EP1697385A2

EP1697385A2 - Aldiminoalkylsilanes

Info

Publication number: EP1697385A2
Application number: EP04804927A
Authority: EP
Inventors: Urs Burckhardt
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2003-12-18
Filing date: 2004-12-17
Publication date: 2006-09-06
Also published as: CN102516286A; CN1894263B; BRPI0417741A; MXPA06006852A; WO2005058921A3; US20080138522A1; AU2004298455A1; CA2549820A1; WO2005058921A2; JP4861188B2; JP2007516264A; CN1894263A; EP1544204A1; US7906673B2

Abstract

The invention relates to aldiminoalkylsilanes ALS, which can be produced by reacting at least one aminoalkylsilane AS of formula (I) with at least one aldehyde ALD of formula (II). The invention also relates to a method for the production thereof, the use of said aldiminoalkylsilanes in compositions containing compounds which can react to amines, in particular polyurethane compositions, in addition to adhesive compositions. The aldiminoalkylsilanes ALS and the compositions containing the aldiminoalkylsilanes have a major advantage in that they have a low-odour or are odour-less and have a long storage life.

Description

aldiminoalkylsilanes

TECHNICAL FIELD The invention relates to novel aldiminoalkylsilanes obtainable from the reaction of aminoalkylsilanes with special aldehydes in a suitable manner, suitable as an adhesion promoter in polymer compositions, in particular moisture-curing polyurethane compositions, and as a constituent of adhesion promoter compositions. The aldiminoalkylsilanes are stable in storage with the exclusion of moisture together with polyurethane compositions containing isocyanate groups and when used they cause little or no odor.

PRIOR ART It is known that organoalkoxysilanes are suitable as

Adhesion promoter between polymer compositions such as polyurethane compositions and substrates such as glass, concrete or various metals, described for example in "Silanes and Other Coupling Agents", ed. KL Mittal, VSP 1992, page 21ff. They can be used, for example, as primers, as additives in Primers, for the pretreatment of fillers or as additives in adhesives, sealants and coatings, whereby they can improve their adhesion to various substrates. Aminoalkylsilanes are of particular interest as adhesion promoters. Their amino group can form a chemical bond with polymer compositions such as polyurethane compositions, for example by Reaction with an isocyanate group to increase the adhesion of polymer compositions to substrates such as glass Aminoalkylsilanes are often used, these being usually applied to the substrate in dilute form, as a primer or as a primer, before the polyurethane composition is applied thereon. In order to save this additional step in substrate pretreatment, it would be desirable to incorporate aminoalkylsilanes as adhesion promoters directly into the polymer composition. In the case of moisture-curing polyurethane compositions which contain free isocyanate groups, however, this is problematic since the aminoalkylsilanes react directly with the isocyanate groups, thereby largely losing their action as adhesion promoters and leading to inadequate storage stability of the compositions. In order to be able to use the good properties of aminoalkylsilanes as adhesion promoters in moisture-curing polyurethane compositions, it would therefore be advantageous to incorporate the aminoalkylsilanes into the composition in a form which is initially non-reactive with isocyanate groups. It is known that amines can be converted into a form which is not reactive toward isocyanate groups by converting them to aldimines. After contact with water, they hydrolyze back to amines with the release of aldehydes. US 2,942,019 and US 3,681,420 describe iminoalkylsilanes, prepared from aminoalkylsilanes and aldehydes (leads to aldiminoalkylsilanes) or ketones (leads to ketiminoalkylsilanes). EP 0 164 520 discloses isocyanate group-containing polyurethane preparations which contain an adhesion promoter in the form of organoalkoxysilanes containing aldimino or ketimino groups. These iminoalkylsilanes known from the prior art have two difficulties. On the one hand, their storage stability together with moisture-curing polyurethane compositions, in particular those which contain reactive aromatic isocyanate groups, is insufficient, that is to say that the viscosity of the polyurethane composition rises sharply during storage, caused by the presence of the iminoalkylsilane. On the other hand, many of the iminoalkylsilanes mentioned release aldehydes or ketones during their hydrolysis, which one have an intense, unpleasant smell, which is unpleasant for people who have close contact with such substances and can cause headaches, nausea or other health problems. Therefore, odor-intensive aldehydes or ketones, or the iminoalkylsilanes derived from them, can only be used to a limited extent, since good ventilation must always be ensured or respiratory protection is required. They are therefore not suitable as adhesion promoters in compositions which should harden as far as possible without odor formation, for example those which are used in the interior of closed rooms. US 5,134,234 also describes iminoalkylsilanes. They are produced in a complex, multi-stage process, which is based on isocyanatoalkylsilanes which are difficult to obtain, expensive and toxicologically unsafe. EP 0 985 693 mentions iminoalkylsilanes which are stable in storage together with special aliphatic isocyanates which contain isocyanate groups bonded to a tertiary or secondary carbon atom and thus have a low reactivity. However, together with the much more reactive aromatic isocyanate groups, most of the iminoalkylsilanes mentioned are not stable on storage. The iminoalkylsilanes mentioned release odor-intensive aldehydes or ketones during their hydrolysis and are therefore not suitable for many applications. Furthermore, in the preparation of the iminoalkylsilanes described in the patent, the water formed is not removed, which inevitably leads to a high proportion of condensation products in the form of organosiloxanes. Experience has shown that the aldiminoalkylsilanes should not be excessively precondensed to be effective adhesion promoters.

Aldiminoalkylsilanes, which can be produced in good quality in a simple process, are stable in storage with the exclusion of moisture together with polyurethane compositions containing isocyanate groups, especially also those with reactive aromatic isocyanate groups, and So far, which cause no or at least a slight odor during their hydrolysis are not known.

SUMMARY OF THE INVENTION The object of the present invention is to provide novel aldiminoalkylsilanes which can be produced in good quality in a simple process, are stable in storage with the exclusion of moisture together with polyurethane compositions containing isocyanate groups, especially those with reactive aromatic isocyanate groups, and in their hydrolysis cause little or no odor. Such aldiminoalkylsilanes can improve the adhesion of polymer compositions to various substrates. They are suitable, for example, as an additive to moisture-curing polyurethane compositions or as a component of adhesion promoter compositions.

