RU2485143C2 - Asymmetric dialdimine-containing polyurethane composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a curable composition consisting of two components K1 and K2, which contain (a) at least one aromatic polyisocyanate P, which contains isocyanate groups, (b) at least one dialdimine A of formula

, where X is a diamine residue DA with two primary amino groups after separating said two amino groups; and Y¹ and Y² are independently a univalent hydrocarbon residue with 1-12 C atoms; and Y³ is a univalent hydrocarbon residue which optionally has at least one heteroatom, particularly oxygen in form of an ether, a carbonyl or ester group, and (c) compounds which are reactive with respect to isocyanate groups, particularly water and/or polyols and/or polyamines, under the condition that at least one of the two primary amino groups of diamine DA is an aliphatic amino group, and that two primary amino groups of diamine DA differ from each other either by the number of hydrogen atoms at the carbon atoms (C_α), which are in the α-position to the corresponding amino group, at least one, or the number hydrogen atoms at the carbon atoms (C_β), which are in the β-to the corresponding amino group, at least two. Described also is a curable composition obtained after reacting said composition with water, use of the disclosed compositions as an adhesive, a sealant, filling compound or coating, methods of gluing, sealing and coating using said curable composition, and an article which is glued, sealed or coated using said methods.

EFFECT: obtaining moisture-curable polyurethane compositions which are stable during storage, are characterised by long curing time before gluing and high rate of hardening and harden without bubbles.

23 cl, 10 tbl, 24 ex

Description

Technical field

The invention relates to the field of moisture-curing polyurethane compositions, as well as their use, in particular as elastic adhesives, sealants and coatings.

State of the art

Moisture-curing compositions based on polyurethane polymers containing isocyanate groups have long been used as elastic adhesives, sealants and coatings. The polyurethane polymers used in this are usually synthesized from simple polyether polyols and polyisocyanates. These compositions, when cured with a liquid, are prone to bubble formation due to the released carbon dioxide in the form of a gas that does not dissolve or emit sufficiently quickly.

To reduce blistering, blocked amines, so-called “latent (latent) hardeners”, such as, for example, polyoxazolidines, polyketimines or polyaldimines, can be added to the polyurethane compositions. However, due to this, the storage stability of the composition may be reduced.

From the patents US 4469831 and US 4853454 known polyurethane compositions containing polyaldimines and therefore have good storage stability.

From the international application WO 2004/013200 polyurethane compositions are known containing special polyaldimines, which are also characterized by good storage stability and which cure without a smell.

Polyurethane compositions containing latent hardeners, especially based on aromatic polyisocyanates, however, in most cases are characterized by such a drawback that they cure very quickly, so that the “exposure time before gluing” is too short and therefore too short processing period. Moreover, in most cases, during curing, volatile and strongly smelling cleavage products are released, in particular aldehydes or ketones, which, depending on the application, interferes with or is completely undesirable.

SUMMARY OF THE INVENTION

The objective of this invention is to create a moisture-curing polyurethane composition that is stable during storage, characterized by a long exposure time before gluing and a high curing rate and cure without the formation of bubbles.

It was unexpectedly found that the compositions according to claim 1 of the claims solve this problem. These compositions contain special asymmetric dialdimines, as a result of which they are both stable during storage, characterized by a long exposure time before gluing and a high curing rate and cure without the formation of bubbles. In one preferred form of execution, these compositions are also characterized by the absence of odor, namely, both before, during and after curing. Compositions can be one-component or two-component and can be used as adhesives, sealants, pouring masses or coatings. Especially preferred was their use as sealants.

The invention further relates to a gluing method according to claim 20, a sealing method according to claim 21, and a coating method according to claim 22.

In conclusion, the objects of this invention are curable compositions according to clause 16 of the claims, as well as products glued by the described method, sealed or coated according to clause 25 of the claims.

Preferred embodiments of the invention are subject to the dependent claims.

The embodiment of the invention

The object of this invention is a composition comprising

a) at least one aromatic polyisocyanate P containing isocyanate groups, and

b) at least one dialdimine A of the formula (I).

Moreover, X means the residue of diamine DA with two primary amino groups after the separation of these two amino groups. Further, Y ¹ and Y ² or, independently from each other, optionally mean a monovalent hydrocarbon residue with 1-12 C atoms, or Y ¹ and Y ² together mean a divalent hydrocarbon residue with 4-20 C atoms, which is part of an optionally substituted carbocyclic rings with 5-8, preferably 6, C. atoms

Further, Y ³ means a monovalent hydrocarbon residue, which optionally contains at least one heteroatom, in particular oxygen in the form of an ether, carbonyl or ester group.

It is important for the invention that at least one of the two primary amino groups of diamine DA is an aliphatic amino group, and that the two primary amino groups of diamine DA differ from each other or

the number of hydrogen atoms of carbon atoms (C _α ) standing in the α-position to the corresponding amino group by at least one,

or

the number of hydrogen atoms of carbon atoms (C _β ) standing in the β-position to the corresponding amino group by at least two.

The term "polymer" in this application, on the one hand, refers to a set of chemically uniform macromolecules, but differing in degree of polymerization, molecular weight and chain length obtained by polyreaction (polymerization, polyaddition, polycondensation). On the other hand, the term “polymer” also includes derivatives of such a plurality of macromolecules from polyreactions, that is, compounds that are obtained by interactions, such as, for example, addition or substitution, of functional groups of the given macromolecules and which can be chemically uniform or chemically diverse. Further, the concept also includes the so-called prepolymers, i.e. reactive oligomeric preformed adducts, the functional groups of which are involved in the structure of macromolecules.

The term "polyurethane polymer" includes all polymers that are produced by the so-called diisocyanate polyaddition process. It also includes those polymers which are almost or completely free from urethane groups. Examples of polyurethane polymers are copolymers of polyethers and polyurethanes, polyesters and polyurethanes, polyethers and polyureas, polyureas, copolymers of polyesters and polyureas, polyisocyanurates and polycarbodiimides.

The prefix "poly" in the names of substances such as polyaldimine, polyisocyanate, polyol or polyamine in this application means substances that formally contain two or more functional groups in its designation per molecule.

The term "aromatic isocyanate group" in this application means an isocyanate group that is associated with an aromatic atom C.

The term "primary amino group" in this application means an NH ₂ group that is linked to one organic residue, while the term "secondary amino group" means an NH group that is linked to two organic residues, which can also be part of a ring together.

By "aliphatic amino group" is meant an amino group that is bound to an aliphatic, cycloaliphatic or arylaliphatic residue. In this, it differs from the “aromatic amino group”, which is directly linked to an aromatic or heteroaromatic residue, such as, for example, in aniline or 2-aminopyridine.

By “exposure time before gluing” is meant in this application the time during which the composition can be processed after the isocyanate groups of the polyisocyanate come in contact with water.

The composition includes at least one aromatic polyisocyanate P containing isocyanate groups.

In a first embodiment, the aromatic polyisocyanate P containing isocyanate groups is an aromatic polyurethane PUP polymer containing isocyanate groups.

Suitable polyurethane polymer PUP, in particular, is obtained by reacting at least one polyol with at least one aromatic polyisocyanate. This interaction can occur due to the fact that the polyol and polyisocyanate are brought to a reaction in a standard manner, for example, at a temperature of 50 ° C-100 ° C, optionally using suitable catalysts, the polyisocyanate being dosed so that its isocyanate groups with respect to hydroxyl groups polyol are in stoichiometric excess. Preferably, the polyisocyanate is dosed so that the NCO / OH ratio is 1.3-5, in particular 1.5-3. Moreover, the ratio NCO / OH is understood to mean the number of used isocyanate groups to the number of used hydroxyl groups. Preferably, in the PUP polyurethane polymer, after the interaction of all the hydroxyl groups of the polyol, the content of free isocyanate groups remains in an amount of 0.5-15% by weight, preferably 0.5-10% by weight.

Optional polyurethane polymer PUP can be obtained by the joint use of plasticizers, and the plasticizers used do not contain groups reactive with isocyanates.

As polyols for producing the PUP polyurethane polymer, for example, the following commercially available polyols or mixtures thereof can be used:

- Polyoxyalkylene polyols, also called simple polyether polyols or simple oligoesters, which are products of polymerization of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized using an initiator molecule with two or more active hydrogen atoms, such as water, ammonia, or compounds with several OH or NH groups, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol diprop isomers ylenglycol and tripropylene glycol, isomers of butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecandiol, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-triethane , 1-trimethylolpropane, glycerin, aniline, as well as mixtures of these compounds. They can be used as polyoxyalkylene polyols characterized by a low degree of unsaturation (measured according to ASTM D-2849-69 and given in milliequivalents of unsaturation per gram of polyol (meq / g)), obtained, for example, using the so-called catalysts of double metal cyanide complexes (DMC -catalysts) and polyoxyalkylene polyols with a high degree of unsaturation, obtained, for example, using anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.

Particularly acceptable are polyoxyalkylenediols or polyoxyalkylenetriols, in particular polyoxypropylenediols or polyoxypropylene triols.

Particularly acceptable are polyoxyalkylenediols and β-triols with a degree of unsaturation below 0.02 meq / g and with a molecular weight in the range from 1000 to 30000 g / mol, as well as polyoxypropylene diols and β-triols with a molecular weight of from 400 to 8000 g / mol.

Especially acceptable are the so-called "EO-terminated" (ending with ethylene oxide) polyoxypropylene polyols. Polyoxypropylene polyols are special polyoxypropylene polyoxyethylene polyols, which are obtained, for example, in such a way that pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, after the completion of the polypropoxylation reaction are further alkoxylated with ethylene oxide and are therefore characterized by primary hydroxyl groups:

- Simple polyether polyols grafted with styrene acrylonitrile or acrylonitrile methyl methacrylate.

- Complex polyether polyols, also called complex oligoesters, obtained, for example, from di-trihydric alcohols such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or a mixture of the named alcohols, with organic dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, cork acid, sebacic acid, dodecandicarboxylic acid Ota, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of these acids, and also polyester polyols from lactones such as, e.g., ε-caprolactone.

- Polycarbonate polyols, which are available due to the interaction of the above-mentioned alcohols used for the synthesis of polyester polyols with dialkyl carbonates, diaryl carbonates or phosgene.

- Polyacrylate and polymethacrylate polyols.

- Polyhydroxyfunctional fats and oils, for example, natural fats and oils, in particular castor oil; or (so-called oleochemical) polyols obtained by chemical modification of natural fats and oils, for example, epoxy polyesters or epoxy polyesters obtained by epoxidation of unsaturated oils and the subsequent opening of the cycle with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils ; or polyols obtained from natural fats and oils by a decomposition process, such as alcoholysis or ozonolysis and subsequent chemical binding, for example, by transesterification or dimerization of the decomposition products thus obtained or their derivatives. Suitable decomposition products of natural fats and oils, in particular, are fatty acids and fatty alcohols, as well as fatty acid esters, in particular methyl esters (FAME), which can be modified, for example, by hydroformylation and hydrogenation to hydroxy fatty acid esters .

