EP2999729A1 - Verfahren zur herstellung von silangruppen-haltigen heissschmelzklebstoffen - Google Patents

Verfahren zur herstellung von silangruppen-haltigen heissschmelzklebstoffen

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Publication number
EP2999729A1
EP2999729A1 EP13802280.1A EP13802280A EP2999729A1 EP 2999729 A1 EP2999729 A1 EP 2999729A1 EP 13802280 A EP13802280 A EP 13802280A EP 2999729 A1 EP2999729 A1 EP 2999729A1
Authority
EP
European Patent Office
Prior art keywords
optionally
hydroxysilane
atoms
groups
adhesive
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.)
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Application number
EP13802280.1A
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German (de)
English (en)
French (fr)
Inventor
Urs Burckhardt
Andreas Kramer
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP13802280.1A priority Critical patent/EP2999729A1/de
Publication of EP2999729A1 publication Critical patent/EP2999729A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • the invention relates to moisture-curing hot-melt adhesives.
  • Hotmelt adhesives are solid polymer compositions at room temperature, which are melted for application and hot applied to the substrates to be bonded, which are added immediately thereafter. After application, the hot-melt adhesive, which is usually applied in a thin layer, cools rapidly, as a result of which the bond builds up strength very quickly.
  • isocyanate group-containing polyurethane hot-melt adhesives are widely used.
  • a disadvantage of these systems is that they tend to form bubbles during crosslinking, in particular in the case of amorphous polymers and at elevated humidity or temperature. The bubbles can greatly affect the aesthetic and mechanical quality as well as the resistance of the bond.
  • Another disadvantage is their content of breathable mo- monomeric isocyanates which may outgas during application and require protective measures. This leads to a higher hazard classification of the products and thus limits their applicability.
  • Silane groups are most easily introduced by reacting an isocyanate group-containing polyurethane hotmelt adhesive with an aminosilane or a mercaptosilane, as described, for example, in EP 0 202 491 and EP 1 801 138.
  • EP 0 354 472 describes STP hot-melt adhesives obtained by means of isocyanatosilanes.
  • the isocyanatosilanes used are obtained starting from mercapto or amino silanes by reaction with diisocyanates and dialcohols. In this process, the silane groups are also bonded to the polymer via urea or thiourethane groups, whereby the aforementioned difficulties persist.
  • the object of the present invention is therefore to provide a process for the preparation of a hot-melt adhesive containing silane groups, which allows a low hazard classification and in the molten state has a good thermal resistance, so does not prone to premature thickening and releases no unpleasant odors.
  • the method according to claim 1 solves this problem.
  • a hydroxysilane which is free of urea and of thiourethane groups is reacted with a solid, isocyanate group-containing polyurethane polymer at room temperature.
  • the silane-group-containing hot-melt adhesive obtainable by the process according to the invention permits a low hazard classification because, depending on the stoichiometry used, it has little or no content of monomeric isocyanates.
  • it has a good thermal resistance even with prolonged heating and does not tend to premature thickening; it can therefore be applied well and does not lead to emissions, since the silane groups are largely irreversibly tethered.
  • it crosslinks at room temperature under the influence of moisture bubble-free and leads to a visually and mechanically high-quality and durable adhesive bond.
  • hydroxysilanes The preparation and handling of hydroxysilanes has the difficulty that they tend to self-condensation due to a rapid reaction of the hydroxyl group with the silane group and therefore are often very impure and / or poor storage stability.
  • the preferred hydroxysilanes having a secondary hydroxyl group are surprisingly stable enough so that high-strength silane group-containing hot-melt adhesives are accessible.
  • the invention relates to a process for the preparation of a hot-melt adhesive containing silane groups, in which at least one isocyanate-group-containing polyurethane polymer which is solid at room temperature and has at least a hydroxysilane which is free of urea and thiourethane groups, is reacted.
  • silane or “organosilane” refers to silicon compounds which on the one hand have at least one, usually two or three, hydrolyzable substituents bonded directly to the silicon atom via Si-O bonds, and on the other hand at least one via a Si -C bond directly to the silicon atom bonded organic radical.
  • the hydrolyzable substituents are in particular alkoxy, acetoxy, ketoximato, amido or enoxy radicals.
  • silane group denotes the silicon-containing group bonded to the organic radical of a silane.
  • hydroxysilane As “hydroxysilane”, “aminosilane”, “isocyanatosilane” and the like organosilanes are referred to, which have on the organic radical a corresponding functional group, ie a hydroxyl group, amino group or isocyanate group.
  • polyurethane polymer encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process
  • polyurethane polymer also encompasses polyurethane polymers containing isocyanate groups, as obtainable from the reaction of polyisocyanates and polyols, which are themselves polyisocyanates and often also called prepolymers.
