Curable polymer composition containing aldehydes, compounds with activated methylene groups, and an accelerator component

Abstract

The invention relates to a curable composition comprising (i) a main component containing at least one compound A with aldehyde groups and at least one compound B with activated methylene groups of formula (I); and (ii) an accelerator component containing at least one accelerator for reacting aldehyde groups with activated methylene groups of formula (I), 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 main component is packaged in a single container separately from the accelerator component and can thus be stored stably. The curable composition can be used without special protective measures, and the main component is storage-stable and cures rapidly and reliably when mixed with the accelerator component so as to form an elastic polymer with high strength, high ductility, and high resistance against heat and water.

Description

[0001] Curable polymer composition containing aldehydes, compounds with activated methylene groups and an accelerator component

[0002] Technical area

[0003] The invention relates to storage-stable polymer compositions containing aldehydes and compounds with activated methylene groups, which can be cured under ambient conditions under the influence of an accelerator component, and to their use as elastic adhesives, sealants or coatings.

[0004] State of the art

[0005] Curable polymer compositions that can be applied under ambient conditions are usually formulated as so-called two-component compositions, in which the reactive compounds involved in the curing reaction are stored in separately packaged components. Shortly before or during application, the two components are mixed, causing the reactive compounds to react with each other, crosslinking, and curing occurs. However, such compositions have disadvantages. In particular, the dosing and mixing of the components must be carried out very precisely to ensure the desired stoichiometry for the crosslinking reaction. Otherwise, an incompletely crosslinked product with poor mechanical properties and a sticky surface can result.

[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 referred to as single-component compositions. They are easy to use because no mixing is necessary. Curing typically occurs through contact with moisture. Well-known moisture-curing systems include, in particular, polyurethane compositions containing isocyanate groups, as well as compositions based on silane-functional polymers or silicones. However, these also have disadvantages. Firstly, their curing is slow and inhomogeneous, as it depends on the availability of moisture, which usually has to penetrate the composition from the air. Secondly, the curing reaction produces substances that are not incorporated into the polymer matrix and can cause problems.Polyurethane compositions release carbon dioxide, which can lead to blistering. This can be prevented with the use of latent hardeners, particularly aldimines. However, curing releases aldehydes that are not incorporated into the polymer matrix and can lead to problems with emissions and / or odor formation, or they remain in the cured composition, where they exert a plasticizing effect and / or can migrate from the composition. Compositions based on silane-functional polymers or silicones release alcohols, especially methanol or ethanol, acetic acid, or oximes, which are toxic and cause emissions. Finally, both systems contain harmful crosslinkers, particularly monomeric diisocyanates or low-molecular-weight silanes, which can endanger the user and require protective measures during handling.

[0007] The disadvantage of slow curing of one-component compositions can be overcome with a water-based accelerator component, also called a "booster." This is added during application and leads to rapid curing regardless of humidity, as described, for example, in WO 03 / 059978. Compared to traditional two-component compositions, such booster systems are easier to use because only a small amount of the accelerator component is mixed in and the mixing ratio does not need to be precisely maintained. However, the polarity difference between the components can lead to incomplete mixing with local weak points due to phase boundaries. Furthermore, the problems caused by the toxicity of the crosslinkers and the release of substances not incorporated into the polymer matrix are not solved.

[0008] US 10,563,040 describes a curable composition comprising a polyacetoacetate, a polyaldehyde, and a basic catalyst, wherein the polyacetoacetate and the polyaldehyde are stored in separate components. US 2002 / 040093 describes an aqueous coating comprising an aldehyde-functional polyurethane dispersion, trimethylolpropane triacetoacetate, and an aqueous tetrabutylammonium hydroxide solution, wherein the aldehyde-functional polyurethane dispersion and the trimethylolpropane triacetoacetate are not stored together.

[0009] US 2020 / 181312 describes, in Example 48, a curable coating containing an acetoacetate-functional polyester resin, tricyclodecanedialdehyde, and morpholine as a catalyst, which is laminated onto a flexible substrate. The polyester resin and the dialdehyde are mixed, and the morpholine is then added. Storing the polyester resin together with the dialdehyde in a separate package for an extended period of time is not described.

