Curable single-component polymer composition containing aldehyde and cyanoacetate

Abstract

The invention relates to a curable single-component composition containing at least one compound A with aldehyde groups, at least one compound B with cyanoacetate groups, and at least one zeolite, wherein at least one of the two compounds A and B is a polymer with an average molecular weight Mn of 500 to 20,000 g / mol, and the composition is packaged in a single packaging so as to be stably storable and can be cured under the effect of humidity. The composition is storage-stable, can be used without special protective measures, and cures upon contacting humidity under environmental conditions so as to form an elastic polymer with a high degree of strength, a high degree of elasticity, and a high degree of resistance against heat and water.

Description

[0001] ONE-COMPONENT CURABLE POLYMER COMPOSITION

[0002] CONTAINING ALDEHYDES AND CYANOACETATE

[0003] Technical area

[0004] The invention relates to storage-stable, one-component polymer compositions containing aldehydes and cyanoacetates which are curable under ambient conditions under the influence of moisture, and to their use as elastic adhesives, sealants or coatings.

[0005] State of the art

[0006] Curable polymer compositions that are storage-stable as a whole, i.e., can be stored in a single package for an extended period of time without losing their applicability, are also referred to as one-component compositions or one-component systems. Systems that can be used under ambient conditions are typically moisture-curing, meaning they cure to form a cross-linked polymer upon application under ambient conditions through contact with atmospheric moisture. Compared to two-component compositions, in which the reactive compounds involved in the curing reaction are stored in separately packaged components that are only mixed together shortly before or during application and thus cure, one-component systems are considerably easier to use and generate significantly less waste.There is no need to dose and mix the two components, and exactly the amount needed can be applied, with any unused portions of the composition remaining in the packaging and being able to be used at a later time.

[0007] Well-known moisture-curing one-component systems include polyurethane compositions containing isocyanate groups. However, their formulation, production, and use pose a number of challenges in practice. They usually contain significant amounts of harmful monomeric diisocyanates, which can endanger the user and require protective measures during handling. Carbon dioxide is produced during the curing reaction, which can lead to blistering. This can be prevented with the use of latent hardeners, particularly aldimines. However, aldehydes are released during curing. These are not incorporated into the polymer matrix and can lead to problems with emissions and / or odor formation, or remain in the cured composition, where they exert a plasticizing effect and / or can migrate from the composition.

[0008] Also known are one-component compositions based on silane-functional polymers or silicones. These cure with atmospheric moisture through hydrolysis and condensation of silane groups, releasing alcohols, especially methanol or ethanol, acetic acid, or oximes, which are toxic and cause emissions. Furthermore, they typically contain high amounts of low-molecular-weight silanes as crosslinkers and / or drying agents, which are also harmful to health.

[0009] US 2020 / 0257202 describes the reaction of polymeric dicyanoacetates with aromatic dialdehydes in solvents, as well as the application of the resulting solution to glass, forming a sticky film. The cyanoacetates and the aldehydes are not present together in a single container as a single-component composition.

[0010] US 10,563,040 describes a curable composition containing a polyacetoacetate, a polyaldehyde and a basic catalyst, wherein the polyacetoacetate and the polyaldehyde are stored in separate components.

[0011] US2020 / 257202 describes polymers dissolved in an organic solvent from the reaction of bis(cyanoacetates) with dialdehydes and their application as coatings in the field of microelectronics. US 5,552,496 describes a polyurethane dispersion containing cyanoacetate groups that was chain-extended with glyoxal. In both cases, the reaction between the cyanoacetates and the aldehydes takes place first, before the reaction product is stored.

[0012] The article "Offretite zeolite templated by amphiphile and its catalytic performance in microwave-assisted Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate" (Materials Chemistry and Physics 272 (2021) 125001) describes the catalytic effect of zeolites on the reaction of an aldehyde with a cyanoacetate in combination with heat. Description of the invention

[0013] The object of the present invention is to provide a one-component composition which is storage-stable and curable with atmospheric moisture and overcomes the disadvantages of the prior art, in particular with regard to toxic ingredients, blistering and emissions due to substances not incorporated into the polymer matrix during curing.

[0014] The composition according to the invention comprises at least one compound A with aldehyde groups, at least one compound B with cyanoacetate groups and a zeolite. The one-component composition according to the invention is storage-stable and cures to form an elastic polymer upon contact with atmospheric moisture under ambient conditions. This is surprising in three respects. Firstly, one would expect the polyaldehydes and the cyanoacetates to react directly with one another and thus cure while still in the packaging. Furthermore, it is surprising that curing occurs via contact with atmospheric moisture, even though none of the reactive groups involved has hydrolytic activity. Finally, it is particularly surprising that the presence of a zeolite is necessary for curing, because without zeolite no curing is observed. In one-component systems known from the prior art, zeolite orMolecular sieve is used as a drying agent, which typically significantly delays curing with atmospheric moisture. Compound A and Compound B are both substances of low toxicity, requiring no hazard labeling and can be handled without special precautions. The composition is readily processable under ambient conditions, requiring no organic solvents for dissolving or diluting, or water for emulsifying or dispersing components. The curing process is not sensitive to blistering and does not produce any emissions. Curing produces a non-sticky, elastic polymer with high strength, high elongation, high tear resistance, and good resistance to heat and water.Due to the combination of these advantageous properties, the composition according to the invention is particularly easy to handle without special protective measures and is highly robust under mechanical, thermal or chemical stress after curing.

