Polymer compositions curable at room temperature and made of polyaldehydes and 1, 3-ketoesters

Abstract

The present invention relates to a curable composition comprising:-a first component comprising a compound comprising aldehyde groups, comprising at least one compound having two or more aldehyde groups, and-a second component comprising a compound comprising 1, 3-ketoester groups, comprising at least one compound having two or more 1, 3-ketoester groups of formula (I), wherein the average molecular weight Mn of at least one of the two components associated with the compounds containing aldehyde or 1, 3-keto ester groups is in the range of 400 to 20000 g / mol. The composition is substantially free of toxic ingredients and can cure rapidly and without problems into non-tacky elastomeric polymers with high strength and stretchability under ambient conditions with conventional catalysts. It is particularly suitable for use as elastic adhesives, sealants or coatings with high robustness in preparation, storage and processing and high resistance after curing.

Description

Technical Field

[0001] The invention relates to a two-component composition and its use as room temperature curable elastic adhesive, sealant or coating. Prior art

[0002] Reactive polymer compositions that are curable at room temperature and can be used as elastic adhesives, sealants or coatings are known. Polyurethane systems that are cured by the reaction of isocyanate groups with polyols and / or moisture and form particularly highly elastic polymers are widely used. The preparation, production and use of polyurethane systems constitute a series of challenges in practice. They usually contain a large amount of monomeric diisocyanates, which can irritate the eyes, skin and mucous membranes. The moisture sensitivity of the isocyanate groups can lead to premature crosslinking reactions associated with increased viscosity until gel formation, and thus affect durability or storage stability. In the case of systems formulated in a one-component form, the water required for curing must penetrate from the outside in the form of air humidity, which complicates the use in thick layers or between moisture-proof substrates. In the case of using a two-component system with a polyol component and an isocyanate component, the problem is that the isocyanate groups can react not only with the hydroxyl groups of the polyol, but also with the water that may be present. In particular, in the case of high ambient humidity, this can trigger bubble formation and cause incomplete polymerization with chain termination due to only partially reacted polyols, which leads to more or less loss of strength and elasticity. These problems hardly occur when using mercury catalysts, which catalyze the reaction with polyols very selectively. However, mercury catalysts have long been out of use due to their high toxicity. As an alternative, two-component polyurethanes are usually catalyzed with tin compounds and / or tertiary amines, but these have significantly lower selectivity, whereby bubbles may form, especially at high ambient humidity. Bismuth or zirconium catalysts have a higher selectivity; however, these and other alternative metal catalysts are sensitive to hydrolysis, which means that the catalytic activity is greatly lost, which in turn can lead to curing defects.

[0003] Also widely used are reactive polymer compositions based on silane-functional polymers (SMP / STP) and silicones. These polymer systems cure by hydrolysis and condensation of the silane groups, releasing alcohols, in particular methanol or ethanol, or oximes, which are toxic and cause VOC emissions; in addition, they usually contain large amounts of low molecular weight silanes as crosslinkers or desiccants, which are likewise harmful to health. Due to the moisture sensitivity of the silane groups, these polymer systems are also demanding in terms of production and use and do not always produce the desired results.

[0004] Also known are water-based polymer systems, which are usually based on acrylate dispersions or polyurethane dispersions. These cure by evaporation and condensation of water and are essentially free of chemically reactive groups. However, they can only be used in relatively thin layers and only between open-pored substrates, the curing rate is highly dependent on the ambient humidity, and they have high shrinkage. After curing, due to the inclusion of surfactants required for the production and stability of the dispersion, water sensitivity increases, which can lead to reduced durability, especially in outdoor applications.

[0005] US Pat. No. 5,452,653 describes the crosslinking of compounds containing acetoacetate groups with aromatic aldimines, wherein acrylate polymers containing acetoacetate groups or aqueous polyurethane acrylate dispersions containing acetoacetate groups having a high solvent content are used. Summary of the invention

[0006] It was therefore an object of the present invention to provide novel polymer compositions which are curable at room temperature and are suitable as elastic adhesives, sealants or coatings and which overcome the disadvantages of the known polymer systems.

[0007] Surprisingly, this object is achieved by a curable composition according to claim 1. The composition comprises a first component containing a compound containing aldehyde groups and a second component containing a compound containing 1,3-ketoester groups, wherein the average molecular weight M of at least one of the two components related to the compound containing aldehyde groups or 1,3-ketoester groups is n The composition has several advantageous and surprising properties compared to room temperature curable polymer systems according to the prior art.

[0008] Compounds containing aldehyde groups and compounds containing 1,3-ketoester groups are both substances with low toxicity risk, which do not require hazard marking and can be handled without special precautions. The composition of the invention is insensitive to moisture and bubble formation and allows a high degree of freedom in formulation, since additives commonly used in curable compositions can be used in both components without causing storage stability problems for the respective components. Surprisingly, the composition is very tolerant of the stoichiometric ratio of the reactive groups, since in each case a cured non-sticky material with high stretchability and strength and good stability to heat and water is formed over the entire range of the ratio of the number of 1,3-ketoester groups to the number of aldehyde groups from 1 to 2 and higher. This is very surprising, since reactive systems according to the prior art usually show a significant reduction in mechanical quality in the case of large deviations from the optimal stoichiometry of the reactive groups (usually close to 1:1). For these reasons, the mixing ratio of the two components can be adjusted almost arbitrarily, which enables a high degree of freedom and simple, very reliable processing and a high tolerance for errors in the application method. The composition has good processability under ambient conditions, does not require organic solvents for dissolving or diluting or water for emulsifying or dispersing components. The composition can be cured quickly and flawlessly under ambient conditions regardless of humidity, and does not cause emissions. It is particularly advantageous here that the curing rate can be very effectively controlled with conventional catalysts, especially non-metallic bases such as tertiary amines, amidines and guanidines. The curing produces a non-viscous elastic polymer of high strength and stretchability, with good tear strength and stability to heat and water. Due to the combination of these favorable properties, the composition of the present invention has particularly simple handling without special protective measures, high robustness (Robustheit) and long life in the production and storage of components, when it is used in a wide range of environmental and application conditions and mixing ratio fluctuations, and after curing under mechanical, thermal or chemical stress.

[0009] The compositions of the invention are therefore very suitable for use as high-quality elastic adhesives, sealants or coatings.

[0010] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.

[0011] Specific embodiments of the present invention

[0012] The subject of the present invention is a curable composition comprising:

[0013] - a first component containing an aldehyde group-containing compound, which comprises at least one compound having two or more aldehyde groups, and

[0014] - a second component containing a compound containing 1,3-ketoester groups, which comprises at least one compound having two or more 1,3-ketoester groups of formula (I)

[0015]

[0016] Where R 1 is a monovalent hydrocarbon radical having 1 to 6 carbon atoms,

[0017] The average molecular weight M of at least one of the two components associated with the compound containing aldehyde or 1,3-ketoester groups is n In the range of 400 to 20000 g / mol.

[0018] "Aldehyde" refers to the formula functional groups.