- Polycarbonate polyols, also called oligohydrocarbonols, such as polyhydroxy functional copolymers of ethylene - propylene, ethylene - butylene or ethylene - propylene - diene, which are produced, for example, by Kraton Polymers, or polyhydroxy functional copolymers from dienes such as 1,3-butadiene or dienes and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols, such as those obtained by copolymerization of 1,3-butadiene and allyl alcohol, and also e can be hydrogenated.

- polyhydroxy-functional acrylonitrile / butadiene may be prepared, for example, from epoxides or aminoalcohols and karboksiterminirovannyh copolymers, acrylonitrile / butadiene (commercially available under the name of Hycar ^® CTBN from Hanse Chemie).

These named polyols are preferably characterized by an average molecular weight of 250-30000 g / mol, in particular 400-20000 g / mol, and preferably an average OH functionality in the range of 1.6 to 3.

In addition to these named polyols for producing a polyurethane polymer PUP can be used together small amounts of low molecular weight di- or polyhydric alcohols, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol isomers, butanediol isomers, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecandiol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, fatty alcohol dimers, 1,1,1-trimethylol ethane, 1,1,1-trimethylolpropane, glycerol pentaerythritol, sugar alcohols such as xyl t, sorbitol or mannitol, sugars such as sucrose and other polyhydric alcohols, low molecular weight alkoxylation products of the aforementioned di- and polyhydric alcohols, and mixtures of the foregoing alcohols. Small amounts of polyols with an average OH functionality of more than 3, for example, sugar alcohols, can also be used together.

As polyisocyanates to obtain an aromatic polyurethane polymer PUP containing isocyanate groups use aromatic polyisocyanates, in particular diisocyanates. Suitable aromatic polyisocyanates are, for example, 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers (TDI, TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI, MDI), mixtures of MDI and homologues of MDI (polymeric MDI or PMDI), 1,3- and 1,4-phenylenediisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene- 1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI, TODI), dianisidinediisocyanate (DADI, DADI), oligomers and polymers of the above isocyanates, as well as any mixture of the above isocyanates. Preferred are MDI and TDI.

The named aromatic polyisocyanates are commercially available.

In a second embodiment, the aromatic polyisocyanate P containing isocyanate groups is an aromatic polyisocyanate PI. The aromatic PI polyisocyanate , in particular, is an aromatic diisocyanate, or a low molecular weight oligomer of an aromatic diisocyanate, or a derivative of an aromatic diisocyanate, or any mixture of these isocyanates. Suitable aromatic polyisocyanate PI are, for example, 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers (TDI, TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any mixtures of these isomers (MDI, MDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1,3- and 1,4-phenylenediisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene -1,5-diisocyanate (NDI, NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI, TODI), dianisidinediisocyanate (DADI, DADI), oligomers and polymers of the above isocyanates, as well as any mixture of the above isocyanates .

As PI polyisocyanate liquid MDI forms at room temperature (the so-called “modified MDI”) are preferred, which are mixtures of MDI and MDI derivatives, such as, for example, MDI carbodiimides, MDI uretonimines or MDI urethanes known, for example, under the trademarks of Desmodur^® CD, Desmodur^® PF, Desmodur^® PC (all from Bayer), Lupranat^® MM 103 (from BASF), Isonate^® M 143 (from Dow), Suprasec^® 2020, Suprasec^® 2388 (both from Huntsman), PMDI technical forms, for example, obtained under the trademarks of Desmodur^® VL, VL 50, VL R 10, VL R 20 and Desmodur^® VKS 20 F (all from Bayer), Lupranat® M 10 R, Lupranat® M 20 R (both from BASF), Isonate^® M 309, Voranate^® M 229, Voranate^® M 580 (all from Dow), Suprasec^® 5025, Suprasec^® 2050, Suprasec^® 2487 (all from Huntsman); as well as technical forms of TDI oligomers, e.g. Desmodur^® IL (Bayer). The above polyisocyanates are usually mixtures of substances with varying degrees of oligomerization and / or chemical structure. Preferably, they are characterized by an average NCO functionality of 2.1 to 4.0, and in particular contain isocyanurate, iminooxadiazinedione, urethdione, urethane, biuret, allofanate, carbodiimide, uretonimine or oxadiazintrione groups.

In a third embodiment, polyisocyanate P is a mixture consisting of at least one polyurethane polymer PUP and at least one polyisocyanate PI, as described above.

In a typical manner, polyisocyanate P is present in an amount of 5-95% by weight, preferably in an amount of 10-90% by weight. based on the entire composition. In filled compositions, i.e. compositions that contain a filler, polyisocyanate P preferably present in an amount of 5-60% by weight, in particular 10-50% by weight. based on the entire composition.

The composition contains, in addition, at least one aromatic polyisocyanate P, containing isocyanate groups, at least one A dialdimin formula (I).

Preferably, Y ¹ and Y ² respectively represent a methyl group.

Preferably, Y ³ is a residue of formula (II) or (III),

where R ³ means a hydrogen atom or an alkyl or arylalkyl group, in particular with 1-12 C atoms, preferably a hydrogen atom;

R ⁴ means a hydrocarbon residue with 1-30, in particular 11-30, C atoms, which optionally contains a heteroatom; and

R ⁵ or

means a hydrogen atom,

or means a linear or branched alkyl residue with 1-30, in particular 11-30, C atoms, optionally with a cyclic part and optionally with at least one heteroatom,

or means a single or multiple unsaturated, linear or branched hydrocarbon residue with 5-30 C atoms,

or means an optionally substituted, aromatic or heteroaromatic 5- or 6-membered ring.

Particularly preferably, Y ³ is a residue of formula (III).

The dashed lines in the formulas in this application are, respectively, the bonds between the substituent and the corresponding moiety of the molecule.

Dialdimine A of formula (I) is obtained by a condensation reaction with the removal of water between at least one diamine DA of formula (IV) and at least one aldehyde ALD of formula (V). Moreover, the aldehyde ALD of formula (V) is used in relation to the amino groups of the diamine stoichiometrically or in stoichiometric excess.

In formulas (IV) and (V), X, Y ¹ , Y ^2, and Y ³ have the meanings already mentioned.

For the present invention, it is essential that the two primary amino groups of diamine DA differ from each other or by the number of hydrogen atoms of carbon atoms (C_α), standing in the α-position (= 1-position) to the corresponding amino group at leastone, or the number of hydrogen atoms of carbon atoms (C_β), standing in the β-position (= 2-position) to the corresponding amino group at leasttwo.

Thus diamine DA characterized by various substituent patterns at the α- or β-carbon atoms of the corresponding amino group. Such diamines, characterized by various substituents, are also referred to in this application as “asymmetric”. These various substituents lead to different reactivities of the two primary amino groups, especially with respect to isocyanate groups.

Thus diamine DA in one embodiment, it differs in the pattern of substituents on carbon atoms that are in the α-position to the primary amino groups.

Similar diamines DA are, for example, 1,2-propanediamine, 2-methyl-1,2-propanediamine, 1,3-butanediamine, 1,3-diaminopentane (DAMP), 4-aminoethylaniline, 4-aminomethylaniline, 4 - [(4-aminocyclohexyl ) methyl] aniline, 2-aminoethylaniline, 2-aminomethylaniline, 2 - [(4-aminocyclohexyl) methyl] aniline and 4 - [(2-aminocyclohexyl) methyl] aniline.

Thus, diamine DA in another embodiment is distinguished by a pattern of substituents on carbon atoms that are in the β-position to the primary amino groups.

Similar diamines DA are, for example, 2,2,4-trimethylhexamethylenediamine (TMD), 1,5-diamino-2-butyl-2-ethylpentane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophorondiamine = IPDA) and 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA).

Diamine DA characterized by two primary groups, of which at least one is aliphatic. The second amino group may be an aliphatic or aromatic amino group.

Not considered diamines DA formulas (IV) diamines whose amino groups differ from each other exclusively by one hydrogen atom at carbon atoms (C_β), standing in the β-position to the corresponding amino group. An example of a similar non-diamine diamine DA, is 2-methylpentamethylene diamine (= 1,5-diamino-2-methylpentane = MPMD). Also not considered diamines DA formulas (IV) diamines whose amino groups differ from each other solely by the number of hydrogen atoms of carbon atoms (C_γ or with_δ) standing inγ- orδ-position to the corresponding amino group. In all these cases, different substituent samples of the diamines do not show different or only show slightly different reactivity of the amino groups, in particular with respect to isocyanate groups.

Preferably Diamine DA of formula (IV) is selected from the group consisting of 1,3-diaminopentane (DAMP), 1,5-diamino-2-butyl-2-ethylpentane, 2,2,4-trimethylhexamethylenediamine (TMD) and 1-amino-3-aminomethyl -3,5,5-trimethylcyclohexane (= isophorondiamine = IPDA).

The ALD aldehyde used to produce dialdimine A of the formula (I) is characterized by the formula (V) and is a tertiary aliphatic or tertiary cycloaliphatic aldehyde. Suitable aldehydes ALD are, for example, pivalic aldehyde (= 2,2-dimethylpropanal), 2,2-dimethylbutanal, 2,2-diethylbutanal, 1-methylcyclopentanecarboxaldehyde, 1-methylcyclohexanecarboxaldehyde; ether from 2-hydroxy-2-methylpropanal and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; an ester of 2-formyl-2-methylpropionic acid or 3-formyl-3-methylbutyric acid and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; an ester of 2-hydroxy-2-methylpropanal and a carboxylic acid such as butyric acid, isobutyric acid and 2-ethylhexanoic acid; and also described below as particularly suitable ethers and esters of 2,2-disubstituted 3-hydroxypropanal, butanal or similar higher aldehydes, in particular 2,2-dimethyl-3-hydroxypropanal.

Particularly acceptable aldehydes of ALD of formula (V) in one embodiment are aldehydes ALD1 of formula (VI), namely aldehydes ALD of formula (V) with a Y ³ residue ^of formula (II).

In the formula (VI), Y ¹ and Y ² , respectively, preferably mean a methyl group and R ³ preferably means a hydrogen atom.