[0015] The composition according to the invention is particularly suitable for use as an elastic adhesive, sealant or coating.

[0016] 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.

[0017] Ways to implement the invention

[0018] The invention relates to a one-component curable composition containing

[0019] - at least one compound A with aldehyde groups,

[0020] - at least one compound B containing cyanoacetate groups, and

[0021] - at least one zeolite, wherein at least one of the two compounds A and B is a polymer having an average molecular weight M n from 500 to 20,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene as standard, whereby the composition can be stored stable when packaged in a single container and is curable by exposure to atmospheric moisture.

[0022] “One-component” refers to a composition that can be stored and stored in a single container.

[0023] “Storage-stable” refers to a composition which can be stored at room temperature in a suitable container for a prolonged period, typically for at least three months up to six months or more, without its application or use properties being changed by storage to an extent relevant to its use, in particular without hardening in the container.

[0024] O

[0025] “Cyanoacetate groups” are reactive groups of the formula A dashed line in the formulas in this document represents the bond between a substituent and the corresponding molecular residue.

[0026] “Zeolite” refers to natural or synthetic zeolites.

[0027] The term “polymer” also includes so-called oligomers with two, three or four repeating units.

[0028] The term “molecular weight” refers to the molar mass (in grams per mole) of a molecule. The term “average molecular weight” refers to the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules. It is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0029] Substance names beginning with “poly”, such as polyaldehyde or polyol, refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0030] “Room temperature” is defined as a temperature of 23 °C.

[0031] 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%) refer to the mass fraction of a component of a composition or molecule relative to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0032] The composition contains at least one zeolite. The zeolite is preferably used in the form of a fine powder. Surprisingly, the zeolite enables the composition to cure upon contact with atmospheric moisture. It appears that the combination of zeolite and moisture exerts a catalytic effect on the reaction of the aldehyde groups with the cyanoacetate groups. This is very surprising and could not be deduced from the prior art.

[0033] Preferably, the zeolite has a pore size of 3 to 10 Å, particularly preferably

[0034] 3 to 5 Å, especially 3 to 4 Å, most preferably 3 Å. Such a zeolite is also called a molecular sieve. This allows for particularly rapid curing. The pore size is preferably determined by gas adsorption.

[0035] The composition preferably contains 1 to 20% by weight, in particular 2 to 10% by weight, of zeolite, based on the total composition. This results in a composition with good storage stability and rapid curing.

[0036] The composition further contains at least one compound A with aldehyde groups.

[0037] Preferably, the compound A has one, two, three or four, in particular two or three, aldehyde groups and a molecular weight, or in the case of an oligomeric or polymeric compound A average molecular weight M n, from 100 to 20,000 g / mol.

[0038] Preferably, the aldehyde groups of compound A are directly bonded to an aromatic ring. Such a compound A enables particularly rapid curing.

[0039] Polyaldehydes such as phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 9,10-anthracenedicarbaldehyde, naphthalenedicarbaldehyde, 1,2-cyclohexanedicarbaldehyde, 1,3-cyclohexanedicarbaldehyde, 1,4-cyclohexanedicarbaldehyde, glutaraldehyde, 1,6-hexanedialdehyde, 1 are particularly suitable ,7-heptanedialdehyde, 1,8-octanedialdehyde, 1,9-nonanedialdehyde, 2-methyl-1,8-octanedialdehyde, 1,10-decanedialdehyde, 1,11-undecanedialdehyde, 1,12-dodecanedialdehyde, maledialdehyde, fumardialdehyde, tricyclo[5.2.1.0 2 ' 6 ]decane-3(4),8(9)-dicarbaldehyde, 3,6,9-trioxaundecane-1,11-dial, and aldehyde group-containing polymers.

[0040] Particularly suitable are phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 9,10-anthracene dicarbaldehyde, naphthalenedicarbaldehyde, or, in particular, aldehyde-containing polymers whose aldehyde groups are directly bonded to an aromatic ring. Compound A is preferably a polymer with an average molecular weight M n from 500 to 20,000 g / mol, particularly preferably 1,000 to 15,000 g / mol, in particular 2,000 to 10,000 g / mol, and an average aldehyde functionality of 1.6 to 4.0, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.2 to 3.0.

[0041] Particularly preferably, compound A is a polymer whose aldehyde groups are directly bonded to an aromatic ring.

[0042] Preferred are aldehyde group-containing polymers with a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

[0043] Preferred oxyalkylene repeating units are selected from the list consisting of oxy-1,2-propylene, oxy-1,3-propylene, oxy-1,4-butylene, oxy-1,2-butylene, and oxyphenylethylene. Additionally, compound A may have a certain content of oxyethylene units, in particular at most 25% by weight of oxyethylene based on the total weight of the poly(oxyalkylene) units.

[0044] A particularly preferred aldehyde-containing polymer contains a poly(oxy-1,2-propylene) backbone, which may contain 0 to 25% by weight of poly(oxyethylene) units based on the poly(oxy-1,2-propylene) backbone, particularly 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.

[0045] Preferred aldehyde-containing polymers with a polyester backbone are derived from dicarboxylic acids and di- or triols, or from triglycerides, or they are polyesters based on dimer or trimer fatty acids. Polyesters derived from dimer fatty acids or polyesters derived 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 heat and water resistance. Furthermore, they are based on renewable raw materials and are therefore potentially particularly sustainable.

