Solvent for aromatic carboxylic acids or sulfonic acids

Abstract

The present invention relates to the use of at least one polyether having blocked hydroxyl groups as a solvent for at least one aromatic carboxylic or sulfonic acid, and to solutions obtained therefrom. The blocked polyether is not volatile and exhibits surprisingly high dissolving power for aromatic carboxylic or sulfonic acids. The acid solution is highly compatible in curable compositions and does not cause any emissions, odors, or migration effects. The acid solution is particularly suitable as a component of polyurethane compositions containing latent curing agents to promote hydrolysis of the latent reactive groups.

Description

Technical Field

[0001] The present invention relates to solvents for aromatic carboxylic acids or sulfonic acids, acid solutions obtained therefrom, and curable compositions containing them, particularly polyurethane compositions.

Background Art

[0002] Aromatic carboxylic acids or sulfonic acids are often used, for example, as catalysts for polymer compositions based on polyurethanes or epoxy resins. These acids are often high-melting solids that must be dissolved for use in polymer compositions. However, conventional solvents are volatile, flammable, often toxic, cause VOC emissions, shrinkage, and odors during use, and often require labor safety measures, so their use is increasingly avoided. Instead, it is possible to use glycols or polyols as non-volatile solvents. However, these are very hydrophilic due to their hydroxyl group components and are not compatible with many polymer compositions. The non-volatile solvents used can also be plasticizers, such as phthalic esters or adipic esters, such as diisodecyl phthalate (DIDP) or di(2-ethylhexyl) adipate (DOA). However, most plasticizers have insufficient acid-dissolving ability. This means that only very dilute solutions can be obtained, or the solution needs to be constantly heated to prevent acid crystallization. In addition, plasticizers can further impart drawbacks such as clouding or migration effects, such as leaching or bleeding, to the polymer composition.

[0003] From the above, there is a need for a solvent that has a high dissolving ability for aromatic carboxylic acids or sulfonic acids, is non-volatile and non-toxic, and is particularly suitable for use in polymer compositions.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Accordingly, an object of the present invention is to provide a solvent for aromatic carboxylic acids or sulfonic acids that overcomes the drawbacks of the prior art with respect to dissolution ability, volatility, and compatibility with polymer compositions.

Means for Solving the Problems

[0005] This object is achieved by using at least one polyether having a blocked hydroxyl group as described in claim 1. The polyether having a blocked hydroxyl group exhibits a surprisingly high dissolution ability for aromatic carboxylic acids or sulfonic acids despite its polymer structure, is highly non-volatile, and is non-toxic. This enables a highly concentrated acid solution that is surprisingly mobile and can be used for a long time without heating and without crystallization or precipitation of the acid. Therefore, such an acid solution can be easily manufactured, transported, and stored. These have excellent compatibility with polymer compositions, particularly polyurethane compositions, and have very good compatibility even with isocyanate groups and do not cause migration or clouding. These are only possible with a small absolute amount of solution in the case of a normal dispensing system, and therefore a high acid concentration is required to ensure the addition of a sufficient amount of acid. For example, in filling a cartridge or a tubular bag, it is particularly advantageous when the acid solution is metered only during the dispensing process of the composition.

[0006] Particularly advantageously, the acid solution of the present invention is used in a one-component moisture-curing polyurethane composition containing isocyanate groups and a latent curing agent such as an aldimine or an oxazolidine. Aromatic carboxylic acids or sulfonic acids function here as catalysts for the hydrolysis of the latent curing agent. Such compositions cure without swelling, without generating odor under the influence of moisture, and show few defects related to migration such as leaching or bleeding after curing, and are particularly suitable as adhesives, sealants or coatings. In the prior art, di(2-ethylhexyl) adipate (DOA) is typically used as a solvent for aromatic carboxylic acids or sulfonic acids in such compositions. However, this can only achieve very dilute solutions, and DOA tends to have a migration effect.

[0007] An additional aspect of the present invention is the subject matter of another independent claim. Particularly preferred embodiments of the present invention are the subject matter of the dependent claims.

Embodiments for Carrying Out the Invention

[0008] The present invention provides the use of at least one polyether having blocked hydroxyl groups as a solvent for at least one aromatic carboxylic acid or sulfonic acid.

[0009] "Polyether" refers to a molecule mainly composed of alkyleneoxy repeating units or a group of oligomeric and / or polymeric molecules.

[0010] "Blocked hydroxyl group" refers to a hydroxyl group that has been converted into a group non-reactive to isocyanate groups by a chemical reaction.

[0011] "Molecular weight" refers to the molar mass (g / mol) of a molecule or a molecular residue. "Average molecular weight" refers to the number average molecular weight Mn of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. n This is typically determined by gel permeation chromatography (GPC) relative to polystyrene as a standard.

[0012] "Aromatic" refers to an acid or isocyanate in which its acid or isocyanate group is directly bonded to an aromatic carbon atom.

[0013] "Curable composition" refers to a composition containing a polymerizable polymer, which can be cured through the crosslinking reaction of its reactive groups or can obtain a state with increased mechanical strength.

[0014] "Plasticizer" refers to a non-volatile substance that is not chemically incorporated into the polymer and exhibits a plasticizing effect on it, reducing the viscosity of the polymer.

[0015] Substance names starting with "poly", such as polyamine, polyol, or polyisocyanate, formally refer to substances containing two or more functional groups in one molecule.

[0016] A curable composition called "storage stability" or "storable" can be stored in a suitable container at room temperature for a long time, typically at least 3 to 6 months or more, without its use or use characteristics being changed within the scope related to its use by this storage.

[0017] "Primary amino group" refers to an amino group bonded to a single organic group and having two hydrogen atoms; "secondary amino group" refers to an amino group bonded to two organic groups that can together form part of a ring and having one hydrogen atom; "tertiary amino group" refers to an amino group bonded to three organic groups where two or three of them can be part of one or more rings and having no hydrogen atom.

[0018] "One-component type" composition refers to a curable composition in which all components of the composition are mixed and stored together in the same container and cured by moisture.

[0019] The "two - liquid type (two - component type)" composition refers to a curable composition in which the components of the composition are stored in separate containers and are not mixed with each other until immediately before or during the application of the composition, and are two different components.

[0020] "Room temperature" refers to a temperature of 23°C.

[0021] The polyether having blocked hydroxyl groups essentially does not contain unblocked hydroxyl groups. In this specification, "essentially does not contain" means that 95%, preferably 99%, particularly 99.9%, and most preferably 100% of the existing hydroxyl groups are blocked.

[0022] The polyether having blocked hydroxyl groups preferably does not contain reactive groups that participate in cross - linking reactions with normal components in water or in the curable composition. Therefore, it particularly does not contain isocyanate groups and silane groups.

[0023] The polyether having blocked hydroxyl groups is particularly liquid at room temperature.

[0024] The polyether having blocked hydroxyl groups preferably has a viscosity in the range of 30 - 5,000 mPa·s at 20°C, more preferably 40 - 2,000 mPa·s, particularly preferably 50 - 1,000 mPa·s, especially 50 - 500 mPa·s. In this specification, the viscosity is determined using a cone - plate viscometer with a cone diameter of 25 mm, a cone angle of 1°, a cone tip - plate distance of 0.05 mm, and a shear rate of 10 s -1 ^-1. This results in a highly concentrated acid solution that is easy to handle.

[0025] The blocked hydroxyl group is preferably selected from the group consisting of ester groups, aceto - ester groups, carbonate groups, and urethane groups.

[0026] These ester groups, acetoester groups, carbonate groups and urethane groups preferably have 1 to 15 carbon atoms.

[0027] Ester groups or urethane groups are particularly preferred. Hydroxyl groups can be particularly easily converted into these groups, which are particularly stable and have compatibility with aromatic carboxylic acids or sulfonic acids.

[0028] Ester groups, particularly ester groups having 1 to 8 carbon atoms, are particularly preferred.