[0019] The dashed lines in the formulae here represent in each case a bond between a substituent and the corresponding molecule residue.

[0020] "Molecular weight" refers to the molar mass of a molecule (g / mole). "Average molecular weight" refers to the number average molecular weight (M) of a polydisperse mixture of oligomer or polymer molecules. n ). It is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0021] A "storage-stable" composition is one that can be stored in a suitable container at room temperature for an extended period of time, typically at least 3 months to 6 months or more, without such storage resulting in a change in its application or use properties to an extent relevant to its use.

[0022] Substance names beginning with "poly", such as polyacetoacetate, polyaldehyde or polyol, refer to substances which contain two or more functional groups occurring in their names per molecule in a formal sense.

[0023] "Room temperature" refers to a temperature of 23°C.

[0024] All industry standards and specifications mentioned in this document refer to the versions in effect on the date of initial application filing.

[0025] Unless otherwise indicated, weight percent (wt%) refers to the mass proportion of a component of a composition or molecule based on the total composition or total molecules. The terms "mass" and "weight" are used synonymously in this document.

[0026] The first and second components of the curable composition are themselves storage-stable and are stored in separate containers from one another until they are mixed with one another shortly before or during application.

[0027] The curable composition is preferably not water-based. It is preferably substantially free of water or contains only a small amount of water. Such a composition cures rapidly regardless of the ambient humidity, can be used in thick layers and / or between waterproof substrates, and exhibits hardly any shrinkage when curing.

[0028] Preferably, the curable composition contains less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight, of water, based on the total composition.

[0029] The curable composition preferably does not contain compounds with aldehyde or 1,3-ketoester groups in the form of an emulsion or dispersion. The compounds with aldehyde or 1,3-ketoester groups thus contained preferably do not contain substantially ionic groups or their precursors, and do not contain substantially longer poly(oxyethylene) chains as commonly used in surfactants. Such compositions have high stability to water. In particular, the aldehyde-containing compound in the first component and the 1,3-ketoester group-containing compound in the second component each have an acid group or ionic group content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the aldehyde-containing compound or the 1,3-ketoester group-containing compound. Ionic groups are especially carboxylate groups, ammonium groups or sulfonate groups.

[0030] In the curable composition, the average molecular weight M of at least one of the two components associated with the compound containing aldehyde or 1,3-ketoester groups is n The composition is cured to obtain a high-strength elastic polymer.

[0031] Preferably, the average molecular weight M of at least one of the two components associated with the compound containing aldehyde or 1,3-ketoester groups is n In the range of 1000 g / mol to 20000 g / mol, preferably 1500 g / mol to 15000 g / mol, in particular 2000 g / mol to 10000 g / mol. This enables particularly high stretchability.

[0032] The compound having two or more aldehyde groups is preferably liquid at room temperature. In particular, its viscosity at 20° C. is 0.2-700 Pa·s, preferably 0.3-500 Pa·s, more preferably 0.5-200 Pa·s, and especially 1-100 Pa·s, which is determined by a cone diameter of 10 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm, a shear rate of 10 s -1 The viscosity is determined by a cone and plate viscometer of 1000 mm and a ball diameter of 50 mm is used for viscosities less than 1 Pa·s. These compounds are easily processed at ambient temperature even without the addition of solvents or diluents.

[0033] Preferred compounds having two or more aldehyde groups are polymers having aldehyde groups.

[0034] Preferably, the average molecular weight M of the first component associated with the aldehyde-containing compound is n 1000-20000 g / mol, preferably 1500-15000 g / mol, especially 2000-10000 g / mol, measured by gel permeation chromatography (GPC) with polystyrene as standard. Even without adding solvents or diluents, this component is easy to process at ambient temperature and gives the polymer high stretchability and elasticity.

[0035] Preferably, the average aldehyde functionality of the aldehyde group-containing compound is 1.6-4, preferably 1.8-3.5, more preferably 2.0-3.0, especially 2.2-3.0. This allows the cured composition to have high stretchability, strength and stability.

[0036] The compound containing an aldehyde group preferably comprises a polymer having a polymer backbone containing a poly(oxyalkylene) unit and / or a polyester unit.

[0037] Preferred poly(oxyalkylene)s are poly(oxyethylene), poly(oxy-1,2-propylene), poly(oxy-1,3-propylene), poly(oxy-1,4-butylene), poly(oxy-1,2-butylene) or mixed forms of these poly(oxyalkylene). Among them, poly(oxy-1,2-propylene), poly(oxy-1,3-propylene) or poly(oxy-1,4-butylene), especially poly(oxy-1,2-propylene), are preferred, wherein these may contain 0 to 25% by weight of poly(oxyethylene) units, based on the poly(oxyalkylene) backbone, especially at the chain ends. Aldehyde-functional polymers having such backbones have low viscosity and can therefore be processed particularly efficiently and are particularly hydrophobic. They give compositions having particularly good processability, high stretchability and good water resistance.

[0038] Preferred polyesters are esters of dicarboxylic acids and diols or triols, triglycerides or polyesters based on dimer or trimer fatty acids. Particularly preferred are polyesters of dimer fatty acids or polyesters derived from castor oil, castor oil or vegetable oil derivatives. Aldehyde-functional polymers with such a backbone are particularly hydrophobic, resulting in compositions having particularly high heat and water resistance. They are also based on renewable raw materials and are therefore particularly sustainable.

[0039] The compound having two or more aldehyde groups preferably additionally contains a urethane group. This allows the composition to have particularly high stretchability.

[0040] Preferably, the compound containing aldehyde groups comprises a polymer containing urethane groups, which is liquid at room temperature and has an average molecular weight M of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, in particular 2000 to 10000 g / mol. n , and an average aldehyde functionality of from 1.8 to 3.5, more preferably from 2.0 to 3.0, especially from 2.2 to 3.0.

[0041] Preferably, the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one polymer containing isocyanate groups or at least one polyisocyanate.

[0042] Suitable hydroxyaldehydes are, in particular, compounds having a molecular weight of 60 to 500 g / mol, preferably 60 to 250 g / mol.

[0043] The following are particularly suitable: 2-hydroxyacetaldehyde, 3-hydroxybutyraldehyde, 3-hydroxypivalaldehyde, 5-hydroxyvaleraldehyde, 2-(2-hydroxyethoxy)acetaldehyde, 3-(2-hydroxyethoxy)propionaldehyde, 5-hydroxymethylfurfural, alkoxylated o-, m- or p-hydroxybenzaldehyde or alkoxylated vanillin, where “alkoxylated” preferably means (mono- or poly-) “ethoxylated” or “propoxylated”, and 4,4′-(2-hydroxypropane-1,3-diyl)-bis(oxy)bis(benzaldehyde) or 4,4′-(2-hydroxypropane-1,3-diyl)bis(oxy)bis(3-methoxybenzaldehyde).