Aldehydes ALD1 of formula (VI) are ethers of aliphatic, arylaliphatic or cycloaliphatic 2,2-disubstituted 3-hydroxyaldehydes with alcohols or phenols of formula R ⁴ -OH, such as, for example, fatty alcohols or phenols. Acceptable 2,2-disubstituted 3-hydroxyaldehydes, for their part, are those obtained by aldol reactions, in particular cross aldol reactions, between primary or secondary aliphatic aldehydes, in particular formaldehyde, and secondary aliphatic, secondary arylaliphatic or secondary aldehydes, for example, cycloaliphides isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleric aldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde, cyclohexane arboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionic aldehyde, 2-phenylpropionic aldehyde (hydratropaldehyde) or diphenylacetaldehyde. Examples of suitable 2,2-disubstituted 3-hydroxyaldehydes are 2,2-dimethyl-3-hydroxypropanal, 2-hydroxymethyl-2-methylbutanal, 2-hydroxymethyl-2-ethylbutanal, 2-hydroxymethyl-2-methylpentanal, 2-hydroxymethyl-2 ethylhexanal, 1-hydroxymethylcyclopentanecarboxaldehyde, 1-hydroxymethylcyclohexanecarboxaldehyde, 1-hydroxymethyl-cyclohex-3-enecarboxaldehyde, 2-hydroxymethyl-2-methyl-3-phenylpropanal, 3-hydroxy-2-methyl-2-phenylpropan , 2-diphenylpropanal.

As examples of such aldehydes ALD1 of formula (VI), 2,2-dimethyl-3- (2-ethylhexyloxy) propanal, 2,2-dimethyl-3-lauroxypropanal, 2,2-dimethyl-3-stearoxypropanal, 3- cyclohexyloxy-2,2-dimethylpropanal; and 2,2-dimethyl-3-phenoxypropanal.

Particularly Acceptable Aldehydes ALD of the formula (V) in the following embodiment are aldehydes ALD2 of the formula (VII), that is, aldehydes ALD of the formula (V) with the remainder Y³ formulas (III).

In the formula (VII), Y ¹ and Y ² , respectively, preferably mean a methyl group and R ³ preferably means a hydrogen atom.

ALD2 aldehydes of formula (VII) are esters of the above 2,2-disubstituted 3-hydroxyaldehydes with acceptable carboxylic acids.

Examples of suitable carboxylic acids are saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valerianic acid, caproic acid, 2-ethylcaproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachinic acid; once unsaturated aliphatic carboxylic acids, such as palmitoleic acid, oleic acid, erucic acid; multiply unsaturated aliphatic carboxylic acids, such as linoleic acid, linolenic acid, eleostearic acid, arachidonic acid; cycloaliphatic carboxylic acids, such as cyclohexanecarboxylic acid; arylaliphatic carboxylic acids such as phenylacetic acid; aromatic carboxylic acids such as benzoic acid, naphthoic acid, toluic acid, anisic acid; isomers of these acids; mixtures of fatty acids from the technical saponification of natural oils and fats, such as rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, palm kernel oil and oil of palm oil; as well as monoalkyl and monoaryl esters of dicarboxylic acids, which are obtained by simple esterification of dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, slug acid, azelaic acid, sebacic acid, 1,12-dodecandicarboxylic acid, maleic acid fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3,6,9-trioxaundecanoic dicarboxylic acid and similar derivatives of polyethylene glycol, s alcohols such as methanol, ethanol, propanol, butanol, higher homologs and isomers of these alcohols.

Preferred aldehydes ALD2 of formula (VII) are 3-benzoyloxy-2,2-dimethylpropanal, 3-cyclohexanoyloxy-2,2-dimethylpropanal, 2,2-dimethyl-3- (2-ethylhexyloxy) propanal, 2,2-dimethyl-3 -lauroxyloxy propanal, 2,2-dimethyl-3-myristoyloxypropanal, 2,2-dimethyl-3-palmitoyloxypropanal, 2,2-dimethyl-3-stearoyloxypropanal, as well as similar esters of other 2,2-disubstituted 3-hydroxyaldehydes.

In one particularly preferred embodiment, R ^{5 is} selected from the group consisting of phenyl, cyclohexyl, 2-ethylhexyl and C ₁₁ -, C ₁₃ -, C ₁₅ - and C ₁₇ alkyl groups.

As the aldehyde of formula (VII), in most cases, 2,2-dimethyl-3-lauroloxypropanal is preferred.

In one preferred method for producing the aldehyde ALD2 of formula (VII), 2,2-disubstituted 3-hydroxyaldehyde, for example 2,2-dimethyl-3-hydroxypropanal, which, for example, can be obtained from formaldehyde (or paraformaldehyde) and isobutyral, optionally in situ, is reacted with a carboxylic acid to form the corresponding ester. This esterification can occur without the use of a solvent by known methods, for example, those described in Houben-Weyl, “Methoden der organischen Chemie”, Vol. VIII, Seiten 516-528.

Aldehydes ALD2 of formula (VII) are more preferred than aldehydes ALD1 of formula (VI) because of their simple preparation method.

In one particularly preferred embodiment, the aldehyde ALD of formula (V) is odorless. The term “odorless” substance is understood to mean a substance that smells so that for most human individuals it is not determined by the sense of smell, that is, it is not felt by the nose.

The odorless aldehyde ALD of formula (V), on the one hand, means the aldehyde ALD1 of formula (VI), in which the residue R ⁴ means a hydrocarbon residue with 11-30 C atoms, optionally containing a heteroatom.

On the other hand, the odorless aldehyde ALD of formula (V), in particular, means the aldehyde ALD2 of formula (VII), in which the residue R ⁵ means either a linear or branched alkyl group with 11-30 C atoms, optionally with a cyclic part, and optionally with at least one heteroatom, in particular with at least one ether oxygen, or a single or multiple unsaturated linear or branched hydrocarbon chain with 11-30 C atoms.

Examples of the odorless aldehydes ALD2 of formula (VII) are esterification products from the already mentioned 2,2-disubstituted 3-hydroxyaldehydes with carboxylic acids, such as for example lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid , nonadecanoic acid, arachinic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, as well as mixtures fatty acids from the technical saponification processes of natural oils and fats, such as rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, palm kernel oil and oil of palm oil.

Preferred odorless aldehydes of formula (VII) are 2,2-dimethyl-3-lauroloxypropanal, 2,2-dimethyl-3-myristoyloxypropanal, 2,2-dimethyl-3-palmitoyloxypropanal and 2,2-dimethyl-3-stearoyloxypropanal. Especially preferred is 2,2-dimethyl-3-lauroloxypropanal.

Dialdimines A of the formula (I) are characterized in that in the absence of water they do not react with isocyanates. In particular, this means that their residues X, Y ¹ , Y ² and Y ³ do not have groups that are reactive with isocyanate groups. In particular, X, Y ¹ , Y ² and Y ³ do not contain hydroxyl groups, do not contain primary or secondary amino groups, do not contain mercapto groups and do not contain other groups with active hydrogen.

Further, dialdimines A of formula (I) are characterized by the fact that their aldimine groups cannot be subjected to tautomerism to enamine groups, since they do not contain hydrogen as substituents in the α-position to the atom C of the aldimine group. Owing to this property, they form, together with aromatic polyisocyanates P containing isocyanate groups, which are especially stable during storage, that is, quite stable with respect to viscosity, of the mixture.

Dialdimines A, which received on the basis of odorless aldehydes of the above preferred forms of execution are odorless. Such odorous dialdimines A are particularly preferred. For many applications, the absence of odor is a great advantage or a prerequisite, in particular in enclosed spaces, such as inside buildings or automobiles, and for extensive use, such as when coating the floor.

Dialdimines A, under suitable conditions, in particular with the exclusion of moisture, are stable during storage. With the access of moisture, their aldimine groups can formally hydrolyze through the intermediate stages to amino groups, whereby the corresponding aldehyde ALD of the formula (V) used for the preparation of dialdimine A is released. Since this hydrolysis reaction is reversible and the chemical equilibrium is clearly shifted towards aldimine, only a part of the aldimine groups is hydrolyzed in the absence of groups reactive with amines.

In the presence of isocyanate groups, the equilibrium of hydrolysis is shifted, since hydrolyzed aldimine groups with isocyanate groups irreversibly react with the formation of urea groups. In this case, the reaction of isocyanate groups with hydrolyzed aldimine groups should not inevitably occur through free amino groups. Of course, reactions with intermediate stages of the hydrolysis reaction are also possible. A valid example is that a hydrolyzable aldimine group in the form of a semiaminal directly reacts with an isocyanate group.

Dialdimine A the composition is preferably present in some stoichiometrically excessive, stoichiometric or stoichiometrically insufficient amount based on isocyanate groups. Preferably dialdimine A formulas (I) is present in the composition in such an amount that the ratio between the number of aldimine groups and the number of isocyanate groups is 0.1-1.1, in particular 0.15-1.0, particularly preferably 0.2-0.9.

Mixtures of various dialdimines A can also be used as dialdimine A.In particular, mixtures of different dialdimines A can be used, which are prepared from mixtures of different diamines DA formulas (IV) and / or mixtures of various aldehydes ALD formulas (V).

It is also possible that, in addition to at least dialdimine A, other polyaldimines may be present in the composition. Thus, for example, it is possible to react diamine DA of formula (IV) with a mixture containing ALD aldehyde and dialdehyde. It is also possible to use for this a mixture of aldehydes, which in addition to the aldehyde ALD contains other aldehydes.

The composition may additionally to at least one aromatic polyisocyanate P characterized by isocyanate groups and to at least one dialdimine A Formulas (I) contain other auxiliaries and additives.

The composition reacts with water or moisture and therefore crosslinked. If enough water is present to react most or all of the isocyanate groups, a cured composition is formed which is characterized by excellent mechanical properties. Therefore, the composition may be referred to as “moisture curing”.

The composition may exist in the form of a one-component composition or in the form of a two-component composition. One-component compositions have the advantage that they are applied without a mixing process, while two-component compositions have the advantage that they quickly harden and may contain substances which, together with isocyanates, are not stable during storage.

In one embodiment, the composition exists in the form of a single component composition.

As the aromatic polyisocyanate P characterized by isocyanate groups, in the one-component composition, the polyurethane PUP polymer described above is preferred.