[0029] Most preferably, it is an acetate group. Polyethers having a hydroxyl group blocked in the form of an acetate group are particularly low in viscosity, can be obtained by a very simple method, and are particularly inexpensive.

[0030] Also preferred are urethane groups, particularly phenylurethane groups or p-toluenesulfonylurethane groups. Polyethers having such blocked hydroxyl groups have a manageable viscosity and can be prepared by a particularly simple method.

[0031] A preferred acetoester group is an acetoacetate group.

[0032] A preferred carbonate group is a methyl carbonate group.

[0033] These are low in viscosity and are obtained from inexpensive raw materials.

[0034] The repeating units present in the polyether having a blocked hydroxyl group are preferably 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups, particularly 1,2-propyleneoxy groups.

[0035] Preferably, 70% to 100% by weight, particularly 80% to 100% by weight, of the repeating units consist of 1,2 - propyleneoxy groups, and 0% to 30% by weight, particularly 0% to 20% by weight, of the repeating units consist of 1,2 - ethyleneoxy groups.

[0036] More preferably, the repeating units consist entirely of 1,2 - propyleneoxy groups.

[0037] Such polyethers are readily available and hydrophobic, and thus are particularly suitable as components of curable compositions having low water absorption and good stability.

[0038] The polyether having blocked hydroxyl groups preferably has an average molecular weight M in the range of 600 to 10,000 g / mol, more preferably 700 to 5,000 g / mol, particularly 800 to 2,500 g / mol, as determined by gel permeation chromatography (GPC) relative to polystyrene as a standard, using tetrahydrofuran as the mobile phase, a refractive index detector, and an evaluation starting from 200 g / mol. n having.

[0039] Such polyethers having blocked hydroxyl groups are of low viscosity, and as a result, enable solutions that are easy to handle and do not cause discharge or odor in curable compositions.

[0040] The polyether having blocked hydroxyl groups preferably - polyoxypropylene monool having an OH value in the range of 25 to 90 mg KOH / g, preferably 50 to 80 mg KOH / g, starting from an alcohol, particularly starting from n - butanol, - polyoxypropylene diol having an OH value in the range of 12 to 155 mg KOH / g, preferably 22 to 125 mg KOH / g, particularly 45 to 125 mg KOH / g, - Polyoxypropylene triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 22 to 230 mg KOH / g, preferably 56 to 165 mg KOH / g, optionally terminated with ethylene oxide, starting from trimethylolpropane or especially glycerol, and - Polyoxypropylene polyol having an average OH functionality in the range of 3 to 6, starting from a sugar alcohol, especially using treitol, erythritol, xylitol, mannitol or sorbitol as the starting molecule (initiator molecule). It is derived from at least one hydroxy-functional polyether selected from the group consisting of. Such polyethers having blocked hydroxyl groups are commercially available as Sanflex® SPX-80 (from Sanyo Chem. Ind.).

[0041] Among these, polyoxypropylene monool or polyoxypropylene diol starting from an alcohol, especially starting from n-butanol, is preferred.

[0042] Polyoxypropylene diol is particularly preferred. These are especially inexpensive.

[0043] Preferred polyethers having blocked hydroxyl groups can be prepared from readily available commercial products by a simple method, have a low viscosity, and, combined with ease of handling, allow for highly concentrated acid solutions.

[0044] Polyethers having blocked hydroxyl groups are obtained in particular by reacting at least one hydroxy-functional polyether with at least one suitable blocking agent for the hydroxyl group.

[0045] For the reaction, the blocking agent is used in at least a stoichiometric amount relative to the hydroxyl groups, so that the hydroxyl groups are essentially completely blocked and thus the resulting polyether is essentially free of hydroxyl groups. Conventional methods are used for each reactive group for blocking, and optionally a catalyst or solvent is additionally used. When the blocking reaction forms elimination products, these are removed from the reaction mixture by suitable methods, in particular by distillation.

[0046] Suitable blocking agents are nucleophilic compounds that undergo an addition or substitution reaction with the hydroxyl group.

[0047] Particularly suitable are carboxylic acids, carbonyl chlorides, carboxylic acid esters or carboxylic acid anhydrides, diketene, 2,2,5-trimethyl-4H-1,3-dioxin-4-one, alkyl acetoacetates, dialkyl carbonates, monoisocyanates, (meth)acrylamides, methylene malonates or cyanoacrylates.

[0048] Preference is given to carboxylic acids, carbonyl chlorides, carboxylic acid esters or carboxylic acid anhydrides which involve the formation of hydroxyl groups blocked in the form of ester groups. Among these, carboxylic acid anhydrides or carboxylic acid esters, in particular acetic anhydride, are preferred.

[0049] In the case of acetic anhydride as the blocking agent, acetic acid is released by the reaction and hydroxyl groups blocked in the form of acetate groups are formed.

[0050] In the case of isopropenyl acetate as the blocking agent, acetone is released by the reaction and similarly hydroxyl groups blocked in the form of acetate groups are formed.

[0051] Furthermore, preference is given to diketene, 2,2,5-trimethyl-4H-1,3-dioxin-4-one or sterically hindered alkyl acetoacetates such as tert-butyl acetoacetate in particular, which involve the formation of hydroxyl groups blocked in the form of acetoester groups.

[0052] Furthermore, dialkyl carbonates, especially dimethyl carbonate, which involve the formation of hydroxyl groups blocked in the form of carbonate groups, especially methyl carbonate groups, are preferred.

[0053] Monoisocyanates that involve the formation of hydroxyl groups blocked in the form of urethane groups are more preferred. Phenyl isocyanate or p-toluenesulfonyl isocyanate is preferred.

[0054] Suitable hydroxy-functionalized polyethers especially have an average OH functionality number in the range of 1 to 6 and an average molecular weight in the range of 500 to 10,000 g / mol, more preferably 600 to 5,000 g / mol, especially 700 to 2,500 g / mol.

[0055] Polyoxypropylene monools having an OH value in the range of 25 to 90 mg KOH / g, preferably 50 to 80 mg KOH / g, especially those starting from alcohols, especially polyoxypropylene monools starting from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol or phenol, are preferred. Among these, polyoxypropylene monools starting from alkyl alcohols, especially those starting from methanol, ethanol or n-butanol, are preferred. Polyoxypropylene monools starting from n-butanol, having an average molecular weight Mn in the range of 650 to 2,000 g / mol, especially 700 to 1,500 g / mol, are particularly preferred. Polyoxypropylene monools starting from n-butanol are commercially available, for example, as Synalox® 100-20B, Synalox® 100-40B or Synalox® 100-85B (all from DowDuPont Inc.).

[0056] Polyoxypropylene diols having an OH number in the range of 12 to 155 mg KOH / g, preferably 22 to 125 mg KOH / g, particularly 45 to 125 mg KOH / g are also preferred.

[0057] Polyoxypropylene triols, optionally terminated with ethylene oxide, starting from trimethylolpropane or particularly glycerol, having an average OH functionality in the range of 2.2 to 3 and an OH number in the range of 22 to 230 mg KOH / g, preferably 56 to 165 mg KOH / g are also preferred.

[0058] Polyoxypropylene polyols starting from sugar alcohols, particularly those starting from threitol, erythritol, xylitol, mannitol or sorbitol as starting molecules (initiator molecules), having an average OH functionality of at least 3, particularly in the range of 3 to 6 are also preferred.

[0059] Suitable aromatic carboxylic acids or sulfonic acids are, in particular, benzoic acid, salicylic acid, 2-nitrobenzoic acid, 2-chlorobenzoic acid, p-toluenesulfonic acid or a mixture of two or more of the aforementioned acids.

[0060] The aromatic carboxylic acid or sulfonic acid is preferably selected from the group consisting of benzoic acid, 2-nitrobenzoic acid, salicylic acid and p-toluenesulfonic acid.