It has been found that aldiminoalkylsilanes which meet the conditions mentioned can be obtained in a simple manner and in good quality by reacting at least one aminoalkylsilane with at least one special aliphatic aldehyde which, in the position relative to the aldehyde carbonyl group, has a tertiary carbon atom which is called a carbon atom that has no bond to a hydrogen atom. Good quality aldiminoalkylsilanes are those which are only present to a small extent in condensed form (as organosiloxanes). The difficulty in producing good quality aldiminoalkylsilanes is that when the aldimino group is formed from an amino and an aldehyde group, one mole of water is released per mole of amino group. This is problematic in that the silane groups present can be undesirably hydrolyzed by the water formed and condensation products can form in the form of organosiloxanes. If this occurs, poor quality aldiminoalkylsilanes are obtained which have no or insufficient action as adhesion promoters, are highly viscous or contain inhomogeneous components in the form of suspended condensation products. It has been found that aldiminoalkylsilanes of excellent quality are obtained if the water formed in the reaction of the aminoalkylsilane with the aldehyde is suitably removed from the reaction mixture before it can hydrolyze the silane group. The aldiminoalkylsilanes according to the invention, together with moisture-curing polyurethane compositions, are stable in storage for several weeks and months. This is especially true when the polyurethane compositions have reactive aromatic isocyanate groups, such as those found in 4,4'-diphenylmethane diisocyanate (MDI) or 2,4- and 2,6-tolylene diisocyanate (TDI). In contrast, most of the prior art iminoalkylsilanes together with polyurethane compositions containing isocyanate groups, especially those with reactive aromatic isocyanate groups, are only stable in storage for a short time or not at all and lead to a marked to strong increase in the viscosity of the polyurethane composition during storage. Another important aspect of the aldiminoalkylsilanes according to the invention is the fact that before, during and after their use they cause no or at least a slight odor. This is achieved in that the aldehyde used to prepare the aldiminoalkylsilanes, which is released again by hydrolysis when the aldiminoalkylsilanes are used, is low-odor or odorless. Thus, the aldiminoalkylsilanes according to the invention are suitable as an additive to polymer compositions, in particular moisture-curing polyurethane compositions which, before, during and after their curing, should cause no or only a slight odor, as is the case, for example, for seals, bonds or coatings in closed rooms, for example in the Inside of vehicles or buildings. They are also suitable as a component of adhesion promoter compositions, especially those with a long open time. WAYS OF CARRYING OUT THE INVENTION The present invention relates to aldiminoalkylsilanes ALS, which are obtainable from at least one aminoalkylsilane AS according to formula (I) and at least one aldehyde ALD according to formula (II).

R ¹ stands for a linear or branched, optionally cyclic, alkylene group with 1 to 20 C atoms, optionally with aromatic components, and optionally with one or more heteroatoms, in particular nitrogen atoms. R ² stands for an alkyl group with 1 to 5 carbon atoms, preferably for a methyl group or for an ethyl group or for an isopropyl group, in particular for a methyl group or for an ethyl group. R ³ represents an alkyl group with 1 to 8 C atoms, preferably one

Methyl or for an ethyl group, especially for a methyl group. a represents 0, 1 or 2. Y ¹ and Y ² each independently represent an organic radical; or together they form a carbocyclic or heterocyclic ring which has a ring size between 5 and 8, preferably 6, atoms. Y ³ represents either a substituted or unsubstituted alkyl group which has at least one hetero atom; or for a branched or unbranched alkyl or alkylene group with at least 10 C atoms; or for a substituted or unsubstituted aryl or arylalkyl group; OOO or for OR ⁴ or OCR or COR ⁴ or CR ⁴ , where R ^{4 in} turn represents an alkyl, arylalkyl or aryl group with at least 3 C atoms and is in each case substituted or unsubstituted. The prefix "poly" in substance names such as "polyol", "polyisocyanate", "polyamine" or "polyaldimine" indicates in the present document that the substance in question formally contains more than one of the functional groups in its name per molecule In the present document, the term “polymer” refers on the one hand to a collective of chemically uniform macromolecules which differ in terms of degree of polymerization, molar mass and chain length and which was produced by a polyreaction (polymerization, polyaddition, polycondensation). On the other hand, the term “polymer” in this document also encompasses derivatives of such a collective of macromolecules from polyreactions, that is to say compounds which have been obtained from reactions, for example additions or substitutions, of functional groups on given macromolecules and which can be chemically uniform or chemically non-uniform In the present document, the term “polymer composition” denotes a homogeneous or heterogeneous mixture of substances which consists of one or more polymers or contains polymers to a substantial extent. In the present document, the term “polyurethane” encompasses all polymers which are produced by the diisocyanate polyaddition process. This also includes those polymers which are almost or completely free of urethane groups, such as polyether-polyurethanes, polyester-polyurethanes, polyether- Polyureas, polyureas, polyester-polyureas, poly-isocyanurates, polycarbodiimides, etc. In the present document, “organoalkoxysilanes” or “silanes” are understood to mean special organosilicon compounds in which at least one, usually two or three alkoxy groups are directly attached the silicon atom are bound (via a Si-O Bond), and which on the other hand have at least one organic radical bonded directly to the silicon atom (via a Si-C bond). Accordingly, the term “silane group” in the present document designates the silicon-containing group bonded to the organic residue of the organoalkoxysilane. The organoalkoxysilanes, or their silane groups, have the property of hydrolyzing on contact with moisture. Organosilanols, that is to say silicon, form during this - Organic compounds containing one or more silanol groups (Si-OH groups) and, by subsequent condensation reactions, organosiloxanes, that is, organic silicon compounds containing one or more siloxane groups (Si-O-Si groups). Under "aminoalkylsilanes" in This document understood special organoalkoxysilanes whose organic radical bonded directly to the silicon atom carries at least one primary amino group (NH ₂ group). In the present document, “aldiminoalkylsilanes” are understood to mean special organoalkoxysilanes whose organic radical bonded directly to the silicon atom carries at least one aldimino group (CH = N group).

Aldiminoalkylsilanes ALS can be prepared from at least one aminoalkylsilane AS according to formula (I) and at least one aldehyde ALD according to formula (II) by a condensation reaction with the liberation of water. Condensation reactions between amines and aldehydes are well known and described, for example in Houben-Weyl, "Methods of Organic Chemistry", Vol. XI / 2, page 73 ff. In the present case, an aminoalkylsilane is used as the amine. This includes the additional difficulty that the water released during the condensation can lead to hydrolysis of the silane groups. However, this reaction is undesirable and must be largely suppressed in order to maintain a good quality product. Otherwise, condensation products in the form of organosiloxanes form in the present case with the release of water Molecules consisting of two or there are more aldiminoalkylsilanes connected via siloxane groups. This is problematic insofar as these condensation products for building up adhesion to a substrate are only available to a limited extent or no longer at all, and therefore such qualitatively poor aldiminoalkylsilanes largely lose their desired effect as adhesion promoters. It is crucial for the production of an aldiminoalkylsilane ALS of good quality to choose a production method in which the hydrolysis of the silane groups is suppressed as much as possible. To produce an aldiminoalkylsilane ALS, a method is preferred in which the aminoalkylsilane AS is initially introduced and the aldehyde ALD is added dropwise. It is crucial that the water formed is already removed from the reaction mixture during the reaction, for example by immediately removing the water released during the condensation by continuously applying a vacuum, or by removing it by means of a water-absorbing substance such as a suitable molecular sieve becomes. The reaction can be carried out at temperatures from 5 ° C to 250 ° C. However, a reaction temperature in the range of 20-100 ° C. is preferred. It is also possible to prepare an aldiminoalkylsilane ALS by introducing the aldehyde ALD and adding the aminoalkylsilane AS dropwise. In this way, however, experience has shown that aldiminoalkylsilanes of inferior quality, which often have a precipitate, are caused by the excessive formation of condensation products. Such reactions are usually carried out in the presence of a solvent which forms an azeotrope with water, the water being removed from the reaction mixture together with the solvent. However, preference is given to producing the aldiminoalkylsilane ALS using that alcohol which is released during the hydrolysis of the silane groups - methanol when using a methoxysilane, or ethanol when using an ethoxysilane. It was observed that when the aminoalkylsilane AS was introduced into the corresponding alcohol and dropwise addition of the aldehyde ALD with immediate removal of the water, aldiminoalkylsilanes ALS of excellent quality were obtained become. However, it is also possible to obtain good quality aldiminoalkylsilanes ALS by completely dispensing with the use of solvents in their manufacture. The aminoalkylsilane AS is initially introduced and the aldehyde ALD is added dropwise in vacuo. In a further preferred production form, aldiminoalkylsilanes ALS are produced in, or together with, polyaldimines. Either a polyaldimine is first prepared by reacting a polyamine with an aldehyde, in particular an aldehyde ALD of the formula (II), with removal of water and then, in this polyaldimine, an aldiminoalkylsilane ALS by reacting an aminoalkylsilane AS with an aldehyde ALD with removal made by water. Or the aldiminoalkylsilane ALS and the polyaldimine are prepared simultaneously by reacting a mixture of an aminoalkylsilane AS and a polyamine with an aldehyde ALD with removal of water. These reactions are preferably carried out without the use of solvents. The solutions of aldiminoalkylsilanes ALS in polyaldimines obtained in this way are distinguished by very low contents of condensation products and low viscosities. The polyaldimines are prepared from at least one polyamine with primary aliphatic amino groups and at least one aldehyde by a condensation reaction with the liberation of water by means of known processes, described for example in Houben-Weyl, "Methods of Organic Chemistry", vol. XI / 2, page 73 The aldehyde groups of the aldehyde ALD are used in a stoichiometric or stoichiometric excess with respect to the primary amino groups of the aminoalkylsilane AS in the preparation of the aldiminoalkylsilane ALS. In the preparation of an aldiminoalkylsilane ALS, catalysts can optionally also be used, for example acids such as alkylbenzene sulfonic acids, such as alkylbenzenesulfones acids, trifluoroacetic acid, acidic phosphoric acid esters, mineral acids, boron trifluoride complexes or aluminum chloride complexes. It is also possible to clean the aldiminoalkylsilanes ALS after production in an additional step, for example by distillation, and thereby completely separate them from any condensation products that may be present.