As excipients and additives for a single-component composition, for example, the following substances are suitable:

- plasticizers, for example, esters of carboxylic acids, such as phthalates, for example, dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example, dioctyl adipate, azelates and sebacinates, organic esters of phosphoric and sulfonic acids or polybutenes;

- solvents;

inorganic and organic fillers, for example, ground or precipitated calcium carbonate, which is optionally coated with stearates, carbon black, in particular industrial carbon black (hereinafter referred to as “carbon black”), barite (BaSO ₄ , also called heavy spar), kaolin, alumina, aluminum hydroxide, silicic acids, in particular finely divided silicic acids from pyrolysis processes, PVC powder or hollow balls;

- fibers, for example, of polyethylene;

- pigments, for example, titanium dioxide or iron oxides;

- catalysts that accelerate the hydrolysis of aldimine groups, in particular acids or compounds hydrolyzable to acids, for example, organic carboxylic acids, such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic anhydrides, such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic carboxylic acids, organic sulfonic acids such as methanesulfonic acid, para-toluenesulfonic acid or 4-dodecylbenzenesulfonic acids a, or other organic or inorganic acids;

- catalysts that accelerate the reactions of isocyanate groups with water, in particular metal compounds, for example, tin compounds, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dibutyltin dichloride acid and II; stannoxanes such as lauryl stannoxane; bismuth compounds such as bismuth (III) octoate, bismuth (III) neodecanoate or bismuth (III) oxinates; as well as tertiary amines, for example, 2,2'-dimorpholine diethyl ether and other derivatives of morpholine ethers;

rheology modifiers, such as, for example, thickeners or thixotropic agents, for example, urea compounds, polyamide waxes, bentonites or pyrogenic silicic acids;

- reaction diluents and crosslinkers, for example, monomeric polyisocyanates such as MDI, TDI, mixtures of MDI and MDI homologs (polymeric MDI or PMDI), as well as oligomers of these polyisocyanates, in particular in the form of isocyanurates, carbodiimides, uretonimines, biurets, allophanates or iminooxadiazinediones, adducts of monomeric polyisocyanates with short chain polyols, as well as adipic acid dihydrazide and other dihydrazides, as well as blocked amines in the form of aldimines, ketimines, oxazolidines or enamines;

- desiccants, for example, molecular sieves, calcium oxide, highly reactive isocyanates, such as paratosyl isocyanate, orthoformate, alkoxysilanes, such as tetraethoxysilane, organoalkoxysilanes, such as vinyltrimethoxysilane and the organoalkoxysilanes in the functional group;

adhesion promoters, in particular organoalkoxysilanes, such as, for example, epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanatosilanes, carbamatosilanes, S- (alkylcarbonyl) mercaptosilanes and aldiminosilanes, as well as oligomeric forms of these silanes;

- stabilizers against heat, light and UV radiation;

- flame retardants;

- surfactants, for example, crosslinkers, spreading agents, ventilation aids, or anti-foaming agents;

- biocides, such as, for example, algicides, fungicides or substances that inhibit the growth of fungi.

It should be taken into account that such additives do not harm the stability of the composition during storage. This means that these additives during storage cannot significantly affect reactions leading to crosslinking, such as hydrolysis of aldimine groups or crosslinking of isocyanate groups. In particular, this means that all of these additives should not contain at all, or at most can contain only traces of water. Therefore, it is possible that rationally defined additives are dried chemically or physically before being mixed into the composition.

Preferably, the single component composition, in addition to at least one polyisocyanate P and at least one dialdimine A of formula (I), contains at least one catalyst. The catalyst, in particular, is one of these acids, such as benzoic acid or salicylic acid, or one of these metal compounds, or one of these tertiary amines. In particular, this is a catalyst that accelerates the hydrolysis of aldimine groups, preferably acid. It is also completely preferred if various catalysts or various types of catalysts are mixed together.

The one-component composition is preferably prepared and stored under exclusion of moisture. In a suitable impermeable packaging or device, such as, for example, a barrel, bag or cartouche, it is characterized by exceptional storage stability. The concepts of "storage stability" and "storage stability" in connection with the composition in this application have such a meaning that the viscosity of the composition at a given application temperature and with suitable storage in the period under consideration does not increase or maximally increases to such an extent that the composition can be recycled in the prescribed manner.

If the single component composition is in contact with moisture or water, the aldimine groups of dialdimine A begin to hydrolyze. The isocyanate groups present in the composition then react with hydrolyzable aldimine groups, wherein at least one ALD aldehyde of formula (V) is released. Isocyanate groups, which are abundant with respect to aldimine groups, react directly with water. As a result of these reactions, the composition is crosslinked and finally cured to form a solid material. The reaction of isocyanate groups with hydrolyzable aldimine groups does not necessarily have to pass through free amino groups; reactions with intermediate stages of hydrolysis reactions are possible. A possible example is that hydrolyzed aldimine groups in the form of a semiaminal react directly with isocyanate groups.

Water necessary for the curing reaction can either be released from the air (air humidity, atmospheric moisture), or the composition can be brought into contact with components containing water, for example by spraying, or components containing water can be added to the composition during application, in particular by mixing.

The composition generally cures without bubbles, in particular also at a high cure rate.

The cure rate can be influenced by the type and quantity of one or more optionally present catalysts, by the temperature prevailing during curing, and also by air humidity or the amount of added water.

If components containing water are added to the composition, curing the composition is much faster than curing solely under the influence of air humidity. For this case, the extended “exposure time to gluing” of the composition described herein is a particularly great advantage. In this way, compositions are obtained which, in practical holding times before gluing, cure very quickly.

In a further embodiment, the composition exists in the form of a two-component composition. The two-component composition consists of component K1 and component K2, which are stored separately from each other and mixed with each other only shortly before use.

In one embodiment of the two-component composition, an aromatic polyisocyanate P containing isocyanate groups and a dialdimine A of formula (I) are part of the first component K1 , and the second component K2 contains compounds reactive with isocyanate groups, in particular water and / or polyols and / or polyamines.

In another embodiment of the two-component composition, the aromatic polyisocyanate P containing isocyanate groups is part of the first component K1,while the second component K2 contains dialdimine A of the formula (I), as well as compounds reactive with isocyanate groups, in particular water, and / or polyols and / or polyamines.

Preferably, component K2 contains at least one dialdimine A of formula (I) and water.

Preferably, component K2 contains at least one dialdimine A of formula (I) and at least one polyol, with 0.3-1 equivalent of aldimine groups per equivalent of hydroxyl groups being preferably present in the composition.

Particularly preferably, component K2 contains at least one dialdimine A of formula (I), at least one polyol, as well as water, with 0.3-1 equivalent of aldimine groups per equivalent of hydroxyl groups of the polyol and water based on aldimine groups is preferably present in a ratio below stoichiometric.

In the two forms of the bicomponent composition described above, the acceptable polyols are the same commercially available polyols that have already been mentioned as suitable for producing the PUP polyurethane polymer, as well as those low molecular weight di- or polyhydric alcohols that have previously been mentioned as suitable for sharing upon receipt of the polyurethane polymer PUP. If component K2 contains water, it is preferable if the amount of water is maximally determined as necessary for the hydrolysis of dialdimine A - and, optionally, possibly another - a hidden hardener. In addition, both components may contain other auxiliary substances and additives that have already been mentioned for the single-component composition. However, in the case of component K2, other auxiliary substances and additives are additionally possible. In particular, these are auxiliary substances and additives that are not suitable for storage together with aromatic isocyanate groups, or are suitable only for short-term storage. In particular, these are catalysts, such as described below:

compounds of zinc, manganese, iron, chromium, cobalt, copper, nickel, molybdenum, lead, cadmium, mercury, antimony, vanadium, titanium, zirconium or potassium, such as zinc (II) acetate, zinc (II) -2-ethylhexanoate, zinc (II) -laurate, zinc (II) -oleate, zinc (II) -naphthenate, zinc (II) -acetylacetonate, zinc (II) -salicylate, manganese (II) -2-ethylhexanoate, iron (III) -2 ethyl hexanoate, iron (III) acetylacetonate, chromium (III) -2 ethyl hexanoate, cobalt (II) naphthenate, cobalt (II) -2 ethyl hexanoate, copper (II) -2 ethyl hexanoate, nickel (II) naphthenate , phenylmercury-neodecanoate, lead (II) -acetate, lead (II) -2-ethylhexanoate, lead (II) -neode canoate, lead (II) -acetylacetonate, aluminum lactate, aluminum oleate, aluminum (III) -acetylacetonate, diisopropoxy titanium bis (ethyl acetoacetate), dibutoxy titanium bis (ethyl acetoacetate), dibutoxy titanium bis (acetylacetate,) potassium; tertiary amines such as triethylamine, tributylamine, N-ethyldiisopropylamine, N, N, N ', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and their higher homologues, N, N, N', N'-tetramethylpropylenediamine, pentamethyldipropylenetriamine and their , N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, bis (dimethylamino) methane, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-dimethylhexadecylamine, bis- (N, N-diethylaminoethyl) adipate, N, N-dimethyl-2-phenylethylamine, tris- (3-dimethylaminopropyl) amine, 1,4-diazabicyclo [ 2.2.2] Oct n (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), N-methylmorpholine, N-ethylmorpholine , N-cocomorpholine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, bis- (dimethylaminoethyl) piperazine, 1,3,5-tris- (dimethylaminopropyl) hexahydrotriazine, bis- (2-dimethylaminoethyl) ) ether; nitrogen-aromatic compounds such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; amidines and guanidines, such as 1,1,3,3-tetramethylguanidine; tertiary amines containing active hydrogen atoms such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, 3- (dimethylamino) propyldiisopropanolamine, bis- (3- (dimethylamino) propyl) isopropanolamine, bis- (3-dimethylamine amine, 3- (dimethylamino) propylurea, Mannich bases such as 2,4,6-tris- (dimethylaminomethyl) phenol or 2,4,6-tris- (3- (dimethylamino) propylaminomethyl) phenol, N-hydroxypropylimidazole, N - (3-aminopropyl) imidazole, as well as the products of alkoxylation and polyalkoxylation of these compounds, for example, dim ethylaminoethoxyethanol; organic ammonium compounds such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; so-called “delayed-action” catalysts, which are modifications of known metal or amine catalysts, such as the reaction products of tertiary amines and carboxylic acids or phenols, for example, from 1,4-diazabicyclo [2.2.2] octane or DBU and formic acid, or acetic acid; as well as combinations of these compounds, in particular metal compounds and tertiary amines.

Preferably component K2 does not contain isocyanate groups.

If the composition contains other blocked amines, in particular aldimines, ketimines, oxazolidines or enamines, they can be part of component K1 and / or K2. As the aldimine, other aldimines, such as dialdimin A, which are derived from other amines according to formula (IV) and / or from other aldehydes according to formula (V), are particularly suitable. All of these blocked amines have the ability to release amino groups upon hydrolysis, which quickly react with existing isocyanate groups.

Obtaining both components K1 and K2 occurs separately from each other, at least for component K1 with the exclusion of moisture. Both components K1 and K2 individually are stable during storage, that is, each of them can be stored in a suitable packaging or device, such as a barrel, tin packaging, bag, tub or cartouche, before being used for several months up to a year or more, without changing their respective properties to the extent necessary for their use.

The ratio of the mixture between both components K1 and K2 is preferably chosen so that the groups of components K1 and K2 reactive with isocyanate groups are in a suitable ratio to the isocyanate groups of component K1. In the two-component composition, before curing, it is expediently comprised of 0.1-1.1, preferably 0.5-0.95, particularly preferably 0.6-0.95 equivalents of the sum of groups reactive with isocyanates per equivalent of isocyanate groups, wherein aldimine groups and, optionally, other blocked amino groups present are assigned to groups that are reactive with isocyanates, and water is not taken into account groups that are reactive with isocyanates. Excess isocyanate groups preferably react directly with water, for example, with air moisture.