[0010] US 2011 / 250257 describes a fabric made of a polysaccharide aldehyde and a polysaccharide acetoacetate for closing wounds, which reacts to form a hydrogel when sprayed with an aqueous base.

[0011] Description of the invention

[0012] The object of the present invention is to provide a curable composition which is easy to use 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.

[0013] Surprisingly, this object is achieved with a curable composition as described in claim 1. The curable composition comprises a main component and an accelerator component. The main component is storage-stable when separated from the accelerator component and contains at least one compound A with aldehyde groups and at least one compound B with activated methylene groups of formula (I), in particular cyanoacetate or acetoacetate groups. The fact that polyaldehydes can be stored together with cyanoacetates or acetoacetates in a common container and can be stored stably was previously unknown in the art. When the accelerator component is mixed into the main component, the composition cures under ambient conditions to form an elastic polymer.Because the reactive groups involved in the curing, aldehyde and activated methylene groups of formula (I), are pre-dosed and pre-mixed in the main component in the desired stoichiometric ratio, the curing reaction is hardly dependent on the mixing process, neither in terms of the mixing ratio between the components nor in terms of the homogeneity of the mixture; even if the accelerator component is incompletely mixed in, the curing takes place largely without disruption.

[0014] Compound A and Compound B are both low-toxicity substances that do not require hazard labeling and can be handled without special precautions. The accelerator component does not require any potentially toxic metal compounds. The curable composition is readily processable under ambient conditions, requiring no organic solvents for dissolving or diluting, or water for emulsifying or dispersing components. Curing is not sensitive to blistering and does not produce emissions. Curing produces a non-sticky, elastic polymer with high strength, high elongation, high tear resistance, and good resistance to heat and water.The combination of these advantageous properties makes the curable composition particularly easy to handle without the need for special protective measures and highly robust when exposed to mechanical, thermal or chemical stress after curing.

[0015] The curable composition 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 curable composition comprising (i) a main component containing

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

[0020] - at least one compound B having activated methylene groups of formula (I), oo

[0021] II II1where Y is a radical of the formula ■ _- CN , ---C— R , ---C— OR or

[0022] O

[0023] II ---C— O-—, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1 represents an alkyl radical having 1 to 6 C atoms, and

[0024] (ii) an accelerator component containing at least one accelerator for the reaction of aldehyde groups with activated methylene groups of the formula (I), 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 main component is packaged separately from the accelerator component in a single container and can thus be stored in a stable manner.

[0025] A component or 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 three months up to six months or more, without its application or use properties changing as a result of storage to an extent relevant to its use, in particular without hardening in the container.

[0026] A dashed line in the formulas in this document represents the bond between a substituent and the corresponding molecular residue. 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.

[0027] The term "polymer" also includes so-called oligomers with two, three, or four repeating units. A "primary amino group" is an amino group that is bonded to a single organic residue and carries two hydrogen atoms; a "secondary amino group" is an amino group that is bonded to two organic residues, which may also be part of a ring, and carries one hydrogen atom; and a "tertiary amino group" is an amino group that is bonded to three organic residues, which may also be part of one or more rings in two or three groups, and does not carry a hydrogen atom.

[0028] Substance names beginning with “poly” such as polyaldehyde, polycyanoacetate, polyacetoacetate or polyol refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0029] “Room temperature” is defined as a temperature of 23 °C.

[0030] 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.

[0031] Preferably, the main component makes up at least 80% by weight, more preferably at least 90% by weight, in particular at least 95% by weight, of the total weight of the entire composition.

[0032] The main component contains at least one compound A with aldehyde groups.

[0033] 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.

[0034] Preferably, the aldehyde groups of compound A are directly bonded to an aromatic ring. Such a compound A enables particularly rapid curing. Surprisingly, a main component containing such a compound A is particularly stable during storage.

[0035] 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.

[0036] Particularly suitable are phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 9,10-anthracene dicarbaldehyde, naphthalenedicarbaldehyde or, in particular, aldehyde group-containing polymers whose aldehyde groups are directly bonded to an aromatic ring.

