Polymer composition which can be cured at room temperature and which is made of polyaldehyde and polymalonate

Abstract

The invention relates to a curable composition comprising – a first component containing aldehyde group-containing compounds which comprise at least one compound with two or more aldehyde groups and – a second component containing malonate group-containing compounds which comprise at least one compound with two or more malonate groups of the formula (I), wherein the average molecular weight Mn of at least one of the two components, with respect to the aldehyde or malonate group-containing compounds, ranges from 400 to 20,000 g / mol. The composition is largely free of toxicologically concerning ingredients and cures in ambient conditions using conventional catalysts quickly and in a trouble-free manner in order to form a non-tacky elastic polymer with a high degree of strength and elasticity. The composition is particularly suitable for use as an elastic adhesive, sealant, or coating with a high degree of robustness during production, storage, and processing as well as a high degree of resistance after curing.

Description

[0001] ROOM TEMPERATURE-CURING POLYMER COMPOSITION OF

[0002] POLYALDEHYDE AND POLYMALONATE

[0003] Technical area

[0004] The invention relates to two-component compositions and their use as room temperature curable elastic adhesives, sealants or coatings.

[0005] State of the art

[0006] Reactive polymer compositions that cure at room temperature and can be used as adhesives, sealants, or coatings with elastic properties are well known. Polyurethane systems, which cure through the reaction of isocyanate groups with polyols and / or moisture, forming particularly highly elastic polymers, are widely used. The formulation, manufacture, and use of polyurethane systems pose a number of challenges in practice. They usually contain significant amounts 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 and even gelling, thus impairing shelf life and storage stability.In single-component systems, the water required for curing must penetrate from the outside in the form of atmospheric moisture, making application in thick layers or between moisture-proof substrates difficult. Two-component systems with a polyol and an isocyanate component pose the problem that the isocyanate groups can react not only with the hydroxyl groups of the polyols, but also with any water present. Particularly in high ambient humidity, this can trigger blistering and cause incomplete polymerization with chain terminations due to only partially reacted polyols, leading to a more or less severe loss of strength and elasticity. These problems are rarely encountered when mercury catalysts are used, which catalyze the reaction with the polyols very selectively.However, due to their high toxicity, mercury catalysts have long been discontinued. As an alternative, two-component polyurethanes are often catalyzed with tin compounds and / or tertiary amines, which are significantly less selective and can lead to bubble formation, especially in high ambient humidity. Bismuth or zirconium catalysts have higher selectivity; however, these and other alternative metal catalysts are sensitive to hydrolysis, resulting in a significant loss of catalytic activity, which in turn can lead to curing problems.

[0007] Reactive polymer compositions based on silane-functional polymers (SMP / STP) and silicones are also widely used. These polymer systems cure through hydrolysis and condensation of silane groups, releasing alcohols, especially methanol or ethanol, or oximes, which are toxic and cause VOC emissions. Furthermore, they usually contain high amounts of low-molecular-weight silanes as crosslinkers or drying agents, which are also harmful to health. Due to the moisture sensitivity of the silane groups, these polymer systems are also challenging to manufacture and use and do not always produce the desired results. Also common are water-based polymer systems, which are usually based on acrylate or polyurethane dispersions. These cure through water evaporation and coalescence and are largely free of chemical reactive groups.However, they can only be used in relatively thin layers and only between open-pored substrates. The curing speed is highly dependent on ambient humidity, and they exhibit high shrinkage. After curing, they are more sensitive to water due to the surfactants they contain, which are necessary for the production and stability of the dispersion, which can lead to reduced durability, especially in outdoor applications.

[0008] US 2018 / 0282477 describes the use of polyesters containing malonate groups for crosslinking compounds with activated C=C double bonds, such as acrylates or methacrylates. Using special catalysts, coatings with high hardness and minimal elasticity are produced. Description of the invention

[0009] The object of the present invention is therefore to provide a novel, room temperature curable polymer composition which is suitable as an elastic adhesive, sealant or coating and overcomes the disadvantages of the known polymer systems.

[0010] Surprisingly, this object is achieved with a curable composition as described in claim 1. The composition comprises a first component containing aldehyde group-containing compounds and a second component containing malonate group-containing compounds, wherein the average molecular weight M n at least one of the two components, with respect to the aldehyde- or malonate-containing compounds, is in the range of 400 to 20,000 g / mol. This composition has several advantageous and surprising properties compared to room-temperature-curable polymer systems of the prior art.

[0011] Both the aldehyde-containing compounds and the malonate-containing compounds are substances of low toxicological concern, do not require hazard labeling, and can be handled without special precautions. The composition according to the invention is not sensitive to moisture and blistering and allows for a high degree of freedom in formulation, as additives commonly used in curable compositions can be used in both components without causing problems with the storage stability of the respective component.Surprisingly, the composition is very tolerant with regard to the stoichiometry of the reactive groups, with a ratio of the number of malonate groups to the number of aldehyde groups ranging from 1 to 2 or more, resulting in a cured, non-sticky material with high extensibility and strength, as well as good resistance to heat and water. This is very surprising, given that state-of-the-art reactive systems typically exhibit a sharp decline in mechanical quality with significant deviations from the optimal stoichiometry of the reactive groups, which is usually close to 1:1. For these reasons, the mixing ratio of the two components can be adjusted almost arbitrarily, allowing considerable freedom in the application method and simple, very reliable processing with a high degree of error tolerance.The composition is easily processable under ambient conditions, without the need for organic solvents for dissolving or diluting, or water for emulsifying or dispersing components. The composition cures surprisingly quickly and smoothly under ambient conditions, regardless of humidity, without generating any emissions. A particularly advantageous feature is that the curing rate is highly controllable with conventional catalysts, particularly non-metallic bases such as tertiary amines, amidines, or guanidines. Curing produces a non-sticky, elastic polymer of high strength and elongation, with good tear resistance and resistance to heat and water.Due to the combination of these advantageous properties, the composition according to the invention has a particularly easy handling without special protective measures as well as a high robustness and durability, both during the production and storage of the components, during their use in a wide range of ambient and application conditions and fluctuations in the mixing ratio, as well as after curing under mechanical, thermal or chemical stress.