  • active hydrogen denotes the hydrogen atoms of hydroxyl, mercapto and primary and secondary amino groups.
  • molecular weight refers to the molar mass (in grams per mole) of a molecule.
  • Average molecular weight refers to the number average M n of an oligomeric or polymeric mixture of molecules, which is usually determined by GPC versus polystyrene as a standard , A dashed line in the formulas in this document represents the bond between a substituent and the associated moiety.
  • primary hydroxyl group is meant an OH group bonded to a C atom with two hydrogens, as a “secondary hydroxyl group "denotes an OH group which is bonded to a C atom with a hydrogen.
  • storage stable refers to the property of a substance or composition that it can be stored at room temperature in a suitable container for several weeks to 6 months and more, without being limited in its application or use properties by storage in a for their use relevant extent changed.
  • room temperature refers to a temperature of about 23 ° C.
  • the reaction of the isocyanate group-containing polyurethane polymer with the hydroxysilane which is solid at room temperature is advantageously carried out with exclusion of moisture and at elevated temperature, in particular at a temperature at which the polyurethane polymer
  • the reaction is preferably carried out by reacting the isocyanate group-containing polyurethane polymer and the hydroxysilane at a temperature in the range from 60 to 180 ° C., in particular from 80 to 160 ° C., hydroxyl groups of the hydroxysilane being present
  • a catalyst can be used, in particular a bismuth (III), zinc (II), zirconium (IV) or tin (II) Compound or an organotin (IV) compound.
  • the bonding of the silane groups via urethane groups has the great advantage that the hot-melt adhesive obtained has a very good thermal resistance both in the non-crosslinked and in the crosslinked state.
  • the thermal stability of the uncrosslinked adhesive is important for its good applicability.
  • Hot-melt adhesives whose silane groups are bonded to the polymer via urea or thiourethane groups show weaknesses here.
  • the thiourethane group is thermal easily fissile, releasing sulfur-containing substances that cause odor emissions.
  • instability is observed which, presumably due to catalytic processes, leads to excessive thickening until gelation of the adhesive in the molten state.
  • the polyurethane polymer and the hydroxysilane are used in such an amount that the OH groups of the hydroxysilane are substoichiometrically present in relation to the isocyanate groups of the polyurethane polymer, that is, the OH / NCO ratio is less than 1.
  • a hot-melt adhesive containing silane groups is obtained, which additionally has isocyanate groups.
  • both the silane and the isocyanate groups contribute to crosslinking under the influence of moisture.
  • Such a hotmelt adhesive has a significantly reduced content of monomeric isocyanates compared to the isocyanate group-containing polyurethane polymer which was used for the method described.
  • Such a hotmelt adhesive has, in particular, a content of monomeric isocyanates of ⁇ 2% by weight, in particular ⁇ 1% by weight.
  • such a hotmelt adhesive has in particular a content of monomeric MDI of ⁇ 1% by weight, or a content of monomeric IPDI of ⁇ 2% by weight, in particular ⁇ 0.5% by weight, where the abbreviation "MDI” stands for " 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers ", and the abbreviation” IPDI “stands for” isophorone diisoyanate ".
  • the polyurethane polymer and the hydroxysilane are used in such an amount that the OH groups of the hydroxysilane are at least stoichiometrically present in relation to the isocyanate groups of the polyurethane polymer
  • OH / NCO ratio is therefore at least 1.
  • This implementation will be a Silane group-containing hotmelt adhesive which is free of isocyanate groups.
  • Such an isocyanate group-free hot-melt adhesive is particularly advantageous from a toxicological point of view.
  • An isocyanate group-free hotmelt adhesive is accordingly also free of monomeric isocyanates.
  • Preferred is an OH / NCO ratio in the range of 1 to 2, particularly preferably 1 to 1 .8, in particular 1 to 1 .5.
  • At least one isocyanate group-containing polyurethane polymer which is solid at room temperature is used.
  • This may be crystalline, partially crystalline or amorphous at room temperature.
  • a partially crystalline or amorphous polyurethane polymer is valid that it is not or only slightly flowable at room temperature. This means in particular that it has a viscosity of more than 5 ⁇ 00 Pa s at 20 ° C.
  • the isocyanate group-containing polyurethane polymer preferably has an average molecular weight M n in the range from 2 ⁇ 00 to 20 ⁇ 00 g / mol, preferably 2 ⁇ 00 to 15 ⁇ 00 g / mol, in particular 2 ⁇ 00 to 10 ⁇ 00 g / mol.
  • the isocyanate group-containing polyurethane polymer 1 to 3, more preferably 2, isocyanate groups per molecule.
