-ketoester and products formed therefrom
US10428177B2 (en) 2016-06-03 2019-10-01 Sirrus, Inc. Water absorbing or water soluble polymers, intermediate compounds, and methods thereof
US10501400B2 (en) 2015-02-04 2019-12-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US11555135B2 (en) 2017-05-05 2023-01-17 Henkel Ag & Co. Kgaa Cyanoacrylate compositions

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Cited By (28)

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US8486498B2 (en) 2008-11-21 2013-07-16 Henkel Corporation Thermally decomposable polymer coated metal powders
US10414839B2 (en) 2010-10-20 2019-09-17 Sirrus, Inc. Polymers including a methylene beta-ketoester and products formed therefrom
US9828324B2 (en) 2010-10-20 2017-11-28 Sirrus, Inc. Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
US9657120B1 (en) 2011-09-06 2017-05-23 Henkel IP & Holding GmbH Cyanoacrylate compositions
US9427829B2 (en) 2011-09-06 2016-08-30 Henkel IP & Holding GmbH Di- or poly-functional electron deficient olefins coated metal powders for solder paste
WO2013036347A1 (fr) 2011-09-06 2013-03-14 Henkel Corporation Poudres métalliques revêtues d'oléfines difonctionnelles ou polyfonctionnelles déficientes en électrons pour pâtes à souder
US9512058B2 (en) 2011-10-19 2016-12-06 Sirrus Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform
US9969822B2 (en) 2011-10-19 2018-05-15 Sirrus, Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom
US10308802B2 (en) 2014-09-08 2019-06-04 Sirrus, Inc. Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof
US10184073B2 (en) 2014-09-08 2019-01-22 Sirrus, Inc. Emulsion including polymers containing a 1,1-disubstituted alkene compound, adhesives, coatings, and methods thereof
US11021617B2 (en) 2014-09-08 2021-06-01 Sirrus, Inc. Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof
US9790295B2 (en) 2014-09-08 2017-10-17 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US9637564B2 (en) 2014-09-08 2017-05-02 Sirrus, Inc. Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions
US9890227B1 (en) 2014-09-08 2018-02-13 Sirrus, Inc. Compositions containing 1,1-di-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US10519257B2 (en) 2014-09-08 2019-12-31 Sirrus, Inc. Compositions containing 1,1-di-carbonyl-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US10081685B2 (en) 2014-09-08 2018-09-25 Sirrus, Inc. Emulson polymers including one or more 1,1-disubstituted alkene compounds, emulson methods, and polymer compositions
US9938223B2 (en) 2015-02-04 2018-04-10 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10501400B2 (en) 2015-02-04 2019-12-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US9416091B1 (en) 2015-02-04 2016-08-16 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10087283B2 (en) 2016-06-03 2018-10-02 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10196481B2 (en) 2016-06-03 2019-02-05 Sirrus, Inc. Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof
US9567475B1 (en) 2016-06-03 2017-02-14 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10150886B2 (en) 2016-06-03 2018-12-11 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10428177B2 (en) 2016-06-03 2019-10-01 Sirrus, Inc. Water absorbing or water soluble polymers, intermediate compounds, and methods thereof
US9718989B1 (en) 2016-06-03 2017-08-01 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9617377B1 (en) 2016-06-03 2017-04-11 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9745413B1 (en) 2016-06-03 2017-08-29 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US11555135B2 (en) 2017-05-05 2023-01-17 Henkel Ag & Co. Kgaa Cyanoacrylate compositions

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