[0046] A particularly preferred polymer containing aldehyde groups also contains urethane groups. This enables compositions with particularly high extensibility and tear resistance.

[0047] Preferably, compound A or the aldehyde group-containing polymer is liquid at room temperature, in particular with a viscosity at 20 °C of 0.01 to 700 Pa s, preferably 0.1 to 500 Pa s, particularly preferably 0.5 to 200 Pa s, in particular 1 to 100 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 Such compounds are easy to handle at ambient temperatures even without the addition of solvents or thinners.

[0048] Particularly preferred as compound A is a urethane group-containing polymer which is liquid at room temperature and has an average molecular weight M n from 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.

[0049] Such a polymer is preferably obtained from the reaction of at least one hydroxyaldehyde with at least one polymer containing isocyanate groups.

[0050] Particularly suitable as hydroxyaldehyde 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 singly or multiply 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).

[0051] Of these, hydroxyaldehydes whose aldehyde group is directly bonded to an aromatic ring are preferred. Particular preference is given to ethoxylated salicylaldehyde, in particular 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillin, in particular 4-(2-hydroxyethoxy)-3-methoxybenzaldehyde, or 5-hydroxymethylfurfural.

[0052] Ethoxylated salicylaldehyde is particularly preferred. This results in particularly color-stable compositions.

[0053] 5-Hydroxymethylfurfural is also particularly preferred. This results in particularly easy-to-process compositions with particularly rapid curing.

[0054] A particularly suitable polymer containing isocyanate groups is a reaction product from the reaction of at least one polyisocyanate with at least one polyol, prepared by a known process.

[0055] A diisocyanate is particularly suitable as polyisocyanate, in particular 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 4(2),4'-diphenylmethane diisocyanate (MDI) or 2,4(6)-toluene diisocyanate, particularly preferably IPDI.

[0056] Particularly suitable as polyol are

[0057] - Polyether polyols, in particular polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, oxetane, tetrahydrofuran or mixtures thereof, where these can be polymerized with the aid of a starter molecule having two or more active hydrogen atoms. Preference is given to poly(oxy-1,2-propylene)diols or polyoxypropylenetriols, in particular propoxylated glycerol or 1,1,1-trimethylolpropane, where these can each additionally be ethoxylated at the chain ends. They are also referred to as EO-terminated (EO-endcapped) poly(oxy-1,2-propylene)diols or polyoxypropylenetriols. Preferred polyether polyols have a degree of unsaturation of less than 0.02 mEq / g, in particular less than 0.01 mEq / g. - Polyester polyols, in particular from the polycondensation of hydroxycarboxylic acids or lactones or of aliphatic and / or aromatic polycarboxylic acids with di- or polyhydric alcohols.Preferred are amorphous polyester polyols which are liquid at room temperature, in particular di- or trimer fatty acid-based polyester polyols, such as those commercially available from Cargill, for example.

[0058] - Polycarbonate polyols, obtainable by reacting diols with dialkyl carbonates, diaryl carbonates or phosgene.

[0059] - Block copolymers containing at least two hydroxyl groups, in particular polyetherpolyesterpolyols.

[0060] - Polyacrylate and polymethacrylate polyols.

[0061] - Polyhydroxy-functional fats or oils, in particular natural fats or oils such as castor oil, ethoxylated or in particular propoxylated castor oil, ketone resin-modified 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).

[0062] - or polyhydrocarbon polyols.

[0063] Preferred are polyether polyols, di- or trimer fatty acid-based polyester polyols, castor oil, derivatives of castor oil or hydroxylated vegetable oils.

[0064] Particularly preferred are polyether polyols, especially poly(oxy-1,2-propylene)diols or polyoxypropylene triols, which may be EO-terminated. These enable compositions with particularly high extensibility and elasticity combined with high water resistance.

[0065] The composition further contains at least one compound B with cyanoacetate groups.

[0066] Compound B preferably contains one to six cyanoacetate groups, particularly preferably two to four, in particular two to three, cyanoacetate groups. Compound B is preferably liquid at room temperature. In particular, it has a viscosity at 20 °C of 0.01 to 50 Pa s, more preferably 0.01 to 25 Pa s, particularly preferably 0.01 to 10 Pa s, in particular 0.02 to 5 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, cone angle of 1°, cone tip-to-plate distance of 0.05 mm, and a shear rate of 10 s. -1 , for viscosities of less than 0.5 Pa s with a cone diameter of 50 mm. Such a connection enables compositions that are easy to process at ambient temperature and without the addition of solvents or thinners.

[0067] Preferably, the compound B has a molecular weight, or in the case of an oligomeric or polymeric compound B average molecular weight M n, from 100 to 10,000 g / mol, preferably 196 to 5,000 g / mol, particularly preferably 240 to 2,500 g / mol, in particular 240 to 1,500 g / mol.

[0068] Preferably, compound B has a cyanoacetate equivalent weight, or in the case of an oligomeric or polymeric compound B average cyanoacetate equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g / eq.

[0069] Preferably, the compound B has a functionality, or in the case of an oligomeric or polymeric compound B, average functionality, of 1 to 4, preferably 1.5 to 4, more preferably 1.8 to 3.5, particularly preferably 2 to 3, in particular 2.3 to 3, with respect to the cyanoacetate groups.

[0070] In particular, the compound B has, with respect to the cyanoacetate groups, an equivalent weight, or in the case of an oligomeric or polymeric compound B average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g, and a functionality, or in the case of an oligomeric or polymeric compound B average functionality, of 1.5 to 4, preferably 1.8 to 3.5, more preferably 2 to 3, in particular 2.3 to 3.