Before or during application of the two-component composition, both components are mixed together in an acceptable manner. Mixing can occur continuously or intermittently. The mixed composition is applied during mixing or at the end of mixing, and it is brought into contact with the surface of the solid, optionally with a specific adjuvant. It should be noted that not too much time has passed between mixing the components K1 and K2 and using, as this may cause difficulties, such as, for example, delayed or full adhesion to the surface of a solid. The maximum period of time during which the mixed composition must be used, means both "viability" and "exposure time before gluing." Often the “exposure time before gluing” is defined as the time during which the viscosity of the mixed composition doubles.

After mixing the components K1 and K2, curing begins. Dialdemin A of formula (I) begins to hydrolyze as described above and react with isocyanate groups as soon as it comes into contact with water. Or water was already in the mixed composition - because it was an ingredient in component K2 or because it was added to the composition before or during mixing of both components K1 and K2 -,or water diffused into the mixed composition in the form of air moisture. In the latter case, dialdemin A reacts with isocyanate groups from outside to inside, in parallel with the penetration of moisture into the composition. As indicated above, the reaction of isocyanate groups with hydrolyzable aldimine groups does not have to be carried out through free amino groups, but can also be carried out through intermediate stages of the hydrolysis reaction. In the same way, the reactive groups of other hidden curing agents optionally present in the composition are released. Further, after mixing the components K1 and K2 compounds reactive with isocyanate groups optionally present in the composition, in particular polyols and polyamines, react with isocyanate groups. Excess isocyanate groups, in particular, directly react with water. As a result of these reactions, the mixed composition is crosslinked and finally solidifies to a solid.

The composition generally cures without bubbles, in particular also at a high cure rate.

The cure rate can be influenced by the type and amount of one or more optionally present catalysts, the temperature prevailing during curing, as well as air humidity or the amount of water introduced with component K2 .

Both in a one-component and in a two-component form of execution, the described composition, on the one hand, has a long exposure time before gluing, and on the other hand, a high curing rate. The combination of a long exposure time before gluing and fast curing for many one-component and two-component compositions is extremely desirable.

Thus, the use of a one-component composition is often simple if after applying it there is still some time to give the composition the desired shape before a crust of cured material forms on the surface. For example, the sealant should be able to be polished for a sufficiently long time after application; the glue must be able to move freely in order to precisely align the mating parts; the coating or cladding should still be aligned or, for example, sprinkled with crumb rubber, sand or colored plates. But then the composition must be quickly cured so that it can be loaded as quickly as possible and / or so that it is not covered with dust.

The use of a two-component composition is also often quite simple if it is characterized by a long exposure time before gluing, since both the mixing process and the application of the composition, and optionally required post-processing steps, for example, to impart the composition, must still be carried out during the exposure time before gluing desired shape. For example, a two-component flooring, which is mixed in portions and then poured onto the base and polished, should have a long exposure time before gluing, so that the application can take place accurately, without time pressure. But then the composition must be quickly cured so that it can be loaded as quickly as possible. For flooring, it is often necessary that the flooring at the very next day after application is generally cured so that it can be rated for the load so that further work can then be carried out.

In the case of a single-component composition, the peeling time is usually determined as a measure of the exposure time before gluing. By “peeling time” is meant a time period between the application of the composition and the formation of a peel of the cured material on the surface of the composition. As a measure of the cure rate of a one-component composition curable from the outside to the inside, a so-called full cure is usually set. When this is measured, for example, the thickness of the cured layer, which was formed under certain conditions after a given period of time in the applied composition; or measure the time that it is necessary that the composition deposited by a layer of a given thickness, under certain conditions, completely hardened.

In the case of a two-component composition, as a measure of the exposure time before gluing, a period of time during which, after mixing both components, for example, a certain increase in viscosity (for example, double increase), or the composition is characterized by a non-adhesive surface, can be determined. As a measure of the cure rate of a two-component composition, for example, an increase in hardness, for example, Shore hardness, over time can be established.

It is only thanks to the composition according to the invention that it is possible to realize in one composition long exposure times combined with each other before gluing and high curing rates.

The effect of a long exposure time before gluing at high cure rates is clearly defined, as the following examples show. The basis of this was still unexplored details. But it can be assumed that the effect can be reduced to the described asymmetry of dialdemin A of formula (I) or the diamine DA of formula (IV) derived from it. When water is accessed, only reactive aldimine groups of dialdimine A , or reactive amino groups of diamine DA, with isocyanate groups of polyisocyanate P first react. However, this still does not lead to crosslinking of the composition, but only to a slight increase in viscosity, which barely limits the exposure time before gluing. Only when the reactive aldimine groups or amino groups are significantly consumed do the slowed aldimine groups or amino groups react with the following isocyanate groups, which now directly leads to crosslinking of the composition and greatly accelerates curing.

As already described, dialdimine A of formula (I) is based on special asymmetric diamines DA of formula (IV) and tertiary aldehydes ALD of formula (V). The different reactivity of both amino groups in diamine DA, based on different substances, is transferred directly to the dialdimine of this diamine DA, in which both aldimine groups are also characterized by different reactivity. In the special case of dialdimine A, there is a difference in reactivity in the aldimine groups, due to the tertiary, and therefore sterically stressed, structure of the ALD aldehyde underlying the aldimine groups, presumably even further strengthened, since the sterically stressed aldehyde residue further limits the availability of the aldimine groups - in in particular, if they exist in a semi-hydrolyzed form as semi-amine groups - and as a result of this, excessively proportionally reduces the reactivity s slow aldimine groups compared with the same rapid aldimine groups.

Due to the use of preferably odorless dialdimines A, it is also possible, first of all, to obtain compositions which are odorless before, during and after curing. This property is a great advantage over the prior art and greatly expands the possibilities of using these compositions.

The compositions described are particularly suitable as one- and two-component adhesives, sealants, grouting materials or floor coverings, in particular floor coverings. In particular, they are suitable as elastic adhesives, elastic sealants, elastic sealing compounds or elastic coatings. They are particularly preferably used as elastic sealants, since the use of special dialdimines A in the cured state gives particularly plastic-elastic properties.

In particular, the described composition is suitable as plastic-elastic sealants for sealing joints of all kinds, in particular expansion joints in structures. The so-called expansion joints are joints that are located in suitable places and in suitable spaces of structures to smooth out movements between parts of rigid building materials such as concrete, stone, polymer and metal. Such movements occur on the one hand, due to vibration and, on the other hand, due to temperature changes. In cold weather, solid materials contract, causing the seams to become wider, and in the heat they expand, so that the seams become denser. The sealant, which should seal such joints for a long time, should be characterized by plastic-elastic properties, so that when it is stretched and compressed in the joint, as little force as possible is transmitted to the substrate, and thereby it is subjected to the least possible load. Under the plastic-elastic properties in the present description understand the high extensibility and low value of tensile stress, and a good ability to return (to its original position). The term "tensile stress" means the stress that acts in a material in a stretched state.

Particularly low values of tensile stress in the cured state are characterized by sealant compositions that contain at least one dialdimine A, in which X in the formula (I) means the diamine residue DA selected from the group consisting of TMD, IPDA and 1.5 diamino-2-butyl-2-ethylpentane.

In a further aspect, the invention relates to a method for bonding a substrate S1 to a substrate S2. This method includes the steps of:

i) applying the above composition to a substrate S1;

ii) contacting the applied composition with the substrate S2 for a holding time before bonding the composition;

or

i ') applying the above composition to the substrate S1 and to the substrate S2;

ii ') contacting the applied compositions with each other during the exposure time before gluing the composition;

moreover, the substrate S2 consists of the same or different material compared to the substrate S1.

In addition, the invention relates to a sealing method, comprising the step of:

i ”) applying the above composition between the substrate S1 and the substrate S2, so that the composition is in contact with the substrate S1 and the substrate S2;

moreover, the substrate S2 consists of the same or different material compared to the substrate S1.

The gap, which in the sealing method is between the substrate S1 and the substrate S2, is called a “seam” by a specialist. In this case, usually the composition is squeezed out of the cartouche into pre-treated seams and then polished by hand, more often with a tool moistened with soapy water, for example, a spatula, or a finger of a processor moistened with soapy water, carried out on top of the applied sealant so that it acquires a smooth and dense surface, with a very small indentation. Since the processor often smooths the applied sealant first, if it fills large areas of the joints, a long time can pass between application and smoothing of the sealant, for example, up to one hour. But to ensure accurate smoothing, it is necessary that a crust of cured material is not yet formed on the surface of the sealant at this time. Therefore, sealants with a short exposure time before gluing are undesirable for sealant processors. Despite this, it is important that the sealant, after a long exposure time before gluing, quickly cures and forms a non-sticky surface, since there is a high risk of contamination, for example, dust and sand, for the sticky, uncured surface of the sealant. On the other hand, the sealant composition in the cured state should be characterized by the most plastic-elastic properties. The described composition can perfectly fulfill these requirements.

Finally, the invention relates to a method for coating a substrate S1, which comprises the step

i '' ') applying the composition according to any one of claims 1 to 16 of the claims on the substrate S1 during the exposure time before gluing the composition.

For all of these methods, substrates S1 and / or S2 can be represented by a large number of materials. In particular, they are inorganic substrates, such as glass, glass ceramics, concrete, building cement, brick, tile, gypsum or natural stone, such as granite or marble; a metal or alloy, such as aluminum, steel, non-ferrous metal, galvanized metal; organic substrates such as wood; polymers such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy, polyurethane (PUR); coated substrates, such as a metal or powder coated alloy; or paint or varnish, in particular automotive topcoat.

In all of these methods, the substrate S1 and / or the substrate S2 can be pretreated before gluing, sealing, or coating, in particular with a primer layer or an adhesion promoter composition. Pretreatments of this kind in particular include physical and / or chemical cleaning and activation methods, such as, for example, grinding, sandblasting, brushing, corona treatment, plasma treatment, flame treatment, surface etching and the like, or treatment with cleaners or solvents or applying an adhesion promoter, a solution of an adhesion promoter, or a primer.

From these described methods with bonding, sealing or coating, an article is formed.

This product is basically a structure, in particular a ground or underground structure, or an industrial product, or a consumer product, such as, in particular, a window, a household machine, or a vehicle, in particular a water or land vehicle, preferably a car , bus, truck, train or ship, or vehicle structural element.

EXAMPLES

Description of Methods

Infrared spectra were measured on a FT-IR 1600 instrument from Perkin-Elmer (horizontal measuring ATR cell with a ZnSe crystal), the substances being applied as a film, undiluted. Absorption bands are given in wave numbers (cm ^-1 ) (measurement range: 4000-650 cm ^-1 ).