  • Such a polyurethane polymer allows a suitable processing viscosity and in the crosslinked state good mechanical properties.
  • a suitable isocyanate group-containing polyurethane polymer which is solid at room temperature is obtained, in particular, by the reaction of at least one polyol with at least one diisocyanate, the diisocyanate being present in a stoichiometric excess.
  • the reaction is advantageously carried out at elevated temperature, in particular at a temperature at which the polyols, diisocyanates and polyurethane polymer used are present in liquid form.
  • a suitable catalyst is present.
  • a residual content of unreacted monomeric diisocyanates remains in the resulting polymer due to the statistical distribution of the possible reaction products.
  • monomeric diisocyanates also referred to for short as “monomeric isocyanates”
  • polyols which are solid at room temperature.
  • Amorphous or partially crystalline or crystalline polyols in particular polyester polyols and polycarbonate polyols, are particularly suitable at room temperature.
  • Suitable polyester polyols are, in particular, those which are prepared from dihydric to trihydric, preferably dihydric, alcohols, such as, in particular, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1 , 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, glycerol, 1, 1, 1-trimethylolpropane or mixtures of the abovementioned alcohols, with organic dicarboxylic acids or their anhydrides or esters, in particular succinic acid, glutaric acid, adipic acid, suberic acid , Sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the abovementioned acids, as well as
  • polyester polyols are polyester polyols of adipic acid, sebacic acid or dodecanedicarboxylic acid as dicarboxylic acid and of hexanediol or neopentyl glycol as dihydric alcohol.
  • the polyesterpolyols preferably have an average molecular weight M n in the range from 1'500 to 15 ⁇ 00 g / mol, preferably 1'500 to 8000 g / mol, in particular 2 ⁇ 00 to 5'500 g / mol.
  • Particularly suitable crystalline or partially crystalline polyester polyols are adipic acid / hexanediol polyester and dodecanedicarboxylic acid / hexanediol polyester.
  • Suitable polycarbonate polyols are those which, in particular, are used by reacting the abovementioned ones - used to prepare the polyesterpolyols - Alcohols are accessible with dialkyl carbonates, diaryl carbonates or phosgene.
  • Preferred as a polyol is a mixture of at least one amorphous polyester estiol and at least one further polyester diol.
  • polyol particularly preferred as polyol are mixtures of amorphous and / or crystalline and / or partially crystalline polyester diols.
  • the polyol is a mixture of an amorphous and a polyester diol which is liquid at room temperature.
  • transparent adhesives can be produced.
  • the polyol is a crystalline or a partially crystalline polyester diol.
  • diisocyanates are commercially available aliphatic, cycloaliphatic, arylaliphatic and aromatic, preferably cycloaliphatic and aromatic, diisocyanates.
  • the diisocyanate is particularly preferably selected from the group consisting of IPDI, MDI and TDI. These diisocyanates are particularly easy to obtain.
  • Hotmelt adhesives based thereon have particularly good mechanical properties and rapid crosslinking.
  • Hot-melt adhesives based thereon have a particularly good light stability and stability to discoloration on. This is particularly advantageous for the bonding of transparent substrates.
  • At least one hydroxysilane which is free of urea and thiourethane groups, is furthermore used.
  • the difficulty in the preparation and storage of hydroxysilanes is basically that a hydroxyl group can react with a silane group to release a hydrolyzable group ("self-condensation"), which is principally possible both intramolecular and intermolecular, with either cyclic silanes or higher condensed or oligomeric silane compounds having a plurality of silicon atoms, such impurities may already be formed during the preparation of hydroxysilanes or during storage.
  • the hydroxysilane preferably has two or three hydrolyzable substituents on the silicon atom, preferably two or three alkoxy groups, in particular ethoxy or methoxy groups.
  • the hydroxysilane particularly preferably has two or three, in particular three, ethoxy groups. Ethoxy-containing hydroxysilanes are particularly stable to self-condensation.
  • the hydroxysilane is preferably a hydroxysilane which contains a secondary hydroxyl group. Surprisingly, these hydroxysilanes are stable enough, so that high-strength silane-containing hotmelt adhesives are obtained.
  • a hydroxysilane of the formula (I) is used
  • A is either a divalent aliphatic or cycloaliphatic hydrocarbon radical having 2 to 30 carbon atoms, optionally with aromatic moieties and optionally with one or more heteroatoms which is free of active hydrogen, or together with B-CH, a divalent cycloaliphatic hydrocarbon radical having 6 to 20 carbon atoms, optionally with aromatic moieties and optionally with one or more heteroatoms which is free of active hydrogen;
  • B is a monovalent aliphatic or cycloaliphatic hydrocarbon radical having 1 to 12 C atoms, optionally with one or more heteroatoms which is free of active hydrogen,
  • CH-A is a divalent cycloaliphatic hydrocarbon radical having 6 to 20 C atoms, optionally with one or more heteroatoms which is free of active hydrogen;
  • R 4 is an alkyl group having 1 to 8 C atoms
  • R 5 is an alkyl group having 1 to 10 C atoms, optionally with one or more ether oxygens;
  • x stands for 0 or 1 or 2.