[0012] The composition according to the invention is thus highly suitable for use as a high-quality elastic adhesive, sealant, or coating. Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

[0013] Ways to implement the invention

[0014] The invention relates to a curable composition comprising

[0015] - a first component containing aldehyde group-containing compounds comprising at least one compound having two or more aldehyde groups and

[0016] - a second component containing malonate group-containing compounds comprising at least one compound having two or more malonate groups of the formula (I), OOX (l > — 0 o - where the average molecular weight M n at least one of the two components in terms of the aldehyde or malonate group-containing compounds is in the range of 400 to 20,000 g / mol.

[0017] “Aldehyde groups” are functional groups of the formula which are bound by the dashed line.

[0018] A dashed line in the formulas in this document represents the bond between a substituent and the corresponding molecular residue. "Molecular weight" refers to the molar mass (in grams per mole) of a molecule. "Mean molecular weight" refers to the number average molecular weight (Mn) of a polydisperse mixture of oligomeric or polymeric molecules. It is determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0019] A composition is described as “storage-stable” if it can be stored at room temperature in a suitable container for a prolonged period, typically for at least 3 months up to 6 months or more, without its application or use properties being changed by storage to an extent relevant to its use.

[0020] Substance names beginning with “poly” such as polymalonate, polyaldehyde or polyol refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0021] “Room temperature” is defined as a temperature of 23 °C.

[0022] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application. Percentages by weight (wt%) indicate the mass fraction of a component of a composition or molecule relative to the entire composition or molecule, unless otherwise stated. The terms "mass" and "weight" are used synonymously in this document. The first and second components of the curable composition are individually stable and are stored in separate containers until mixed shortly before or during application.

[0023] In the curable composition, the average molecular weight M n at least one of the two components, with respect to the aldehyde- or malonate-containing compounds, in the range of 400 to 20,000 g / mol. Such a composition cures to form an elastic, high-strength polymer.

[0024] Preferably, at least one of the two components has an average molecular weight Mn in relation to the aldehyde-containing or malonate-containing compounds in the range of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol. This enables particularly high extensibility.

[0025] Preferably, the compound with two or more aldehyde groups is liquid at room temperature. In particular, it has a viscosity at 20 °C of 0.2 to 700 Pa s, preferably 0.3 to 500 Pa s, particularly preferably 0.5 to 200 Pa s, in particular 1 to 100 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a cone-tip-to-plate distance of 0.05 mm, and a shear rate of 10 s -1 , for viscosities of less than 1 Pa s with a cone diameter of 50 mm. Such compounds are easy to handle at ambient temperatures, even without the addition of solvents or thinners.

[0026] Preferred compounds with two or more aldehyde groups are polymers containing aldehyde groups.

[0027] The average molecular weight Mn of the first component with respect to the aldehyde group-containing compounds is preferably in the range from 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene as standard. Such a component is easy to handle at ambient temperatures even without the addition of solvents or thinners and enables polymers with high extensibility and elasticity.

[0028] The average aldehyde functionality of the aldehyde-containing compounds in the first component is preferably in the range of 1.6 to 4, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, especially 2.2 to 3.0. This enables cured compositions with high extensibility, strength, and durability.

[0029] Preferably, the aldehyde group-containing compounds comprise a polymer having a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

[0030] 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 a mixture of these poly(oxyalkylenes). Of these, preference is given to poly(oxy-1,2-propylene), poly(oxy-1,3-propylene), or poly(oxy-1,4-butylene), especially poly(oxy-1,2-propylene), which may contain from 0 to 25% by weight of poly(oxyethylene) units based on the poly(oxyalkylene) backbone, especially at the chain ends. Aldehyde-functional polymers with such a backbone are low-viscosity and thus particularly easy to handle and particularly hydrophobic. They enable compositions with particularly good processability, high extensibility, and good water resistance.

[0031] Preferred polyesters are esters of dicarboxylic acids and di- or triols, triglycerides, or polyesters based on dimer or trimer fatty acids. Polyesters derived from dimer fatty acids or from castor oil, castor oil derivatives, or vegetable oils are particularly preferred. Aldehyde-functional polymers with such a backbone are particularly hydrophobic and enable compositions with particularly good resistance to heat and water. Furthermore, they are based on renewable raw materials and are therefore particularly sustainable. Preferably, the compound with two or more aldehyde groups also contains urethane groups. This results in compositions with particularly high extensibility.

[0032] The aldehyde group-containing compounds preferably comprise a urethane group-containing polymer which is liquid at room temperature and has an average molecular weight Mn of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol, and an average aldehyde functionality of 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.2 to 3.0.

[0033] Preferably, the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one isocyanate group-containing polymer or at least one polyisocyanate.

[0034] Particularly suitable as hydroxyaldehyde are compounds having a molecular weight in the range of 60 to 500 g / mol, preferably 60 to 250 g / mol.

[0035] Particularly suitable are 2-hydroxyacetaldehyde, 3-hydroxybutanal, 3-hydroxypivalaldehyde, 5-hydroxypentanal, 2-(2-hydroxyethoxy)acetaldehyde, 3-(2-hydroxyethoxy)propanal, 5-hydroxymethylfurfural, alkoxylated o-, m- or p-hydroxybenzaldehyde or alkoxylated vanillin, where "alkoxylated" preferably stands for (mono- or poly-) "ethoxylated" or "propoxylated", as well as 4,4'-(2-hydroxypropane-1,3-diyl)-bis(oxy)-bis(benzaldehyde) or 4,4'-(2-hydroxypropane-1,3-diyl)-bis(oxy)-bis(3-methoxybenzaldehyde).