[0061] Salicylic acid is particularly preferred.

[0062] Preferred aromatic carboxylic acids or sulfonic acids are readily available and enable particularly rapid hydrolysis of latent curing agents having an aldimino, ketimino, enamino or oxazolidino group. Since these are solids and have a high melting point at room temperature, solvents readily available in curable compositions are required.

[0063] An acid solution is obtained by the use described herein.

[0064] Accordingly, the present invention further provides an acid solution from the use described herein.

[0065] Such an acid solution is particularly suitable as a catalyst for the hydrolysis of latent curing agents having aldimino, ketimino, enamino or oxazolidino groups, especially in curable compositions containing isocyanate groups.

[0066] More specifically, the acid solution is liquid at room temperature and essentially contains no fraction of undissolved aromatic carboxylic acid or sulfonic acid.

[0067] This solution is preferably liquid at 4 °C and can be stored at 4 °C for 7 days in a sealed container without crystallization of the fraction of aromatic carboxylic acid or sulfonic acid.

[0068] The acid solution preferably contains 2.5 wt% to 25 wt% of an aromatic carboxylic acid or sulfonic acid and 50 wt% to 97.5 wt%, especially 75 wt% to 97.5 wt%, of a polyether having blocked hydroxyl groups.

[0069] The acid solution more preferably contains 5 wt% to 20 wt%, especially 7.5 wt% to 15 wt%, of an aromatic carboxylic acid or sulfonic acid and 80 wt% to 95 wt%, especially 85 wt% to 92.5 wt%, of a polyether having blocked hydroxyl groups.

[0070] The acid solution preferably has a viscosity in the range of 40 to 8,000 mPa·s at 20 °C, more preferably 50 to 4,000 mPa·s, particularly preferably 60 to 2,000 mPa·s, especially 70 to 1,000 mPa·s. In this specification, this viscosity is determined using a cone-plate viscometer with a cone diameter of 25 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm, and a shear rate of 10 s -1 determined using a cone-plate viscometer.

[0071] The acid solution is preferably prepared by weighing an aromatic carboxylic acid or sulfonic acid into the initial charge of the polyether having blocked hydroxyl groups with stirring at a temperature in the range of 15 to 100 °C, particularly 20 to 90 °C, or by dissolving a mixture containing the polyether having blocked hydroxyl groups and the aromatic carboxylic acid or sulfonic acid at a temperature in the range of 15 to 100 °C, particularly 20 to 90 °C. In either case, the stirring is continued until the aromatic carboxylic acid or sulfonic acid is completely dissolved. The acid solution is preferably stored in a sealed container until subsequent use.

[0072] Optionally, in addition to the polyether having blocked hydroxyl groups and the aromatic carboxylic acid or sulfonic acid, the acid solution may contain additional substances, particularly plasticizers, additional acids, acid esters, acid anhydrides or silyl esters of acids or catalysts, particularly at least one catalyst for promoting the reaction of isocyanates, particularly organotin(IV) compounds, complexes of bismuth(III) or zirconium(IV) or compounds containing a tertiary amino group such as 2,2'-dimorpholinodiethyl ether (DMDEE).

[0073] The solution preferably contains no additional substances.

[0074] Preference is given to using the acid solution as a catalyst for crosslinking the curable composition.

[0075] The curable composition preferably has isocyanate groups and / or silane groups, particularly isocyanate groups.

[0076] The acid solution is preferably used in a composition containing isocyanate groups in order to promote the hydrolysis of at least one latent curing agent. The polyether having blocked hydroxyl groups has particularly good compatibility in such a composition and has particularly very high storage stability even in combination with isocyanate groups.

[0077] Accordingly, the present invention further provides a curable composition containing the acid solution described in this specification.

[0078] The acid solution present in the composition can be separately prepared and mixed into the composition, or it can be directly prepared in the composition at any time.

[0079] The acid solution present in the composition is preferably prepared separately.

[0080] The curable composition preferably contains 0.01% to 0.5% by weight, particularly 0.02% to 0.25% by weight, of dissolved aromatic carboxylic acid or sulfonic acid.

[0081] The curable composition preferably - at least one polyisocyanate or a polymer containing isocyanate groups, - at least one latent curing agent having at least one aldimino group, ketimino group, enamino group or oxazolidino group, - at least one polyether having the blocked hydroxyl groups described above, and - at least one aromatic carboxylic acid or sulfonic acid is included.

[0082] Aliphatic, alicyclic or aromatic diisocyanates, particularly hexamethylene 1,6 - diisocyanate (HDI), 1 - isocyanato - 3,3,5 - trimethyl - 5 - isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro(diphenylmethane 2,4’ - and / or 4,4’ - diisocyanate)(H 12 MDI), diphenylmethane 4,4’ - diisocyanate (MDI) with or without a fraction of diphenylmethane 2,4’ - and / or 2,2’ - diisocyanate, or tolylene 2,4 - diisocyanate or a mixture thereof with tolylene 2,6 - diisocyanate (TDI), a mixture of MDI and MDI analogs (polymeric MDI or PMDI) or oligomeric isocyanates are preferred.

[0083] Suitable oligomeric isocyanates are, in particular, HDI biurets such as Desmodur® N100 or N3200 (from Covestro AG), Tolonate® HDB or HDB-LV (from Vencorex Holding SAS), or Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur® N3300, N3600 or N3790 BA (all from Covestro AG), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex Holding SAS), Duranate® TPA-100 or THA-100 (from Asahi Kasei Corporation), or Coronate® HX (from Tosoh Corporation); HDI uretdiones such as Desmodur® N3400 (from Covestro AG); HDI iminooxadiazinediones such as Desmodur® XP2410 (from Covestro AG); HDI allophanates such as Desmodur® VP LS 2102 (from Covestro AG); IPDI isocyanurates in solution such as Desmodur® Z4470 (from Covestro AG) or in solid form such as Vestanat® T1890 / 100 (from Evonik Industries AG); TDI oligomers such as Desmodur® IL (from Covestro AG); or mixed isocyanurates based on TDI / HDI such as Desmodur® HL (from Covestro AG).

[0084] Particularly preferred polyisocyanates are in the form of HDI, IPDI, TDI, MDI or MDI which is liquid at room temperature.

[0085] The form of MDI that is liquid at room temperature is 4,4'-MDI liquefied by partial chemical modification (especially carbodiimidization or uretonimine formation or adduct formation with polyols), or it is selectively obtained by blending with 4,4'-MDI or is other MDI isomers (2,4'-MDI and / or 2,2'-MDI) obtained by the manufacturing process, and / or a mixture with MDI oligomers, and / or MDI analogs (polymeric MDI or PMDI).

[0086] Even more particularly preferred polyisocyanates are mixed isocyanurates based on IPDI isocyanurate or TDI oligomers or TDI / HDI or HDI oligomers.

[0087] Suitable polymers containing isocyanate groups are obtained, in particular, from the reaction of at least one diisocyanate in a stoichiometric excess with at least one polyol, preferably MDI, TDI, IPDI or HDI. The reaction is preferably carried out at a temperature in the range of 20 to 160 °C, particularly 40 to 140 °C, with the exclusion of moisture and optionally in the presence of a suitable catalyst. The polymer is optionally prepared using additional plasticizers or solvents, in which case the plasticizers or solvents used do not contain groups reactive towards isocyanates.

[0088] When used in two-component compositions, the excess diisocyanate is preferably selected such that, in the polymer containing isocyanate groups, after the reaction of all hydroxyl groups, the content of isocyanate groups ranges from 1 wt% to 30 wt%, preferably 1.5 wt% to 25 wt%, more preferably 2 wt% to 20 wt% based on the total polymer.

[0089] Such polymers containing isocyanate groups preferably have an average molecular weight M n in the range of 350 to 6,000 g / mol.