[0044] Preferred are ethoxylated salicylaldehydes, especially 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillins, especially 4-(2-hydroxyethoxy)-3-methoxybenzaldehyde, 5-hydroxymethylfurfural, N'-2-hydroxyethyl-N-piperazinyl-2,2-dimethylpropanal or N'-3-hydroxypropyl-N-piperazinyl-2,2-dimethylpropanal. These hydroxyaldehydes are obtainable in a simple manner and impart low viscosity and thus good processability to the compounds containing aldehyde groups, and good processability and high strength and high stretchability to the compositions.

[0045] A particularly preferred hydroxyaldehyde is 5-hydroxymethylfurfural. This hydroxyaldehyde is obtainable from renewable raw materials and surprisingly enables particularly low-viscosity compounds with aldehyde groups and curable compositions having particularly good processability and high strength, stretchability and heat and water resistance to be obtained.

[0046] Suitable polymers containing isocyanate groups for preparing compounds having two or more aldehyde groups are, in particular, reaction products of polyols with diisocyanates, in particular in an NCO / OH molar ratio of 1.5 / 1 to 10 / 1, unconverted monomeric diisocyanates being optionally removed from the polymers.

[0047] The polymer containing isocyanate groups preferably has a content of free isocyanate groups of 0.5% to 15% by weight, more preferably 1% to 10% by weight and in particular 1.5% to 6% by weight, based on the polymer.

[0048] Very particularly preferred polymers containing isocyanate groups are reaction products from at least one diisocyanate and at least one polyol in an NCO / OH ratio of at least 3 / 1, preferably from 3 / 1 to 10 / 1, in particular from 4 / 1 to 8 / 1, and then removing the majority of the monomeric diisocyanate by suitable separation methods, so that the polymer containing isocyanate groups ultimately has a monomeric diisocyanate content of not more than 0.2% by weight, based on the polymer. Such polymers containing isocyanate groups allow aldehyde-functional polymers to have a particularly low content of reaction products of monomeric diisocyanates and hydroxyaldehydes, in particular a content of these reaction products of less than 0.5% by weight, based on the aldehyde-functional polymer. This allows for particularly simple processing, long open times and rapid curing of curable compositions and particularly good flexibility.

[0049] Suitable diisocyanates are, in particular, hexane 1,6-diisocyanate (HDI), 2,2(4),4-trimethylhexane-1,6-diisocyanate (TMDI), 1-methyl-2,4(6)-diisocyanatocyclohexane (H6TDI), isophorone diisocyanate (IPDI), 4,4′-diisocyanatodicyclohexylmethane (H 12 MDI), 4(2),4′-diphenylmethane diisocyanate (MDI) or toluene-2,4(6)-diisocyanate. HDI, IPDI, TDI or MDI are preferred. IPDI is particularly preferred. This provides a composition with particularly good processability, which cures to give a polymer with high strength and stretchability.

[0050] Suitable polyols are especially

[0051] - polyether polyols, in particular polyoxyalkylene diols or triols, in particular the 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, where these can be polymerized with the aid of starter molecules having two or more active hydrogen atoms, in particular starter molecules such as water, ammonia or compounds having two or more OH or NH groups, for example ethane-1,2-diol, Propane-1,2- or -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycol or tripropylene glycol, isomeric butanediols, 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 thereof.

[0052] Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-terminated or EO-terminated) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene mixed polyols, which are obtained, in particular, by further alkoxylating polyoxypropylene diols or triols with ethylene oxide after the propoxylation reaction is complete, whereby they ultimately have primary hydroxyl groups.

[0053] Preferred polyether polyols have an unsaturation of less than 0.02 meq / g, especially less than 0.01 meq / g.

[0054] - Polyester polyols, especially those obtained from the polycondensation of hydroxycarboxylic acids or lactones or of aliphatic and / or aromatic polycarboxylic acids with diols or polyols. Preference is given to amorphous polyester polyols based on dimer or trimer fatty acids, such as are commercially available from Croda.

[0055] - Polycarbonate polyols, obtainable, for example, by reaction of diols with dialkyl carbonates, diaryl carbonates or phosgene.

[0056] - Block copolymers with at least two hydroxyl groups, in particular polyether polyester polyols.

[0057] - Polyacrylate polyols and polymethacrylate polyols.

[0058] - polyhydroxy-functional fats or oils, in particular natural fats or oils, such as, in particular, castor oil, castor oil derivatives; or polyols obtained by chemical modification of natural fats and oils - so-called oleochemical polyols - for example, those available under the trade name Hydroxylated vegetable oil obtained from BASF.

[0059] - Polyolefin polyols, such as, in particular, polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional ethylene / propylene, ethylene / butylene or ethylene / propylene / diene copolymers, such as those produced, for example, by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular 1,3-butadiene, which can also be prepared, in particular, by anionic polymerization; polyhydroxy-functional copolymers of dienes (for example 1,3-butadiene or diene mixtures) and vinyl monomers (for example styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene), such as polyhydroxy-functional acrylonitrile / butadiene copolymers, which can be prepared, for example, from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (for example, which can be prepared as CTBN or CTBNX or ETBN designations are commercially available from Emerald Performance Materials); and hydrogenated polyhydroxy-functional polymers or diene copolymers.

[0060] Polyols that are liquid at room temperature are preferred.

[0061] Preference is given to polyols having OH values ​​of 9 to 115 mg KOH / g, preferably 14 to 60 mg KOH / g and in particular 18 to 40 mg KOH / g.

[0062] Particularly preferred are polyether polyols, polyester polyols based on dimerized or trimerized fatty acids, castor oil, castor oil derivatives or hydroxylated vegetable oils. Most preferred are polyether polyols.

[0063] Likewise suitable as compounds having two or more aldehyde groups are the reaction products of at least one polyisocyanate with at least one hydroxyaldehyde, in particular the abovementioned hydroxyaldehydes.

[0064] Suitable polyisocyanates are especially oligomeric diisocyanates, especially HDI biuret, for example N 100 or N 3200 (from Covestro), HDB or HDB-LV (from Vencorex) or 24A-100 (from Asahi Kasei); HDI isocyanurate, such as N 3300, N3600 or N 3790BA (all from Covestro), HDT, HDT-LV or HDT-LV2 (from Vencorex), TPA-100 or THA-100 (from Asahi Kasei) or HX (from Nippon Polyurethane); HDI uretdione, such as N 3400 (from Covestro); HDI iminooxadiazinedione, such as XP 2410 (from Covestro); HDI allophanates, such as VPLS2102 (from Covestro); IPDI isocyanurate, for example as Z 4470 (from Covestro) as a solution or as Solid forms of T1890 / 100 (from Evonik); TDI oligomers such as IL (from Covestro); or mixed isocyanurates based on TDI / HDI, such as HL (from Covestro), where "HDI" stands for hexane-1,6-diisocyanate, "IPDI" stands for isophorone diisocyanate, and "TDI" stands for toluene-2,4-diisocyanate or a mixture thereof with toluene-2,6-diisocyanate. Oligomeric diisocyanates derived from HDI, especially HDI biuret, are preferred.