[0036] Preferred hydroxyaldehydes are ethoxylated salicylaldehyde, especially 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillin, 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 accessible using simple processes and enable aldehyde-containing compounds with low viscosity and thus good handling, as well as compositions with good processability and high strength with high extensibility. 5-hydroxymethylfurfural is particularly preferred as a hydroxyaldehyde. This hydroxyaldehyde is accessible from renewable starting materials and, surprisingly, enables particularly low-viscosity compounds with aldehyde groups and curable compositions with particularly good processability and high strength, extensibility, and resistance to heat and water.

[0037] Particularly suitable as isocyanate group-containing polymers for the production of compounds having two or more aldehyde groups are reaction products of polyols with diisocyanates, in particular in a molar NCO / OH ratio of 1.5 / 1 to 10 / 1, wherein unreacted monomeric diisocyanates have optionally been removed from the polymer.

[0038] The isocyanate group-containing polymer preferably has a content of free isocyanate groups in the range from 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, in particular 1.5 to 6% by weight, based on the isocyanate group-containing polymer.

[0039] A particularly preferred isocyanate group-containing polymer is a reaction product from the reaction of at least one diisocyanate and at least one polyol in an NCO / OH ratio of at least 3 / 1, preferably 3 / 1 to 10 / 1, in particular 4 / 1 to 8 / 1, and subsequent removal of a large part of the monomeric diisocyanate by means of a suitable separation process, so that the isocyanate group-containing polymer ultimately has a monomeric diisocyanate content of at most 0.2% by weight, based on the isocyanate group-containing polymer.

[0040] Such an isocyanate-containing polymer enables aldehyde-functional polymers with a particularly low content of reaction products from monomeric diisocyanate and hydroxyaldehyde, in particular less than 0.5% by weight of these reaction products based on the aldehyde-functional polymer. This enables curable compositions with particularly simple processing, long open times, rapid curing, and particularly good flexibility. Particularly suitable diisocyanates are 1,6-hexane diisocyanate (HDI), 2,2(4),4-trimethyl-1,6-hexane diisocyanate (TMDI), 1-methyl-2,4(6)-diisocyanatocyclohexane (HeTDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 4(2),4'-diphenylmethane diisocyanate (MDI), or 2,4(6)-toluene diisocyanate. HDI, IPDI, TDI, or MDI are preferred. IPDI is particularly preferred. This results in particularly easy-to-process compositions that cure to form polymers with high strength and ductility.

[0041] Particularly suitable as polyol are

[0042] - Polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, in particular 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 a starter molecule having two or more active hydrogen atoms, in particular a starter molecule such as water, ammonia or a compound having several OH or NH groups such as, for example, 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- or 1 ,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline, or mixtures of the aforementioned compounds.

[0043] Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-endcapped or EO-tipped) 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 completion of the propoxylation reaction, thus ultimately exhibiting primary hydroxyl groups.

[0044] Preferred polyether polyols have a degree of unsaturation of less than 0.02 mEq / g, in particular less than 0.01 mEq / g.

[0045] - Polyester polyols, especially those obtained from the polycondensation of hydroxycarboxylic acids or lactones or from the polycondensation of aliphatic and / or aromatic polycarboxylic acids with di- or polyhydric alcohols. Amorphous, di- or trimer fatty acid-based polyester polyols, such as those commercially available from Croda, are preferred.

[0046] - Polycarbonate polyols, obtainable for example by reacting diols with dialkyl carbonates, diaryl carbonates or phosgene.

[0047] - Block copolymers containing at least two hydroxyl groups, in particular polyetherpolyesterpolyols.

[0048] - Polyacrylate and polymethacrylate polyols.

[0049] - Polyhydroxy-functional fats or oils, in particular natural fats or oils, such as castor oil, derivatives of castor oil; or so-called oleochemical polyols obtained by chemical modification of natural fats and oils, such as hydroxylated vegetable oils available under the trade name Sovermol® (from BASF).

[0050] - Polyhydrocarbon polyols, such as, in particular, polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; 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 of 1,3-butadiene, which may also be produced, in particular, from 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 and isoprene, for example polyhydroxy-functional acrylonitrile / butadiene copolymers, such as those that can be produced from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (for example commercially available under the name Hypro® CTBN or CTBNX or ETBN from Emerald Performance Materials);and hydrogenated polyhydroxy-functional polymers or copolymers of dienes.;

[0051] Polyols that are liquid at room temperature are preferred.

[0052] Preferred are polyols with an OH number in the range of 9 to 115 mg KOH / g, preferably 14 to 60 mg KOH / g, in particular 18 to 40 mg KOH / g. Particular preference is given to polyether polyols, di- or trimer fatty acid-based polyester polyols, castor oil, castor oil derivatives, or hydroxylated vegetable oils. Polyether polyols are most preferred.

[0053] Also suitable as compounds having two or more aldehyde groups are reaction products of at least one polyisocyanate with at least one hydroxyaldehyde, in particular the previously mentioned hydroxyaldehydes.

[0054] Suitable polyisocyanates are in particular oligomeric diisocyanates, in particular HDI biurets such as Desmodur® N 100 or N 3200 (from Covestro), Tolonate® HDB or HDB-LV (from Vencorex) or Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur® N 3300, N 3600 or N 3790 BA (all from Covestro), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate® TPA-100 or THA-100 (from Asahi Kasei) or Coronate® HX (from Nippon Polyurethane); HDI uretdiones such as Desmodur® N 3400 (from Covestro); HDI iminooxadiazinediones such as Desmodur® XP 2410 (from Covestro); HDI allophanates such as Desmodur® VP LS 2102 (from Covestro); IPDI isocyanurates such as in solution as Desmodur® Z 4470 (from Covestro) or in solid form as Vestanat® T1890 / 100 (from Evonik); TDI oligomers such as Desmodur® IL (from Covestro);or mixed isocyanurates based on TDI / HDI such as Desmodur® HL (from Covestro), where "HDI" stands for 1,6-hexane diisocyanate, "IPDI" for isophorone diisocyanate, and "TDI" for 2,4-tolylene diisocyanate or mixtures thereof with 2,6-tolylene diisocyanate. HDI-derived oligomeric diisocyanates, especially HDI biurets, are preferred.