[0090] When used in a one-component composition, the NCO / OH ratio is preferably in the range of 1.3 / 1 to 10 / 1. The monomeric diisocyanate remaining in the reaction mixture after the reaction of the OH groups can be removed, particularly by distillation. The resulting polymer preferably has an isocyanate group content in the range of 0.5 wt% to 10 wt%, particularly 1 wt% to 5 wt%, more preferably 1 wt% to 3 wt%, and also preferably has an average molecular weight M n in the range of 1,500 to 20,000 g / mol, particularly 2,000 to 15,000 g / mol. When the excess monomeric diisocyanate is removed by distillation, the NCO / OH ratio during the reaction is preferably in the range of 4 / 1 to 7 / 1, and the resulting isocyanate group-containing polymer preferably contains 0.5 wt% or less, more preferably 0.3 wt% or less of monomeric diisocyanate after distillation. The monomeric diisocyanate is particularly removed by short-path distillation under reduced pressure.

[0091] When the excess monomeric diisocyanate is not removed from the polymer, the NCO / OH ratio in the reaction is preferably in the range of 1.3 / 1 to 2.5 / 1.

[0092] Suitable polyols are commercially available polyols or mixtures thereof, particularly the following: - Polyether polyols, especially polyoxyalkylene diols and / or polyoxyalkylene triols, especially polymerization products of ethylene oxide, or 1,2-propylene oxide, or 1,2- or 2,3-butylene oxide, or oxetane, or tetrahydrofuran or mixtures thereof, which are starting molecules (initiator molecules) having two or three active hydrogen atoms, especially water, ammonia or compounds having a plurality of OH or NH groups, such as ethane-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycol or tripropylene glycol, isomeric butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, cyclohexane-1,3- or -1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline or mixtures of the aforementioned compounds, etc. as starting molecules (initiator molecules). Also suitable are polyether polyols in which polymer particles are dispersed therein, especially those containing styrene / acrylonitrile (SAN) particles or polyurea or polyhydrazodicarbonamide (PHD) particles.

[0093] Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols or so-called ethylene oxide-terminated (capped with EO or having EO at the tip) polyoxypropylene diols or triols. The latter are mixed polyoxyethylene / polyoxypropylene polyols, which are obtained, in particular, as a result of the polypropoxylation reaction, by further alkoxylating polyoxypropylene diols or triols with ethylene oxide, resulting in having primary hydroxyl groups.

[0094] Preferred polyether polyols have an unsaturation level of less than 0.02 meq / g, especially less than 0.01 meq / g. - Polyester polyols, also known as oligoesterols, prepared by known processes, in particular by polycondensation of hydroxycarboxylic acids or lactones or by polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. In particular, dihydric alcohols such as 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 aforementioned alcohols, and organic dicarboxylic acids or their anhydrides or esters, such as in particular succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid or mixtures of the aforementioned acids. Polyester diols resulting from the reaction are preferred, or polyester polyols formed from lactones such as in particular ε-caprolactone. In particular, polyester polyols formed from adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentyl glycol are preferred. - Polycarbonate polyols obtained by reaction of the above-mentioned alcohols used to form polyester polyols with dialkyl carbonates, diaryl carbonates or phosgene. - Block copolymers having at least two OH groups and having at least two different blocks with the above-mentioned types of polyether, polyester and / or polycarbonate structures, in particular polyether polyester polyols. - Polyacrylate or polymethacrylate polyols. - Polyhydroxy-functional oils, such as natural oils, especially castor oil; or polyols obtained by chemical modification of natural oils (referred to as oleochemical polyols), such as epoxy polyesters or epoxy polyethers obtained by epoxidation of unsaturated oils followed by ring opening with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural oils by decomposition processes such as alcoholysis or ozonolysis and subsequent chemical bonding such as transesterification or dimerization of the decomposition products or their derivatives thus obtained. Suitable decomposition products of natural oils are, in particular, fatty acids and aliphatic alcohols and fatty acid esters, especially methyl esters (FAME) which can be derivatized to hydroxy fatty acid esters, for example by hydroformylation and hydrogenation. - Especially polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene, etc., polyhydrocarbon polyols also called oligohydrocarbonols; for example polyhydroxy-functional ethylene / propylene, ethylene / butylene or ethylene / propylene / diene copolymers such as those manufactured by Kraton Polymers; polyhydroxy-functional polymers of dienes, especially 1,3-butadiene, which can also be prepared especially by anionic polymerization; polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, especially polyhydroxy-functional acrylonitrile / butadiene copolymers which can be prepared specifically from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (for example commercially available under the names Hypro® CTBN or CTBNX or ETBN from Emerald Performance Materials); or hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0095] Mixtures of polyols are also particularly suitable.

[0096] Polyether polyol, polyester polyol, polycarbonate polyol, poly(meth)acrylate polyol or polybutadiene polyol is preferred.

[0097] Polyether polyol, polyester polyol, especially aliphatic polyester polyol or polycarbonate polyol, especially aliphatic polycarbonate polyol is particularly preferred.

[0098] Particularly preferred is polyether polyol, especially polyoxyalkylene polyol.

[0099] Most preferred is polyoxypropylene di- or triol or ethylene oxide-terminated polyoxypropylene di- or triol.

[0100] Polyols with an average molecular weight Mn in the range of 400 to 20,000 g / mol, preferably 1,000 to 15,000 g / mol, are preferred.

[0101] Polyols having an average OH functionality number in the range of 1.6 to 3 are preferred.

[0102] Polyols that are liquid at room temperature are preferred.

[0103] In the preparation of polymers containing isocyanate groups, it is also possible to use fractions of bifunctional or polyfunctional alcohols, in particular ethan-1,2-diol, propan-1,2-diol, propan-1,3-diol, 2-methylolpropane-1,3-diol, butan-1,2-diol, butan-1,3-diol, butan-1,4-diol, pentan-1,3-diol, pentan-1,5-diol, 3-methylpentan-1,5-diol, neopentyl glycol, dibromoneopentyl glycol, hexan-1,2-diol, hexan-1,6-diol, heptan-1,7-diol, octan-1,2-diol, octan-1,8-diol, 2-ethylhexan-1,3-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,3- or -1,4-dimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, dimer fatty alcohol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols (in particular xylitol, sorbitol or mannitol etc.) or sugars (in particular sucrose etc.) or alkoxylated derivatives of the alcohols mentioned or mixtures of the alcohols mentioned.

[0104] In particular, combinations of one or more polyisocyanates with one or more polymers containing isocyanate groups are also preferred.

[0105] For use in hot melt adhesives, isocyanate group-containing polymers that are solid at room temperature are preferred, which are prepared starting from at least one polyol that is solid at room temperature and a diisocyanate, in particular MDI. Suitable polyols that are solid at room temperature are crystalline, partially crystalline or amorphous at room temperature. Their melting point is preferably in the range of 50 to 180 °C, in particular 70 to 150 °C. Polyester polyols, in particular those derived from hexanediol and adipic acid or dodecanedicarboxylic acid or acrylate polyols are preferred.

[0106] The latent curing agent preferably contains at least one group selected from aldimino groups, ketimino groups, enamino groups and oxazolidino groups, and at least one further group selected from hydroxyl groups, primary and secondary amino groups, aldimino groups, ketimino groups, enamino groups and oxazolidino groups.

[0107] Latent curing agents containing hydroxyl groups or primary or secondary amino groups are particularly suitable for two-component or multi-component compositions. When these are used in one-component compositions, they react upon mixing with isocyanates to form reaction products having aldimino groups, ketimino groups, enamino groups or oxazolidino groups. Here, it is possible to reduce the content of monomeric diisocyanates in polymers containing isocyanate groups, which is advantageous for toxicological reasons.

[0108] The latent curing agent more preferably contains two or three reactive groups selected from aldimino groups and oxazolidino groups. Such latent curing agents are particularly suitable for one-component compositions.

[0109] Di- or trialdimines or bisoxazolidines are preferred.