[0065] Preferably, the polymer or polyisocyanate containing isocyanate groups and the hydroxyaldehyde are reacted in an OH / NCO ratio of 1 / 1 to 1.2 / 1 at a temperature of 40 to 140° C., preferably 60 to 120° C., optionally in the presence of a suitable catalyst.

[0066] The curable composition comprises as a constituent of the second component at least one compound having two or more 1,3-ketoester groups of formula (I),

[0067]

[0068] Where R 1 It is a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0069] Preferably, R 1 It is methyl, ethyl, propyl, isopropyl, butyl or phenyl.

[0070] More preferably, R 1 It is methyl or phenyl.

[0071] The best choice is R 1 This 1,3-ketoester group is also called acetoacetate group.

[0072] The compound having two or more 1,3-ketoester groups is preferably liquid at room temperature. In particular, its viscosity at 20° C. is 0.01-100 Pa·s, preferably 0.02-50 Pa·s, and especially 0.05-20 Pa·s, which is determined by a cone diameter of 10 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm, a shear rate of 10 s-1 The viscosity is measured with a cone and plate viscometer of 1000 mm and a ball diameter of 50 mm is used for viscosities less than 1 Pa·s. This compound is easy to process at ambient temperature even without the addition of solvents or diluents and enables a well processable composition to be achieved.

[0073] Preferably, the average functionality of the second component related to the compound containing 1,3-ketoester groups is in the range of 1.6 to 4, preferably 1.8 to 3.5, more preferably 2.0 to 3.0. This allows the cured composition to have high stretchability, strength and stability.

[0074] Preferably, the average molecular weight M of the second component associated with the compound containing 1,3-ketoester groups is n In the range of 230 to 10000 g / mol, preferably 250 to 2000 g / mol.

[0075] In a preferred embodiment of the present invention, the average molecular weight M of the second component associated with the compound containing 1,3-ketoester groups is n The second component can achieve a high-strength composition that is particularly easy to process.

[0076] In another preferred embodiment of the present invention, the average molecular weight M of the second component associated with the compound containing 1,3-ketoester groups is n In the range of 2000-10000 g / mol. n In combination with a first component associated with a compound containing aldehyde groups, such a second component enables in a particularly simple manner the composition to have a mixing ratio of the two components in the range of 1:1, which is particularly advantageous in certain applications, especially in the case of processing by means of a static mixer.

[0077] Preferably, the second component contains at least one 1,3-ketoester group-containing organic solvent having an average molecular weight M of 500 to 10000 g / mol, preferably 500 to 2000 g / mol. n and polymers having an average functionality of from 1.8 to 3.5, more preferably from 2.0 to 3.0, especially from 2.5 to 3.0.

[0078] Preferably, the compound having two or more 1,3-ketoester groups of formula (I) is obtained by transesterification of at least one 1,3-ketoester of formula (II) with at least one polyfunctional alcohol, wherein a 1,3-ketoester of formula R is liberated and removed. 2 OH alcohol,

[0079]

[0080] Where R 2It is C 1-6 Alkyl, and R 1 With the definition already given.

[0081] Preferably, R 2 is methyl, ethyl or tert-butyl, especially ethyl.

[0082] The reaction is preferably carried out at a temperature of 50 to 150° C., optionally by distillation under reduced pressure and optionally in the presence of a catalyst to remove the liberated alcohol R 2 OH.

[0083] Preferred 1,3-ketoesters of the formula (II) are methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, ethyl propionylacetate, ethyl 3-oxohexanoate, ethyl isobutyrylacetate or ethyl benzoylacetate, in particular ethyl acetoacetate.

[0084] It is likewise possible to prepare compounds having two or more 1,3-ketoester groups by reaction of diketene or an adduct of diketene with acetone (=2,2,6-trimethyl-4H-1,3-dioxin-4-one) with at least one polyfunctional alcohol, wherein in the case of the acetone-diketenyl adduct acetone is released.

[0085] Suitable polyfunctional alcohols are commercial compounds or polymers having two or more OH groups, such as, in particular, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, diethylene glycol, dipropylene glycol, 1,1,1-trimethylolpropane, glycerol, ethoxylated or especially propoxylated glycerol, ethoxylated or especially propoxylated glycerol, Oxylated 1,1,1-trimethylolpropane, castor oil, ethoxylated or, in particular, propoxylated castor oil, ketone resin-modified castor oil, hydroxylated vegetable oils, dimerized fatty acid diols or trimerized fatty acid triols, amorphous polyester diols or triols based on dimerized or trimerized fatty acids, and the other polyols already mentioned above for the preparation of polymers containing isocyanate groups, in particular poly(oxy-1,2-propylene) diols or triols or ethylene oxide-terminated poly(oxy-1,2-propylene) diols or triols.

[0086] Particularly preferred polyfunctional alcohols are ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, dipropylene glycol or 1,1,1-trimethylolpropane.

[0087] Further particularly preferred polyfunctional alcohols are those having an average molecular weight M nThe propoxylated 1,1,1-trimethylolpropane is 300 to 1700 g / mol.

[0088] Further particularly preferred polyfunctional alcohols are those having an average molecular weight M of 400 to 10 000 g / mol. n Poly(oxy-1,2-propylene) glycol or having an average molecular weight M of 2000 to 10000 g / mol n The poly(oxy-1,2-propylene) triol is a poly(oxy-1,2-propylene) diol or triol, wherein the poly(oxy-1,2-propylene) diol or triol is optionally ethylene oxide terminated.

[0089] Other particularly preferred polyfunctional alcohols are those having an average molecular weight M of 800 to 3000 g / mol. n Amorphous polyester diols based on dimerized fatty acids or amorphous polyester triols based on trimerized fatty acids.

[0090] More preferably, the compound containing a 1,3-ketoester group is selected from ethane-1,2-diol bis(acetoacetate), propane-1,2-diol bis(acetoacetate), propane-1,3-diol bis(acetoacetate), butane-1,4-diol bis(acetoacetate), hexane-1,6-diol bis(acetoacetate), cyclohexane-1,4-dimethanol bis(acetoacetate), dipropylene glycol bis(acetoacetate), 1,1,1-trimethylolpropane tris(acetoacetate), glycerol tris(acetoacetate), an average molecular weight M n Propoxylated 1,1,1-trimethylolpropane tris(acetoacetate) with an average molecular weight M of 500 to 2000 g / mol n Poly(oxy-1,2-propylene) glycol bis(acetoacetate) of 600 to 10000 g / mol, average molecular weight M n Poly(oxy-1,2-propylene)triol tri(acetoacetate) of 2000 to 10000 g / mol, containing ethylene oxide units and having an average molecular weight M of 2000 to 10000 g / mol n Poly(oxy-1,2-propylene) triol tri(acetoacetate), polyester diol bis(acetoacetate) based on dimer fatty acid, and polyester triol tri(acetoacetate) based on trimer fatty acid.

[0091] Most preferably, the compound containing 1,3-ketoester groups is room temperature liquid polyester diol diacetoacetate based on dimer fatty acid or room temperature liquid polyester triol triacetoacetate based on trimer fatty acid. This allows the cured composition to have particularly high stretchability.