Compounds of the formula (I) are suitable as aminoalkylsilane AS for the preparation of an aldiminoalkylsilane ALS.

R ¹ stands for a linear or branched, optionally cyclic, alkylene group with 1 to 20 carbon atoms, optionally with aromatic components, and optionally with one or more heteroatoms, in particular nitrogen atoms. R ² stands for an alkyl group with 1 to 5 carbon atoms, preferably for a methyl group or for an ethyl group or for an isopropyl group, in particular for a methyl group or for an ethyl group. R ³ stands for an alkyl group with 1 to 8 carbon atoms, preferably for a methyl or for an ethyl group, in particular for a methyl group. a stands for 0, 1 or 2. Preferred R ¹ is a methylene, propylene, methyl propylene,

Butylene or dimethylbutylene group, especially a propylene group.

Examples of suitable aminoalkylsilanes AS of the formula (I) which may be mentioned are the following: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane,

3-amino-2-methylpropyl-trimethoxysilane, 4-aminobutyl-trimethoxysilane, 4-amino-butyl-dimethoxymethylsilane, 4-amino-3-methylbutyl-trimethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, 4-amino-3, 3-dimethylbutyldimethoxymethylsilane, 2-aminoethyltrimethoxysilane, 2-aminoethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyldimethoxymethylsilane, Aminomethylmethoxydimethylsilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-dimethoxymethylsilane, 7-amino-4-oxaheptyldimethoxymethylsilane, and their analogues with ethoxy or isopropoxy instead of methoxy groups. Preferred aminoalkylsilanes AS of the formula (I) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyl-triethoxysilane, in particular 3-aminopropyl-trimethoxysilane and 3-aminopropyl-triethoxysilane.

If aldiminoalkylsilanes ALS are to be produced in a mixture with polyaldimines, then commercially available polyamines with primary aliphatic amino groups, such as are used, inter alia, for two-component polyurethanes, are suitable for producing the polyaldimines. Such polyamines formally contain two or more primary amino groups (NH ₂ groups) per molecule which are bonded to an aliphatic, cycloaliphatic or arylaliphatic radical. The following polyamines may be mentioned as examples: ethylenediamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3 and 1, 4-butanediamine, 1,3- and 1,5-pentanediamine, 1,6-hexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,7-heptanediamine, 1,8 - octanediamine, 4-aminomethyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, methyl-bis- (3-aminopropyl) amine, 1,5-diamino-2-methylpentane (MPMD), 1,3-diaminopentane (DAMP), 2,5-dimethyl-1,6-hexamethylene diamine, cycloaliphatic polyamines such as 1,2-, 1,3- and 1 , 4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino) 3,5-dimethylcyclohexyl) methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophoronediamine or IPDA), 2- and 4-methyl-1, 3-diaminocyclohexane and mixtures thereof, 1 , 3- and 1,4-bis (aminomethyl) cyclohθxa n, 1-Cyclohexylamino-3-aminopropane, 2.5 (2.6) bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA, manufactured by Mitsui Chemicals), 3 (4), 8 (9) -Bis (aminomethyl) tricyclo [5.2.1.0 ^{2 &} decan, 1, 4-diamino-2,2,6-tri- methylcyclohexane (TMCDA), 3,9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro- [5.5] undecane, 1,3- and 1,4-xylylenediamine, ether group-containing aliphatic polyamines such as bis - (2-aminoethyl) ether, 4,7-dioxadecane-1, 10-diamine, 4,9-dioxadodecane-1, 12-diamine and higher oligomers thereof, polyoxyalkylene polyamines with theoretically two or three amino groups, available, for example, under the Names Jeffamine ^® (manufactured by Huntsman Chemicals), as well as mixtures of the aforementioned polyamines. Preferred polyamines are 1, 6-hexamethylenediamine, MPMD, DAMP, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 4-aminomethyl-1, 8-octanediamine, IPDA, 1,3- and 1,4 -Xylylenediamine, 1,3- and 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 3 (4) , 8 (9) -bis- (aminomethyl) tricyclo [5.2.1.0 ² - ^6] decane _I 1,2-, 1,3- and 1, 4-diaminocyclohexane, 1,4-diamino-2,2,6 -trimethylcyclohexane, polyoxy alkylene-polyamines having theoretically two or three amino groups, especially Jeffamine ^® EDR-148, Jeffamine ^® D-230, Jeffamine ^® D-400 and Jeffamine ^® T-403, as well as in particular mixtures of two or more of the aforementioned polyamines ,

An aldehyde ALD of the following formula (II) is used to prepare an aldiminoalkylsilane ALS starting from an aminoalkylsilane AS.

Y ¹ and Y ² either independently represent an organic radical; or together they form a carbocyclic or heterocyclic ring, which preferably has a ring size between 5 and 8

6, has atoms. Y ¹ and Y ² are preferably identical and in particular represent a methyl group. Y ³ can represent a substituted or unsubstituted alkyl group which has at least one heteroatom, in particular in the form of an ether oxygen, a carboxyl or an ester group. Y ³ can also stand for a branched or unbranched alkyl or alkylene group with at least 10 C atoms. Furthermore, Y ^{3 can} also represent a substituted or unsubstituted aryl or arylalkyl group. Finally, Y ^{3 can} also be used for a radical of the formula for OR or OOO II ₄ II 4 II 4 ₄

Are O-C-R or C-O-R or C-R, where R in turn represents an alkyl, arylalkyl or aryl group with at least 3 C atoms and is in each case substituted or unsubstituted.