¹ H-NMR spectra were measured in a Bruker DPX-300 type spectrometer at 300.13 MHz; chemical shifts δ are given in ppm (ppm) relative to tetramethylsilane (TMS). The interaction constant J is given in Hz. Genuine and pseudo-samples do not distinguish between interactions.

Viscosity was measured on a thermostatic cone - plate Physica UM viscometer (cone diameter 20 mm, cone angle 1 °, distance from the top of the cone to the plate 0.05 mm, shear rate 10-1000 s ^-1 ).

The amine content of the resulting dialdimine, i.e. the content of blocked amino groups in the form of aldimine groups, was determined titrimetrically (with 0.1 N HClO ₄ in glacial acetic acid, crystalline violet) and always converted to mmol N / g.

a) Preparation of dialdimines

Dialdimine A-1

55.0 g (0.19 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 15.6 g (0.18 mol of N) 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophorondiamine, IPDA; Vestamin® IPD, Degussa; amine content 11, 68 mmol N / g), the mixture being heated and becoming denser. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 67.1 g of a clear, colorless oil with an amine content of 2.73 mmol N / g and a viscosity of 190 MPa ∙ s at 20 ° C.

IR: 2952, 2922, 2852, 2819 shortened, 1738 (C = O), 1666 (C = N), 1464, 1418, 1394, 1378, 1364, 1350, 1298, 1248, 1236 shortened, 1158, 1112, 1048, 1020, 1000, 938, 928, 910, 894, 868, 772, 722.

¹ H-NMR (CDCl ₃ , 300 K): δ 7.59 and 7.57 (2 × s, total 1H, CH = N ([isomer]), 7.47 (s, 1H, CH = N), 4.03 and 4.01 (2 × s, 2 × 2H, C (CH ₃ ) ₂ —C H ₂ —O), 3.37 (m, 1H, N-CH ^Cy ), 3.08 (dd, 2H, J≈11.1, N-CH ₂ -C ^Cy ), 2.30 (t, 4H, J≈7.5, OC (O) -CH ₂ -CH ₂ ), 1.61 (m, 4H OC (O) —CH ₂ —CH ₂ ), 1.60-0.85 (m, 65H, the rest is CH).

Dialdimin A-2

55.0 g (0.19 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring from the dropping funnel was slowly added 9.4 g (0.18 mol N) 1,3-diaminopentane ^{(DAMP; Dytek ® EP Diamine,} Invista; amine content 19.42 mmol N / g), and the mixture was heated and became all is thicker. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 60.9 g of a clear, light yellow oil with an amine content of 3.01 mmol N / g and a viscosity of 50 MPa ∙ s at 20 ° C.

IR: 2955 shortened, 2922, 2868 shortened, 2852, 1737 (C = O), 1666 (C = N), 1466, 1419, 1394, 1373, 1346, 1300, 1248, 1233, 1159, 1112, 1057, 1019, 1000, 935, 884, 769 broadened, 722.

Dialdimin A-3

50.0 g (0.18 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 15.8 g (0.17 mol N) 1,5-diamino-2-butyl-2-ethylpentane (amine content 10.52 mmol N / g) were slowly added from the dropping funnel, the mixture being heated and everything became thicker. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 62.6 g of a transparent, almost colorless oil with an amine content of 2.64 mmol N / g and a viscosity of 100 MPa ∙ s at 20 ° C.

IR: 2951, 2922, 2871 shortened, 2852, 2831 shortened, 1738 (C = O), 1669 (C = N), 1463, 1418, 1393, 1375, 1341, 1302, 1248, 1234, 1159, 1112, 1019, 999, 935, 874 shortened, 848 shortened, 777, 722.

Dialdimine A-4

79.4 g (0.28 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 20.0 g (0.25 mol N) 2.2 (4), 4-trimethylhexamethylenediamine (Vestamin® TMD, Degussa; amine content 12.64 mmol N / g) was slowly added from the dropping funnel, and the mixture was heated and it was getting thicker. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 94.4 g of a clear, light yellow oil with an amine content of 2.66 mmol N / g and a viscosity of 63 MPa ∙ s at 20 ° C.

IR: 2954, 2920, 2852, 2822 shortened, 1737 (C = O), 1668 (C = N), 1466, 1418, 1392 shortened, 1374, 1365, 1348, 1301 shortened, 1248, 1234, 1158, 1112, 1020 , 999, 932, 867, 722.

Dialdimin A-5

24.3 g (85 mmol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 5.0 g (81 mmol N) of 4-aminomethylaniline (= 4-aminobenzylamine; amine content 16.24 mmol N / g) was slowly added from the dropping funnel, the mixture being heated and slightly thickened. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 27.6 g of a clear, light yellow oil with an amine content of 2.93 mmol N / g and a viscosity of 125 MPa · s at 20 ° C.

Dialdimin A-6 (comparative)

60.0 g (0.21 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring from the dropping funnel was slowly added 11.8 g (0.20 mol N) 1,5-diamino-2-methylpentane ^{(MPMD; Dytek ® A, Invista} ; amine content 17.04 mmol N / g), the mixture heated up and became thicker. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 68.2 g of a clear, pale yellow oil with an amine content of 2.94 mmol N / g and a viscosity of 53 MPa ∙ s at 20 ° C.

Dialdimin A-7 (comparative)

80.9 g (0.27 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 25.2 g (0.26 mol N) 3 (4), 8 (9) bis (aminomethyl) tricyclo [5.2.1.0 ^2.6 ] decane (TCD-diamine, Celanese) were slowly added from the dropping funnel. ; amine content 10.23 mmol N / g), the mixture being heated and becoming thicker. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 100.8 g of a clear, almost colorless oil with an amine content of 2.56 mmol N / g.

Dialdimin A-8 (comparative)

74.3 g (0.26 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 30.0 g (0.25 mol N) of polyether diamine (polyoxypropylene diamine with an average molecular weight of about 240 g / mol; Jeffamine ^® D-230, Huntsman; amine content of 8.29 mmol N / g was slowly added from a dropping funnel ), and the mixture was heating up and becoming denser. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 99.5 g of a clear, pale yellow oil with an amine content of 2.50 mmol N / g.

Dialdimine A-9 (comparative)

50.9 g (0.18 mol) of distilled 2,2-dimethyl-3-lauroloxypropanal were placed in a round bottom flask under a nitrogen atmosphere. With vigorous stirring, 10.0 g (0.17 mol N) of 1,6-hesamethylenediamine (BASF; amine content of 17.04 mmol N / g) was slowly added from the heated dropping funnel, the mixture being heated and thickened. After that, the volatile components were distilled off in vacuo (10 mbar, 80 ° C). Yield: 57.7 g of a clear, pale yellow oil with an amine content of 2.94 mmol N / g.

b) Preparation of compositions

Examples 1-5 and comparative examples 6-8

For each example, the corresponding components according to Table 1 were weighed in predetermined weight parts without preliminary drying in a polypropylene jar with a screw cap and mixed using a centrifugal mixer (SpeedMixer ^TM DAC 150, FlackTek Inc .; 1 min at 2500 rpm), the mixture was immediately loaded into the inside lacquered aluminum tube and closed it tightly.

The polyurethane polymer PUP-1 was prepared as follows.

1300 g of polyoxypropylene diol (Acclaim ^® 4200 N, Bayer; OH number 28.5 mg KOH / g) 2600 g polyoxypropylene polyoxyethylene triol (Caradol ^® MD34-02, Shell; OH number 35.0 mg KOH / g), 600 g 4, 4'-methylenediphenyl diisocyanate (MDI; Desmodur ^® 44 MC L, Bayer) and 500 g of diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF) were reacted at 80 ° C. to an NCO-terminated polyurethane polymer with 2.05% free isocyanate groups by weight . and a viscosity of 31.6 Pa ∙ s at 20 ° C.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0 / 0.70.

Table 1 The composition of examples 1-5 and comparative examples 6-8 Example one 2 3 four 5 6 Wed 7 Wed 8 Wed PUR polymer PUP-1 50,0 50,0 50,0 50,0 50,0 50,0 50,0 50,0 Dialdimine A-1,
6.26 A-2,
5.67 A-3,
6.47 A-4,
6.42 A-5,
5.82 A-6,
5.81 A-7,
6.67 A-8
6.84 Acid catalyst ^a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

^a Salicylic acid (5% wt. in dioctyl adipate).

The compositions thus obtained were tested for storage stability, holding time before gluing, and curing speed.

Storage stability was determined by the change in viscosity during storage in heat. For this, the composition was kept in a closed tube in an oven at 60 ° C, and the viscosity was measured at 20 ° C for the first time after 12 hours, and the second time after 7 days of aging. Storage stability is given as a percentage increment of the second viscosity with respect to the first.

As a measure for the exposure time before gluing, the crust formation time (time without glue, “tack-free”) was used. To measure the time of formation of a crust, a small part of the composition with room temperature, aged at 40 ° C for 2 hours, was applied with a layer thickness of about 2 mm onto cardboard, and at 23 ° C and 50% relative humidity, the time was determined until lightly touching the surface of the composition with an LDPE pipette on the pipette for the first time, there is no more residue.

As a measure of cure rate, the time to complete cure of the composition was used. The time to complete curing of the composition was established by the fact that the composition in the form of a film with a layer thickness of 5 mm was poured into a PTFE mold, stored under normal conditions, and the time in days was determined by periodically raising the edges of the film so that the film could tear off the first time forms without residues.

The test results are shown in table 2.

table 2 Properties of examples 1-5 and comparative examples 6-8 Example one 2 3 four 5 6 Wed 7 Wed 8 Wed Viscosity after 12 hours ^a 22.8 27.1 21.7 19.7 23.8 22.4 23.1 20.5 Viscosity after 7 days ^a 27.0 30.6 25.0 23,2 26,4 26.2 27.7 25,2 Viscosity increase ^b eighteen% 13% fifteen% eighteen% eleven% 17% twenty% 23% Peeling Time (min) 70 150 90 65 60 40 45 45 Full cure (d.) 2,5 3 3 3 2,5 2,5 2,5 2,5 ^a V Pa ∙ s, keeping at 60 ° С.
^b (viscosity after 7 days / viscosity after 12 hours) × 100%.

Examples 9-10 and comparative example 11

For each example, the corresponding components according to table 3 were weighed in predetermined weight parts without preliminary drying in a polypropylene jar with a screw cap and mixed using a centrifugal mixer (SpeedMixer ^TM DAC 150, FlackTek Inc .; 1 min at 2500 rpm), the mixture was immediately loaded into the inside lacquered aluminum tube and closed it tightly.