[0092] Suitable compounds having two or more acetoacetate groups are also commercially available, in particular as 7301 or XM-B301 (both from King Industries).

[0093] Preferably, the overall composition has an average functionality based on reactive aldehyde and 1,3-ketoester groups of at least 1.9, especially at least 2.0. This means that a composition having an average aldehyde functionality of, for example, 1.8 in the first component is preferably combined with a second component having an average 1,3-ketoester functionality of at least 2.0, preferably at least 2.1, in order to obtain an overall average reactive group functionality of 1.9, preferably 2.0.

[0094] More preferably, the curable composition contains as a component of the first component at least one room temperature liquid polymer containing urethane groups and having an average molecular weight M of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, in particular 2000 to 10000 g / mol. n , and an average aldehyde functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, especially 2.2 to 3, and contains as a constituent of the second component at least one polymer containing acetoacetate groups and having an average molecular weight Mn of 500 to 10 000 g / mol, preferably 500 to 2000 g / mol and an average acetoacetate functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, especially 2.5 to 3.0, wherein the average reactive group functionality preferably totals at least 1.9, especially at least 2.0.

[0095] Furthermore, the first component of the curable composition may contain a certain proportion of low molecular weight polyaldehydes, such as, in particular, hexane-1,6-dialdehyde, heptane-1,7-dialdehyde, octane-1,8-dialdehyde, nonane-1,9-dialdehyde, 2-methyloctane-1,8-dialdehyde, decane-1,10-dialdehyde, undecane-1,11-dialdehyde, dodecane-1,12-dialdehyde, hexahydrophthalaldehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, octa ... Hydrogen-4,7-methylene-1H-indene dicarboxaldehyde, 3,6,9-trioxaundecane-1,11-dialdehyde, 1,3-bis(2,2-dimethyl-3-oxopropyl)imidazolidin-2-one, N,N'-bis(2,2-dimethyl-3-oxopropyl)piperazine, N,N'-bis(2,2-dimethyl-3-oxopropyl)urea, o-phthalaldehyde, isophthalaldehyde, terephthalaldehyde, anthracene-9,10-diacetaldehyde or naphthalene diacetaldehyde.

[0096] The curable composition may additionally contain other ingredients, in particular the following:

[0097] - fillers, in particular ground or precipitated calcium carbonate, optionally coated with fatty acids, in particular stearates, barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, sheet silicates such as mica or talc, zeolites, aluminum hydroxide, magnesium hydroxide, silicon dioxide, including highly dispersed silicon dioxide from pyrogenic processes, industrially produced carbon black, graphite, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow beads;

[0098] - fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, Hanf fibers, cellulose fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

[0099] – nanofillers, such as graphene or carbon nanotubes;

[0100] -dye;

[0101] – pigments, in particular titanium dioxide, chromium oxide, iron oxide or organic pigments;

[0102] – plasticizers, in particular phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, in particular diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl) terephthalate or diisononyl terephthalate (DINT), hydrogenated terephthalates, in particular bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalates, trimellitic acid Esters, adipates, especially dioctyl adipate (DOA), azelates, sebacates, benzoates, glycol ethers, glycol esters, plasticizers with a polyether structure, especially polyoxypropylene mono-, di- or triols, or polyoxypropylene mono-, di- or triols with blocked hydroxyl groups, especially in the form of acetate groups, and organic sulfonates or phosphates, especially diphenylcresyl phosphate (DPK), polybutene, polyisobutene or plasticizers derived from natural fats or oils, especially epoxidized soybean oil or linseed oil, especially phthalates, hydrogenated phthalates, adipates or plasticizers with a polyether structure;

[0103] – solvents;

[0104] – modifiers, such as hydrocarbon resins, natural or synthetic waxes or bitumens;

[0105] - rheology modifiers, in particular urea compounds, layered silicates such as bentonites, castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, pyrogenic silica or hydrophobically modified polyoxyethylenes;

[0106] – Desiccants, especially molecular sieves, calcium oxide, monooxazolidines such as 2 (from Incorez) or orthoformate;

[0107] - adhesion promoters, in particular titanates or organoalkoxysilanes, for example aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes, (meth)acryloylsilanes, carbamatesilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;

[0108] - a catalyst, in particular a non-metallic base, such as a tertiary amine, in particular 2-dimethylaminoethyl ether, 2,2'-dimorpholinodiethyl ether (DMDEE) or 1,4-diazabicyclo[2.2.2]octane (DABCO), an amidine, in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1-(2-hydroxy-3-(3-trimethoxysilylpropoxy)prop-1-yl)-2-methyl-1,4,5,6-tetrahydropyrimidine, or a guanidine, in particular 1,1,3,3-tetramethylguanidine, 1-hexyl-2,3-diisopropylguanidine or a tertiary amine having an average molecular weight of 1. n about 250 to 500 g / mol of 1,1′-(α,ω-polyoxypropylene)bis(2,3-diisopropylguanidine), and in particular basic salts, such as in particular potassium acetate, potassium benzoate, potassium carbonate, potassium hydrogencarbonate, potassium phosphate, and the corresponding salts with sodium or lithium instead of potassium, wherein such basic salts are preferably used in the form of aqueous solutions, for example with a salt concentration of 10 to 30% by weight, based on the total weight of the solution;

[0109] - non-reactive thermoplastic polymers, such as homopolymers or copolymers of unsaturated monomers, in particular selected from ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymers (EVA) and atactic poly-α-olefins (APAO);

[0110] - flame-retardant substances, in particular the already mentioned aluminium hydroxide or magnesium hydroxide fillers, organic phosphates, ammonium polyphosphate, melamine or its derivatives, boron compounds or antimony compounds;

[0111] – additives, in particular wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation, or biocides;

[0112] and other materials commonly used in curable compositions.

[0113] These additives can be present as a component of the first or second component. The substances that react with 1,3-ketoester groups are preferably a component of the first component. The substances that react with aldehyde groups are preferably a component of the second component.

[0114] The curable composition preferably additionally contains at least one further ingredient selected from plasticizers, fillers and catalysts. The curable composition preferably contains several such further ingredients.

[0115] The curable composition preferably contains at least one basic catalyst having a pKa of at least 8, preferably at least 8.5, especially an aqueous solution of a nitrogen-containing compound or a basic salt. Such compositions exhibit particularly rapid curing.

[0116] In a preferred embodiment of the invention, the curable composition contains 10-95% by weight, preferably 20-90% by weight, and in particular 30-80% by weight of filler, based on the total composition. Preference is given to fillers selected from calcium carbonate, barite, quartz powder, quartz sand, kaolin, aluminum hydroxide, titanium dioxide and carbon black. Such a composition is particularly suitable for applications with a layer thickness of at least 1 mm, preferably 1-500 mm, and in particular 1.5-250 mm. In this case, the cured composition exhibits significant elasticity.