[0037] Preferably, compound A is a polymer having 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.

[0038] Particularly preferably, compound A is a polymer whose aldehyde groups are directly bonded to an aromatic ring.

[0039] Preferred are aldehyde group-containing polymers with a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

[0040] 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. Compound A may additionally contain a certain amount of oxyethylene units, in particular a maximum of 25% by weight of oxyethylene based on the total weight of the poly(oxyalkylene) units.

[0041] 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.

[0042] 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.

[0043] A particularly preferred polymer containing aldehyde groups also contains urethane groups. This enables compositions with particularly high extensibility and tear resistance.

[0044] 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. A particularly preferred compound A is a urethane-containing polymer with an average molecular weight M that is liquid at room temperature. 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.

[0045] Such a polymer is preferably obtained from the reaction of at least one hydroxyaldehyde with at least one polymer containing isocyanate groups.

[0046] 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).

[0047] Preferred are hydroxyaldehydes whose aldehyde group is directly bonded to an aromatic ring, such as in particular 5-hydroxymethylfurfural, alkoxylated o-, m- or p-hydroxybenzaldehyde or alkoxylated vanillin, where "alkoxylated" preferably stands for singly or multiply ethoxylated or propoxylated.

[0048] Particularly preferred is ethoxylated salicylaldehyde, in particular 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillin, in particular 4-(2-hydroxyethoxy)-3-methoxybenzaldehyde, or 5-hydroxymethylfurfural.

[0049] Ethoxylated salicylaldehyde is particularly preferred. This results in particularly color-stable compositions.

[0050] 5-Hydroxymethylfurfural is also particularly preferred. This results in particularly easy-to-process compositions with particularly rapid curing. 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.

[0051] 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.

[0052] Particularly suitable as polyols are:

[0053] - 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.

[0054] - 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. Amorphous, di- or trimer fatty acid-based polyester polyols, such as those commercially available from Cargill, are preferred.

[0055] - Polycarbonate polyols, obtainable by reacting diols with dialkyl carbonates, diaryl carbonates or phosgene.

[0056] - Block copolymers containing at least two hydroxyl groups, in particular polyetherpolyesterpolyols.

[0057] - Polyacrylate and polymethacrylate polyols.

[0058] - 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).

[0059] - or polyhydrocarbon polyols.

[0060] Preferred are polyether polyols, di- or trimer fatty acid-based polyester polyols, castor oil, derivatives of castor oil or hydroxylated vegetable oils.

[0061] 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.

[0062] The main component further contains at least one compound B with activated methylene groups of formula (I).

[0063] The compound B preferably contains one to six activated methylene groups of the formula (I), particularly preferably two to four, in particular two to three, activated methylene groups of the formula (I).

[0064] Preferably, compound B is 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, 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 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.

[0065] 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.

[0066] Preferably, the compound B has, with respect to the activated methylene groups of the formula (I), an equivalent weight, or in the case of an oligomeric or polymeric compound B, an average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g / eq.

[0067] Preferably, the compound B has, with respect to the activated methylene groups of the formula (I), a functionality, or in the case of an oligomeric or polymeric compound B, an 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.

[0068] In particular, the compound B has, with respect to the activated methylene groups of formula (I), 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.

[0069] In the main component, the ratio of the number of activated methylene groups of formula (I) to the number of aldehyde groups is preferably in the range of 0.7 to 3.0, particularly preferably 0.9 to 2.5, especially 0.9 to 2.0. This enables reliable curing and a cured product with high strength and high ductility.

[0070] Compound B contains activated methylene groups of formula (I), OO

[0071] II II where Y is a radical of the formula "" _ CN , ---C— , ---C— OR 1 or

[0072] O

[0073] II

[0074] ---C— O—, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1 stands for an alkyl radical with 1 to 6 C atoms.

[0075] R is preferably an alkyl radical having 1 to 6 carbon atoms or phenyl, particularly preferably methyl, ethyl, propyl, isopropyl, butyl, or phenyl. Most preferably, R is methyl.