PUP-2 polyurethane polymer was prepared as follows:

180 g polyoxypropylenediol (Acclaim ^® 4200 N, Bayer; OH number 28.5 mg KOH / g), 50 g polyoxypropylene diol (Acclaim ^® 6300, Bayer; OH number 28.0 mg KOH / g) and 21 g toluene diisocyanate (TDI ; Desmodur ^® T 80 P, Bayer) were reacted at 80 ° C until NCO-terminated polyurethane polymer with a content of free isocyanate group of 1.89% by weight. and viscosity 13.8 Pa ∙ s at 20 ° C.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0 / 0.70.

Table 3 The composition of examples 9-10 and comparative example 11 Example 9 10 11 (comparative) Polyurethane Polymer PUP-2 50,0 50,0 50,0 Dialdimine A-1,
5.77 A-2,
5.23 A-8
6.31 Acid catalyst ^a 0.1 0.1 0.1 ^a Salicylic acid (5% wt. in dioctyl adipate).

The compositions thus obtained were tested for storage stability, holding time before gluing (peeling time), and curing speed (full cure), as described in Example 1.

The test results are shown in table 4.

Table 4 Properties of examples 9, 10 and comparative example 11 Example 9 10 11 (comparative) Viscosity after 12 h (Pa ∙ s) ^a 12.8 13.0 12.0 Viscosity after 7 d. (Pa ∙ s) ^a 15.6 15.6 14.0 Viscosity increase ^b 22% twenty% 17% Peeling Time (min) 130 295 70 Full cure (d.) four 3,5 3 ^a Holding at 60 ° C.
^b (viscosity after 7 days / viscosity after 12 hours) × 100%

Examples 12-15 and comparative examples 16-18:

One-component elastic adhesives

For each example, the corresponding components according to table 5 were processed in predetermined weight parts without preliminary drying in a vacuum mixer with the exception of moisture to a homogeneous paste, it was immediately loaded into the inside of the lacquered aluminum cartridge, and the cartridge was hermetically sealed.

PUP-3 polyurethane polymer was prepared as follows.

3560 g of polyoxypropylene diol (Acclaim ^® 4200 N, Bayer; OH number of 28.1 mg KOH / g), 1000 g of polyoxypropylene diol (Acclaim ^® 6300, Bayer; OH number of 28.0 mg KOH / g) and 440 g of toluene diisocyanate (TDI ; Desmodur ^® T 80 P, Bayer) were reacted at 80 ° C until NCO-terminated polyurethane polymer titrimetrically specific content of free isocyanate groups of 2.19% by weight. and viscosity 10 Pa ∙ s at 20 ° C.

The thickener was prepared as follows:

3000 g of diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF) and 480 g of 4,4'-methylenediphenyl diisocyanate (MDI; Desmodur ^® 44 MC L, Bayer) were charged into a vacuum mixer and slightly heated. Then, with vigorous stirring, 270 g of monobutylamine were slowly added dropwise. The resulting paste was further stirred under vacuum and cooling for one hour.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0 / 0.67.

Table 5 Compositions of one-component elastic adhesives of examples 12-15 and comparative examples 16-18 Example 12 13 fourteen fifteen 16 Wed 17 Wed 18 Wed PUR-polymer PUP-3 24.0 24.0 24.0 24.0 24.0 24.0 24.0 Dialdimine A-1,
3.07 A-2,
2.78 A-3,
3.18 A-4,
3.15 A-6,
2.85 A-7,
3.27 A-8
3.36 Plasticizer ^a 1.93 2.22 1.82 1.85 3.15 1.73 1,64 a piece of chalk 38,0 38,0 38,0 38,0 38,0 38,0 38,0 Thickener 28.0 28.0 28.0 28.0 28.0 28.0 28.0 Titanium dioxide 4,5 4,5 4,5 4,5 4,5 4,5 4,5 Epoxysilane ^B 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Acid catalyst ^with 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ^and diisodecyl phthalate ^{(DIDP; Palatinol ® Z, BASF} ).
^b 3-glycidoxypropyltriethoxysilane (Dynasylan ^® GLYEO, Degussa).
^c Salicylic acid (5% by weight in dioctyl adipate).

The thus obtained one-component elastic adhesives were tested for consumer properties, holding time before gluing, curing speed and mechanical properties after curing.

As a measure of consumer properties, stability and stretching of the thread were used. To determine the stability, glue using a cartouche gun through a triangular nozzle was applied in the form of a horizontal triangular "caterpillar" with a main diameter of 8 mm and a height (distance of the top of the triangle from the base) of 20 mm on a vertically standing piece of cardboard. After 5 minutes, we measured how the top fell, i.e. shifted from the initial position to the center of the triangular "caterpillar". They evaluated it as “very good” if the top was completely or approximately unchanged, as “good” if the top was between the center and the end of the base. The stretch of the thread was determined qualitatively, so that a little glue was applied by means of a cartouche gun to a piece of cardboard mounted on the wall, the cartouche gun was quickly pulled away from the applied glue at the end of the application and the length of the thread that was behind at the breakage point was measured.

As a measure for the exposure time before gluing, the crust formation time (time without glue) was used. Peeling time determined as described in example 1.

As a measure of cure speed, the time to complete curing of the adhesive was used. The time until complete curing was determined by the fact that glue was applied by means of a cartouche gun through a round tip (10 mm hole) in the form of a horizontal freely hanging cone with a length of about 50 mm and a thickness in the center of 30 mm on a piece of cardboard mounted on the wall, left for 7 days under normal conditions, then vertically cut in the center and measured the thickness of the cured adhesive layer using a scale.

To determine the mechanical properties after curing, Shore A-hardness, tensile strength, elongation at break, and tensile stress of 100% were measured. A-Shore hardness of test samples cured for 14 days under normal conditions was determined in accordance with DIN 53505. To test the following mechanical properties, the adhesive was pressed 2 hours after pressing to a film about 2 mm thick, the film was cured for 14 days under normal conditions conditions and tested according to DIN EN 53504 for tensile strength, elongation at break and tensile stress at 100% (tensile speed: 200 mm / min)

All adhesives fully cured without bubbles.

The test results are shown in table 6.

Table 6 The properties of the elastic adhesives of examples 12-15 and comparative examples 16-18 Example 12 13 fourteen fifteen 16 Wed 17 Wed 18 Wed Sustainability Very well Very well Very well Very well Very well Very well Good Hood (cm) 10 8 four 5 10 four four Peeling Time (min) 105 280 180 one hundred 55 60 65 Full cure (mm) 9 8 8 8 eleven 10 four A-Shore Hardness 38 42 34 31 39 37 31 Tensile strength (MPa) 2.1 2.1 1.4 1.7 2.1 1.9 1.8 Elongation at break (%) 1350 1070 1010 1040 1140 1310 1040 100% tensile stress (MPa) 1.00 1.46 0.93 1.01 1.39 1,04 1.44

Example 19 and comparative examples 20 and 21

One-component elastic sealants

For each example, the corresponding components according to table 7 were processed in predetermined weight parts without preliminary drying in a vacuum mixer with the exception of moisture to a homogeneous paste, it was immediately loaded into an aluminum lacquered inside cartridge, and the cartridge was hermetically closed.

The polyurethane polymer PUP-4 was prepared as follows.

1190 g polyoxypropylene diol (Acclaim ^® 4200 N, Bayer; OH number 28.1 mg KOH / g), 620 g polyoxypropylene polyoxyethylene triol (Caradol ^® MD34-02, Shell; OH number 35.0 mg KOH / g) and 190 g of 2,4-toluene diisocyanate (Scuranate ^® T-100, Lyondell) was reacted at 80 ° C to an NCO-terminated polyurethane polymer with a titrimetrically determined content of free isocyanate groups of 2.32% by weight. and a viscosity of 5 Pa ∙ s at 20 ° C. A thickener was prepared as described in Example 12.

The ratio between isocyanate groups and aldimine groups in all examples was 1.0 / 0.67.

Table 7 Compositions of one-component elastic sealants of example 19 and comparative examples 20 and 21 Example 19 20 Comp. 21 Comp. Polyurethane Polymer PUP-4 24.0 24.0 24.0 Dialdimine A-1,
3.26 A-7,
3.47 A-8,
3.56 Plasticizer ^a 1.74 1,53 1.44 a piece of chalk 38,0 38,0 38,0 Thickener 28.0 28.0 28.0 Titanium dioxide 4,5 4,5 4,5 Epoxysilane ^B 0.2 0.2 0.2 Acid catalyst ^with 0.3 0.3 0.3 ^and diisodecyl phthalate ^{(DIDP; Palatinol ® Z, BASF} ).
^b 3-glycidoxypropyltriethoxysilane (Dynasylan ^® GLYEO, Degussa).
^c Salicylic acid (5% by weight in dioctyl adipate).

The one-component elastic sealants obtained in this way were tested for consumer properties (stability, thread drawing), holding time before gluing (crust formation time), curing speed (full cure) and mechanical properties after curing (A-Shore hardness, tensile strength, relative elongation at break and tensile stress by 100%) were tested as described in example 12.

Further, the sealants were qualitatively tested for stickiness. This happened in such a way that a thumb was pressed on the Shore-cured sample one or three days after application, and after that it was established how long the sample remained glued to the thumb when lifting the hand. The stickiness was evaluated as “high” (the sample remains glued for more than 3 seconds), “medium” (the sample remains glued for 1-2 seconds) and “no” (the sample remains glued for less than 1 second).

All sealants cured completely without bubbles.

The test results are shown in table 8.

Table 8 Properties of one-component elastic sealants of example 19 and comparative examples 20 and 21 Example 19 20 Comp. 21 Comp. Sustainability Very well Very well Very well Hood (cm) 5 four 8 Peeling Time (min) 250 95 70 Full cure (mm) 8 7 3 A-Shore Hardness thirty 32 23 Tensile strength (MPa) 2.0 2.0 1.4 Relative extension (%) 1180 1150 1200 100% tensile stress (MPa) 0.35 0.42 0.34 Stickiness after 1 day small small high 3 days stickiness no no average

Examples 22, 23 and comparative example 24

Two-component elastic adhesives

For all examples, component K1 was prepared as follows:

In a planetary mixer in a nitrogen atmosphere, 200 g of partially carbodiimidized 4,4'-methylenediphenyl diisocyanate (Desmodur ^® CD, Bayer; NCO content = 29.5% weight) with 280 g of PUP-1 polyurethane polymer and 20 g of hydrophobic pyrogenic silicon were mixed to a homogeneous paste acid (Aerosil ^® R972, Degussa) and loaded onto a cartouche.

Then, component K2 according to table 9 was weighed in predetermined weight parts without preliminary drying in a polypropylene cartouche and mixed to a homogeneous paste using a centrifugal mixer (SpeedMixer^TM DAC 150, FlackTek Inc .; 2 min at 3000 rpm). To this was added the weight parts of component K1 shown in table 9 and immediately mixed (30 sec at 3000 rpm). PUP-1 polyurethane polymer was prepared as described in Example 1. A thickener was prepared as described in Example 12.