[0117] In another preferred embodiment of the present invention, the curable composition contains 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizer, based on the total composition. Preferred plasticizers are selected from DINP, DIDP, DPHP, DINCH, bis(2-ethylhexyl) terephthalate, DINT, bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, diisononyl cyclohexane-1,4-dicarboxylate, DOA, polyoxypropylene monool, polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene monool acetate, polyoxypropylene diol diacetate, polyoxypropylene triol triacetate and DPK.

[0118] In a particularly preferred embodiment of the present invention, the curable composition contains fillers and plasticizers, in particular, 20% to 90% by weight, especially 30% to 80% by weight, of fillers and 5% to 60% by weight of plasticizers, based on the total composition.

[0119] The curable composition preferably contains less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of volatile organic solvents having a boiling point at standard pressure below 250° C., based on the entire composition. Such compositions lead to particularly low emissions.

[0120] The first component of the curable composition preferably does not contain aldimine groups or only contains less than 0.2 mol, especially less than 0.1 mol of imide groups per mole of 1,3-ketoester groups in the second component. This means that the first component is essentially free of primary amines. Primary amino groups react with aldehydes to obtain aldimines. It is not within the scope of the present invention to convert the aldehyde groups in the first component into aldimine groups. The curable composition of the present invention is cured mainly by the reaction of 1,3-ketoester groups with free aldehyde groups.

[0121] The curable composition preferably comprises in total:

[0122] - 5% to 100% by weight, preferably 10% to 70% by weight, of the sum of compounds having aldehyde groups or 1,3-ketoester groups of the formula (I),

[0123] - 0% to 50% by weight, preferably 10% to 40% by weight, of plasticizers,

[0124] - 0 to 90% by weight, preferably 20 to 80% by weight, of fillers,

[0125] – and optionally other substances,

[0126] Based on the total composition.

[0127] In the curable composition, the ratio of the number of 1,3-ketoester groups to the number of aldehyde groups is preferably in the range of 0.5 to 2.5, more preferably in the range of 0.8 to 2.2, in particular in the range of 1 to 2. Such a ratio enables rapid, defect-free curing to give a polymer of high mechanical quality with high strength, stretchability and stability. Particularly surprising is the fact that the ratio can be varied within this range and a non-sticky material with good mechanical properties is always obtained. As a result, the composition is particularly robust to fluctuations in the mixing ratio of the two components during processing.

[0128] The consistency of the first and second components of the curable composition is suitable so that the components can be mixed well with one another by simple methods under ambient conditions. For this purpose, liquid or pasty components are particularly suitable.

[0129] The first and second components of the curable composition are prepared separately from each other. The ingredients of the individual components are mixed with each other to obtain a macroscopically homogeneous substance. Each component is stored in a separate container. Suitable containers are especially drums, containers, kegs, barrels, cans, bladders, bags, hose bags, magazines or tubes. The components are storage-stable.

[0130] To use the curable composition, the two components and any further components present are mixed with one another shortly before or during application. The mixing ratio is selected such that the ratio of the number of 1,3-ketoester groups to the number of aldehyde groups is within a suitable range, in particular about 1 to 2. The mixing ratio between the first and second components is generally about 100:1 to 1:5, in particular 50:1 to 1:2, based on parts by weight.

[0131] If the components are mixed with one another before application, it must be ensured that not too much time elapses between mixing of the components and application, since otherwise the onset of reaction and the viscosity increase associated therewith can lead to problems such as inadequate leveling or slow or incomplete adhesion to the substrate. More particularly, the open time of the composition should not be exceeded during application.

[0132] "Open time" as used herein means the time span between mixing of the components and the conclusion of a state in which the composition is suitable for processing.

[0133] Mixing is preferably carried out at ambient temperature, in particular at a temperature of -5 to 50°C, especially 0 to 40°C.

[0134] As the two components are mixed, the composition begins to cure by the onset of a chemical reaction. Here, it is primarily the 1,3-ketoester groups that react with the aldehyde groups, with the result that the composition eventually cures to give a solid polymer material. It is expected that the curing reaction will form the following formula In addition, it can be expected that further 1,3-ketoester groups which are optionally present will be able to add to the C=C double bonds formed and thus increase the crosslinking density. Curing is preferably carried out at ambient temperature, in particular at a temperature of -5 to 50° C., in particular 0 to 40° C.

[0135] Another subject of the invention is a cured composition obtained from the curable composition after mixing of the two components.

[0136] The cured composition is preferably elastic and has high strength and high stretchability.

[0137] The cured composition preferably has a tensile strength, determined as described in the examples to DIN EN 53504, of at least 1 MPa, preferably at least 1.5 MPa and in particular at least 2 MPa.

[0138] The cured composition preferably has an elongation at break of at least 50%, preferably at least 75%, more preferably at least 100%, particularly preferably at least 150%, in particular at least 200%, as determined in accordance with DIN EN 53504 as described in the examples.

[0139] The cured composition preferably has a Shore A hardness of 10 to 90, in particular 20 to 80, determined in accordance with DIN 53505 as described in the examples.

[0140] In addition, the cured composition has good heat resistance and water resistance. The cured composition preferably has high strength, stretchability and hardness even after storage at 100° C. or 70° C. and 100% relative humidity for 7 days.

[0141] The curable composition is suitable for a variety of uses. It can be used in particular as an adhesive, sealant, coating, casting resin or filling material.

[0142] A further subject matter of the invention is the use of the curable composition as an elastic adhesive, elastic sealant or elastic coating, wherein the first and second and optionally further components are mixed with one another and the mixed composition is applied in liquid form to at least one substrate.

[0143] In the case of use as elastic adhesive, elastic sealant or elastic coating, the layer thickness of the cured composition is preferably at least 1 mm, preferably 1 to 50 mm, in particular 1.5 to 25 mm.

[0144] Suitable substrates are in particular:

[0145] – glass, glass ceramics, concrete, mortar, cement mortar, fibre cement, bricks, tiles, plaster or natural rock such as granite or marble;

[0146] – Repair or leveling materials based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar);

[0147] - metals or alloys such as aluminium, iron, steel, copper, other non-ferrous metals, including metals or alloys with surface finishing such as zinc or chromium plating;

[0148] – bitumen or asphalt;

[0149] – leather, textiles, paper, wood, wooden materials bonded with resins (e.g. phenolic resins, melamine resins or epoxy resins), resin-textile composites or other so-called polymer composites;

[0150] – plastics, such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by plasma, corona or flame treatment;

[0151] – Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFK), glass fiber-reinforced plastics (GFK), natural fiber-reinforced plastics (NFK) and sheet molding compounds (SMC);

[0152] – insulating foams, in particular those made of EPS, XPS, PUR, PIR, rock wool, glass wool, aerogel or foam glass;

[0153] – coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets;

[0154] – Paint, lacquer or varnish.

[0155] If desired, the substrate can be pretreated prior to application, in particular by physical and / or chemical cleaning methods or by application of an activator or primer.

[0156] Two identical or two different substrates may be bonded and / or sealed.