[0076] Preferably R 1 for methyl, ethyl or tert-butyl, particularly preferably for ethyl or tert-butyl, in particular for ethyl.

[0077] Preferably, compound B is obtained from the transesterification of at least one hydroxyl-containing compound with at least one compound of formula (II),

[0078] O

[0079] A / Y 1 (")

[0080] R1 O' / X /

[0081] OO

[0082] II II1where Y 1 for a remainder of the formula ■ __ CN , ---C— R or - _ -C— OR stands and R and R 1 have the meanings already described.

[0083] 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.

[0084] It is also possible to produce a compound B containing cyanoacetate groups by esterifying cyanoacetic acid with at least one hydroxyl-containing compound. It is also possible to produce a compound B containing acetoacetate groups by reacting the hydroxyl-containing compound underlying compound B with diketene or the adduct of diketene with acetone (= 2,2,6-trimethyl-4H-1,3-dioxin-4-one), whereby acetone is released in the case of the acetone-diketene adduct.

[0085] It is also possible to produce a compound B with malonate groups by esterification of malonic acid with at least one hydroxyl group-containing compound.

[0086] Particularly suitable compounds of formula (II) are methyl cyanoacetate, ethyl cyanoacetate, tert-butyl cyanoacetate, methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, ethyl 3-oxohexanoate, ethyl benzoyl acetate, dimethyl malonate, diethyl malonate, diisopropyl malonate or di-(tert-butyl) malonate.

[0087] Preferred are ethyl cyanoacetate or tert-butyl cyanoacetate, ethyl acetoacetate or tert-butyl acetoacetate, and malonic acid diethyl ester.

[0088] 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 an average molecular weight Mn of 300 to 6,000 g / mol, propoxylated and / or ethoxylated 1,1,1-trimethylolpropane with an average 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.

[0089] In a particularly preferred embodiment of the invention, Y stands for “ -_ CN and the activated methylene groups of formula (I) are thus cyanoacetate groups. Such compounds B enable particularly reliable and rapid curing upon contact with atmospheric moisture and, after curing, particularly high tensile strength and high tear resistance.

[0090] Preferred as compound B with cyanoacetate groups is 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate or a polymer with 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. This enables cured compositions with particularly high extensibility.

[0091] In a preferred embodiment of the invention, the compound B with cyanoacetate groups is a polymer with 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.

[0092] 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).

[0093] Particularly preferred is the tricyanoacetate of propoxylated 1,1,1-trimethylolpropane) with a total average molecular weight M n from 500 to 750 g / mol.

[0094] In a particularly preferred embodiment of the invention, Y is

[0095] In particular, R represents methyl, and the activated methylene groups of formula (I) are thus acetoacetate groups. Such compounds B are particularly readily available and enable particularly color-stable compositions with particularly good processability.

[0096] Preferably, a compound B with acetoacetate groups is selected from the list consisting of 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, 1,3-propanediol diacetoacetate, 1,4-butanediol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, 1,5-pentanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-trimethylolethane diacetoacetate, 1,1,1-trimethylolethane tri- acetoacetate, 1,1,1-trimethylolpropane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, the triacetoacetate of propoxylated and / or ethoxylated 1,1,1-trimethylolpropane, the triacetoacetate of propoxylated and / or ethoxylated glycerol, poly(oxy-1,2-propylene)diol bis(acetoacetate), poly(oxy-1,2-propylene)diol bis(acetoacetate) containing ethylene oxide units,Castor oil bis-(acetoacetate), castor oil tris(acetoacetate), dimer fatty acid-based polyesterdiol bis(acetoacetate) and trimer fatty acid-based polyestertriol tris(acetoacetate).

[0097] Of these, 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-trimethylolpropane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, a triacetoacetate of propoxylated 1,1,1-trimethylolpropane with medium molecular weight M n from 500 to 1,000 g / mol or a poly(oxy-1,2-propylene)diol bis(acetoacetate) with medium molecular weight M n from 550 to 5,000 g / mol.