[0071] In the composition according to the invention, the ratio of the number of cyanoacetate groups to the number of aldehyde groups is preferably in the range of 0.7 to 2.0, in particular 0.9 to 1.5. This enables reliable curing and a cured product with high strength and high extensibility.

[0072] Preferably, compound B is obtained from the transesterification of at least one hydroxyl-containing compound with at least one compound of formula (I), where R1 stands for C1-6 alkyl.

[0073] Preferably R 1 for methyl, ethyl or tert. butyl, in particular for ethyl or tert. butyl.

[0074] The transesterification is preferably carried out at a temperature of 50 to 150 °C with distillative removal of the released alcohol R 1 OH and optionally fragmentation products thereof, optionally under vacuum and optionally in the presence of catalysts.

[0075] It is also possible to produce it by esterifying cyanoacetic acid with at least one compound containing hydroxyl groups.

[0076] Particularly suitable compounds of formula (I) are methyl cyanoacetate, ethyl cyanoacetate or tert. butyl cyanoacetate, in particular ethyl cyanoacetate or tert. butyl cyanoacetate.

[0077] Preferred hydroxyl-containing compounds are commercially available OH-functional compounds or polymers, such as in particular 1,2-ethanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,2-pentanediol, neopentyl glycol, 2-methyl-1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 1,10-decanediol, 1,12-dodecanediol, Polytetrahydrofurandiol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, propoxylated and / or ethoxylated glycerol with medium molecular weight M n from 300 to 6'000 g / mol, propoxylated and / or ethoxylated 1,1,1-trimethylolpropane with medium molecular weight M nfrom 300 to 6,000 g / mol, poly(oxy-1,2-propylene)diols with an average molecular weight of 400 to 4,000 g / mol, EO-terminated poly(oxy-1,2-propylene)diols with an average molecular weight of 1,000 to 4,000 g / mol, poly(oxy-1,2-propylene)triols with an average molecular weight of 400 to 6,000 g / mol, EO-terminated poly(oxy-1,2-propylene)triols with an average molecular weight of 3,000 to 6,000 g / mol, di- or trimer fatty acid-based polyester polyols with an average molecular weight of 1,000 to 3,000 g / mol, castor oil, derivatives of castor oil or hydroxylated vegetable oils.

[0078] Preferred as compound B is 2-methyl-1,3-propanediol dicyanoacetate, neopentyl glycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate or a polymer having an average molecular weight M nfrom 500 to 6,000 g / mol, particularly preferably 500 to 2,000 g / mol, in particular 500 to 1,000 g / mol, and an average cyanoacetate functionality of 1.5 to 4, preferably 1.8 to 3.5, more preferably 2 to 3, in particular 2.3 to 3. This enables cured compositions with particularly high extensibility.

[0079] In a preferred embodiment of the invention, compound B is a polymer having an average molecular weight M n from 500 to 6,000 g / mol, particularly preferably 500 to 2,000 g / mol, in particular 500 to 1,000 g / mol, and an average cyanoacetate functionality of 1.5 to 4, preferably 1.8 to 3.5, more preferably 2 to 3, in particular 2.3 to 3.

[0080] In particular, such a polymer is compound B selected from the list consisting of 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate, the tricyanoacetate of ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, the tricyanoacetate of ethoxylated and / or propoxylated glycerol, poly(oxy-1,2-propylene)diol bis(cyanoacetate), ethylene oxide unit-containing poly(oxy-1,2-propylene)diol bis(cyanoacetate), dimer fatty acid-based polyesterdiol bis(cyanoacetate) and trimer fatty acid-based polyestertriol tris(cyanoacetate).

[0081] Particularly preferred is the tricyanoacetate of propoxylated 1,1,1-trimethylolpropane) with a total average molecular weight M n from 500 to 1,000 g / mol.

[0082] In a preferred embodiment of the invention, the average functionality of the entire composition with respect to the reactive groups, aldehyde and cyanoacetate, is at least 2.2. This means that a composition with an average aldehyde functionality of, for example, 1.8 preferably has an average cyanoacetate functionality of at least 2.4 in order to achieve an overall average reactive group functionality of at least 2.2. Such a composition enables particularly high strength with high extensibility.

[0083] The composition according to the invention may additionally contain further components, in particular:

[0084] - 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, silica, silicic acid kaolinites, calcined silicic acid kaolinites, phyllosilicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, highly dispersed silicas from pyrolysis processes, industrially produced carbon blacks, graphite, ground fillers from agricultural sources such as olive kernel flour or nutshell flour, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow spheres; - Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, hemp fibers, cellulose fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

[0085] - Nanofillers or nanofibers such as graphene or carbon nanotubes;

[0086] - dyes;

[0087] - pigments, in particular titanium dioxide, chromium oxide, iron oxides or organic pigments;

[0088] - 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 polyether structure, in particular polypropylene oxide monols, diols or triols, or polypropylene oxide 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) or tris-2-ethylhexyl phosphate (TOF), polybutenes,Polyisobutenes or plasticizers derived from natural fats or oils, in particular epoxidized soy or linseed oil or rapeseed oil methyl ester, with phthalates, hydrogenated phthalates, adipates or plasticizers with a polyether structure being preferred;

[0089] - solvents;

[0090] - Modifiers such as hydrocarbon resins, natural or synthetic waxes or bitumen;

[0091] - 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;

[0092] - drying agents, in particular calcium oxide, mono-oxazolidines such as Incozol® 2 (from Incorez), orthoesters or alkoxysilanes; - adhesion promoters, in particular titanates or organoalkoxysilanes such as epoxysilanes, mercaptosilanes, (meth)acrylsilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;

[0093] - 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);

[0094] - 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;

[0095] - 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.