  • the hydroxysilane of the formula (I) has a secondary hydroxyl group and is particularly advantageous in the use according to the invention, since it can be prepared in high purity and has good storage stability and thus enables very clean functionalization of the isocyanate group-containing polyurethane polymer with silane groups, whereby a silane group-containing hot melt adhesive with high strength is available.
  • A is either a divalent aliphatic or cycloaliphatic hydrocarbon radical having 4 to 30 carbon atoms, which optionally contains ether oxygen, a tertiary amino group, an amido group or a urethane group, or together with B-CH for a divalent cycloaliphatic Hydrocarbon radical having 6 to 20 carbon atoms, which optionally contains ether groups and / or tertiary amino groups.
  • B is preferably an alkyl group having 1 to 12 C atoms, which optionally contains ether groups and / or tertiary amino groups, or together with CH-A is a divalent cycloaliphatic hydrocarbon radical having 6 to 20 C atoms, which optionally contains ether groups and / or tertiary amino groups.
  • R 4 is an alkyl group having 1 to 4 carbon atoms, in particular methyl.
  • R 5 is an alkyl group having 1 to 4 carbon atoms, in particular methyl or ethyl.
  • Hydroxysilanes having these preferred radicals A, B, R 4 and R 5 are particularly readily available.
  • R 5 is in particular a methyl group. This silane-containing hot melt adhesives are accessible with particularly fast networking with moisture.
  • R 5 is in particular an ethyl group.
  • This silane-containing hot melt adhesives are accessible, which do not split off methanol when crosslinked with moisture, which is advantageous for toxicological reasons.
  • x is 1 or 0, in particular 0.
  • hot-melt adhesives are accessible with these hydroxysilanes which, on contact with moisture, crosslink particularly rapidly and have particularly good mechanical properties.
  • the hydroxysilane of the formula (I) is preferably a hydroxysilane which was not obtained from the addition of an aminosilane to a methyl-substituted cyclic carbonate, in particular propylene carbonate.
  • This addition is not very selective, with the result that the reaction product contains a relatively high content of hydroxysilane with primary OH group in addition to the secondary OH group hydroxysilane.
  • a complex purification of the reaction product is necessary and / or the storage stability and purity of the silane is greatly reduced, whereby the strength of the resulting hot melt adhesive in the crosslinked state is only mediocre.
  • a suitable hydroxysilane of formula (I) is a hydroxysilane having a tertiary amino group.
  • Such hydroxysilanes are particularly obtainable from the reaction of at least one epoxysilane with at least one secondary amine.
  • a hydroxysilane having a tertiary amino group especially suitable for reaction with a polyurethane polymer based on aliphatic isocyanates, in particular IPDI.
  • Hotmelt adhesives derived therefrom have a good thermal stability in the undiluted state and good light stability.
  • a preferred hydroxysilane having a tertiary amino group is a hydroxysilane of the formula (I a)
  • R ' is hydrogen and R "is a radical of formula (II);
  • R 1a and R 2a either individually each represent an alkyl radical having 1 to 12 C atoms, which optionally has heteroatoms in the form of ether oxygen, thio ether sulfur or tertiary amine nitrogen, or together for an alkylene radical having 2 to 12 C atoms, which optionally hetero atoms in the form of ether oxygen, thioether sulfur or tertiary amine nitrogen, are;
  • R 3a is a linear or branched alkylene or cycloalkylene radical having 1 to 20 C atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms;
  • R 4 , R 5 and x have the meanings already mentioned.
  • the hydroxysilane of the formula (I a) corresponds to either the formula (I a ') or the formula (I a ").
  • R 1a , R 2a , R 3a , R 4 , R 5 and x have the meanings already mentioned.
  • R 1a and R 2a are preferred
  • an alkylene radical having 4 to 8 C atoms which in particular has a heteroatom in the form of ether oxygen, thioether sulfur or tertiary amine nitrogen and form a 5 or 6 or 7 with the inclusion of the nitrogen atom Ring, in particular a 5- or 6-ring.
  • R 1a and R 2a are particularly preferred
  • Ethoxypropyl 2- (2-methoxyethoxy) ethyl, 2-octyloxyethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 2-ethylhexyl, or N, N-dimethylaminopropyl,
  • nitrogen atom for a, optionally substituted, pyrrolidine, piperidine, hexamethyleneimine, morpholine, thiomorpholine or 4-methylpiperazine ring.