[0098] In a further embodiment of the invention, Y is a radical of the formula

[0099] OO

[0100] II II

[0101] ---C— OR 1 or ---C— O— and the activated methylene groups of formula (I) are thus malonate groups.

[0102] Preferably, a compound B with malonate groups is selected from the list consisting of malonic acid diethyl ester, malonic acid diisopropyl ester, 1,2-ethanediol bis(ethylmalonate), 1,2-propanediol bis(ethylmalonate), 1,3-propanediol bis(ethylmalonate), 1,4-butanediol bis(ethylmalonate), 2-methyl-1,3-propanediol bis(ethylmalonate), neopentyl glycol bis(ethylmalonate), 1,6-hexanediol bis(ethylmalonate), 3-methyl-1,5-pentanediol bis(ethylmalonate), 2-ethyl-1,3-hexanediol bis(ethylmalonate), 1,4-cyclohexanedimethanol bis(ethylmalonate), diethylene glycol bis(ethylmalonate), di- propylene glycol bis(ethylmalonate), glycerol tris(ethylmalonate), 1,1,1-trimethylolpropane tris(ethylmalonate), castor oil tris(ethylmalonate), poly(oxy-1,2-propylene)diol bis(ethylmalonate) with medium molecular weight M nfrom 500 to 2,000 g / mol, propoxylated 1,1,1-trimethylolpropane with three ethyl malonate end groups and an average molecular weight M n from 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 and 1,4-cyclohexanedimethanol with malonic acid and diethyl malonate and optionally adipic acid or diethyl adipic acid.

[0103] Suitable compounds with malonate groups are also commercially available, in particular as Acure® 510-200 (from Allnex). In a preferred embodiment of the invention, the average functionality of the entire main component with respect to the reactive groups, aldehyde and activated methylene groups of formula (I), is at least 2.2. This means that a composition with an average aldehyde functionality of, for example, 1.8 preferably has an average functionality with respect to the activated methylene groups of formula (I) 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.

[0104] The main component may also contain other ingredients, in particular

[0105] - 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 aluminum, copper, iron, silver or steel, PVC powders or hollow spheres;

[0106] - 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;

[0107] - Nanofillers or nanofibers such as graphene or carbon nanotubes;

[0108] - dyes;

[0109] - pigments, in particular titanium dioxide, chromium oxide, iron oxides or organic pigments;

[0110] - 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 thols, 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;

[0111] - solvents;

[0112] - Modifiers such as hydrocarbon resins, natural or synthetic waxes or bitumen;

[0113] - 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;

[0114] - drying agents, in particular molecular sieves, calcium oxide, mono-oxazolidines such as lncozol® 2 (from Incorez), orthoesters or alkoxysilanes;

[0115] - adhesion promoters, in particular titanates or organoalkoxysilanes such as epoxysilanes, mercaptosilanes, (meth)acrylsilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;

[0116] - 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);

[0117] - 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;

[0118] - 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.

[0119] The main component preferably contains at least one further component selected from plasticizers, fillers, and adhesion promoters. The main component preferably contains several such further components.

[0120] In a preferred embodiment of the invention, the main component contains 10 to 95% by weight, preferably 20 to 90% by weight, in particular 30 to 80% by weight, of fillers, based on the total main component. Fillers are preferably 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.

[0121] In a further preferred embodiment of the invention, the main component contains 5 to 80% by weight, in particular 10 to 60% by weight, of plasticizer, based on the total main component. 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, polypropylene oxide monols, polypropylene oxide diols, polypropylene oxide triols, polypropylene oxide monol acetates, polypropylene oxide diol diacetates, polypropylene oxide triol triacetates, and DPK.

[0122] In a particularly preferred embodiment of the invention, the main component 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. The main component preferably contains, based on the total main component, less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight, of volatile organic compounds (VOCs) with a boiling point at atmospheric pressure of less than 250°C, in particular organic solvents. Such a composition causes particularly low emissions.

[0123] The main component preferably contains less than 0.5% by weight, more preferably less than 0.1% by weight, and especially less than 0.05% by weight, of water based on the total main component. Such a component is particularly stable during storage.