[0110] Suitable bisoxazolidines are in particular of the formula

Chemical formula

[0111] The latent curing agent is preferably of the formula [Chemical formula] (wherein y is 2 or 3, A is an organic group having 2 to 23 carbon atoms, and B is an organic group having 6 to 30 carbon atoms) is an aldimine of

[0112] A is preferably an alkylene group which may optionally have a cyclic component or a divalent or trivalent polyoxyalkylene group having 5 to 15 carbon atoms, especially 1,6-hexylene, having an average molecular weight Mn in the range of 170 to 300 g / mol of (1,5,5-trimethylcyclohexan-1-yl)methane-1,3 or α,ω-polyoxypropylene or tris(ω-polyoxypropylene) starting from trimethylolpropane having an average molecular weight Mn in the range of 330 to 500 g / mol)

[0113] B is preferably an organic group having 7 to 22 carbon atoms, especially 2,2-dimethyl-3-acetoxypropylidene, 2,2-dimethyl-3-lauroyloxypropylidene, 2,2-dimethyl-3-(N-morpholino)propylidene, benzylidene or alkyl-substituted benzylidene, especially 4-decylbenzylidene, 4-undecylbenzylidene, 4-dodecylbenzylidene, 4-tridecylbenzylidene or 4-tetradecylbenzylidene, and the 4-alkyl groups among these are mainly branched)

[0114] More preferably, B is a group having at least 15 carbon atoms, particularly 2,2-dimethyl-3-lauroxypropylidene or an alkyl-substituted benzylidene. Such aldimines are odorless.

[0115] Formula

Chemical formula

[0116] Preferred amines A-(NH 2 ) y are aliphatic or alicyclic primary diamines or triamines, particularly hexamethylene-1,6-diamine, isophoronediamine, α,ω-polyoxypropylene diamine having an average molecular weight Mn in the range of 200 to 350 g / mol, particularly Jeffamine® D-230 (from Huntsman Corp.) or tris(ω-polyoxypropyleneamine) starting from trimethylolpropane, particularly Jeffamine® T-403 (from Huntsman Corp.).

[0117] Preferred aldehydes O=B are aldol esters of carboxylic acids, particularly 2,2-dimethyl-3-acetoxypropanal, 2,2-dimethyl-3-lauroxyloxypropanal, 2,2-dimethyl-3-(N-morpholino)propanal, benzaldehyde or benzaldehyde substituted with an alkyl group, particularly 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde or 4-tetradecylbenzaldehyde in which the 4-alkyl group is mainly branched, and mixtures of these benzaldehydes substituted with an alkyl group.

[0118] When exposed to moisture, the latent curing agent releases an amino group and optionally a hydroxyl group, which react with the isocyanate and function as a crosslinking agent. As a result, an aldehyde or a ketone is released.

[0119] In the case of a preferred aldehyde of the formula O=B where B is a long-chain group, especially a group having 15 or more carbon atoms, this does not cause an odor problem, remains in the composition after curing, has excellent compatibility, and functions as a plasticizer.

[0120] Compared with the direct reaction of water and isocyanate, crosslinking by the latent curing agent has the advantage of not releasing CO 2 and the tendency for blisters to form during the curing process is significantly reduced.

[0121] The composition preferably contains an amount of latent curing agent such that the ratio between the number of reactive groups that can be released therefrom and the number of isocyanate groups is in the range of 0.1 to 1.5, preferably 0.2 to 1.1, particularly 0.3 to 1.0.

[0122] The curable composition preferably further contains one or more additional components selected especially from plasticizers, fillers, and catalysts for the reaction of isocyanate groups.

[0123] Suitable plasticizers are, in particular, phthalic esters, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalic esters or cyclohexane-1,2-dicarboxylates, in particular diisononyl hydrogenated phthalate or diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalic esters, in particular bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalic esters or cyclohexane-1,4-dicarboxylates, in particular bis(2-ethylhexyl) hydrogenated terephthalate or bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate or diisononyl hydrogenated terephthalate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalic esters, trimellitic esters, adipic esters, in particular dioctyl adipate, azelaic esters, sebacic esters, benzoic esters and other carboxylic acid esters, glycol ethers, glycol esters, in particular plasticizers having a polyether structure such as the polyethers described herein having blocked hydroxyl groups, organic phosphoric esters or sulfonic esters, polybutene, polyisobutene or plasticizers derived from natural fats and oils (in particular epoxidized soybean oil or linseed oil).

[0124] Preferred plasticizers are diisononyl phthalate, diisodecyl phthalate or the polyethers described herein having blocked hydroxyl groups.

[0125] Suitable fillers are, in particular, ground or precipitated calcium carbonate, which may optionally be coated with a fatty acid (in particular a stearic acid ester), barite, quartz powder, quartz sand, dolomite, wollastonite, calcined kaolin, mica or talc and other layered silicates, zeolites, aluminum hydroxide, magnesium hydroxide, silica (including finely divided silica from a pyrolysis process), cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders such as aluminum, copper, iron, silver or steel, PVC powder or hollow beads.

[0126] Calcium carbonate, calcined kaolin, or industrially produced carbon black, which can optionally be coated with a fatty acid (especially a stearic acid ester), is preferred.

[0127] Suitable catalysts for promoting the reaction of isocyanate groups are, in particular specifically, organotin(IV) compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate, or dioctyltin diacetylacetonate; complexes of bismuth(III) or zirconium(IV) having ligands selected especially from alkoxides, carboxylates, 1,3-diketonates, oxinates, 1,3-ketoesters, and 1,3-ketoamides; or compounds containing a tertiary amino group such as especially 2,2'-dimorpholinodiethyl ether (DMDEE).

[0128] The curable composition can especially contain the following further additives: - Inorganic or organic pigments, especially titanium dioxide, chromium oxide, or iron oxide; - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers, polymer fibers (such as polyamide fibers or polyethylene fibers), or natural fibers (such as wool, cellulose, hemp, or sisal); - Nanofillers such as graphene or carbon nanotubes; - Dyes; - Desiccants, especially molecular sieve powder, calcium oxide, highly reactive isocyanates such as p-tolyl isocyanate, monooxazolidines such as Incozol® 2 (from Incorez), or orthoformates; - Then accelerators, especially organic alkoxysilanes, especially epoxysilanes such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acrylosilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms of these silanes or titanates; - Additional catalysts that promote the reaction of isocyanate groups, especially salts, soaps or complexes of tin (II), zinc, iron, aluminum, molybdenum, dioxomolybdenum, titanium or potassium, especially tin (II) 2-ethylhexanoate, tin (II) neodecanoate, zinc (II) acetate, zinc (II) 2-ethylhexanoate, zinc (II) laurate, zinc (II) acetylacetonate, aluminum lactate, aluminum oleate, diisopropoxytitanium bis(ethylacetoacetate) or potassium acetate; compounds containing a tertiary amino group, especially N-ethyldiisopropylamine, N,N,N’,N’-tetramethylalkylenediamine, pentamethylalkylenetriamine and their higher analogues, bis(N,N-diethylaminoethyl) adipate, tris(3-dimethylaminopropyl)amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-alkylmorpholine, N,N’-dimethylpiperazine; aromatic nitrogen compounds such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; organic ammonium compounds such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; and so-called "delayed action" catalysts that are modified products of known metal or amine catalysts; - Rheology modifiers, especially thickeners, especially layered silicates such as bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, fumed silica, cellulose ethers or hydrophobically modified polyoxyethylene; - Solvents, especially acetone, methyl acetate, tert-butyl acetate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, acetals (such as propylal, butylal, 2-ethylhexylal, dioxolane, glycerol formal or 2,5,7,10-tetraoxaundecane (TOU), etc.), toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or gasoline, especially Solvesso TM Grade (from ExxonMobil Chemical Co.) and propylene carbonate, dimethyl carbonate, butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, p-chlorobenzotrifluoride or benzotrifluoride; - Natural resins and oils such as rosin, shellac, linseed oil, castor oil or soybean oil; - Non-reactive polymers, especially homopolymers or copolymers of unsaturated monomers, especially those selected from the group containing ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, especially polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymer (EVA) or atactic poly-α-olefin (APAO); - Flame retardant substances, in particular the aluminum hydroxide or magnesium hydroxide fillers described above, and in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris(isopropylphenyl) phosphate with various degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate) or ammonium polyphosphate, in particular organic phosphate esters; - Additives, in particular wetting agents, leveling agents, defoamers, degassing agents, stabilizers against oxidation, heat, light or ultraviolet rays or biocides; or Further substances commonly used in curable compositions.