The aldehydes ALD of the formula (II) have the property that they are either low-odor or odorless, and therefore cause little or no odor. A "low-odor" substance and a substance that "causes little odor" is understood to mean without distinction a substance whose smell is only perceptible to a small extent by human individuals, i.e. is smellable, that is, it does not have an intense odor such as formaldehyde, acetaldehyde, isobutyraldehyde, pivalaldehyde or solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and this low odor is not perceived by most human individuals as unpleasant or repulsive. An “odorless” substance is understood to mean a substance which is not smellable for most human individuals and which therefore has no perceptible smell.

Examples of compounds of the formula (II) are: ethers of 2-hydroxy-2-methylpropanal and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; Esters of 2-formyl-2-methyl-propionic acid and alcohols such as propanol, isopropanol, butanol and 2- ethylhexanol; Esters of 2-hydroxy-2-methylpropanal and carboxylic acids such as butyric acid, isobutyric acid and 2-ethylhexanoic acid; and the aldehydes listed below as being particularly suitable.

On the one hand, compounds of the formula (III) are particularly suitable,

where R ^{5 represents} a hydrogen atom or an alkyl or arylalkyl or aryl group and Y ^{4 represents} an alkyl, arylalkyl or aryl group and Y ¹ and Y ^{2 have} the meaning already described. Examples of compounds of the formula (III) which should be mentioned are ethers from β-hydroxyaldehydes, such as those obtained from a crossed aldol reaction from formaldehyde and a second aldehyde, such as 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentane - Carboxaldehyde, cyclohexane carboxaldehyde, 1, 2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde (hydropropaldehyde), diphenylacetaldehyde and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol or fatty alcohols such as 3-methoxy and 3-ethoxy and 3-propoxy and 3-isopropoxy and 3-butoxy, as well as 3- (2-ethylhexoxy) -2,2-dimethylpropanal.

On the other hand, compounds of formula (IV)

wherein Y ¹ , Y ² and R ^{5 have} the meaning already described, and Y ^{5 represents} either a hydrogen atom; or represents an alkyl or arylalkyl or aryl group which optionally has at least one heteroatom, in particular an ether oxygen, optionally contains at least one carboxyl group and optionally contains at least one ester group; or a mono- or polyunsaturated, linear or branched

Represents hydrocarbon chain.

Examples of preferred aldehydes of the formula (IV) are products of an esterification from the already mentioned β-hydroxyaldehydes, such as 3-hydroxypivalaldehyde, 3-hydroxyisobutyraldehyde, 3-hydroxypropionaldehyde, 3-hydroxybutyraldehyde, 3-hydroxyvaleraldehyde, 2-hydroxymethyl-2- methyl-butyr-aldehyde, 2-hydroxymethyl-2-ethyl-butyraldehyde, 2-hydroxymethyl-2-methyl-valeraldehyde, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentane-carbaldehyde, 1-hydroxymethyl-cyclohexane carbaldehyde 1 -Hydroxymethyl-cyclo-hex-3-encarbaldehyde, 2-hydroxymethyl-2-methyl-3-phenyl-propionaldehyde, 3-hydroxy-2-methyl-2-phenyl-propionaldehyde and 3-hydroxy-2,2-diphenyl-propionaldehyde with carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethyl-caproic acid and benzoic acid, and the aldehydes listed below as particularly preferred.

In a particularly preferred embodiment, aldehydes ALD of the formula (IV) are used which are odorless and whose radicals R ⁵ and Y ⁵ are restricted as follows: R ⁵ stands for a hydrogen atom and Y ⁵ stands for a linear or branched alkyl chain with 11 up to 30 carbon atoms, optionally with at least one heteroatom, in particular with at least one ether oxygen; or for a mono- or polyunsaturated, linear or branched hydrocarbon chain with 11 to 30 carbon atoms; or for a radical of the formula (V) or (VI).

In the formulas (V) and (VI), R J6 stands for a, linear or branched or cyclic, alkylene chain with 2 to 16 carbon atoms, optionally with at least one heteroatom, in particular with at least one ether oxygen, or for a simple or polyunsaturated, linear or branched or cyclic hydrocarbon chain with 2 to 16 carbon atoms, and R ⁷ stands for a linear or branched alkyl chain with 1 to 8 carbon atoms, and Y ¹ and Y ² have the meaning already described. The dashed line in formulas (V) and (VI) denotes the connection point. The embodiment of the invention just described makes it possible not only to produce aldiminoalkylsilanes ALS with a low odor formation, but also without any perceptible odor. This is particularly advantageous for applications in the interior of buildings and vehicles.

Examples of the particularly preferred odor-free aldehydes ALD of the formula (IV) which lead to odor-free aldiminoalkylsilanes ALS are esterification products from the β-hydroxyaldehydes already mentioned, such as 3-hydroxy-pivalaldehyde, 3-hydroxy-isobutyraldehyde, 3-hydroxypropanal, 3-hydroxybutyraldehyde , 3-hydroxyvaleraldehyde 2-hydroxymethyl-2-methylbutyraldehyde, 2-hydroxymethyl-2-ethylbutyraldehyde, 2-hydroxymethyl-2-methylvaleraldehyde, 2-hydroxymethyl-2-ethylhexanal, 1-hydroxymethyl cyclopentane carbaldehyde, 1-hydroxymethyl-cyclohexane carbaldehyde 1-hydroxymethyl-cyclohex-3-encarbaldehyde, 2-hydroxymethyl-2-methyl-3-phenyl-propionaldehyde, 3-hydroxy-2-methyl-2-phenyl-propionaldehyde and 3-hydroxy - 2,2-diphenyl-propionaldehyde with carboxylic acids such as lauric acid, tridecanoic acid, Pentadecaπsäure, margaric acid, stearic acid, nonadecanoic, arachidic, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, succinic acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3,6,9-trioxaundecanedioic acid and similar derivatives of polyethylene glycol, technical acids and dehydrogenated ricinols from dehydrogenated ricinole Oils and fats such as rapeseed oil, sunflower oil, linseed oil, lbaumöl, coconut oil, oil palm kernel oil and oil palm oil. Preferred carboxylic acids are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, succinic acid, adipic acid, azelaic acid and sebacic acid and technical mixtures of fatty acids which contain these acids. In a preferred method of producing an aldehyde ALD of the formula

(IV) is a ß-hydroxyaldehyde, for example one of the already mentioned ß-hydroxyaldehydes such as 3-hydroxypivalaldehyde, which can be prepared, for example, from formaldehyde (or paraformaldehyde or 1,3,5-trioxane) and isobutyraldehyde, optionally in situ a carboxylic acid, in particular a long-chain fatty acid, to the corresponding ester, namely either with a carboxylic acid Y ^ COOH to the corresponding carboxylic acid ester of, for example, 3-hydroxypivalaldehyde; and / or with a dicarboxylic acid monoalkyl ester HOOC-R ⁶ -COOR ⁷ to the aldehyde of the formula (IV) with the radical Y ⁵ according to formula (VI); and / or with a dicarboxylic acid HOOC-R ⁶ -COOH to the aldehyde of the formula (IV), in this case a dialdehyde, with the radical Y ⁵ according to formula (V). The formulas (V) and (VI) and Y ⁵ , R ⁶ and R ⁷ have the meaning already described. This esterification can be carried out without the use of solvents according to known Methods are described, for example, in Houben-Weyl, “Methods of Organic Chemistry”, vol. VIII, pages 516-528. Suitable carboxylic acids for esterification with a β-hydroxyaldehyde, for example with 3-hydroxypivalaldehyde, are, for example, the short-chain and long-chain ones already mentioned carboxylic acids.