[0055] Preferably, the isocyanate group-containing polymer or the polyisocyanate 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.

[0056] In addition to polymers containing aldehyde groups, the first component of the curable composition can contain proportions of low molecular weight polyaldehydes, such as in particular 1,6-hexanedialdehyde, 1,7-heptanedialdehyde, 1,8-octanedialdehyde, 1,9-nonanedialdehyde, 2-methyl-1,8-octanedialdehyde, 1,10-decanedialdehyde, 1,11-undecanedialdehyde, 1,12-dodecanedialdehyde, hexahydrophthalaldehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, octahydro-4,7-methano-1H-indenedicarbaldehyde, 3,6,9-trioxaundecan-1,11-dial, 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, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 9,10-anthracenedicarbaldehyde or naphthalenedicarboxaldehyde.

[0057] The curable composition comprises as a component of the second component at least one compound having two or more malonate groups of formula (I).

[0058] OO — o ÄA o— (l)

[0059] Preferably, the compound with two or more malonate groups is liquid at room temperature. In particular, it has a viscosity at 20 °C of 0.01 to 50 Pa s, preferably 0.02 to 20 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a cone-tip-to-plate distance of 0.05 mm, and a shear rate of 10 s -1 , for viscosities of less than 1 Pa s with a cone diameter of 50 mm. Such a compound is easy to handle at ambient temperatures even without the addition of solvents or thinners and enables easy-to-process compositions.

[0060] Preferably, the average functionality of the second component with respect to the malonate group-containing compounds is in the range of 1.6 to 6, preferably 1.8 to 5, in particular 2.0 to 4. This enables cured compositions with high extensibility, strength and durability.

[0061] The average molecular weight Mn of the second component with respect to the malonate group-containing compounds is preferably in the range from 260 to 10,000 g / mol, preferably 300 to 3,000 g / mol. Such a second component enables particularly easy-to-process compositions with high strength.

[0062] Preferably, the compound having two or more malonate groups is obtained by reacting at least one polyfunctional alcohol with malonic acid or at least one compound of formula (II),

[0063] OOX Ä (i i) R 1 O X ^ / ^OR 2 where R 1 and R 2 each represents an alkyl radical having 1 to 6 C atoms.

[0064] Preference is given to R 1 and R 2 each represents methyl, ethyl or isopropyl, in particular ethyl.

[0065] Suitable polyfunctional alcohols are commercially available compounds or polymers having two or more OH groups, such as in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, 1,1,1-trimethylolpropane, glycerol, ethoxylated or in particular propoxylated glycerol, ethoxylated or in particular propoxylated 1,1,1-trimethylolpropane, castor oil, ethoxylated or in particular propoxylated castor oil, ketone resin-modified castor oil, hydroxylated vegetable oils, dimer fatty acid diols or Trimer fatty acid triols, dimer- or trimer fatty acid-based amorphous polyester diols or triols, as well as the other polyols already mentioned above for the production of a polymer containing isocyanate groups, in particular poly(oxy-1,2-propylene)diols or triols or ethylene oxide-endcapped poly(oxy-1,2-propylene)diols or triols.

[0066] In particular, the polyfunctional alcohol is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, glycerol, 1,1,1-trimethylolpropane, dimer fatty acid diols, trimer fatty acid trioies, castor oil, poly(oxy-1,2-propylene)diols having an average molecular weight M n from 300 to 2,000 g / mol, in particular 300 to 1,000 g / mol, and propoxylated 1,1,1-trimethylolpropane with an average molecular weight M n from 300 to 1,700 g / mol.

[0067] Preferred compounds of formula (II) are dimethyl malonate, diethyl malonate, diisopropyl malonate, butylethyl malonate, tert-butylethyl malonate, or di-tert-butyl malonate. Particular preference is given to dimethyl malonate, diethyl malonate, or diisopropyl malonate, especially diethyl malonate.

[0068] The reaction is preferably carried out at a temperature in the range from 50 to 150 °C with distillative removal of the released water or alcohol, optionally under vacuum and optionally in the presence of catalysts.

[0069] In one embodiment, the reaction is carried out with at least one compound of formula (II) and an excess of ester groups. The stoichiometry in the reaction is preferably in the range of 0.8 to 10 mol, in particular 1 to 5 mol, of compounds of formula (II) per molar equivalent of OH groups of the polyfunctional alcohol. This results in, in particular, a mixture of compounds with malonate groups, as exemplified in the following formula for a difunctional alcohol: where R represents the remainder of the difunctional alcohol after removal of the two OH groups, x represents 0 or a value from 1 to about 6, and R 1 and R 2have the meanings already mentioned.

[0070] The mean value of x is smaller, the higher the excess of ester groups was during the reaction. Unreacted compounds of formula (II) together with the released alcohol R are preferred. 1 OH or R 2 OH is removed by distillation. In a further embodiment, the reaction is preferably carried out with malonic acid and with an excess of OH groups. The stoichiometry during the reaction is preferably in the range of 2.2 to 3.5, preferably 2.3 to 3.3, mole equivalents of OH groups of the polyfunctional alcohol per mole of malonic acid. This results in, in particular, in a mixture of compounds with malonate groups, as exemplified in the following formula for a difunctional alcohol: where R represents the remainder of the difunctional alcohol after removal of the two OH groups and y represents a value from 1 to about 8, especially 2 to 6. The lower the excess of OH groups in the reaction, the higher the average value of y.

[0071] Reactions in which other substances are used are also possible.