[0096] The composition preferably contains at least one further component selected from plasticizers, fillers, and adhesion promoters. The composition preferably contains several such further components.

[0097] 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, coated calcium carbonates, quartz powder, quartz sand, kaolin, calcined kaolin, silica, silicic acid kaolinite, calcined silicic acid kaolinite, 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 50 mm, in particular 1.5 to 25 mm. The cured composition exhibits pronounced elastic properties. 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 plasticizers.Preferably, plasticizers are selected from DINP, DIDP, DPHP, DINCH, bis(2-ethylhexyl)terephthalate, DINT, bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate, diisononyl-1,4-cyclohexanedicarboxylate, DOA, polypropylene oxide monols, polypropylene oxide diols, polypropylene oxide triols, polypropylene oxide monol acetates, polypropylene oxide diol diacetates, polypropylene oxide triol triacetates and DPK.

[0098] In a particularly preferred embodiment of the invention, the curable composition contains fillers and plasticizers, in particular 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 and 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizers.

[0099] The curable composition preferably contains less than 10% by weight, more preferably less than 5% by weight, and especially less than 1% by weight, of volatile organic compounds (VOCs) with a boiling point at atmospheric pressure of less than 250°C, particularly organic solvents, based on the total composition. Such a composition causes particularly low emissions.

[0100] The composition preferably contains less than 0.5% by weight, more preferably less than 0.1% by weight, and especially less than 0.01% by weight, of water based on the total composition. Such a composition is particularly stable during storage.

[0101] The one-component curable composition preferably comprises, based on the total composition, 5 to 100% by weight, preferably 5 to 99% by weight, in particular 10 to 70% by weight, of the sum of compounds A and B. The one-component curable composition preferably comprises, based on the total composition

[0102] - 5 to 99% by weight, preferably 10 to 70% by weight, of the sum of compounds A and B,

[0103] - 1 to 20% by weight, preferably 2 to 10% by weight, zeolite,

[0104] - 0 to 50% by weight, preferably 10 to 40% by weight, plasticizer,

[0105] - 0 to 90% by weight, preferably 20 to 80% by weight, fillers,

[0106] - and if necessary other substances,

[0107] The composition is preferably prepared by mixing the components together using a suitable method to produce a macroscopically homogeneous mass. The zeolite and fillers are preferably used in a largely dry state. It may be advantageous to dry the zeolite and / or fillers beforehand using a suitable method, for example, in a forced-air oven. Production preferably takes place in the absence of moisture. After production, the mixed composition is stored in a suitable moisture-proof container, in particular drums, containers, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges, or tubes. The moisture-proof packaged composition is stable in storage.This means that it can be stored at room temperature for a long period of time, typically for at least 3 months up to 6 months or more, without its application or usage properties changing as a result of storage to an extent relevant to its use, in particular without hardening in the container.

[0108] The composition preferably has a liquid or pasty consistency. Depending on the application, a liquid or pasty consistency may be preferred.

[0109] For use, the composition is applied to at least one substrate under ambient conditions. The applied composition comes into contact with moisture, in particular atmospheric humidity and / or additional moisture, for example, from the substrate to which it is applied or additional moisture that has been introduced into the environment of the applied composition.

[0110] Upon contact with moisture, the composition begins to harden due to the chemical reaction that begins. The cyanoacetate groups primarily react with the aldehyde groups, causing the composition to cure reliably and smoothly into a solid, polymeric material.

[0111] A further subject matter of the invention is thus a process for curing the one-component curable composition, characterized in that the composition is applied to at least one substrate and cures under the influence of atmospheric moisture.

[0112] Curing preferably takes place under ambient conditions, in particular at a temperature in the range of -5 to 50 °C, preferably 0 to 40 °C, in particular 5 to 35 °C.

[0113] Suitable substrates to which the composition is applied are in particular

[0114] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble;

[0115] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECO (epoxy resin-modified cement mortar);

[0116] - 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;

[0117] - asphalt or bitumen;

[0118] - 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;

[0119] - 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;

[0120] - 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);

[0121] - Insulating materials, in particular foams, in particular EPS, XPS, PUR, PIR, aerogel or foamed glass (foam glass), or fibres made of rock wool or glass wool,

[0122] - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0123] - Coatings, paints or varnishes.

[0124] 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.

[0125] Two similar or two different substrates can be bonded and / or sealed.

[0126] In order to accelerate the curing, the one-component curable composition can be mixed shortly before or during application with an accelerator component containing at least one accelerator for the reaction of cyanoacetate groups with aldehyde groups.

[0127] The accelerator component enables particularly fast curing regardless of the ambient humidity, even in thick layers and between moisture-proof substrates.

[0128] Preferably, the accelerator for the reaction of cyanoacetate groups with aldehyde groups is a nitrogen-containing catalyst or an aqueous solution of a basic salt, in particular with a concentration of 10 to 30% by weight of the salt based on the total weight of the solution, or water.