The reaction of at least one aminoalkylsilane AS according to formula (I) with at least one aldehyde ALD according to formula (II) produces, for example, aldiminoalkylsilanes ALS of the formula (VII).

A dialdehyde can also be used as the aldehyde ALD for producing an aldiminoalkylsilane ALS. If desired, a dialdehyde can be reacted twice with an aminoalkylsilane AS, so that all aldehyde groups are condensed to form aldimino groups. However, it is also possible to use an excess of aldehyde groups in relation to the amino groups, so that some of the aldehyde groups are not reacted. If, for example, an aldehyde ALD according to formula (IV) with Y ⁵ according to formula (V) is used to produce an aldiminoalkylsilane ALS and completely, ie twice, reacted with an aminoalkylsilane AS, compounds as shown in formula (VIII) are formed.

Mixtures of different aminoalkylsilanes AS and / or different aldehydes ALD can also be used to produce an aldiminoalkylsilane ALS. The aldiminoalkylsilane ALS can contain certain proportions of condensation products in the form of organosiloxanes. Even when using optimized production methods that largely suppress the formation of such condensation products, the aldiminoalkylsilanes ALS obtained nevertheless always contain a, albeit small, proportion of condensation products which, however, does not pose any question as to their action as adhesion promoters. As already mentioned, the aldiminoalkylsilane ALS can, if desired, be purified, for example by means of distillation, in order to remove any condensation products. The aldiminoalkylsilanes ALS are stable in storage in the absence of moisture, either alone or in combination with components which are reactive towards amines, such as isocyanates. Upon contact with water, both the aldimino groups and the silane groups hydrolyze. Water can be brought into contact with the aldiminoalkylsilane ALS in the liquid or gaseous state of aggregation or in bound form. In a hydrolysis process, for example, water in the form of atmospheric moisture can act on the aldiminoalkylsilane ALS or on a composition containing the aldiminoalkylsilane ALS. Another example of a hydrolysis process is the mixing of water or a water-containing component or a water-releasing component into a composition containing aldiminoalkylsilane ALS. The water is preferably brought into contact with aldiminoalkylsilane ALS in the gaseous state, particularly preferably in the form of atmospheric moisture. The aldimino groups of the aldiminoalkylsilane ALS react in the

Hydrolysis formally to amino groups, the corresponding aldehyde ALD being released. In the presence of groups reactive towards amines, such as, for example, isocyanate groups, the amino groups continue to react, for example with the formation of urea groups. As a result, the hydrolysis of the aldimino groups proceeds quickly and completely. The released aldehyde ALD is odorless or low-odor. It therefore causes little or no odor in a composition such as an adhesive, sealant or covering. The reaction of components reactive towards amines with the hydrolyzing aldiminoalkylsilane ALS does not necessarily have to take place via the aminoalkylsilane. Reactions with intermediate stages of the hydrolysis of the aldiminoalkylsilane to the aminoalkylsilane are of course also possible. For example, it is conceivable that the hydrolyzing aldiminoalkylsilane in the form of a semiaminal reacts directly with the components reactive towards amines. The silane groups of the aldiminoalkylsilane ALS react in the hydrolysis to organosilanols and, through subsequent condensation reactions, to organosiloxanes. The aldiminoalkylsilanes have the ability to build up strong adhesion to various substrates or to improve the buildup of adhesion of a polymer composition to a substrate. When building up a liability, the silanol groups may be mainly involved, which, instead of exclusively condensing with one another to form organosiloxanes, form a connection with the respective substrate. In order to accelerate the hydrolysis of both the aldimino groups and the silane groups, it can be advantageous to combine the aldiminoalkylsilane ALS with suitable catalysts. Suitable catalysts for the hydrolysis of the aldimino groups are, for example, organic carboxylic acids such as benzoic acid or salicylic acid, an organic carboxylic acid anhydride such as phthalic anhydride or hexahydrophthalic anhydride, a silyl ester of organic carboxylic acids, an organic sulfonic acid such as p-toluenesulfonic acid or 4-dodecyl or an organic benzene sulfonic acid Acid, or mixtures of the aforementioned acids. Suitable catalysts for the hydrolysis of the silane groups are, for example, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate, bismuth-organic compounds or bismuth compliments, or compounds containing amino groups such as, for example, 1,4-diazabicyclo [2.2.2] octane or 2,2'-dimo-holinodiethyl ether. The aldiminoalkylsilanes ALS are suitable, for example, as

Adhesion promoter for polymer compositions such as adhesives, sealants or coatings on various substrates. They can be used either as a constituent of the polymer compositions, in particular of moisture-curing polymer compositions, preferably isocyanate groups and / or polymer compositions containing silane groups, particularly preferably moisture-curing polyurethane compositions. Or they can be used as a component of an adhesion promoter composition, for example in the form of a cleaner, an adhesion promoter solution, a pretreatment agent or a primer, in order to improve the adhesion of a polymer composition on the substrate pretreated with the adhesion promoter composition. Suitable substrates for the use of aldiminoalkylsilanes ALS as adhesion promoters are, for example, inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble; Metals such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyester, epoxies; coated substrates such as powder-coated metals; as well as paints and varnishes, in particular automotive topcoats. Glass, glass ceramic, concrete, natural stone, aluminum and automotive top coats are preferred.

The aldiminoalkylsilanes ALS are particularly suitable as a constituent of polymer compositions which have components which are reactive toward amines, such as, for example, polyurethane compositions containing isocyanate groups, in particular those which contain reactive aromatic isocyanate groups. Such polyurethane compositions, namely as a mixture with aldiminoalkylsilanes ALS, have a shelf life of several months to one year without losing their applicability to lose. In contrast, isocyanate-containing polyurethane compositions, in particular those with reactive aromatic isocyanate groups, which contain aminoalkylsilanes or most of the iminoalkylsilanes according to the prior art, are not stable in storage. For example, ketiminoalkylsilanes are not stable in storage together with polyurethane compositions containing aromatic isocyanate groups. Experience has also shown that aldiminoalkylsilanes, which are reaction products of aminoalkylsilanes and primary or secondary aliphatic aldehydes such as butyraldehyde or isobutyraldehyde, that is to say aldiminoalkylsilanes, which have a CH or a CH _{2 group} in the α-position to the carbon atom of the aldimino group, are likewise not stable in storage in such compositions. The same applies to aldiminoalkylsilanes, which are reaction products of aromatic aldehydes such as, for example, benzaldehyde and aminoalkylsilanes, the primary amino group of which is bonded to a primary carbon atom, such as, for example, 3-aminopropyltrimethoxysilane and most of the commercially available aminoalkylsilanes. The terms “storage stability” and “storage stability” in connection with an isocyanate group-containing polyurethane composition which contains an organoalkoxysilane mean in the present document that the viscosity of this composition during storage with exclusion of moisture for several months to a year or longer , caused by the presence of the organoalkoxysilane, does not increase or increases only slightly, and that the applicability of the composition remains after storage.