  • R 1a and R 2a each individually represent 2-methoxyethyl, butyl or isopropyl, or together with the inclusion of the nitrogen atom for morpholine, 2,6-dimethylmorpholine, thiomorpholine, pyrrolidine or 4-methylpiperazine.
  • R 1a and R 2a are inclusive of the nitrogen atom for morpholine or pyrrolidine. These hydroxysilanes can be produced in a particularly pure quality and are particularly stable on storage. They allow silane-containing hotmelt adhesives of high strength.
  • R 3a is preferably a linear or branched alkylene radical having 1 to 6 C atoms, particularly preferably a 1, 2-ethylene radical.
  • a preferred hydroxysilane of the formula (Ia) is in particular selected from the group consisting of 2-bis (2-methoxyethyl) amino-4- (2-triethoxysilyl-ethyl) cyclohexan-1-ol, 2-dibutylamino-4- (2 triethoxysilylethyl) cyclohexan-1-ol, 2-diisopropylamino-4- (2-triethoxysilylethyl) cyclohexan-1-ol, 2-morpholino-4- (2-triethoxysilylethyl) cyclohexan-1-ol, 2- (2,6- Dimethylmorpholino) -4- (2-triethoxysilylethyl) cyclohexan-1-ol, 2-thiomorpholino-4- (2-triethoxysilylethyl) cyclohexan-1-ol, 2-pyrrolidino-4- (2-triethoxysilylethyl
  • 2-morpholino-4- (2-trimethoxysilylethyl) cyclohexan-1-ol 2-morpholino-4- (2-triethoxysilylethyl) cyclohexan-1-ol
  • hot-melt adhesives containing silane groups having good processing viscosity and good storage stability are obtained, which cure with moisture quickly to crosslinked adhesives of high strength.
  • each case is a mixture of the two molecules in which the silane radical is in the 4- and 5-position.
  • Such mixtures are also represented by the notation "4 (5)".
  • a hydroxysilane of the formula (Ia) is reacted with a polyurethane polymer having aliphatic isocyanate groups.
  • the resulting hot Melt adhesives have a good thermal stability in the uncrosslinked state and good light stability.
  • Another preferred hydroxysilane having a tertiary amino group is a hydroxysilane of the formula (I b)
  • R 1b and R 2b either individually each represent an alkyl radical having 1 to 12 C atoms, which optionally has heteroatoms in the form of ether oxygen, thio ether sulfur or tertiary amine nitrogen, or together for an alkylene radical having 2 to 12 C atoms optionally having heteroatoms in the form of ether oxygen, thioether sulfur or tertiary amine nitrogen;
  • R 3b is a linear or branched alkylene or cycloalkylene radical with 1 to
  • R 4 , R 5 and x have the meanings already mentioned.
  • R 1b and R 2b are preferred
  • alkylene radical having 4 to 8 C atoms which in particular has a heteroatom in the form of ether oxygen, thioether sulfur or tertiary amine nitrogen, forming a 5- or 6- or 7-ring with the inclusion of the nitrogen atom, in particular a 5 or 6 ring.
  • R 1b and R 2b are particularly preferred
  • R 1b and R 2b are each individually 2-methoxy-ethyl, butyl or isopropyl, or together with the inclusion of the nitrogen atom for morpholine, 2,6-dimethylmorpholine, thiomorpholine, pyrrolidine or 4-methylpiperazine.
  • R 1b and R 2b are inclusive of the nitrogen atom for morpholine or pyrrolidine.
  • hydroxysilanes can be produced in a particularly pure quality and are particularly stable on storage. They allow silane-containing hotmelt adhesives of high strength.
  • R 3b is preferably a linear or branched alkylene radical having 1 to 6 C atoms, in particular a 1, 3-propylene radical. These hydroxysilanes are particularly accessible.
  • a preferred hydroxysilane of the formula (I b) is in particular selected from the group consisting of 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol, 1- (2,6-dimethylmorpholino) -3 (3- (triethoxysilyl) propoxy) propan-2-ol, bis (2-methoxyethyl) amino-3- (3- (triethoxysilyl) propoxy) propan-2-ol, 1-pyrrolino-dino-3- (3- (triethoxysilyl) propoxy) propan-2-ol, 1-piperidino-3- (3- (triethoxysilyl) propoxy) propan-2-ol, 1- (2-methylpiperidino) -3- (3- (triethoxysilyl) propoxy) Propan-2-ol, dibutylamino-3- (3- (triethoxysilyl) propoxy) propan-2-ol, diisopropylamino-3- (3
  • 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol preferred is 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.