[0129] It may be desirable to dry them chemically or physically before mixing the specific substances into the composition.

[0130] The curable composition preferably comprises - 10% to 70% by weight, in particular 20% to 50% by weight, of a polymer containing isocyanate groups, - 0.1% to 20% by weight, in particular 1% to 15% by weight, of a latent curing agent, - 20% to 60% by weight of a filler, - 5% to 40% by weight of a plasticizer, and - 0.01% to 0.5% by weight, in particular 0.02% to 0.25% by weight, of an aromatic carboxylic acid or sulfonic acid dissolved in a polyether having blocked hydroxyl groups and contains.

[0131] Optionally, the polyether having blocked hydroxyl groups may also be present at least partially as a plasticizer in the curable composition.

[0132] The curable composition is produced, in particular, by excluding moisture and stored at ambient temperature in a moisture-proof container. Suitable moisture-proof containers are made, in particular, of optionally coated metal and / or plastic and are, in particular, drums, transport boxes, kegs, buckets, canisters, cans, bags, tubular bags, cartridges or tubes.

[0133] The curable composition can be in the form of a one-component composition or can be a multi-component, in particular two-component, composition.

[0134] The curable composition is preferably a one-component moisture-curable composition. When properly packaged and stored, it has storage stability and is typically stable over several months to up to one year or more.

[0135] In one embodiment, the curable composition has two components and consists of a first component containing at least one polyol and a second component containing at least one polyisocyanate and optionally at least one isocyanate group-containing polymer. The latent curing agent or acid solution described herein can be present in one or both of the two components, respectively. Suitable polyols are, in particular, the polyols described above for the preparation of isocyanate group-containing polymers.

[0136] When the curable composition is applied, the curing process begins.

[0137] In the case of a one-component moisture-curable composition, it is applied as such and then begins to cure under the influence of moisture or water. To accelerate the curing, an accelerator component containing and / or releasing water and / or a catalyst can be mixed into the composition during application or the composition can be brought into contact with such an accelerator component after its application.

[0138] In the case of a two-component composition, it is applied after the mixing of the two components, starts to cure by an internal reaction, and the curing can be completed by the action of external moisture. The two components can be mixed continuously or in batch form using a dynamic mixer or a static mixer.

[0139] During the curing process, the isocyanate groups present react with each other and / or with any additional reactive groups present in the composition, particularly hydroxyl or amino groups, under the influence of moisture. Furthermore, the isocyanate groups react with the reactive groups of the latent curing agent that are present when they are hydrolyzed.

[0140] The acid solution present in the composition accelerates, in particular, the hydrolysis of the latent curing agent and promotes rapid and non-bulging curing.

[0141] The moisture required for the curing of the moisture-curing composition preferably enters the composition by diffusion from the air (the moisture in the air). During this process, a solid layer (skin) of the cured composition is formed on the surface of the composition in contact with the air. The curing continues in the direction of diffusion from the outside to the inside, and the skin becomes thicker and finally surrounds the entire applied composition. Moisture can also enter the composition additionally or completely from one or more substrates on which the composition is applied, and / or be mixed into the composition during application, or be provided from an accelerator component that comes into contact with it, for example, after application by painting or spraying.

[0142] The curable composition is preferably applied at ambient temperature, particularly in the range of about -10 to 50 °C, preferably in the range of -5 to 45 °C, particularly 0 to 40 °C.

[0143] The composition is preferably cured at ambient temperature as well.

[0144] The composition is suitable for various applications.

[0145] The composition is preferably an adhesive, or a sealant, or a coating.

[0146] The adhesive, or sealant, or coating preferably has elasticity.

[0147] The curable polyurethane composition as an adhesive and / or sealant is particularly suitable for adhesion and sealing applications in construction and manufacturing or automotive assembly, especially for veneer adhesion, assembly, adhesion of attachable parts, adhesion of modules, adhesion of window glass, sealing of joints, sealing of the vehicle body, seam sealing or cavity sealing.

[0148] Elastic adhesion in automotive structures is, for example, the adhesive attachment of parts such as plastic covers, trim strips, flanges, fenders, driver's cabs or other attachable components to the painted body of a vehicle, especially an automobile, truck, bus, railway vehicle or ship, or the adhesion of window glass to the vehicle body.

[0149] The curable polyurethane composition as a sealant is particularly suitable for elastic sealing of joints or civil engineering floor joints of all kinds of joints, seams or cavities, especially expansion joints or joint joints between components in structures.

[0150] The curable polyurethane composition as a coating is particularly suitable for protecting and / or sealing building structures or parts thereof, especially for balconies, terraces, roofs, especially flat roofs, or slightly sloping roof areas, or roof gardens, or for wet rooms, or for floor tiles in kitchens, or for building interiors such as ceramic plates, or in collection pans, conduits, shafts, silos, tanks or wastewater treatment systems.

[0151] For example, it can also be used for repair purposes as a seal or coating for leaking roof membranes or floor covers that no longer meet the requirements, or as a repair compound for highly reactive spray seals.

[0152] The curable composition can be formulated to have a high yield point and a pasty consistency, especially for use as an adhesive or a sealant. Such a composition can be applied under pressure by a spatula or a suitable device, such as a cartridge gun, or a drum pump, or a coating robot, and the composition is particularly discharged in the form of a bead having an essentially circular or triangular cross-sectional area.

[0153] The curable composition can also be formulated to be fluid and "self-leveling" or only slightly thixotropic, especially for use as a sealing compound or a coating. Such a composition can be poured or applied by a spatula. Thereafter, this can be distributed over the entire area to obtain the desired thickness, for example, by a roller, a doctor blade, a trowel or a rubber squeegee, in the form of a coating. In a single operation, a layer thickness in the range of typically 0.5 to 5 mm, especially 1 to 3 mm, is applied.

[0154] Suitable substrates to which the curable composition can be used for adhesion or sealing or coating are, in particular, - glass, glass ceramic, concrete, mortar, cement screed, fiber cement, especially fiber cement board, brick, tile, gypsum, especially gypsum board or anhydrous screed or natural stone such as granite or marble; - repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar); - metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-finished metals or alloys such as zinc-plated metal or chromium-plated metal; - asphalt or bitumen; - leather, textile products, paper, wood, wood adhered with resin (such as phenolic resin, melamine resin or epoxy resin), resin / textile product composite materials or polymer composite materials called further materials; - Plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example, by plasma, corona or flame; - Fiber-reinforced plastics such as carbon fiber-reinforced plastic (CFP), glass fiber-reinforced plastic (GFP) and sheet molding compound (SMC); - Heat-insulating foams, especially those made of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass; - Coated or painted substrates, especially painted tiles, coated concrete, powder-coated metal or alloy or painted metal sheets; - Paints or varnishes, especially automotive topcoats is.

[0155] If necessary, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by applying an activator or primer.

[0156] It is possible to bond and / or seal the same or different substrates.

[0157] An article is obtained by applying and curing the curable composition.

[0158] Accordingly, the present invention further provides an article adhered, or sealed, or coated using the composition described herein.