[0124] The main component preferably comprises, based on the total main component, 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.

[0125] Preferably, the main component comprises, based on the entire main component

[0126] - 5 to 99% by weight, preferably 5 to 90% by weight, in particular 10 to 70% by weight, of the sum of compounds A and B,

[0127] - 0 to 50% by weight, preferably 10 to 40% by weight, plasticizer,

[0128] - 0 to 90% by weight, preferably 20 to 80% by weight, fillers,

[0129] - and if necessary other substances,

[0130] The main component is preferably produced by mixing the ingredients together using a suitable method to create a macroscopically homogeneous mass. The fillers are preferably used in a largely dry state. It may be advantageous to dry the fillers beforehand using a suitable method, for example, in a convection 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 main component 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.

[0131] The curable composition further comprises at least one accelerator component containing at least one accelerator for the reaction of aldehyde groups with activated methylene groups of the formula (I).

[0132] The accelerator component is kept separate from the main component and is only mixed with the main component immediately before or during the application of the curable composition.

[0133] Preferably, the accelerator for the reaction of aldehyde groups with activated methylene groups of the formula (I) 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.

[0134] More preferably, the accelerator is a nitrogen-containing catalyst selected from secondary amines, tertiary amines, amidines and guanidines, or a basic salt selected from 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 and lithium phosphate, or water.

[0135] 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.

[0136] 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.

[0137] Suitable amidines or guanidines are in particular 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1-(2-hydroxy-3-(3-trimethoxysilylpropoxy)prop-1-yl)-2-methyl-1,4,5,6-tetrahydropyrimidine, 2-imidazoline, 2-methylimidazoline, 2-ethylimidazoline, 2-phenylimidazoline, 1,1,3,3-tetramethylguanidine, 1-hexyl-2,3-diisopropylguanidine or 1,1'-(α,®-polyoxypropylene)bis(2,3-diisopropylguanidine) with medium molecular weight M n from 250 to 500 g / mol.

[0138] In the case of cyanoacetate groups as activated methylene groups of formula (I), preferred accelerators are tertiary amines or basic salts such as in particular potassium acetate, potassium carbonate, potassium phosphate, sodium acetate, sodium carbonate or sodium phosphate, or water

[0139] In the case of activated methylene groups of formula (I) with Y = ---C— R , especially acetoacetate groups, preferred accelerators are secondary amines, amidines or guanidines.

[0140] Morpholine is particularly preferred. This provides particularly high elongation and / or tear resistance.

[0141] In addition, the accelerator component preferably contains a plasticizer and optionally a filler, as well as optionally some water.

[0142] The main and accelerator components are mixed using a suitable process, particularly a static mixer or a dynamic mixer. Mixing can be done continuously or in batches.

[0143] If the main and accelerator 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 the 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.

[0144] The "open time" refers to the period of time between mixing the components and the end of a composition suitable for processing. The open time can also be referred to as the "processing time." The time until a tack-free surface forms is a measure of the open time.

[0145] The mixing ratio between the main component and the accelerator component in parts by weight is preferably in the range of 100 / 0.1 to 100 / 10, in particular 100 / 0.5 to 100 / 5. Such an asymmetric mixing ratio allows the accelerator component to be mixed in via a dosing attachment screwed onto the packaged main component, for example, a SikaBooster®. During application, the accelerator component contained in the dosing attachment is conveyed from the dosing attachment by a rotating mechanism and mixed with the main component by a short static mixer, ultimately applying the mixed curable composition.

[0146] Another object of the invention is a method for curing the curable composition, wherein the main component and the accelerator component are mixed together and the mixed composition is applied to at least one substrate and cured.

[0147] 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.

[0148] In the mixed composition, the accelerator enables the reaction of the activated methylene groups of formula (I) with the aldehyde groups, whereby the composition cures quickly, reliably and smoothly into a solid, polymeric material.

[0149] Suitable substrates to which the mixed curable composition is applied are in particular

[0150] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble;

[0151] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECO (epoxy resin-modified cement mortar);

[0152] - 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;

[0153] - Asphalt or bitumen; - 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;

[0154] - 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;

[0155] - 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);

[0156] - 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,

[0157] - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0158] - Coatings, paints or varnishes.