  • hot-melt adhesives containing silane groups having a low processing viscosity and good storage stability are obtained, which cure with moisture rapidly to crosslinked adhesives, which have good mechanical properties.
  • a hydroxysilane of formula (I b) is reacted with a polyurethane polymer having aliphatic isocyanate groups.
  • the hotmelt adhesives obtained in this way have good thermal stability in the uncrosslinked state and good light stability.
  • hydroxysilane of the formula (I) is a hydroxysilane which is free of tertiary amino groups. These hydroxysilanes are particularly suitable for reaction with a polyurethane polymer based on very reactive aromatic isocyanates, in particular MDI. Hot-melt adhesives derived therefrom have good thermal stability in the uncrosslinked state and particularly good mechanical properties.
  • Such hydroxysilane in one embodiment is a hydroxysilane having a urethane group. Such is obtained in particular from the reaction of at least one isocyanatosilane with at least one diol, in particular a diol having at least one secondary hydroxyl group.
  • reaction products of isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane and diols such as 1, 2- or 1, 3-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, 2-ethyl-1, 3-hexanediol or 2,2,4-trimethyl-1,3-pentanediol in a molar ratio of about 1: 1.
  • a suitable hydroxysilane of the formula (I) which is free of tertiary amino groups is furthermore a hydroxysilane having an amido group.
  • Such is obtained, in particular, from the reaction of at least one amino silane with at least one lactone, in particular with a lactone substituted in alpha position relative to the ring oxygen.
  • a preferred hydroxysilane having an amido group is a hydroxysilane of the formula (I c)
  • R 1c is an alkyl group having 1 to 12 C atoms
  • R 2c is a hydrogen atom or an alkyl group having 1 to 12 C atoms, which optionally has ether oxygen or amine nitrogen;
  • R 3c is a linear or branched alkylene or cycloalkylene radical having 1 to 20 C atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms;
  • n 2 or 3 or 4;
  • R 4 , R 5 and x have the meanings already mentioned.
  • R 1c preferably represents a linear alkyl group having 1 to 8 C atoms, in particular methyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.
  • R 2c is preferably a hydrogen atom.
  • N is preferably 2 or 3, in particular 2.
  • hydroxysilanes can be produced in a particularly pure quality and are particularly stable on storage. They enable high-strength silane-containing hotmelt adhesives with particularly good thermal stability in the un-wetted state, in particular also those based on aromatic isocyanates, in particular MDI.
  • R 3c is preferably a linear or branched alkylene radical having 1 to 6 C atoms; in particular a radical selected from the group consisting of 1, 3-propylene, 2-methyl-1, 3-propylene, 1, 4-butylene, 3-methyl-1, 4-butylene and 3,3-dimethyl-1, 4-butylene, preferably for 1, 3-propylene and 3,3-dimethyl-1, 4-butylene, in particular for 1, 3-propylene.
  • hydroxysilanes are particularly accessible.
  • a preferred hydroxysilane of the formula (Ic) is in particular selected from the group consisting of N- (3-triethoxysilylpropyl) -4-hydroxypentanamide, N- (3-triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -4 -hydroxynonanamide, N- (3-triethoxysilylpropyl) -4-hydroxydecanamide, N- (3-triethoxysilylpropyl) -4-hydroxyundecanamide, N- (3-triethoxysilylpropyl) -4-hydroxydoamide decanamide, N- (3-triethoxysilylpropyl) -5-hydroxyhexanannide, N- (3-triethoxysilylpropyl) -5-hydroxynonanamide, N- (3-triethoxysilylpropyl) -5-hydroxydecaneamide, N- (3-triethoxysily
  • N- (3-triethoxysilylpropyl) -4-hydroxypentanamide N- (3-triethoxysilylpropyl) -4-hydroxyoctanamide.
  • hot-melt adhesives containing silane groups having good storage stability are obtained, which in the uncrosslinked state have good thermal stability-also in the case of hot-melt adhesives based on aromatic isocyanates-curing adhesives which are rapidly crosslinked with moisture and have good mechanical properties.
  • Particularly preferred in the process described are the hydroxysilanes of the formula (Ia). These hydroxysilanes are particularly storage-stable, which simplifies their handling in the process described.
  • hydroxysilanes of the formula (I c) are the hydroxysilanes of the formula (I c). They allow hot-melt adhesives based on aromatic isocyanates containing silane groups with good thermal stability in the uncrosslinked state.