[0072] In one embodiment of the invention, at least one further dicarboxylic acid or at least one ester of a dicarboxylic acid, which is not malonic acid or an ester of malonic acid, is additionally used in the reaction. This is particularly preferred in a reaction with an excess of OH groups. Adipic acid or a dimer fatty acid is preferred as a further dicarboxylic acid.

[0073] Particularly preferred compounds with two or more malonate groups are 1,2-ethanediol bis(ethylmalonate), 1,2-propanediol bis(ethylmalonate), 1,3-propanediol bis(ethylmalonate), 1,4-butanediol bis(ethylmalonate), 1,6-hexanediol bis(ethylmalonate), 1,4-cyclohexanedimethanol bis(ethylmalonate), diethylene glycol bis(ethylmalonate), dipropylene glycol bis(ethylmalonate), glycerol tris(ethylmalonate), 1,1,1-trimethylolpropane tris(ethylmalonate), dimer fatty acid diol bis(ethylmalonate), trimer fatty acid triol tris(ethylmalonate), castor oil tris(ethylmalonate), poly(oxy-1,2-propyl- len)diol bis(ethylmalonate) with an average molecular weight M n from 500 to 2,000 g / mol, propoxylated 1,1,1-trimethylolpropane with three ethyl malonate end groups and an average molecular weight M nfrom 650 to 2,500 g / mol, corresponding oligomeric compounds of these reaction products, as well as polyesterdiols containing malonate groups from the reaction of diols such as 1,6-hexanediol or 1,4-cyclohexanedimethanol with malonic acid or diethyl malonate and optionally further dicarboxylic acids or their esters such as in particular adipic acid or diethyl adipic acid or dimer fatty acids.

[0074] Suitable compounds with two or more malonate groups are also commercially available, in particular as Acure® 510-200 (from Allnex).

[0075] Preferably, the average functionality of the entire composition with respect to the reactive groups, aldehyde and malonate, is at least 1.9, in particular at least 2.0. This means that a composition with an average aldehyde functionality in the first component of, for example, 1.8 is preferably combined with a second component with an average malonate functionality of at least 2.0, preferably at least 2.1, to achieve an overall average reactive group functionality of 1.9, preferably 2.0.

[0076] The curable composition may additionally contain other ingredients, in particular the following:

[0077] - Fillers, in particular ground or precipitated calcium carbonates, which may be coated with fatty acids, in particular stearates, barytes (heavy spars), quartz flours, quartz sands, dolomites, wollastonites, kaolins, calcined kaolins, layered silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, silicas including highly dispersed silicas from pyrolysis processes, industrially produced carbon blacks, graphite, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powders or hollow spheres;

[0078] - fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres, hemp fibres, cellulose fibres or plastic fibres such as polyamide fibres or polyethylene fibres;

[0079] - Nanofillers such as graphene or carbon nanotubes; - Dyes;

[0080] - pigments, in particular titanium dioxide, chromium oxide, iron oxides or organic pigments;

[0081] - Plasticizers, in particular phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, in particular diisononyl 1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl)terephthalate or diisononyl terephthalate (DINT), hydrogenated terephthalates, in particular bis(2-ethylhexyl)1,4-cyclohexanedicarboxylate or diisononyl 1,4-cyclohexanedicarboxylate, isophthalates, trimellitates, adipates, in particular dioctyl adipate (DOA), azelates, sebacates, benzoates, glycol ethers, glycol esters, plasticizers with a polyether structure, in particular polyoxypropylene monols, diols or triols, or polyoxypropylene monols, diols or -triols with blocked hydroxyl groups, in particular in the form of acetate groups, as well as organic sulfonates or phosphates, in particular diphenyl cresyl phosphate (DPK), polybutenes, polyisobutenes or plasticizers derived from natural fats or oils,in particular epoxidized soy or linseed oil, in particular phthalates, hydrogenated phthalates, adipates or plasticizers with polyether structure;,

[0082] - solvents;

[0083] - Modifiers such as hydrocarbon resins, natural or synthetic waxes or bitumen;

[0084] - Rheology modifiers, in particular urea compounds, layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, fumed silicas or hydrophobically modified polyoxyethylenes;

[0085] - drying agents, in particular molecular sieves, calcium oxide, mono-oxazolidines such as Incozol® 2 (from Incorez) or orthoformic acid esters;

[0086] - adhesion promoters, in particular titanates or organoalkoxysilanes such as aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes, (meth)acrylsilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;

[0087] - Catalysts, in particular non-metallic bases such as tertiary amines, in particular 2-dimethylaminoethyl ether, 2,2'-dimorpholinodiethyl ether (DMDEE) or 1,4-diazabicyclo[2.2.2]octane (DABCO), amidines, 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 guanidines, in particular 1,1,3,3-tetramethylguanidine, 1-hexyl-2,3-diisopropylguanidine or 1,1'-( a,®-Polyoxypropylene)bis(2,3-diisopropylguanidine) with medium molecular weight M nof about 250 to 500 g / mol, and in particular basic salts such as in particular potassium acetate, potassium benzoate, potassium carbonate, potassium hydrogen carbonate, potassium phosphates, and the corresponding salts with sodium or lithium instead of potassium, such basic salts preferably being used as aqueous solutions, for example with a concentration of 10 to 30% by weight of the salt based on the total weight of the solution;

[0088] - non-reactive thermoplastic polymers, such as homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth)acrylates, in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) and atactic poly-α-olefins (APAO);

[0089] - flame-retardant substances, in particular the fillers already mentioned, aluminium hydroxide or magnesium hydroxide, organic phosphoric acid esters, ammonium polyphosphates, melamine or derivatives thereof, boron compounds or antimony compounds;

[0090] - Additives, in particular wetting agents, flow control agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides; as well as other substances commonly used in curable compositions.