The aldiminoalkylsilanes ALS have the property of being low-odor or odorless, and also release a low-odor or odor-free aldehyde ALD during their hydrolysis. This makes them particularly well suited for applications that have as little odor pollution as possible

Allow the product before, during or after its use. As already mentioned, the aldiminoalkylsilanes ALS described can be used, for example, as a constituent of moisture-curing polyurethane compositions. Such a polyurethane composition consists of an isocyanate group-containing polyurethane polymer and optionally further components. A suitable polyurethane polymer for such a polyurethane composition is produced from at least one polyisocyanate and at least one polyol. The reaction can be carried out in that the polyol and the polyisocyanate are reacted using customary methods, for example at temperatures from 50 ° C. to 100 ° C., optionally with the use of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups in the Ratio to the hydroxyl groups of the polyol are present in a stoichiometric excess. The excess polyisocyanate is chosen such that, after the reaction of all the hydroxyl groups of the polyol, the content of free isocyanate groups of 0.1 to 15% by weight, preferably 0.5 to 5% by weight, based on the entire polyurethane polymer, remains in the resulting polyurethane polymer. If appropriate, the polyurethane polymer can be prepared with the use of plasticizers, the plasticizers used not containing any groups that are reactive toward isocyanates.

The following commercially available polyols or any mixtures thereof can be used as polyols for the production of such a polyurethane polymer:

Polyoxyalkylene polyols, also called polyether polyols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1, 2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter 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, the iso- mer dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1, 1, 1-1-trimethylol , 1, 1-trimethylolpropane, glycerol, aniline and mixtures of the aforementioned compounds. Both polyoxyalkylene polyols which have a low degree of unsaturation (measured according to ASTM D-2849-69 and stated in milliequivalents of unsaturation per gram of polyol (mEq / g)) can be used, produced, for example, using so-called double metal cyanide complex catalysts (DMC catalysts), as well as polyoxyalkylene polyols with a higher unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH or alkali alcoholates. Polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxypropylene diols or polyoxypropylene triols, are particularly suitable. Particularly suitable are polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation lower than 0.02 meq / g and with a molecular weight in the range from 1,000 to 30,000 g / mol, and polyoxypropylene diols and triols with a molecular weight from 400 to 8,000 g / mol. In this document, “molecular weight” or “molecular weight” always means the molecular weight average M _n . So-called “EO-endcapped” (ethylene oxide-endcapped) polyoxypropylene diols or triols are also particularly suitable. The latter are special polyoxypropylene polyoxyethylene polyols which are obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after completion of the polypropoxylation and thereby having primary hydroxyl groups ,

-Hydroxyfunctionaltθ polybutadienes. -Polyesterpolyole, made for example from di- to 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-trimethylol propane or mixtures of the aforementioned Alcohols with organic dicarboxylic acids or their anhydrides or esters such as, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the above-mentioned acids, such as lactone polyolactone, and polyesterpolyolacton.

Polycarbonate polyols, such as are obtainable by reacting, for example, the abovementioned alcohols - used to construct the polyester polyols - with dialkyl carbonates, diaryl carbonates or phosgene.

-Polyacrylate and polymethacrylate polyols.

These polyols mentioned have an average molecular weight of 250 to 3000 g / mol, in particular 1000 to 3000 g / mol, and an average OH functionality in the range from 1.6 to 3.

In addition to these polyols mentioned, 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, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols , Heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1,1-trimethylolethane, 1,1, 1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols and other high-quality alcohols, low-molecular alkoxylation products of the abovementioned dihydric and polyhydric alcohols and mixtures of the abovementioned alcohols are also used in the production of the polyurethane polymer. Commercial polyisocyanates are used as polyisocyanates for the production of such a polyurethane polymer. The following polyisocyanates, best known in polyurethane chemistry, may be mentioned as examples: 2,4- and 2,6-tolylene diisocyanate (TDI) and any mixtures of these isomers, 4,4'-diphenylmethane diisocyanate (MDI), the positionally isomeric diphenylmethane diisocyanates, 1,3- and 1,4-phenylene diisocyanate, 2,3,5, 6- tetramethyl-1,4-diisocyanatobenzene, 1,6-hexamethylene diisocyanate (HDI), 2- methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexa- methylene diisocyanate (TMDI), 1, 12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1, 4-diisocyanate and any mixtures of these isomers, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= isophorone diiso - cyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI), 1,4-diisocyanato-2,2 _I 6-trimethylcyclohexane (TMCDI), m- and p-xylylene diisocyanate (XDI), 1,3- and 1,4-tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, as well as oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates. MDI, TDI, HDI and IPDI and mixtures thereof are particularly preferred. Most preferred are MDI and TDI and their mixtures.

Further possible constituents of the moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, are polyaldimines, as have already been described in connection with the production of the aldiminoalkylsilanes ALS. Preference is given to polyaldimines which have been prepared by reacting a primary aliphatic polyamine with an aldehyde, in particular an aldehyde ALD of the formula (II), with removal of water. It is particularly advantageous to use such polyaldimines in the form of the solutions of aldiminoalkylsilanes ALS already described in polyaldimines.

As further possible constituents of the moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, the following auxiliaries and additives, which are well known in the polyurethane industry, should be mentioned by way of example: Plasticizers, for example esters of organic carboxylic acids or their anhydrides, phthalates, for example dioctyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, sebacates, organic phosphoric and sulfonic acid esters, polybutenes and other compounds which do not react with isocyanates; Reactive diluents and crosslinkers, for example polyhydric alcohols, polyamines, polyaldimines, polyketimines or aliphatic isocyanates, for example 1,6-hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodeca - Methylene diisocyanate, cyclohexane-1, 3- and 1, 4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4 '- and -4,4'-diphenylmethane diisocyanate, 1, 3- and 1, 4-tetramethylxylylene diisocyanate, isocyanurates of these isocyanates, oligomers and polymers of these isocyanates and their adducts with polyols; inorganic and organic fillers, for example ground or precipitated calcium carbonates, which are optionally coated with stearates, in particular finely divided coated calcium carbonate, carbon black, kaolins, aluminum oxides, silicas and PVC powder or hollow spheres; Fibers, for example made of polyethylene; pigments; Catalysts for the reaction of the isocyanate groups, for example organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dicarboxylate, dibutyltin dichloride, dibutyltin diacetylacetonate, alkyltin thioester, bismuth organic compounds or bismuth complexes, such as, usual catalysts; Catalysts for the hydrolysis of aldimino groups, for example organic carboxylic acids such as benzoic acid or salicylic acid, organic carboxylic acid anhydrides such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic carboxylic acids, organic sulfonic acids such as p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, or other organic or inorganic acids, or mixtures of the aforementioned acids; Rheology modifiers such as thickeners, for example urea compounds, polyamide waxes, bentonites or pyrogenic silicas; further adhesion promoters in addition to those according to the invention Aldiminoalkylsilanes ALS, in particular silanes such as alkylsilanes, epoxyalkylsilanes, vinylsilanes, methacryloxyalkylsilanes and isocyanatoalkylsilanes, and also oligomeric forms of these silanes; Drying agents, for example p-tosyl isocyanate and other reactive isocyanates, orthoformic acid esters, calcium oxide or molecular sieves; Stabilizers against heat, light and UV radiation; flame retardant substances; surface-active substances, for example wetting agents, leveling agents, deaerating agents or defoamers; Fungicides or antifungal substances; as well as other substances commonly used in the polyurethane industry.