  • the silane-containing hotmelt adhesive obtained by the process described may contain further constituents, in particular the following auxiliaries and additives:
  • crosslinkable polymers in particular silane groups and / or isocyanate groups having polymers
  • Non-reactive thermoplastic polymers in particular homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylate, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymers (EVA) and atactic poly (a) Olefins (APAO); furthermore polyesters, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, polyimides, polyamides, polyvinyl chlorides, polysiloxanes, polyurethanes, polystyrenes, and combinations thereof, in particular polyetheramide copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-
  • Tackifier resins in particular a hydrocarbon resin, in particular coumarone-indene resins, terpene resins, phenol-modified terpene resins, natural, optionally modified, resins, in particular rosin, root resin or tall oil resin, furthermore a-methyl-styrene resins and polymeric lactic acid;
  • Plasticizers especially carboxylic acid esters such as phthalates or adipates, polyols, organic phosphoric and sulfonic acid esters or polybutenes;
  • Catalysts for the crosslinking reactions in particular metal catalysts and / or nitrogen-containing compounds, in particular organotin compounds, organotitanates, amines, amidines, guanidines and imidazoles; Stabilizers against oxidation, heat, hydrolysis, light and UV radiation, biocides, fungicides and flame retardants;
  • Desiccants in particular tetraethoxysilane, vinyltrimethoxy- or vinyltriethoxysilane and organoalkoxysilanes which have a functional group in the ⁇ -position relative to the silane group, in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, methoxy methylsilanes, orthoformic acid esters, as well as calcium oxide or molecular sieves;
  • Adhesion promoters and / or crosslinkers in particular silanes, such as aminosilanes, mercaptosilanes, epoxysilanes, (meth) acrylosilanes, anhydridosilanes, carbamosilanes, alkylsilanes and iminosilanes;
  • inorganic and organic fillers in particular mineral fillers, molecular sieves, silicic acids including highly dispersed silicas from pyrolysis processes, industrially produced carbon black, graphite, metal powder, PVC powder or hollow spheres; - dyes;
  • auxiliaries and additives can already be present before carrying out the described process, in particular as a constituent of the isocyanate group-containing polyurethane polymer which is solid at room temperature. However, such auxiliaries and additives can also be added to the resulting hot-melt adhesive containing silane groups only after carrying out the process described.
  • the silane group-containing hot-melt adhesive preferably has a content of room-temperature-stable silane-containing polyurethane polymer in the range of 5 to 100% by weight, in particular 15 to 95% by weight, particularly preferably 30 to 90% by weight, most preferably 50 to 80 Weight%, up.
  • the silane group-containing hot-melt adhesive preferably contains at least one further polymer selected from the group consisting of non-reactive thermoplastic polymers and tackifier resins.
  • the silane-group-containing hot-melt adhesive preferably has a content of polymers including the room temperature silane-containing polyurethane polymer in the range of 70 to 100% by weight, particularly preferably 80 to 100% by weight, in particular 90 to 100% by weight.
  • the silane-containing hotmelt adhesive is in a preferred embodiment free of organotin compounds. This can be advantageous for ecological and / or toxicological reasons.
  • the silane group-containing hotmelt adhesive does not release methanol when it is crosslinked in a further preferred embodiment. This can be advantageous for ecological and / or toxicological reasons.
  • the silane group-containing hotmelt adhesive contains an isocyanate- as well as silane-containing polyurethane polymer.
  • Such a hot-melt adhesive contains a significantly reduced content of monomeric isocyanates in comparison to prior to carrying out the method described. This is advantageous for toxicological reasons.
  • the silane group-containing hotmelt adhesive is finally free of isocyanates.
  • Such a hotmelt adhesive is particularly advantageous for toxicological reasons.
  • the silane-containing hotmelt adhesive is very stable in storage, excluding moisture. It may be stored in a suitable package or arrangement for a period of several months to a year and longer before being used.
  • silane groups Upon contact with moisture, the silane groups hydrolyze, eventually leading to crosslinking of the adhesive.
  • silanol groups can condense with, for example, hydroxyl groups of the substrate to which the adhesive is applied, whereby an additional improvement in the adhesion of the adhesive to the substrate can take place during crosslinking.
  • the hotmelt adhesive contains not only the silane groups but also isocyanate groups, these also react with moisture, which additionally contributes to crosslinking of the adhesive.
  • the moisture needed for crosslinking can either come from the air (humidity), or the adhesive can be contacted with a component containing water, for example by painting or spraying.
  • the silane-containing hotmelt adhesive is applied to at least one substrate when applied in the liquid state.
  • the adhesive is previously heated at least to the extent that it is liquid.
  • the application of the adhesive typically takes place at a temperature in the range from 80 to 200.degree. C., in particular from 100 to 180.degree.
  • the uncrosslinked adhesive has good thermal resistance. This manifests itself in the fact that the adhesive can be left in a liquid hot state for a sufficient time for the proper application, in particular for up to several hours, without its viscosity rising excessively, in particular without gelling, and without Odor immissions occur.