[0091] Such additives can be present as part of the first or second component. Substances reactive with 1,3-ketoester groups are preferably a component of the first component. Substances reactive with aldehyde groups are preferably a component of the second component. The curable composition preferably additionally contains at least one further component selected from plasticizers, fillers, and catalysts. The curable composition preferably contains several such further components.

[0092] The curable composition preferably contains at least one basic catalyst with a pKa of at least 8, preferably at least 8.5, in particular a nitrogen-containing compound or an aqueous solution of a basic salt. Such a composition exhibits particularly rapid curing.

[0093] In a preferred embodiment of the invention, the curable composition contains, based on the total composition, 10 to 95% by weight, preferably 20 to 90% by weight, in particular 30 to 80% by weight, of fillers. Preferably, fillers are selected from calcium carbonates, barite, quartz powder, quartz sand, kaolin, aluminum hydroxide, titanium dioxide, and carbon black. Such a composition is particularly suitable for applications in layer thicknesses of at least 1 mm, preferably 1 to 500 mm, in particular 1.5 to 250 mm. The cured composition exhibits pronounced elastic properties.

[0094] In a further preferred embodiment of the invention, the curable composition contains, based on the total composition, 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizer. Plasticizers are preferably selected from DINP, DIDP, DPHP, DINCH, bis(2-ethylhexyl) terephthalate, DINT, bis(2-ethylhexyl) 1,4-cyclohexanedicarboxylate, diisononyl 1,4-cyclohexanedicarboxylate, DOA, polyoxypropylene monols, polyoxypropylene diols, polyoxypropylene triols, polyoxypropylene monol acetates, polyoxypropylene diol diacetates, polyoxypropylene triol triacetates, and DPK.

[0095] In a particularly preferred embodiment of the invention, the curable composition contains fillers and plasticizers, in particular, based on the total composition, 20 to 90% by weight, especially 30 to 80% by weight, of fillers and 5 to 60% by weight of plasticizer. The curable composition preferably contains less than 10% by weight, particularly preferably less than 5% by weight, especially less than 1% by weight, of volatile organic solvents having a boiling point at atmospheric pressure of less than 250°C, based on the total composition. Such a composition causes particularly low emissions.

[0096] A compound of formula (II), such as diethyl malonate in particular, is also particularly suitable as a solvent, as this can react with the cured polymer during curing.

[0097] The curable composition is preferably not water-based. It is preferably largely free of water or contains only a low water content. Such a composition cures rapidly regardless of ambient humidity, can be used in thick layers and / or between waterproof substrates, and exhibits hardly any shrinkage during curing. The curable composition preferably 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.

[0098] The curable composition is preferably free of compounds containing aldehyde or malonate groups that are present as an emulsion or dispersion. Thus, the compounds containing aldehyde or malonate groups are preferably largely free of ionic groups or precursors thereof, and largely free of longer poly(oxyethylene) chains, as are common in surfactants. Such a composition has high water resistance. In particular, the aldehyde-containing compounds of the first component and the malonate-containing compounds of the second component each contain less than 0.1% by weight, preferably less than 0.05% by weight, of acid groups or ionic groups, based on the aldehyde-containing or malonate-containing compounds, respectively. The ionic groups are, in particular, carboxylate groups, ammonium groups, or sulfonate groups.The first component of the curable composition is preferably free of aldimine groups or contains only a low aldimine group content of less than 0.2 mol, in particular less than 0.1 mol, of aldimine groups per mole of malonate groups in the second component. This means that the first component is largely free of primary amines. Primary amine groups react with aldehydes to form aldimines. It is not within the scope of the present invention to convert the aldehyde groups in the first component to aldimine groups. The curing of the curable composition according to the invention occurs primarily through the reaction of malonate groups with free aldehyde groups.

[0099] Preferably, the curable composition comprises a total of

[0100] - 5 to 100% by weight, preferably 10 to 70% by weight, of the sum of compounds with aldehyde groups or malonate groups of the formula (I),

[0101] - 0 to 50% by weight, preferably 10 to 40% by weight, plasticizer,

[0102] - 0 to 90% by weight, preferably 20 to 80% by weight, fillers,

[0103] - and, where appropriate, other substances, based on the total composition.

[0104] In the curable composition, the ratio of the number of malonate groups to the number of aldehyde groups is preferably in the range of 0.5 to 2.5, particularly preferably 0.8 to 2.2, and especially 1 to 2. Such a ratio enables rapid, trouble-free curing to form a mechanically high-quality polymer with high strength, extensibility, and durability. Particularly surprising is the fact that the ratio can be varied within such a wide range, while always yielding a non-sticky material with good mechanical properties. This makes the composition particularly robust with respect to fluctuations in the mixing ratio of the two components during processing.

[0105] The consistency of the first and second components of the curable composition is suitably such that the components can be easily mixed together under ambient conditions using simple methods. Liquid or pasty components are particularly suitable for this purpose. The first and second components of the curable composition are prepared separately. The constituents of each component are mixed together to form a macroscopically homogeneous mass. Each component is stored in a separate container. Suitable containers include, in particular, a drum, container, hobbock, bucket, canister, can, bag, tubular bag, cartridge, or tube. The components are storage-stable.

[0106] To apply the curable composition, the two components and any additional components present are mixed together shortly before or during application. The mixing ratio is selected such that the ratio of the number of malonate groups to the number of aldehyde groups is within a suitable range, in particular approximately 1 to 2. In parts by weight, the mixing ratio between the first and second components is typically in the range of approximately 100:1 to 1:5, in particular 50:1 to 1:2.

[0107] If the components are mixed together prior to application, care must be taken to ensure that not too much time elapses between mixing the components and application, as otherwise the onset of reaction and the associated increase in viscosity may lead to problems such as insufficient flow or slow or incomplete adhesion to the substrate. In particular, the open time of the composition during application should not be exceeded.

[0108] The “open time” is the period of time between the mixing of the components and the end of a state of the composition suitable for processing.