Furthermore, the polymer composition can contain polymers which have hydrolyzable silane groups. The following are examples of such silane group-containing polymers: reaction products of isocyanate group-containing polyurethane polymers with isocyanate-reactive organosilanes such as, for example, mercaptoalkylsilanes or aminoalkylsilanes, described, for example, in US Pat Maleic or fumaric acid diesters, described for example in EP 0403 921; Products from hydrosilylation reactions of polymers with terminal double bonds, in particular of allyl-terminated polyoxyalkylene polymers, with alkoxysilanes, described, for example, in US Pat. Nos. 3,971, 751 and 6,207,766; Reaction products of polymers containing active hydrogen atoms, for example in the form of hydroxyl or mercapto groups, with isocyanatoalkylsilanes, described for example in US 4,345,053 and US 5,990,257; Polymers containing 3- (N-silylalkyl) amino propenoate groups, which are reaction products of polymers containing 3-oxopropanoate groups and aminoalkylsilanes, described for example in WO 2004/056905.

Furthermore, the polymer composition can contain polymers which have isocyanate group and silane groups. The content of the aldiminoalkylsilane ALS in the moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, is 0.01-10% by weight, preferably 0.1-5% by weight, in particular 0.25-2.5% by weight.

The described moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, is produced and stored in the absence of moisture and can be in a suitable packaging or arrangement, such as, for example, in a barrel, a bag or a cartridge, for several months up to a year and before use can be kept longer without losing their applicability.

The moisture-curing polymer composition described, in particular the moisture-curing polyurethane composition, is suitable, for example, as a sealant of all kinds, for example for sealing joints in construction, as an adhesive for bonding various substrates, for example for bonding components in the production of automobiles, rail vehicles, ships or other industrial goods, as well as a coating or covering for various articles or variable substrates. Due to its property of being low-odor or odorless and not releasing any odor-intensive substances, it is particularly suitable for adhesive and sealing applications in the interior of closed rooms, for example in the interior of buildings or vehicles, where high demands are made on the materials used in terms of smell, since the occurrence of intense or unpleasant smells would make the use of the finished object difficult or impossible within a reasonable time. Protective paints, seals and protective coatings are preferred as coatings. Among the coverings, floor coverings are particularly preferred. Such coverings are made by typically pouring a reactive composition onto the substrate and leveling it where it cures to form a floor covering. For example, such floor coverings for Offices, living areas, hospitals, schools, warehouses, parking garages and other private or industrial uses. Since many of these applications take place over a large area, even a slight release of substances from the covering can lead to occupational hygiene problems and / or unpleasant odors, even if it is an outdoor application. However, a large part of the flooring is applied indoors, which is why special emphasis is placed on low odor. Suitable substrates for use of the moisture-curing polymer composition described, in particular the moisture-curing polyurethane composition, are, for example, inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble; Metals such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyester, epoxies; coated substrates such as powder-coated metals; as well as paints and varnishes, in particular automotive topcoats. Glass, glass ceramic, concrete, natural stone, aluminum and automotive top coats are preferred. The moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, is at least partially contacted with the surface of the respective substrate. Uniform contacting in the form of an adhesive or sealant, a coating or a covering is preferred, specifically in the areas which require a connection in the form of an adhesive bond or seal or whose surface is to be covered. It may well be necessary that the substrate or the article to be contacted must be subjected to a physical pretreatment prior to contacting, for example by grinding, sandblasting, brushing or the like, or by treatment with cleaners or solvents. However, it is not necessary to apply an adhesion promoter composition, for example in the form of a primer, because of the aldiminoalkylsilane ALS present in the moisture-curing polymer composition, in particular in the moisture-curing polyurethane composition. When the moisture-curing polymer composition, in particular the moisture-curing polyurethane composition, is used, it comes into contact with moisture, whereupon both the isocyanate groups and other water-reactive compounds react with water. If the moisture-curing polymer composition contains polyaldimines, their hydrolysis products react with some of the isocyanate groups before they can react with water. As a result of these and other reactions, the composition hardens. At the same time, the aldiminoalkylsilane ALS contained in the moisture-curing polymer composition hydrolyzes in the manner already described and consequently contributes to an improvement in the adhesion to the substrate. The aldehyde ALD released during the hydrolysis preferably remains essentially completely in the cured polymer composition. Either the water required for curing can come from the air (air humidity), or the polymer composition can be brought into contact with a component containing water, for example by brushing, for example with a smoothing agent, by spraying or by means of immersion processes, or it can be the polymer composition a water-containing component can be added, for example in the form of a water-containing paste, which is mixed in, for example, using a static mixer.