[0159] This article can in particular be a building structure on or under the ground or a part thereof, especially a bridge, roof, staircase or facade, or it can be an industrial or consumer product, especially a window, pipe, rotor blade of a wind turbine, household appliance or means of transport (especially a motor vehicle, bus, truck, railway vehicle, ship, aircraft or helicopter) or an attachable component thereof.

[0160] The hardening composition has advantageous properties. Due to the acid solution of the present invention, which is particularly at a low concentration and enables a high acid concentration, it is very easy to manufacture. It hardens rapidly, does not cause swelling, does not generate odor or emissions, and after hardening, due to the excellent compatibility of the acid solution, it shows almost no drawbacks related to migration such as leaching or bleeding.

Examples

[0161] Hereinafter, examples for clarifying the described present invention are presented. Naturally, the present invention is not limited to these described examples.

[0162] "Standard climatic conditions" ("SCC") refer to a temperature of 23 ± 1 °C and a relative humidity of air of 50 ± 5%.

[0163] Unless otherwise stated, the chemicals used were from Sigma - Aldrich Chemie GmbH.

[0164] Commercially available plasticizers used: DIDP: Diisodecyl phthalate (Palatinol® 10 - P, from BASF SE) DOA: Di(2 - ethylhexyl) adipate (Plastomoll® DOA, from BASF SE) SPX - 80: Branched polyether polyol having esterified hydroxyl groups, average molecular weight about 5,000 g / mol (Sanflex® SPX - 80, from Sanyo Chem. Ind.)

[0165] Preparation of polyether having blocked hydroxyl groups: The viscosity was measured with a Rheotec RC30 cone - plate viscometer equipped with a thermostat (cone diameter 25 mm, cone angle 1°, cone tip - plate distance 0.05 mm, shear rate 10 s -1 )

[0166] The infrared spectrum (FT-IR) was measured as undiluted film using a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measurement unit having a diamond crystal. The absorption bands are reported at a wave number (cm -1 ).

[0167] 1 The 1H NMR spectrum was measured at 400.14 MHz using a Bruker Ascend400 type spectrometer. The chemical shift δ is reported in ppm relative to tetramethylsilane (TMS). True coupling patterns and pseudo-coupling patterns were not distinguished.

[0168] Acetylated PPG monoalcohol with an average molecular weight of about 800 g / mol starting from polyether-1:n-butanol 120.00 g of polyoxypropylene monoalcohol starting from n-butanol (Synalox® 100-20B, average molecular weight about 750 g / mol; from DowDuPont Inc.) and 18.74 g of acetic anhydride were first placed in a round-bottom flask equipped with a distillation attachment under a nitrogen atmosphere. Then, the reaction mixture was stirred under a gentle nitrogen flow at 130 °C while acetic acid was recovered as a distillate. Subsequently, volatile components were removed from the reaction mixture under reduced pressure at 80 °C and 10 mbar. A colorless transparent liquid with a viscosity of 75 mPa·s at 20 °C was obtained.

[0169] FT-IR: 2970, 2931, 2867, 1738, 1454, 1372, 1345, 1296, 1241, 1098, 1014, 959, 925, 866, 827.

[0170] 1 1H NMR (CDCl 3 ): 5.02 (hept., 1H, CH 2 (CH 3 )CH-OAc), 3.75 - 3.34 (2xm, ca. 39H, OCH 2 CH(CH 3 )O), 3.33 - 3.28 (m, 2H, CH3 CH 2 CH 2 CH 2 O), 2.04 (s, 3H, O(CO)CH 3 ), 1.55 (quint., 2H, CH 3 CH 2 CH 2 CH 2 O), 1.36 (sext., 2H, CH 3 CH 2 CH 2 CH 2 O), 1.22 (d, 3H, CH 2 (CH 3 )CH - OAc), 1.17 - 1.10 (m, about 36H, OCH 2 CH(CH 3 )O), 0.91 (t, 3H, CH 3 CH 2 CH 2 CH 2 O).

[0171] Acetylated PPG mono - ol with an average molecular weight of about 1,150 g / mol using polyether - 2:n - butanol as the starting material 176.00 g of polyoxypropylene mono - ol (Synalox® 100 - 40B, average molecular weight about 1,100 g / mol; from DowDuPont Inc.) using n - butanol as the starting material and 18.74 g of acetic anhydride were converted as described for polyether - 1. A colorless, transparent liquid with a viscosity of 140 mPa·s at 20 °C was obtained.

[0172] Acetylated PPG mono - ol with an average molecular weight of about 1,850 g / mol using polyether - 3:n - butanol as the starting material 288.00 g of polyoxypropylene mono - ol (Synalox® 100 - 85B, average molecular weight about 1,800 g / mol; from DowDuPont Inc.) using n - butanol as the starting material and 18.74 g of acetic anhydride were converted as described for polyether - 1. A colorless, transparent liquid with a viscosity of 350 mPa·s at 20 °C was obtained.

[0173] Polyether - 4: Diacetylated PPG diol with an average molecular weight of about 800 g / mol 58.00 g of polyoxypropylene diol (polypropylene glycol, average molecular weight about 725 g / mol; from Sigma Aldrich Chemie GmbH) and 18.74 g of acetic anhydride were converted as described for Polyether - 1. A colorless and transparent liquid with a viscosity of 100 mPa·s at 20 °C was obtained.

[0174] Polyether - 5: Diacetylated PPG diol with an average molecular weight of about 1,100 g / mol 80.00 g of polyoxypropylene diol (Voranol® P1010, OH value 110 mg KOH / g; from DowDuPont Inc.) and 18.74 g of acetic anhydride were converted as described for Polyether - 1. A colorless and transparent liquid with a viscosity of 145 mPa·s at 20 °C was obtained.

[0175] Polyether - 6: Diacetylated PPG diol with an average molecular weight of about 2,100 g / mol 160.00 g of polyoxypropylene diol (Voranol® P2000L, OH value 56 mg KOH / g; from DowDuPont Inc.) and 18.74 g of acetic anhydride were converted as described for Polyether - 1. A colorless and transparent liquid with a viscosity of 400 mPa·s at 20 °C was obtained.

[0176] Polyether - 7: Diacetylated PPG diol with an average molecular weight of about 4,100 g / mol 600.0 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g; from Covestro AG) and 33.7 g of acetic anhydride were converted as described for Polyether - 1. A colorless and transparent liquid with a viscosity of 1,150 mPa·s at 20 °C was obtained.

[0177] Polyether - 8: Diacetylated PPG diol with an average molecular weight of about 8,100 g / mol 600.0 g of polyoxypropylene diol (Acclaim® 8200, OH value 14 mg KOH / g; from Covestro AG) and 16.8 g of acetic anhydride were converted as described for Polyether-1. A colorless transparent liquid with a viscosity of 3,800 mPa·s at 20 °C was obtained.

[0178] Polyether-9: Triacetylated PPG triol with an average molecular weight of approximately 850 g / mol 74.40 g of polyoxypropylene triol (Desmophen® 28HS98, OH value 230 mg KOH / g; from Covestro AG) and 37.48 g of acetic anhydride were converted as described for Polyether-1. A colorless transparent liquid with a viscosity of 135 mPa·s at 20 °C was obtained.

[0179] Polyether-10: Triacetylated PPG triol with an average molecular weight of approximately 1650 g / mol 80.00 g of polyoxypropylene triol (Arcol® LHT-112, OH value 112 mg KOH / g; from Covestro AG) and 18.74 g of acetic anhydride were converted as described for Polyether-1. A colorless transparent liquid with a viscosity of 285 mPa·s at 20 °C was obtained.

[0180] Polyether-11: Triacetylated PPG triol with an average molecular weight of approximately 3150 g / mol 160.00 g of polyoxypropylene triol (Desmophen® 3061BT, OH value 56 mg KOH / g; from Covestro AG) and 18.74 g of acetic anhydride were converted as described for Polyether-1. A colorless transparent liquid with a viscosity of 575 mPa·s at 20 °C was obtained.