[0109] Mixing preferably takes place at ambient temperature, especially at a temperature in the range of -5 to 50°C, especially 0 to 40°C. Upon mixing the two components, the composition begins to harden due to the chemical reaction that begins. The malonate groups mainly react with the aldehyde groups, whereby the composition finally hardens into a solid, polymeric material. It can be assumed that the curing reaction causes structural units of the

[0110] formula formed. Furthermore, it can be assumed that any additional malonate group present can add to the resulting C=C double bond and thus increase the crosslinking density. Curing preferably takes place at ambient temperature, particularly at a temperature in the range of -5 to 50°C, especially 0 to 40°C.

[0111] Another object of the invention is the cured composition obtained from the curable composition after mixing the two components.

[0112] Preferably, the cured composition is elastic and has high strength and high extensibility.

[0113] Preferably, the cured composition has a tensile strength, determined according to DIN EN 53504 as described in the examples, of at least 1 MPa, preferably at least 1.5 MPa, in particular at least 2 MPa.

[0114] Preferably, the cured composition has an elongation at break, determined according to DIN EN 53504 as described in the examples, of at least 50%, preferably at least 75%, more preferably at least 100%, particularly preferably at least 150%, in particular at least 200%.

[0115] The cured composition preferably has a Shore A hardness, determined according to DIN 53505 as described in the examples, in the range of 10 to 90, in particular 20 to 80. Furthermore, the cured composition has good resistance to heat and water. The cured composition preferably exhibits high strength, ductility, and hardness even after storage for 7 days at 100°C or at 70°C and 100% relative humidity.

[0116] The curable composition is suitable for a wide range of applications. It can be used, in particular, as an adhesive, sealant, coating, casting resin, or filler.

[0117] A further object of the invention is the use of the curable composition as an elastic adhesive, elastic sealant or elastic coating, wherein the first and the second and optionally present further components are mixed together and the mixed composition is applied in the liquid state to at least one substrate.

[0118] When used as an 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.

[0119] Suitable substrates include:

[0120] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble;

[0121] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECO (epoxy resin-modified cement mortar);

[0122] - Metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals;

[0123] - asphalt or bitumen;

[0124] - Leather, textiles, paper, wood, wood materials bonded with resins, for example phenolic, melamine, or epoxy resins, resin-textile composites, or other so-called polymer composites; - Plastics such as rigid and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM, or EPDM, each untreated or surface-treated, for example by means of plasma, corona, or flames;

[0125] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP), natural fiber-reinforced plastics (NFRP) and sheet molding compounds (SMC);

[0126] - insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool, aerogel or foamed glass (foam glass);

[0127] - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0128] - Coatings, paints or varnishes.

[0129] If necessary, the substrates may be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.

[0130] Two similar or two different substrates can be bonded and / or sealed.

[0131] An article is obtained from the use of the curable composition. The article is in particular bonded, sealed, or coated with the composition. This article may be a building or a part thereof, in particular a building or civil engineering structure, a bridge, a roof, a staircase, or a facade, or it may be an industrial or consumer good, in particular a window, a pipe, a rotor blade of a wind turbine, a household appliance, or a means of transport, such as in particular an automobile, a bus, a truck, a rail vehicle, a ship, an aircraft, or a helicopter, or an attachment thereof.

[0132] Examples

[0133] The following are exemplary embodiments intended to further illustrate the described invention. Naturally, the invention is not limited to these described exemplary embodiments. A temperature of 23±1 °C and a relative humidity of 50±5% are referred to as "standard climate" (“NC”).

[0134] Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH.

[0135] Description of the measurement methods:

[0136] The viscosity was measured on a thermostatted cone-plate viscometer Rheotec RC30 (cone diameter 10 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s' 1 ) were measured. Viscosities of less than 1 Pa s were measured with a cone diameter of 50 mm.

[0137] Infrared spectra (FT-IR) were measured on undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal diamond crystal ATR measurement unit. The absorption bands are given in wavenumbers (cm -1 ) is indicated.

[0138] Production of polymers containing isocyanate groups:

[0139] Polymer P-1 :

[0140] 780 g of ethylene oxide-terminated polyoxypropylenetriol (Desmophen® 5031 BT, OH number 28.0 mg KOH / g, OH functionality approx. 2.3, from Covestro) and 303 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80 °C using a known method to form a reaction mixture with an NCO content of 9.1% by weight. The volatile components, particularly unreacted isophorone diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 to 0.005 mbar), yielding a polymer with an NCO content of 1.84% by weight and a monomeric isophorone diisocyanate content of 0.02% by weight.

[0141] Preparation of compounds with two or more aldehyde groups:

[0142] Connection A-1 :

[0143] 500.0 g of the isocyanate-containing polymer P-1 was reacted with 27.7 g of 5-hydroxymethylfurfural in the presence of 0.1 g of dibutyltin dilaurate at 110 °C under exclusion of moisture until no isocyanate groups were detectable by IR spectroscopy. A clear, colorless liquid was obtained with a viscosity at 20 °C of 63.7 Pa s, an average aldehyde functionality of 2.3, and a calculated aldehyde equivalent weight of 2381 g / eq.

[0144] The average molecular weight M n by gel permeation chromatography (GPC) against polystyrene (474 ​​to 2,520,000 g / mol) as a standard with tetrahydrofuran as the mobile phase and a refractive index detector. The average molecular weight M n was 6,100 g / mol.

[0145] Preparation of compounds with two or more malonate groups:

[0146] Connections M-1 to M-6:

[0147] For each compound, the amount (in parts by weight) of the corresponding polyhydric alcohol specified in Table 1 was added to the specified amount (in parts by weight) of diethyl malonate and 0.1 wt.% tetra-n-butyl titanate (Tyzor® TnBT, ex Dorf Ketal) and reacted under vacuum at 140 °C with volatiles removed. A clear, colorless liquid was obtained in each case.

[0148]

[0149] Table 1: Preparation and properties of compounds M-1 to M-6.