[0159] 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.

[0160] Two similar or two different substrates can be bonded and / or sealed.

[0161] A further object of the invention is the cured composition obtained from the process for curing the curable composition, wherein the main component and the accelerator component are mixed together and the mixed composition is applied to at least one substrate.

[0162] Preferably, the cured composition is elastic and has high strength with high extensibility and high tear resistance.

[0163] 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).

[0164] 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).

[0165] 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.

[0166] The described composition is suitable for a wide range of applications. It can be used as an adhesive, sealant, coating, casting resin, or filler, particularly as an elastic adhesive, elastic sealant, or elastic coating.

[0167] Another object of the invention is the use of the curable composition as an elastic adhesive, elastic sealant or elastic coating.

[0168] 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 or structural 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. Examples

[0169] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0170] The “standard climate” (“NK”) is defined as a temperature of 23±1 °C and a relative humidity of 50±5%.

[0171] Unless otherwise stated, the chemicals used were from Merck.

[0172] Description of the measurement methods:

[0173] 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 ) measured.

[0174] 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.

[0175] 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.

[0176] Production of polymers with aldehyde groups:

[0177] Polymer A-1 :

[0178] 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 nwas 6,100 g / mol, determined 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. Polymer A-2:

[0179] 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.

[0180] 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.

[0181] 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.%. Preparation of compounds with activated methylene groups:

[0182] Compound B-1 :

[0183] 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.

[0184] Connection B-2:

[0185] 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.

[0186] Production of main components: substances used:

[0187] Plasticizer-1 : n-butanol-initiated acetylated PPG monol, produced from the reaction of Synalox® 100-20B (average molecular weight M napprox. 750 g / mol, from Dow) and acetic anhydride with distillative removal of acetic acid

[0188] Calcined kaolin: Satintone® W (from HM Royal)

[0189] Soot: Monarch® 570 (from Cabot)

[0190] Molecular sieve: Sylosiv® A 3 (from Grace)

[0191] Epoxysilane: 3-Glycidoxypropyltrimethoxysilane Main components K1 to K4:

[0192] For each composition, the ingredients listed in Table 1 were mixed together in the specified amounts (in parts by weight) using a centrifugal mixer (Thinky ARE-250), processed into a macroscopically homogeneous paste, and stored in a moisture-proof container. The molecular sieve, carbon black, and kaolin were previously dried in a convection oven at 130 °C.

[0193] The storage stability of the main components 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 main component cured after storage for 7 days at 40 °C in a sealed container.

[0194] Table 1: Composition and storage stability of the main components K1 to K4.

[0195] 1 Ratio of the number of activated methylene groups of formula (I) to the number of aldehyde groups Preparation of curable compositions with accelerator component: Compositions Z1 to Z11:

[0196] For each composition, the main component specified in Tables 2 to 3 in the specified amount (in parts by weight) was mixed with the accelerator component specified in Tables 2 to 3 in the specified amount using a centrifugal mixer and the mixed composition was immediately tested as follows:

[0197] 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.

[0198] To determine the mechanical properties, the mixed composition was applied to a 2 mm thick film on a silicone-coated release paper. This film was cured for 7 days under standard 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 tested according to DIN EN 53504 at a tensile speed of 200 mm / min for tensile strength, elongation at break, and 5% modulus of elasticity (at 0.5-5% elongation). Furthermore, several 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.

[0199] 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."

[0200] The results are shown in Tables 2 to 3.

[0201] Table 2: Compositions Z1 to Z8.

[0202] 1 1,8-Diazabicyclo[5.4.0]undec-7-ene (Lupragen® N700, from BASF)

[0203] belle 3: Compositions Z9 to Z11.