  • the applied adhesive is advantageously added to a second substrate to a bond before it is excessively solidified by cooling.
  • the solidification of the adhesive by cooling causes a very fast strength build-up and a high initial adhesion strength of the bond.
  • the crosslinking takes place in the adhesive, even after solidification, via silane groups and optionally isocyanate groups by means of moisture, as described above. This chemical crosslinking finally leads to a cured crosslinked adhesive, which can not be remelted by renewed heating to the application temperature.
  • Preferred substrates which can be adhered to the silane-containing hotmelt adhesive from the process described are - glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble;
  • Metals and alloys such as aluminum, iron, steel and non-ferrous metals, as well as surface-treated metals and alloys, such as galvanized or chromium-plated metals;
  • resins for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites and other so-called polymer composites;
  • Plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA), epoxy resins, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) and ethylene / propylene / diene terpolymers (EPDM), as well as fiber-reinforced plastics such as Carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GRP) and
  • Sheet molding compounds wherein the plastics may preferably be surface treated by means of plasma, corona or flame;
  • coated substrates such as powder-coated metals or alloys
  • plastics particularly preferred are plastics, textiles, leather, wood, wood-based materials, polymer composites, paper, metals, paints and varnishes.
  • the substrates may be pretreated prior to application of the adhesive, for example by physical and / or chemical cleaning or by the application of an adhesion promoter, a primer solution or a primer.
  • Two similar substrates or two different substrates can be bonded.
  • the adhesive is either applied to one of the two substrates and joined with the other to a bond, or it can be applied to both substrates to be bonded.
  • silane-containing hotmelt adhesive from the process described can be used in particular for construction and industrial applications, in particular as laminating adhesive, laminate adhesive, packaging adhesive, textile adhesive or wood adhesive. It is particularly suitable for adhesions in which the bonding site is visible, in particular for gluing glass, for example in vehicle and window construction, as well as for gluing transparent packaging.
  • silane-containing hotmelt adhesive From the use of the silane-containing hotmelt adhesive from the described method results in an article.
  • Preferred articles are automotive interior trim parts such as in particular headliner, sun visor, instrument panel, door side panel, parcel shelf and the like, wood fiber materials from the shower and bathing area, furniture decorative films, membrane films with textiles such as in particular cotton, polyester films in the clothing sector, composites of textiles and foams for car equipment, as well as transparent packaging.
  • the silane-containing hot-melt adhesive obtained from the process described has a number of advantages.
  • standard climate refers to a temperature of 23 + 1 ° C and a relative humidity of 50 + 5%.
  • Viscosities were determined on a Rheostec RC30 thermostated plate-plate viscometer (plate diameter 25 mm, distance 1 mm, shear rate 10 s -1 ) at a temperature of 160 ° C.
  • a mixture of 1 '200.0 g solid at room temperature, amorphous polyester estiol (Dynacoll ® 7150 from Evonik, OH number 43 mg KOH / g) and 1' 200.0 g at room temperature liquid polyester diol (Dynacoll ® 7250 from Evonik, OH number 22 mg KOH / g) was dried for 2 h at 120 ° C under vacuum and degassed, then 348.4 g of 4,4'-methylene diphenyl diisocyanate (Desmodur ® 44 MC L from Bayer), stirred for 2 h at 130 ° C under vacuum and then cooled and stored in the absence of moisture.
  • the polyurethane polymer obtained was solid at room temperature and had a content of free isocyanate groups of 2.15% by weight.
  • the hotmelt adhesive K-1 is free of isocyanate groups.
  • the hot-melt adhesive K-2 contains not only the silane groups but also isocyanate groups.
  • the content of monomeric isocyanate was determined by HPLC.
  • the polymer P1 contained 2.60% by weight of 4,4'-methylene diphenyl diisocyanate.
  • the hot-melt adhesive K-2 contained 0.63% by weight of 4,4'-methylene diphenyl diisocyanate, ie a significantly reduced content.
  • Table 1 Viscosity of the novel hot-melt adhesives K-1 and K-2 and Comparative Adhesive Ref-1.
  • Table 2 Mechanical properties of the novel hotmelt adhesives K-1 and K-2 and of the polymer P1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP13802280.1A 2013-05-22 2013-11-25 Verfahren zur herstellung von silangruppen-haltigen heissschmelzklebstoffen Withdrawn EP2999729A1 (de)

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PL3067377T3 (pl) * 2015-03-12 2023-05-02 Henkel Ag & Co. Kgaa Poliuretany o bardzo niskiej zawartości monomeru
EP3448771B1 (en) * 2016-04-28 2020-08-26 H. B. Fuller Company Pallet with stacked packages
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