[0129] Secondary or tertiary amines are preferred as nitrogen-containing catalysts. Suitable secondary amines are in particular dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di(2-ethylhexyl)amine, N-methylbutylamine, N-ethylbutylamine, di(2-methoxyethyl)amine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, piperidine, pyrrolidine, morpholine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-dibenzyl-1,2-ethanediamine, piperazine, N-methylpiperazine, N-ethylpiperazine, N-hydroxyethylpiperazine, imidazolidine, N-methylimidazolidine, proline or imidazole.

[0130] Geeignete tertiäre Amine sind insbesondere Triethylamin, Tripropylamin, Tributylamin, Tri(2-ethylhexyl)amin, N,N-Dimethylisopropylamin, N-Ethyldiisopropylamin, N,N-Dimethylcyclohexylamin, N,N-Dimethyl-Ci2-i4-alkylamin, N,N-Dimethylbenzyl- amin, a-Methylbenzyldimethylamin, Tetramethyl-1 ,2-ethandiamin, Tetramethyl- 1 ,6-hexandiamin, Pentamethyldiethylentriamin, T ris(3-dimethylaminopropyl)amin, Triethanolamin, Triisopropanolamin, N,N-Dimethylethanolamin, N,N-Diethyletha- nolamin, N,N-Dibutylethanolamin, N,N-Dimethyl-1 ,3-propanolamin, N-Methyl- diethanolamin, N-Methylpiperidin, N,N'-Dimethylpiperazin, N-Methyl-N'-dimethyl- aminoethylpiperazin, Bis(dimethylaminoethyl)piperazin, 1 ,4-Diazabicyclo[2.2.2]-octane (DABCO), 1,3,5-trimethylhexahydrotriazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 1,3-bis(dimethylaminopropyl)urea, bis(2-dimethylaminoethyl)ether, tris(2-(2-methoxyethoxy)ethyl)amine, 2,2'-Dimorpholinodiethyl ether (DMDEE), N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole.

[0131] Preferred basic salts are potassium acetate, potassium benzoate, potassium carbonate, potassium bicarbonate, potassium phosphate, sodium acetate, sodium benzoate, sodium carbonate, sodium bicarbonate, sodium phosphate, lithium acetate, lithium benzoate, lithium carbonate, lithium bicarbonate or lithium phosphate.

[0132] The invention further relates to the cured composition obtained from the process for curing the one-component curable composition as described, optionally with the use of an accelerator component. The cured composition is preferably elastic and exhibits high strength with high extensibility and high tear resistance.

[0133] The cured composition preferably has an elongation at break of at least 50%, 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 (thickness 2 mm, length 75 mm, web length 30 mm, web width 4 mm).

[0134] Preferably, the cured composition has a tensile strength of at least 1 MPa, preferably at least 1.5 MPa, more preferably at least 2 MPa, more preferably at least 2.5 MPa, in particular at least 3 MPa, determined according to DIN EN 53504 at a tensile speed of 200 mm / min on dumbbell-shaped test specimens (thickness 2 mm, length 75 mm, web length 30 mm, web width 4 mm).

[0135] Furthermore, the cured composition exhibits good resistance to heat and water. Preferably, the cured composition exhibits high strength and ductility even after storage for 7 days at 100 °C or at 70 °C and 100% relative humidity.

[0136] The described composition is suitable for a wide range of applications. It can be used, in particular, as an adhesive, sealant, coating, casting resin, or filler, especially as an elastic adhesive, elastic sealant, or elastic coating.

[0137] Another object of the invention is the use of the composition as an elastic adhesive, elastic sealant or elastic coating.

[0138] 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 civil engineering structure, a bridge, a roof, a staircase, or a facade, or it may be an industrial or consumer product or an attachment thereof, 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.

[0139] Examples

[0140] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0141] The “standard climate” (“NK”) is defined as a temperature of 23±1 °C and a relative humidity of 50±5%.

[0142] Unless otherwise stated, the chemicals used were from Merck.

[0143] 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, using a cone diameter of 50 mm for viscosities of less than 0.5 Pa s.

[0144] Infrared spectra (FT-IR) were measured as undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal diamond crystal ATR measurement unit.

[0145] The content of monomeric diisocyanate was determined by HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivation using N-propyl-4-nitrobenzylamine.

[0146] Production of polymers with aldehyde groups:

[0147] Polymer A-1 :

[0148] 500 g of the isocyanate-containing polymer-1 (NCO content 1.84 wt. %, based on IPDI, prepared as described below) was reacted with 27.7 g of 5-hydroxymethylfurfural in the presence of 0.1 g of dibutyltin dilaurate under exclusion of moisture at 110 °C until no isocyanate groups were detectable by IR spectroscopy. A clear, colorless liquid was obtained with a viscosity of 63.7 Pa s at 20 °C, an average aldehyde functionality of approximately 2.3, and a theoretical aldehyde equivalent weight of 2381 g / eq. The average molecular weight M n was 6,100 g / mol, determined by gel permeation chromatography (GPC) against polystyrene (474 ​​to 2,520,000 g / mol) as standard, with tetrahydrofuran as mobile phase and refractive index detector.

[0149] Polymer A-2:

[0150] 500 g of the isocyanate-containing polymer-2 (NCO content 1.68 wt. %, based on MDI, prepared as described below) was reacted with 25.5 g of 5-hydroxymethylfurfural at 80 °C under exclusion of moisture until no isocyanate groups were detectable by IR spectroscopy. A clear, colorless liquid with a viscosity of 187.1 Pa s at 20 °C, an average aldehyde functionality of approximately 2.3, and a theoretical aldehyde equivalent weight of 2632 g / eq was obtained.