The ratio between the isocyanate groups of component K1 and the sum of reactive groups (hydroxyl groups, primary amino groups and aldimine groups) of component K2 has always been 0.6 / 1.

Table 9 Compositions of two-component elastic adhesives of examples 22, 23 and comparative example 24 Example 22 23 24 (Comp.) Component K1 18.2 18.7 18,4 Component K2: Polyol ^a 47.0 47.0 47.0 Dialdimine A-1
4.7 A-2
4.7 A-9
4.7 Diamine ^b 1,0 1,0 1,0 Thickener 10.0 10.0 10.0 Amine catalyst ^c 0.1 0.1 0.1 Acid catalyst ^d 0.2 0.2 0.2 Water 0.139 0.153 0.145 Molecular sieves ^e 2.0 2.0 2.0 a piece of chalk 35.0 35.0 35.0 Polioksipropilenpolioksietilendiol ^a low monol ^{(Preminol ® S-X5006, Asahi} Glass; OH- number of 28.0 mg KOH / g).
^b 1,3-xylylenediamine.
^c DABCO ^® 33-LV, Air Products.
^d Salicylic acid (5% by weight in dioctyl adipate).
^e Molecular sieves 8 angstroms (Purmol ^® 13, Zeochem Europe).

The bicomponent elastic adhesives thus obtained were applied immediately after mixing both components and were tested for the exposure time before gluing, the curing speed, and also the mechanical properties after curing.

As a measure of the exposure time before gluing, we considered time up to the non-stickiness of the adhesive. This test was carried out similarly to determining the time of formation of the crust, as in example 1.

As a measure of cure speed, cure time was considered. To determine the cure time of the cured adhesive, the Shore A-hardness (measured according to DIN 53505) was measured in relative segments and the adhesive was evaluated as fully cured, when the Shore A-hardness remained practically constant.

To determine the mechanical properties after curing, Shore A-hardness, tensile strength, elongation, and E-modulus were measured. A-Shore hardness was determined according to DIN 53505 in samples cured for 4 days under normal conditions. To test other mechanical properties, the adhesive was pressed directly after pressing to a film about 2 mm thick, the film was cured for 4 days under normal conditions and tested in accordance with DIN EN 53504, tensile strength, elongation and E-module (drawing speed: 200 mm / min).

All adhesives cured completely without bubbles.

The test results are shown in table 10.

Table 10 Properties of two-component elastic adhesives of examples 22, 23 and comparative example 24 Example 22 23 24 (Comparative) Time up to non-stickiness (min) 120 105 45 Cure time (hour) 12 eleven 9 A-Shore Hardness 47 46 49 Tensile strength (MPa) 2,4 2.0 2,3 Relative extension (%) 600 600 610 E-module at 0.5-5% elongation (MPa) 2,4 2.1 2,3

It can be seen from the examples that the compositions according to the invention at a comparable cure speed are characterized by a clearly longer exposure time before gluing than the compositions from comparative examples. In the corresponding other specific properties, such as storage stability, consumer properties, mechanical properties after curing or stickiness, no significant differences were found between the compositions according to the invention and the compositions from comparative examples.

Claims (23)

1. Curable composition consisting of two components K1 and K2 containing
a) at least one aromatic polyisocyanate P containing isocyanate groups, and
b) at least one dialdimine A of the formula (I)

where X represents the residue of diamine DA with two primary amino groups after the separation of these two amino groups; and
Y ¹ and Y ² independently from each other represent a monovalent hydrocarbon residue with 1-12 C atoms; and
Y ³ represents a monovalent hydrocarbon residue, which possibly has at least one heteroatom, in particular oxygen in the form of an ether, carbonyl or ester group;
c) compounds reactive with isocyanate groups, in particular water, and / or polyols and / or polyamines;
provided that at least one of the two primary amino groups of diamine DA is an aliphatic amino group and that the two primary amino groups of diamine DA are different from each other or
the number of hydrogen atoms of carbon atoms (C _α ) located in the α-position to the corresponding amino group by at least one, or
the number of hydrogen atoms of carbon atoms (C _β ) located in the β-position to the corresponding amino group by at least two. 2. The composition according to claim 1, characterized in that the diamine DA is selected from the group consisting of 1,2-propanediamine, 2-methyl-1,2-propanediamine, 1,3-butanediamine, 1,3-diaminopentane (DAMP) , 4-aminoethylaniline, 4-aminomethylaniline, 4 - [(4-aminocyclohexyl) methyl] aniline, 2-aminoethylaniline, 2-aminomethylaniline, 2 - [(4-aminocyclohexyl) methyl] aniline, 4 - [(2-aminocyclohexyl) methyl ] aniline; 2,2,4-trimethylhexamethylenediamine (TMD), 1,5-diamino-2-butyl-2-ethylpentane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophorone diamine = IPDA) and 1.4 diamino-2,2,6-trimethylcyclohexane (TMCDA). 3. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups is an aromatic polyurethane polymer PUP containing isocyanate groups, in particular obtained by reacting at least one polyol with at least at least one aromatic polyisocyanate. 4. The composition according to claim 3, characterized in that the polyisocyanate used to produce the aromatic polyurethane polymer PUP containing isocyanate groups is an aromatic polyisocyanate selected from the group consisting of 2,4- and 2,6-toluene diisocyanates and any mixtures thereof isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanates and any mixtures of these isomers (MDI), mixtures of MDI and MDI homologues (polymeric MDI or PMDI), 1,3- and 1,4-phenylenediisocyanates, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanato diphenyl (TODI), dianisidinediisocyanate (DADI), oligomers and polymers of the above isocyanates, as well as any mixtures of the above isocyanates. 5. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups is an aromatic polyisocyanate PI selected from the group consisting of 2,4- and 2,6-toluene diisocyanates and any mixtures of these isomers (TDI ), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanates and any mixtures of these isomers (MDI), mixtures of MDI and homologs of MDI (polymeric MDI or PMDI), 1,3- and 1,4 -phenylenediisocyanates, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisidinediisocyanate (DADI ), oligome s and polymers of the aforementioned isocyanates, and also any mixtures of the above isocyanates. 6. The composition according to claim 1 or 2, characterized in that the diamine DA is selected from the group consisting of 1,3-diaminopentane (DAMP), 1,5-diamino-2-butyl-2-ethylpentane, 2,2,4 trimethylhexamethylenediamine (TMD) and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophorone diamine = IPDA). 7. The composition according to claim 1 or 2, characterized in that Y ³ means a residue of formula (II) or (III), preferably a residue of formula (III)

where R ³ represents a hydrogen atom or an alkyl group, in particular with 1-12 C atoms, preferably a hydrogen atom;
R ⁴ represents a hydrocarbon residue with 1-30, in particular 11-30, C atoms, which possibly contains a heteroatom; and
R ⁵ either represents a hydrogen atom or a linear or branched alkyl residue with 1-30, in particular 11-30, C atoms, possibly with a cyclic moiety and possibly with at least one heteroatom, or is a mono- or polyunsaturated, a linear or branched hydrocarbon residue with 5-30 C atoms, or represents a possibly substituted aromatic or heteroaromatic 5- or 6-membered ring. 8. The composition according to claim 1 or 2, characterized in that each of Y ¹ and Y ² represent a methyl group. 9. The composition according to claim 1 or 2, characterized in that the polyisocyanate P is present in an amount of 5-95 wt.%, Preferably in an amount of 10-90 wt.%, Based on the entire composition. 10. The composition according to claim 1 or 2, characterized in that the dialdimine A of the formula (I) is present in the composition in such an amount that the ratio of the number of aldimine groups to the number of isocyanate groups is 0.1-1.1, preferably 0.15- 1.0, particularly preferably 0.2-0.9. 11. The composition according to claim 1 or 2, characterized in that it contains at least one catalyst, in particular a catalyst that accelerates the hydrolysis of aldimines, preferably an acid. 12. The composition according to claim 1 or 2, characterized in that said aromatic polyisocyanate P containing isocyanate groups and dialdimine A of formula (I) are part of component K1 and component K2 contains compounds reactive with isocyanate groups, in in particular water and / or polyols and / or polyamines. 13. The composition according to claim 1 or 2, characterized in that the aromatic polyisocyanate P containing isocyanate groups is part of component K1 and component K2 contains dialdimine A of formula (I), as well as compounds reactive with respect to isocyanate groups, in particular water and / or polyols and / or polyamines. 14. The cured composition obtained by mixing the two components K1 and K2 of the composition according to any one of claims 1, 12 or 13 after its interaction with water. 15. The use of the composition according to any one of claims 1 to 14 as an adhesive, sealant, pouring mass or coating. 16. The use of the composition according to any one of claims 1 to 14 for sealing seams, in particular seams of the construction of ground and underground buildings. 17. A method of bonding a substrate S1 to a substrate S2, comprising the steps of:
i) applying the composition according to any one of claims 1 to 14 on a substrate S1;
ii) contacting the deposited composition with the substrate S2 for the exposure time before bonding the composition;
or
i ') applying the composition according to any one of claims 1 to 14 on a substrate S1 and on a substrate S2;
ii ') contacting the applied compositions with each other during the exposure time before gluing the composition;
moreover, the substrate S2 consists of the same or different material compared to the substrate S1. 18. The method of compaction, including stage
I '') applying the composition according to any one of claims 1 to 13 between the substrate S1 and the substrate S2, so that the composition is in contact with the substrate S1 and the substrate S2;
moreover, the substrate S2 consists of the same or different material compared to the substrate S1. 19. A method of coating a substrate S1, comprising the step of
I ''') applying the composition according to any one of claims 1 to 13 on the substrate S1 during the exposure time of the composition. 20. The method according to any one of paragraphs.17-19, characterized in that the substrate S1 and / or substrate S2 before gluing, or sealing, or coating is pre-treated, in particular, with a primer layer or an adhesion promoter composition. 21. The method according to 17, characterized in that the substrate S1 and / or substrate S2 is an inorganic substrate, such as glass, glass ceramics, concrete, building cement, brick, tile, gypsum or natural stone, such as granite or marble; a metal or alloy, such as aluminum, steel, non-ferrous metal, galvanized metal; an organic substrate such as wood; a polymer such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy resin, polyurethane (PUR); a coated substrate, such as a metal or powder coated alloy; or paint or varnish, in particular automotive topcoat. 22. A product that is glued, sealed or coated by the method according to any one of paragraphs.17-21. 23. The product according to item 22, characterized in that it is a structure, in particular a ground or underground structure, or an industrial product, or a consumer product, such as, in particular, a window, a household machine, or a vehicle, in particular a water or land vehicle, preferably a car, bus, truck, train or ship, or a structural member of the vehicle.