[0157] An article is obtained by using the curable composition. The article is especially bonded, sealed or coated with the composition. The article can be a building or a part thereof, especially a building, a bridge, a roof, a stairwell or a facade of an above-ground or underground structure, or it can be an industrial or consumer article, especially a window, a pipe, a rotor blade for a wind turbine, a household appliance or a means of transport, such as in particular a car, a bus, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or a mountable part thereof. Example

[0158] Examples are described below which are intended to further illustrate the invention described. It is obvious that the invention is not limited to these described examples.

[0159] “Standard climatic conditions” (“NK”) mean a temperature of 23±1° C. and a relative air humidity of 50%±5%.

[0160] Unless otherwise stated, chemicals used were from Sigma-Aldrich Chemie GmbH.

[0161] Description of measurement method:

[0162] The viscometer was Rheotec RC 30 (cone diameter 10 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ) The viscosity was measured on a cone with a diameter of 50 mm. Viscosities less than 1 Pa·s were measured using a cone with a diameter of 50 mm.

[0163] Infrared spectra (FT-IR) were measured as undiluted films on a FT-IR instrument Nicolet iS5 from Thermo Scientific equipped with a horizontal ATR measurement cell with a diamond crystal. The absorption bands are expressed in wavenumbers (cm-1 )Report.

[0164] Preparation of polymers containing isocyanate groups:

[0165] Polymer P-1:

[0166] 780 g of ethylene oxide-terminated polyoxypropylene triol ( 5031BT, OH value 28.0 mgKOH / g, OH functionality about 2.3, from Covestro) and 303 g isophorone diisocyanate ( IPDI, from Evonik) was converted by known methods at 80° C. into a reaction mixture having an NCO content of 9.1% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160° C., pressure 0.1 to 0.005 mbar) to give a polymer having an NCO content of 1.84% by weight and a content of monomeric isophorone diisocyanate of 0.02% by weight.

[0167] Polymer P-2:

[0168] 590 g of polyoxypropylene glycol ( 4200, OH value 28mg KOH / g, from Coves tro), 1180g ethylene oxide terminated polyoxypropylene triol ( MD34-02, OH value 35 mg KOH / g, from Shell) and 230 g isophorone diisocyanate ( IPDI, from Evonik) was converted at 80° C. by known methods into a polymer having an NCO content of 2.1% by weight.

[0169] Polymer P-3:

[0170] 818 g of polyoxypropylene glycol ( 4200, OH value 28.5 mg KOH / g, from Covestro) and 227 g isophorone diisocyanate ( IPDI, from Evonik) was converted by known methods at 80° C. into a reaction mixture having an NCO content of 6.6% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160° C., pressure 0.1 to 0.005 mbar) to give a polymer having an NCO content of 1.91% by weight and a content of monomeric isophorone diisocyanate of 0.03% by weight.

[0171] Polymer P-4:

[0172] 727.0 g of polyoxypropylene glycol ( 4200, OH value 28 mg KOH / g, from Covestro) and 273.0 g diphenylmethane 4,4'-diisocyanate ( 44MC L, from Covestro) was converted by known methods at 80° C. into a reaction mixture having an NCO content of 7.6% by weight. Subsequently, the volatile components, in particular unconverted diphenylmethane 4,4′-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180° C., pressure 0.1-0.005 mbar, condensation temperature 47° C.) to give a polymer having an NCO content of 1.7% by weight and a content of monomeric diphenylmethane 4,4′-diisocyanate of 0.08% by weight.

[0173] Polymer P-5:

[0174] 513.3 g of polyoxypropylene glycol ( 4200, OH value 28 mg KOH / g, from Covestro), 256.7 g ethylene oxide-terminated polyoxypropylene triol ( MD34-02, OH value 35 mg KOH / g, from Shell) and 64.2 g toluene diisocyanate ( T 80P from Covestro) was converted at 80° C. by known methods into a polymer having an NCO content of 1.5% by weight.

[0175] Polymer P-6:

[0176] 600g polyoxypropylene glycol ( 1010L, OH value 112 mg KOH / g, from Dow) and 533.3 g isophorone diisocyanate ( IPDI, from Evonik) was converted by known methods at 80° C. into a reaction mixture having an NCO content of 15.6% by weight. Subsequently, the volatile constituents, in particular unconverted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160° C., pressure 0.1 to 0.005 mbar) to give a polymer having an NCO content of 5.18% by weight and a content of monomeric isophorone diisocyanate of 0.03% by weight.

[0177] Preparation of compounds having two or more aldehyde groups:

[0178] Compounds D-1 to D-7:

[0179] For each compound, the amounts (in parts by weight) of the corresponding isocyanate group-containing polymers specified in Table 1 were reacted with the amounts (in parts by weight) of the corresponding hydroxy-functional aldehydes specified in Table 1 in the presence of 0.02% by weight of dibutyltin dilaurate at 110° C. with exclusion of moisture until isocyanate groups were no longer detectable by IR spectroscopy. In the case of polymers P-4 and P-5 having aromatic isocyanate groups, the reaction was carried out in the absence of dibutyltin dilaurate and at 80° C. A clear, colorless liquid was obtained in each case.

[0180] The properties of compounds D-1 to D-7 are reported in Table 1.

[0181]

[0182] Table 1: Preparation and properties of compounds D-1 to D-7.

[0183] The average molecular weight M of compound D-1 n The average molecular weight M is also determined by gel permeation chromatography (GPC) using polystyrene (474-2520000 g / mol) as the standard, tetrahydrofuran as the mobile phase and a refractive index detector. n It is 6100g / mol.

[0184] Preparation of compounds having two or more 1,3-ketoester groups:

[0185] Compounds B-1 to B-5:

[0186] For each compound, the corresponding polyfunctional alcohol in the amount specified in Table 2 (in parts by weight) was mixed with the corresponding 1,3-ketoester in the amount specified in Table 2 (in parts by weight) and 0.1 wt % of tetra-n-butyl titanate ( TnBT from Dorf Ketal) was mixed and the mixture was reacted at a temperature of 140° C. under reduced pressure and the volatile constituents were removed. A clear, colorless liquid was obtained in each case.

[0187]

[0188]

[0189] Table 2: Preparation and properties of compounds B-1 to B-5.

[0190] 1 Trimethylolpropane-initiated polyoxypropylene triol ( 4011T, OH value 550mgKOH / g, from Covestro)

[0191] 2 Amorphous polyester diol based on dimerized fatty acid ( 1837, OH value 115mg KOH / g, from Croda)

[0192] Production of curable compositions:

[0193] Examples E-1 to E-29

[0194] For each example, a centrifugal mixer (SpeedMixer TM DAC 150, Flacktek Inc.) The ingredients of the first component (K1) specified in Tables 3 to 7 were mixed with one another in the specified amounts (parts by weight) and stored in a closed container.

[0195] The ingredients of the second component (K2) specified in Tables 3 to 7 were processed and stored likewise.

[0196] The "precipitated CaCO3" used is U1S2 (from Imerys), a precipitated and stearate-coated calcium carbonate.

[0197] The "carbon black" used is 570 (from Cabot).