[0151] The isocyanate group-containing polymer-1 was prepared by reacting 780 g of ethylene oxide-terminated polyoxypropylenetriol (Desmophen® 5031 BT, OH number 28.0 mg KOH / g, OH functionality approx. 2.3, from Covestro) with 303 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) at 80 °C according to a known method to form a reaction mixture with an NCO content of 9.1% by weight. The volatile components, in particular unreacted isophorone diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 to 0.005 mbar), whereby a polymer with an NCO content of 1.84% by weight and a content of monomeric isophorone diisocyanate of 0.02% by weight was obtained. was received.

[0152] The isocyanate group-containing polymer-2 was prepared by reacting 725 g of ethylene oxide-terminated polyoxypropylenetriol (Desmophen® 5031 BT, OH number 28.0 mg KOH / g, OH functionality approx. 2.3, from Covestro) with 275 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) at 80 °C according to a known method to form a reaction mixture with an NCO content of 7.6% by weight and then removing the volatile components, in particular unreacted 4,4'-diphenylmethane diisocyanate, by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 to 0.005 mbar), whereby a polymer with an NCO content of 1.68% by weight and a content of monomeric 4,4'-diphenylmethane diisocyanate of 0.04 wt.%.

[0153] Preparation of compounds with cyanoacetate or acetoacetate groups:

[0154] Compound B-1 :

[0155] 555.2 g (5.4 mol OH) of propoxylated 1,1,1-trimethylolpropane (Desmophen® 4011 T, OH number 550 mg KOH / g, from Covestro) were treated with 633.5 g (5.6 mol) of ethyl cyanoacetate and 1.2 g of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) and reacted at a temperature of 80 to 140 °C under vacuum until the broad OH band in the range of 3,300 to 3,600 cm -1 had disappeared and no more volatiles were deposited. 866.2 g of a clear, yellowish liquid with a viscosity of 1.72 Pa s at 20 °C, an average cyanoacetate functionality of approximately 3, and a theoretical cyanoacetate equivalent weight of 169 g / eq were obtained.

[0156] Compound R-1 :

[0157] 154.2 g (1.5 mol OH) of propoxylated 1,1,1-trimethylolpropane (Desmophen® 4011 T, OH number 550 mg KOH / g, from Covestro) were treated with 201.7 g (1.55 mol) of ethyl acetoacetate and 0.4 g of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) and reacted at a temperature of 80 to 140 °C under vacuum until the broad OH band in the range of 3,300 to 3,600 cm was observed in the FT-IR. -1 had disappeared and no more volatiles were separated. 265.1 g of a clear, yellowish liquid with a viscosity of 0.8 Pa s at 20 °C, an average acetoacetate functionality of approximately 3, and a theoretical acetoacetate equivalent weight of 186 g / eq were obtained.

[0158] Preparation of single-component compositions: substances used:

[0159] Zeolite: Sylosiv® A 3 (from Grace)

[0160] Plasticizer-1 : n-butanol-initiated acetylated PPG monol, produced from the reaction of Synalox® 100-20B (average molecular weight M n approx. 750 g / mol, from Dow) and acetic anhydride with distillative removal of acetic acid

[0161] Epoxysilane: 3-Glycidoxypropyltrimethoxysilane Carbon black: Monarch® 570 (from Cabot)

[0162] Compositions Z1 to Z9:

[0163] For each composition, the ingredients listed in Table 1 were blended in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) to form a macroscopically homogeneous paste. The blended composition was stored in a moisture-proof container. The zeolite, fillers, and carbon black were previously dried in a convection oven at 130 °C.

[0164] Each composition was tested as follows:

[0165] The storage stability of the composition was determined by measuring the viscosity after a storage period of 1 day in a sealed container under standard conditions (SC) and after 7 days in a convection oven at 40 °C. A slight increase in viscosity after 7 days at 40 °C compared to 1 day SC indicates particularly good storage stability. A non-storage-stable composition cured after storage for 7 days at 40 °C in a sealed container.

[0166] The tack-free time (TFT) was determined by applying 20 g of the mixed composition in a layer thickness of approximately 2 mm to cardboard and determining the time required for the first time when the surface of the applied composition was lightly tapped using an LDPE pipette to leave no residue on the pipette.

[0167] The curing rate was determined by applying a bead-shaped sample with a thickness of approximately 10 mm under standard conditions. After 1 day (24 hours), 2 days, 3 days, 4 days, and 7 days, the bead was cut open at an undamaged area and the thickness of the externally cured skin was measured. A thickness of 10 mm corresponds to complete curing of the bead.

[0168] To determine the mechanical properties, the 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 conditions. 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 tested according to DIN EN 53504 at a tensile speed of 200 mm / min for tensile strength, elongation at break, 5% modulus of elasticity (at 0.5-5% elongation), and 50% modulus of elasticity (at 0.5-50% elongation). Furthermore, some test specimens were punched out to determine tear resistance and tested according to DIN ISO 34-1, Method B (angular test specimen) at a tensile speed of 500 mm / min.

[0169] The Shore A hardness was determined according to DIN 53505 on test specimens (diameter 20 mm, thickness 5 mm) cured for 7 days under standard conditions. These results are designated "7d NK." To determine heat and water resistance, additional Shore A test specimens were either stored for an additional 7 days in a convection oven at 100°C or stored for an additional 7 days at 70°C and 100% relative humidity, after curing for 7 days under standard conditions. The Shore A hardness was determined after cooling to room temperature. These results are designated "+7d 100°C" or "+7d 70 / 100."