[0150] 1 Polyoxypropylene diol (Voranol® P400, OH number 263 mg KOH / g, from Dow)

[0151] 2 Trimethylolpropane-launched polyoxypropylene triol (Desmophen®

[0152] 4011T, OH number 550 mg KOH / g, from Covestro)

[0153] 3 OH number 170 mg KOH / g

[0154] Preparation of curable compositions: Examples Z-1 to Z-8

[0155] For each example, the ingredients of the first component (K1) listed in Table 2 were mixed together in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and stored in a sealed container. The ingredients of the second component (K2) listed in Table 2 were processed and stored in the same way.

[0156] Socal® U1S2 (from Imerys), a precipitated and stearate-coated calcium carbonate, was used as "CaCOs precipitated".

[0157] Monarch® 570 (from Cabot) was used as the carbon black. The two components of each composition were then blended into a homogeneous paste using a centrifugal mixer and tested as described below. The setting time was determined by stirring a freshly mixed amount of approximately 3 g at standard conditions with a spatula at regular intervals until the mixture began to gel.

[0158] To determine the mechanical properties, the mixed composition was applied to a silicone-coated release paper to form a 2 mm thick film. This film was cured for 7 days under standard climate conditions. Several dumbbell-shaped test specimens with a length of 75 mm, a web length of 30 mm and a web width of 4 mm were punched out of the film and these were tested according to DIN EN 53504 at a tensile speed of 200 mm / min for tensile strength, elongation at break, Young's modulus 5% (at 0.5-5% elongation) and Young's modulus 50% (at 0.5-50% elongation). Furthermore, some test specimens were punched out to determine the tear propagation resistance and tested according to DIN ISO 34-1, method B (angular test specimen) at a tensile speed of 500 mm / min. The Shore A hardness was determined according to DIN 53505 on test specimens cured for 7 days under standard climate conditions. These results are marked with the suffix "7d NK".To determine heat and water resistance, additional Shore A test specimens were cured for 7 days under standard conditions and either stored for an additional 7 days in a convection oven at 100°C or for an additional 7 days at 70°C and 100% relative humidity. After cooling to room temperature, the Shore A hardness was determined as described. These results are designated "+7d 100°C" or "+7d 70 / 100."

[0159] When the examples according to the invention were cured, a non-sticky, elastic material was formed.

[0160] The results are shown in Table 2.

[0161]

[0162] Table 2: Composition and properties of Z-1 to Z-8.

[0163] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (Lupragen® N700, from BASF)

[0164] 2 estimated ratio of the number of malonate groups to aldehyde groups

Claims

Patent claims: 1 . Curable composition comprising - a first component containing aldehyde group-containing compounds comprising at least one compound having two or more aldehyde groups and - a second component containing malonate group-containing compounds comprising at least one compound having two or more malonate groups of formula (I), OO — o AA o— <'> where the average molecular weight M n at least one of the two components in terms of the aldehyde or malonate group-containing compounds is in the range of 400 to 20,000 g / mol.

2. Composition according to claim 1, characterized in that the compound with two or more aldehyde groups is liquid at room temperature, in particular with a viscosity at 20 °C of from 0.2 to 700 Pa s, preferably 0.3 to 500 Pa s, particularly preferably 0.5 to 200 Pa s, measured by means of a cone-plate viscometer with a cone diameter of 10 mm, cone angle of 1 °, cone tip-plate distance of 0.05 mm, shear rate of 10 s 1 , for viscosities of less than 1 Pa s with cone diameter 50 mm.

3. Composition according to one of claims 1 or 2, characterized in that the average molecular weight M n the first component with respect to the aldehyde group-containing compounds is in the range of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene as standard.

4. Composition according to one of claims 1 to 3, characterized in that the aldehyde group-containing compounds are a polymer with a polymer backbone containing poly(oxyalkylene) units and / or polyester units. Composition according to one of claims 1 to 4, characterized in that the aldehyde-containing compounds comprise a urethane-containing polymer that is liquid at room temperature and has an average molecular weight Mn of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol, and an average aldehyde functionality of 1.8 to 3.5, preferably 2.0 to 3.0, in particular 2.2 to 3.

0. Composition according to one of claims 1 to 5, characterized in that the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one isocyanate-containing polymer or at least one polyisocyanate. Composition according to one of claims 1 to 6, characterized in that the compound having two or more malonate groups is liquid at room temperature.A composition according to any one of claims 1 to 7, characterized in that the average functionality of the second component with respect to the compounds containing malonate groups is in the range from 1.6 to 6, preferably 1.8 to 5, in particular 2.0 to 4. A composition according to any one of claims 1 to 8, characterized in that the compound having two or more malonate groups is obtained by reacting at least one polyfunctional alcohol with malonic acid or at least one compound of formula (II). OO Ä Ä (l l) R 1 O' z ^ xX ^OR 2 where R 1 and R 2 each represents an alkyl radical having 1 to 6 C atoms, preferably methyl, ethyl or isopropyl, in particular ethyl.

10. Composition according to one of claims 1 to 9, characterized in that, based on the total composition, 10 to 95% by weight, preferably 20 to 90% by weight, in particular 30 to 80% by weight, of fillers are contained.

11. Composition according to 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 are contained.

12. Composition according to one of claims 1 to 11, characterized in that 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 at atmospheric pressure of less than 250 °C, based on the total composition, are contained.

13. Cured composition obtained from the curable composition according to one of claims 1 to 12 after mixing the 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%, determined according to DIN EN 53504 at a tensile speed of 200 mm / min on dumbbell-shaped test specimens with a thickness of 2 mm and a length of 75 mm with a web length of 30 mm and a web width of 4 mm.

14. Use of the composition according to any one of claims 1 to 13 as an elastic adhesive, elastic sealant or elastic coating, wherein the first and the second and optionally present further Components are mixed together, and the mixed composition is applied in the liquid state to at least one substrate. Use 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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