[0198] Subsequently, the two components of each composition were processed with the aid of a centrifugal mixer to obtain a homogeneous paste, which was tested as described below.

[0199] The gel time is determined by stirring a freshly mixed amount of about 3 g with a spatula at regular intervals under standard climatic conditions until stirring is no longer possible due to gelling of the mass.

[0200] To determine the mechanical properties, the mixed composition was applied to a silicone-coated release paper to give a film with a thickness of 2 mm, the film was cured for 7 days under standard climatic conditions, several dumbbell-shaped specimens with a length of 75 mm, a beam length of 30 mm, and a beam width of 4 mm were punched out of the film, and these specimens were tested for tensile strength, elongation at break, and modulus of elasticity 5% (at 0.5%-5% elongation) and modulus of elasticity 50% (at 0.5%-50% elongation) at a strain rate of 200 mm / min according to DIN EN 53504. In addition, several specimens were punched out to determine the tear strength and tested according to DIN ISO 34-1, method B (angle specimens) at a tensile rate of 500 mm / min.

[0201] The Shore A hardness is determined in accordance with DIN 53505 on specimens cured under standard climatic conditions for 7 days. These results are given the notation "7d NK". To determine the heat and water resistance, after curing for 7 days under standard climatic conditions, further Shore A specimens are additionally stored in an air-circulating oven at 100° C. for 7 days or else at 70° C. and 100% relative humidity for 7 days, cooled to room temperature and then the Shore A hardness stated in each case is determined. These results are given the notation "+7d 100° C." or "+7d 70 / 100".

[0202] In each case, a non-sticky elastic material was obtained in the curing of the examples of the invention.

[0203] The results are reported in Tables 3 to 7.

[0204]

[0205] Table 3: Composition and properties of E-1 to E-7.

[0206] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (from BASF N700)

[0207] 2 Ratio of the number of acetoacetate groups to aldehyde groups

[0208]

[0209] Table 4: Composition and properties of E-4 and E-8 to E-13.

[0210] “nb” stands for “not determined”

[0211] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (from BASF N700)

[0212] 2 Ratio of the number of acetoacetate groups to aldehyde groups

[0213]

[0214] Table 5: Composition and properties of E-14 to E-21.

[0215] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (from BASF N700)

[0216] 2 Ratio of the number of acetoacetate groups to aldehyde groups

[0217]

[0218] Table 6: Composition and properties of E-4, E-15, and E-22 to E-25.

[0219] “nb” stands for “not determined”

[0220] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (from BASF N700)

[0221] 2 Ratio of the number of acetoacetate groups to aldehyde groups

[0222]

[0223] Table 7: Composition and properties of E-26 to E-29.

[0224] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (from BASF N700)

[0225] 2 Ratio of the number of 1,3-ketoester groups to aldehyde groups.

Claims

1. A curable composition comprising: - a first component containing an aldehyde group-containing compound, which comprises at least one compound having two or more aldehyde groups, and - a second component containing a compound containing 1,3-ketoester groups, which comprises at least one compound having two or more 1,3-ketoester groups of formula (I) Where R 1 is a monovalent hydrocarbon radical having 1 to 6 carbon atoms, The average molecular weight M of at least one of the two components associated with the compound containing aldehyde or 1,3-ketoester groups is n In the range of 400 to 20000 g / mol.

2. The composition according to claim 1, characterized in that Based on the total composition, less than 10% by weight, preferably less than 5% by weight, in particular less than 2% by weight, of water is contained.

3. The composition according to claim 1 or 2, characterized in that The compound having two or more aldehyde groups is liquid at room temperature, especially has a viscosity of 0.2-700 Pa·s, preferably 0.3-500 Pa·s, more preferably 0.5-200 Pa·s at 20°C, the viscosity being determined by a cone diameter of 10 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm and a shear rate of 10 s -1 The viscosity was measured with a cone-plate viscometer using a ball diameter of 50 mm for viscosities less than 1 Pa·s.

4. The composition according to any one of claims 1 to 3, characterized in that The average molecular weight M of the first component associated with the aldehyde group-containing compound is measured by gel permeation chromatography (GPC) relative to polystyrene as a standard. n It is 1000 g / mol to 20000 g / mol, preferably 1500 g / mol to 15000 g / mol, and especially 2000 g / mol to 10000 g / mol.

5. The composition according to any one of claims 1 to 4, characterized in that The aldehyde group-containing compound comprises a polymer having a polymer backbone comprising a poly(oxyalkylene) unit and / or a polyester unit.

6. The composition according to any one of claims 1 to 5, characterized in that The compound containing aldehyde groups comprises a polymer containing urethane groups, which is liquid at room temperature and has an average molecular weight M of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, in particular 2000 to 10000 g / mol. n and an average aldehyde functionality of from 1.8 to 3.5, preferably from 2.0 to 3.0, especially from 2.2 to 3.

0.

7. The composition according to any one of claims 1 to 6, characterized in that In the 1,3-ketoester group of formula (I), R 1 is methyl, ethyl, propyl, isopropyl, butyl or phenyl, preferably methyl or phenyl, especially methyl.

8. The composition according to any one of claims 1 to 7, characterized in that The average functionality of the second component related to the compound containing 1,3-ketoester groups is from 1.6 to 4, preferably from 1.8 to 3.5, more preferably from 2.0 to 3.

0.

9. The composition according to any one of claims 1 to 8, characterized in that The average molecular weight M of the second component related to the compound containing 1,3-ketoester groups n It is 230 to 10000 g / mol, preferably 250 to 2000 g / mol.

10. The composition according to any one of claims 1 to 9, characterized in that Based on the total composition, the filler comprises 10% to 95% by weight, preferably 20% to 90% by weight, and in particular 30% to 80% by weight.

11. The composition according to any one of claims 1 to 10, characterized in that Based on the total composition, 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizer is contained.

12. The composition according to any one of claims 1 to 11, characterized in that Based on the total composition, less than 10% by weight, preferably less than 5% by weight, in particular less than 1% by weight, of volatile organic solvents having a boiling point of less than 250° C. at standard pressure are contained.

13. A cured composition obtained from a curable composition according to any one of claims 1 to 12 after mixing two components, wherein the cured composition has in particular a tensile strength of at least 1 MPa, preferably at least 1.5 MPa, in particular at least 2 MPa, and / or an elongation at break of at least 75%, preferably at least 100%, in particular at least 150%, measured according to DIN EN 53504 at a tensile rate of 200 mm / min on dumbbell-shaped test pieces with a thickness of 2 mm, a length of 75 mm, a beam length of 30 mm, and a beam width of 4 mm.

14. Use of the composition according to any one of claims 1 to 12 as an elastic adhesive, elastic sealant or elastic coating, wherein the first component and the second component and optionally other components are mixed with one another and the mixed composition is applied in liquid form to at least one substrate.

15. The method according to claim 14, wherein the cured composition has a layer thickness of at least 1 mm, preferably 1 to 50 mm, in particular 1.5 to 25 mm.

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