[0204] 1Bis(2-dimethylaminoethyl)ether

[0205] 2 25% by weight in water

Claims

Patent claims: 1 . Curable composition comprising (i) containing a main component - at least one compound A with aldehyde groups, and - at least one compound B having activated methylene groups of formula (I), OO where Y is a radical of the formula ■ __ CN , -- or O II C— O— -, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1 represents an alkyl radical having 1 to 6 C atoms, and (ii) an accelerator component containing at least one accelerator for the reaction of aldehyde groups with activated methylene groups of the formula (I), wherein at least one of the two compounds A and B is a polymer having an average molecular weight M nfrom 500 to 20,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene as standard, whereby the main component is packaged separately from the accelerator component in a single container and can thus be stored in a stable manner.

2. Curable composition according to claim 1, characterized in that the aldehyde groups of compound A are directly bonded to an aromatic ring.

3. Curable composition according to one of claims 1 to 2, characterized in that the compound A is a polymer having 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 is from 1.6 to 4.0, preferably 1.8 to 3.5, particularly preferably 2.0 to 3.0, especially 2.2 to 3.

0.

4. Curable composition according to one of claims 1 to 3, characterized in that the compound B, with respect to the activated methylene groups of the formula (I), has 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.

5. Curable composition according to one of claims 1 to 4, characterized in that the ratio of the number of activated methylene groups of the formula (I) to the number of aldehyde groups in the entire composition is in the range from 0.7 to 3.0, particularly preferably 0.9 to 2.5, in particular 0.9 to 2.

0.

6. Curable composition according to one of claims 1 to 5, characterized in that Y is -_ "CN and the activated methylene groups of the formula (I) are thus cyanoacetate groups, wherein the compound B with cyanoacetate groups is in particular 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate or a polymer with 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, is in particular 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 Glycerin, 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).

7. Curable composition according to one of claims 1 to 5, characterized O II indicates that Y for ■ _ _C—R, where R is in particular methyl and the activated methylene groups of the formula (I) are thus acetoacetate groups, where a compound B with acetoacetate groups is in particular selected from the list consisting of 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, 1,3-propanediol diacetoacetate, 1,4-butanediol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, 1,5-pentanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-T trimethylolethane diacetoacetate, 1,1,1-trimethylolethane triacetoacetate, 1,1,1-trimethylolpropane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, the triacetoacetate of propoxylated and / or ethoxylated 1,1,1-trimethylolpropane, the triacetoacetate of propoxylated and / or ethoxylated glycerol,Poly(oxy-1,2-propylene)diol bis(acetoacetate), ethylene oxide-containing poly(oxy-1,2-propylene)diol bis(acetoacetate), castor oil bis(acetoacetate), castor oil tris(acetoacetate), dimer fatty acid-based polyesterdiol bis(acetoacetate) and trimer fatty acid-based polyestertriol tris(acetoacetate).

8. Curable composition according to one of claims 1 to 7, characterized in that the average functionality of the entire composition with respect to the reactive groups aldehyde and activated methylene groups of the formula (I) is at least 2.

2.

9. Curable composition according to one of claims 1 to 8, characterized in that the main component comprises at least one further Contains a component selected from plasticizers, fillers and adhesion promoters.

10. Curable composition according to one of claims 1 to 9, characterized in that the accelerator for the reaction of aldehyde groups with activated methylene groups of the formula (I) 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.

11. Curable composition according to claim 10, characterized in that the accelerator is a nitrogen-containing catalyst selected from secondary amines, tertiary amines, amidines and guanidines, or a basic salt selected from 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 and lithium phosphate, or water.

12. Curable composition according to one of claims 1 to 11, characterized in that the mixing ratio between the main component and the accelerator component in parts by weight is in the range from 100 / 0.1 to 100 / 10, in particular 100 / 0.5 to 100 / 5.

13. A method for curing the curable composition according to any one of claims 1 to 12, characterized in that the main component and the accelerator component are mixed together and the mixed composition is applied to at least one substrate and cured.

14. Cured composition obtained from the process according to claim 13, wherein the cured composition is in particular elastic tic and in particular has an elongation at break of at least 50%, preferably at least 100%, 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 after storage for 7 days in standard climate.

15. Use of the curable composition according to any one of claims 1 to 12 as an elastic adhesive, elastic sealant or elastic coating.

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