[0170] The results are shown in Table 1.

[0171] The compositions marked "(Ref.)" are comparative examples.

[0172]

[0173] Table 1 : Compositions Z1 to Z9.

[0174] 1 Voranol® 1010 L, M n approx. 1000 g / mol (from Dow) (as plasticizer)

[0175] 2 calcined kaolin (Satintone® W, from HM Royal)

[0176] 3 Silicic acid kaolinite (Sillitin® Z86, from Hoffmann Mineral)

[0177] 4 calcined silica kaolinite (Silfit® Z91, from Hoffmann Mineral)

[0178] 5 ground calcium carbonate (Omyabond® 420-OG, from Omya)

[0179] 6 coated calcium carbonate (Omyacarb® 1T-AV, from Omya)

[0180] 7 not measurable because no curing

[0181] Table 1 : (continued)

[0182] From Table 1 it can be seen that the one-component

[0183] Compositions Z1 to Z6 are storage-stable and, when applied under the influence of atmospheric humidity in standard conditions, cure reliably and smoothly to form an elastic polymer with high strength, extensibility, tear resistance, and good resistance to heat and water. Curing occurs from the outside inward, according to the penetration of atmospheric humidity into the applied composition. Furthermore, it can be seen that the comparative examples, compositions Z7 (Ref.) without zeolite and Z8 (Ref.) and Z9 (Ref.) with acetoacetate groups instead of cyanoacetate groups, with and without zeolite, had not formed a skin on the surface after 7 days in standard conditions and no curing occurred.

[0184] Compositions Z10 to Z12: Composition Z1 was cured with the addition of an accelerator component as specified in Table 2 (in parts by weight). The accelerator component was mixed in using a centrifugal mixer. The freshly mixed composition was tested as described for composition Z1. The results are shown in Table 2.

[0185] Table 2: Compositions Z10 to Z12.

[0186] 1 Bis(2-dimethylaminoethyl)ether

[0187] 2 25% by weight in water

Claims

Patent claims: 1 . One-component curable composition containing - at least one compound A with aldehyde groups, - at least one compound B containing cyanoacetate groups, and - at least one zeolite, wherein at least one of the two compounds A and B is a polymer having an average molecular weight Mn of 500 to 20,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene as standard, wherein the composition can be stored in a single container and is curable by exposure to atmospheric moisture.

2. Composition according to claim 1, characterized in that the zeolite has a pore size of 3 to 10 Å, preferably 3 to 5 Å.

3. Composition according to claim 1 or 2, characterized in that, based on the total composition, 1 to 20% by weight, preferably 2 to 10% by weight, of zeolite is present.

4. Composition according to one of claims 1 to 3, characterized in that the aldehyde groups of compound A are directly bonded to an aromatic ring.

5. Composition according to one of claims 1 to 4, characterized in that the compound A is a polymer having an average molecular weight M n from 500 to 20,000 g / mol, preferably 1,000 to 15,000 g / mol, in particular 2,000 to 10,000, and an average aldehyde functionality of 1.6 to 4.0, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, in particular 2.2 to 3.

0.

6. Composition according to one of claims 1 to 5, characterized in that the compound B, with respect to the cyanoacetate groups, is a Equivalent weight, or in the case of an oligomeric or polymeric compound B average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g, and a functionality, or in the case of an oligomeric or polymeric compound B average functionality, of 1.5 to 4, preferably 1.8 to 3.5, more preferably 2 to 3, in particular 2.3 to 3.

7. Composition according to one of claims 1 to 6, characterized in that the ratio of the number of cyanoacetate groups to the number of aldehyde groups in the entire composition is in the range from 0.7 to 2.0, in particular 0.9 to 1.

5.

8. Composition according to one of claims 1 to 7, characterized in that the compound B is selected from the list consisting of 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate, the tricyanoacetate of ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, the tricyanoacetate of ethoxylated and / or propoxylated glycerol, poly(oxy-1,2-propylene)diol bis(cyanoacetate), ethylene oxide units-containing poly(oxy-1,2-propylene)diol bis(cyanoacetate), dimer fatty acid-based polyesterdiol bis(cyanoacetate) and trimer fatty acid-based Polyestertriol-tris(cyanoacetate).

9. Composition according to one of claims 1 to 8, characterized in that the average functionality of the entire composition with respect to the reactive groups aldehyde and cyanoacetate groups is at least 2.

2.

10. Composition according to one of claims 1 to 9, characterized in that at least one further component selected from plasticizers, fillers and adhesion promoters is included.

11. Composition according to one of claims 1 to 10, 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 and 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizers are contained.

12. A process for curing the composition according to any one of claims 1 to 11, characterized in that the composition is applied to at least one substrate and cures under the action of atmospheric moisture.

13. The method according to claim 12, characterized in that shortly before or during the application of the composition, an accelerator component containing at least one accelerator for the reaction of cyanoacetate groups with aldehyde groups is mixed with the composition.

14. Cured composition obtained from the process according to one of claims 12 or 13, wherein the cured composition is in particular elastic and in particular has an elongation at break of at least 50%, 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, a length of 75 mm, a web length of 30 mm and a web width of 4 mm.

15. Use of the one-component curable composition according to any one of claims 1 to 11 as an elastic adhesive, elastic sealant or elastic coating.

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