[0181] Preparation of acid solution: Solutions L-1 to L-24 To 5 g of the initial charge of the solvent specified in Table 1 in a vial, a sufficient amount of salicylic acid or 2-nitrobenzoic acid was added to obtain a concentration of 2.0 wt%, or 4.8 wt%, or 9.1 wt%, or 13.0 wt%, or 16.7 wt%, or 20.0 wt%, or 23.1 wt% of acid (100% = acid + solvent), and the mixture was heated to 80 °C in an air-circulation oven. Subsequently, in each case, an attempt was made to completely dissolve the acid by stirring. If this was possible, the solution was then stored in an air-circulation oven at 50 °C for 7 days, then at 23 °C for a further 7 days, and finally in a refrigerator at 4 °C for a further 7 days. For each case, at the end of the storage times at 50 °C, 23 °C and 4 °C, an evaluation was made as to whether the acid had crystallized out of the solution. The maximum stable concentration refers to the concentration of the solution in which no crystallization of the acid was observed within 7 days at 4 °C.

[0182] The results are reported in Table 1.

[0183] The examples designated as "(Ref.)" are comparative examples.

[0184]

Table 1

[0185] Solutions L-25 to L-38 In each case, 1.0 g of the acid specified in Table 2 was dissolved in 9.0 g of the solvent specified in Table 2, and a 10% acid solution was prepared by storing the solution in a sealed container.

[0186] The viscosity of each solution at 20 °C was measured as described above.

[0187] The results are reported in Table 2.

[0188]

Table 2

[0189] Production of a curable (one-component) composition: Polymer P1: 400 g of polyoxypropylene diol (Acclaim® 4200, from Covestro AG; OH number 28.5 mg KOH / g) and 52 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44MCL, from Covestro AG) were reacted at 80 °C by a known method to obtain an NCO-terminated polymer that is liquid at room temperature and has an isocyanate group content of 1.85% by weight.

[0190] Polymer P2: 1,300 g of polyoxypropylene diol (Acclaim® 4200, from Covestro AG; OH number 28 mg KOH / g), 2,600 g of ethylene oxide-terminated polyoxypropylene triol (Voranol® CP4755, from DowDuPont Inc.; OH number 35 mg KOH / g), 600 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44MCL, from Covestro AG) and 500 g of diisodecyl phthalate were reacted at 80 °C by a known method to obtain an NCO-terminated polymer that is liquid at room temperature and has an isocyanate group content of 2.05% by weight.

[0191] Aldimine-1: N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine (= latent curing agent) First, 598 g (2.1 mol) of 2,2-dimethyl-3-lauroyloxypropanal was placed in a round-bottom flask under a nitrogen atmosphere. Then, 170.3 g (1 mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD, from Evonik Industries AG) was added with good stirring, and then the volatile components were removed under reduced pressure at 80 °C and 10 mbar. 732 g of a colorless liquid with an amine content of 2.73 mmol N / g was obtained, which corresponds to a calculated aldimine equivalent of 367 g / mol.

[0192] Compositions Z1 to Z9 For each composition, the components specified in Tables 3 to 4 were mixed at 3000 rpm for 1 minute in the specified amount (parts by weight) while excluding moisture using a centrifugal mixer (SpeedMixer (trademark) DAC150, FlackTek Inc.), and stored after excluding moisture.

[0193] Each composition was tested as follows.

[0194] Viscosity was measured using a Rheotec RC30 cone-plate viscometer with a thermostat (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm) at the specified temperature, at a shear rate of 5 s -1 for measurements at 0 °C, and at a shear rate of 10 s -1 for measurements at 10 °C, 20 °C and 30 °C.

[0195] Each composition was tested as follows: Skin time (ST) was determined as a measure of open time. For this purpose, several grams of the composition were applied to cardboard at a layer thickness of approximately 2 mm, and the first time when no residue remained on the LDPE pipette used to gently tap the surface of the composition under standard climatic conditions was determined.

[0196] Shore A hardness was determined in accordance with DIN53505 on test specimens cured for 14 days under standard climatic conditions.

[0197] To determine the mechanical properties, the composition was applied to a PTFE-coated film to obtain a film with a thickness of 2 mm, and then this film was stored under standard climatic conditions for 14 days. Several dumbbells with a length of 75 mm, a bar length of 30 mm and a bar width of 4 mm were punched out from the film, and these were tested for tensile strength (breaking load), elongation at break point, modulus of elasticity at 5% (elongation from 0.5% to 5%) and modulus of elasticity at 25% (elongation from 0.5% to 25%) at a strain rate of 200 mm / min in accordance with DIN EN53504.

[0198] The appearance of the produced film was visually evaluated. "Good" was used to represent a non-sticky film without swelling.

[0199] The odor was evaluated by smelling with the nose at a distance of 2 cm from the freshly produced film. "None" means that no odor was perceived.

[0200] The results are reported in Tables 3 to 4.

[0201]

Table 3

[0202]

Table 4

Claims

1. Use of at least one polyether having a blocked hydroxyl group as a solvent for obtaining an acid solution of at least one aromatic carboxylic acid or sulfonic acid, wherein the acid solution is used in a curable composition for producing polyurethane, wherein the aromatic carboxylic acid or sulfonic acid is selected from the group consisting of benzoic acid, 2-nitrobenzoic acid, salicylic acid, and p-toluenesulfonic acid, 70% to 100% by weight of the repeating units in the polyether consist of 1,2-propyleneoxy groups, and 0% to 30% by weight of the repeating units in the polyether consist of 1,2-ethyleneoxy groups, Use of a polyether wherein the blocked hydroxyl group is an acetate group.

2. The polyether having the blocked hydroxyl group has an average molecular weight M in the range of 600 to 10,000 g / mol, determined by gel permeation chromatography (GPC) relative to polystyrene as a standard, using tetrahydrofuran as the mobile phase, a refractive index detector, and an evaluation starting from 200 g / mol. ｎ Use according to claim 1, characterized in that it has

3. The use according to claim 1 or 2, characterized in that the polyether having a blocked hydroxyl group is derived from at least one hydroxy-functional polyether selected from the group consisting of: - Polyoxypropylene monool having an OH value in the range of 25 to 90 mg KOH / g starting from an alcohol, - Polyoxypropylene diol having an OH value in the range of 12 to 155 mg KOH / g, - Polyoxypropylene triol having an average OH functionality in the range of 2.2 to 3 and an OH value in the range of 22 to 230 mg KOH / g, optionally terminated with ethylene oxide, starting from trimethylolpropane or glycerol, and - Polyoxypropylene polyol having an average OH functionality in the range of 3 to 6 starting from a sugar alcohol.

4. An acid solution obtained from the use according to any one of claims 1 to 3.

5. The acid solution according to claim 4, characterized in that 2.5% to 25% by weight of an aromatic carboxylic acid or sulfonic acid and 50% to 97.5% by weight of a polyether having a blocked hydroxyl group are present.

6. A curable composition comprising the acid solution according to claim 4 or 5.

7. The curable composition according to claim 6, characterized by comprising: - At least one polyisocyanate or a polymer containing isocyanate groups, - At least one latent curing agent having at least one aldimino group, ketimino group, enamino group, or oxazolidino group - at least one polyether having blocked hydroxyl groups, and - at least one aromatic carboxylic acid or sulfonic acid.

8. The curable composition according to claim 7, wherein the latent curing agent is an aldimine of the following formula: 【Chemical 1】 (In the formula, y is 2 or 3, A is an organic group having 2 to 23 carbon atoms, and B is an organic group having 6 to 30 carbon atoms).

9. The curable composition according to claim 7 or 8, which is a one-component moisture-curable composition.

10. The curable composition according to any one of claims 6 to 9, which is an adhesive, a sealant, or a coating.

11. An article adhered, sealed, or coated with the curable composition according to any one of claims 6 to 10.

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