As already mentioned, the aldiminoalkylsilanes ALS according to the invention can also be present as a component of adhesion promoter compositions such as adhesion promoter solutions, pretreatment agents, primers, cleaners or primers. Adhesion promoter compositions of this type contain, in addition to an aldiminoalkylsilane ALS, at least one solvent and, optionally, further components which are customarily used in the coating industry. The following are suitable, for example, as solvents in such an adhesion promoter composition: alcohols such as, for example, methanol, ethanol, isopropanol or butanol; Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, Acetonylacetone, mesityl oxide, and cyclic ketones such as methylcyclohexanone and cyclohexanone; Esters, for example acetates such as ethyl acetate, propyl acetate or butyl acetate, formates, propionates or malonates; Ethers such as ketone ethers, ester ethers and dialkyl ethers such as diisopropyl ether, diethyl ether, dibutyl ether, diethylene glycol diethyl ether and ethylene glycol diethyl ether; aliphatic and aromatic hydrocarbons such as toluene, xylene, heptane, octane and various petroleum fractions such as naphtha, white spirit, petroleum ether or petrol; halogenated hydrocarbons such as methylene chloride; and N-alkylated lactams such as N-methylpyrrolidone. A binder can be present as a further component in the adhesion promoter composition, polyurethane polymers with isocyanate groups and / or silane groups being mentioned in particular; or there may be polyisocyanates, for example tris (4-isocyanatophenyl) methane, tris (4-isocyanatophenyl) thiophosphate, the monomeric MDI, TDI, HDI and IPDI mentioned above, and oligo-, poly- or copolymers of these monomers, such as polymeric HDI, polymeric MDI, available commercially for example as Voranate ^® M 229 (Dow), Desmodur ^® VL R 20 (Bayer), or allophanates, biurets, uretdiones and isocyanurates of these monomers, in particular HDI biurets, such as commercially available as Desmodur ^® N-100 (Bayer), Luxate ^® HDB 9000 (Lyondell / Bayer), HDI trimers, such as commercially available as Desmodur ^® N-3300 (Bayer), Desmodur ^® N-3600 (Bayer), Luxate ^® HT 2000 (Lyondell / Bayer), Desmodur ^® XP 2410, HDI dimers, such as commercially available as Desmodur ^® N-3400 (Bayer), Luxate® ^® HD 100 (Lyondell / Bayer), IPDI trimers, such as commercially available as Desmodur ^® Z 4470 (Bayer), Vestanat ^® T 1890 (Degussa), L uxate ^® IT 1070 (Lyondell / Bayer), HDI and IPDI allophanates, TDI trimers, such as commercially available as Desmodur ^® IL (Bayer), TDI adducts, such as commercially available as Desmodur ^® L (Bayer), TDI - / HDI-polymers such as, for example, commercially available as Desmodur HL ^® (Bayer), Polurene IK ^® D (SAPICI), Hartben AM 29 (Benasedo). As other water-reactive compounds may, for example, polyaldimines polyketimines, oxazolidines, more organoalkoxysilanes such as aminoalkylsilanes be present aminosilanes with secondary amino groups, Epoxyalkylsilane, mercaptoalkylsilanes, vinylsilanes, Ureidoalkylsilane, Methacryloxyalkylsilane, alkylsilanes, isocyanatoalkylsilanes in the adhesion promoter composition, said crosslinker and / or can act as a drying agent. Aminosilanes and / or mercaptoalkylsilanes can also be present in the form of adducts with epoxyalkylsilanes, for example with 3-glycidyloxypropylsilanes. Aminoalkylsilanes AS of the formula (I) are particularly preferred as additional constituents of the adhesion promoter composition. Catalysts for the hydrolysis of both aldimino groups and silane groups can also be used as part of the adhesion promoter composition, for example in the form of organic carboxylic acids such as benzoic acid or salicylic acid, organic carboxylic acid anhydrides such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic carboxylic acids such as organic sulfonic acids, organic sulfones Toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, or other organic or inorganic acids, or mixtures of the aforementioned acids; as well as catalysts for the reaction of isocyanate groups, for example tin compounds such as tin (II) octoate, monobutyltin trichloride, dibutyltin pentichloride, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetate (dibutyltin, dicinodio thio) dioctinate, dibutyltin, dioquinodiothiobutane, dibutyltin, dicutinate, dibutyltin, dibutyltin, iodotin, dibutyltin, dibutyltin, dibutyltin, dibutyltin, (III) neodecanoate, zinc compounds such as zinc (II) octoate, and compounds containing amino groups such as, for example, 2,2'-dimorpholinodiethyl ether, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0 ] undec-7-ene; as well as other catalysts such as titanates and zirconates. Furthermore, customary wetting agents, fillers and additives can be used in primer chemistry. Examples of a non-limiting type include silica, talc, carbon black, organic and inorganic pigments, Stabilizers, bentonites, and chemical and physical drying agents.

The adhesion promoter composition described is produced and stored in the absence of moisture.

The adhesion promoter composition described is used as an adhesive bridge between a substrate and a polymer composition, for example an adhesive, sealant or a coating. In order to obtain a reliable build-up of adhesion to a substrate by means of the adhesion promoter composition, the adhesion promoter composition must have a certain minimum period of time, the so-called “flash-off time”, before the polymer composition is applied. The period between the application of the adhesion promoter composition and the application of the polymer composition, within which a reliable build-up of liability to the substrate is still guaranteed is called "open time" and is usually limited. After exceeding the open time, there is no longer any incomplete or no liability build-up to the substrate. An adhesion promoter composition which contains an aldiminoalkylsilane ALS has a long open time of at least one week. The long open time is made possible by the fact that the aldimino groups of the aldiminoalkylsilanes ALS, in contrast to the amino groups of aminoalkylsilanes AS, do not or only very little react with the carbon dioxide contained in the air, which makes them essential for the reaction with a subsequently applied polymer composition are available longer.

Suitable substrates for an application of the bonding agent composition described are, for example, inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble; Metals such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyester, epoxies; coated substrates such as for example powder coated metals; as well as paints and varnishes, in particular automotive topcoats. Glass, glass ceramic, concrete, natural stone, aluminum and automotive top coats are preferred. It is advantageous if the substrates are pretreated before application. Suitable pretreatment methods are physical and / or chemical in nature and include, for example, grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents. The adhesion promoter composition is applied to the substrate using a brush, felt, cloth or sponge. This order can be done manually or automatically, in particular by means of a robot. Furthermore, several layers of the adhesion promoter composition can also be applied.

The bonding agent composition described is advantageously used as an adhesive bridge for adhesives, sealants or coatings such as floor coverings, in particular moisture-curing adhesives or sealants based on polyurethanes with isocyanate groups and / or silane groups. This bonding agent composition is particularly suitable for applications in which a long open time is required. The adhesion promoter composition reacts on contact with water, for example in the form of atmospheric moisture, the aldiminoalkylsilane ALS hydrolyzing in the manner already described and consequently contributing to an improvement in the adhesion to the substrate, and further water-reactive components present in the adhesion promoter composition, such as compounds containing isocyanate groups or silane groups, also react with water. A polymer composition in the form of an adhesive, sealant, a coating or a covering is applied to the adhesion promoter composition while observing a minimum flash-off time and a maximum open time, the adhesion promoter composition brought into contact with water as an adhesion bridge between the substrate and the cured polymer composition serves. The solvents present in the adhesion promoter composition evaporate, either completely or partially within the flash-off time, or after the polymer composition has been applied through them into the environment.

Examples

Description of the measurement methods The infrared spectra were measured on a FT-IR device 1600 from Perkin-Elmer (horizontal ATR measurement unit with ZnSe crystal); the samples were applied undiluted as films. The absorption bands are given in wave numbers (cm ^-1 ) (measurement window: 4000-650 cm ^-1 ).

¹ H-NMR spectra were measured on a Bruker DPX-300 spectrometer at 300.13 MHz; the chemical shifts δ are given in ppm relative to internal tetramethylsilane (TMS), coupling constants J are given in Hz.

The viscosity was measured at 20 ° C. on a cone-plate viscometer from Haake (PK100 / VT-500).

Preparation and Characterization of Aldiminoalkylsilanes Example 1 (Aldiminoalkylsilane ALS1) 15.0 g of 3-

Aminopropyltrimethoxysilane (Silquest ^® A-1110, Crompton OSi) dissolved in 25 ml of dry Methanoi. About 2 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring, 13.3 g of 2,2-dimethyl-3-acetoxy-propanal were added from a dropping funnel in the course of 10 minutes, the temperature of the reaction mixture not exceeding 30 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C.). This gave a colorless, clear and fruity liquid at room temperature smelling liquid which had an aldimine content, determined as the amine content, of 3.23 mmol NH ₂ / g.

IR: 2972, 2941, 2876sh, 2839, 1740 (C = O), 1668 (C = N), 1471, 1410, 1396, 1374, 1240, 1190, 1082, 1037, 929, 874, 816, 771 sh, 698 ¹ H-NMR (CDCI ₃ , 300 K): δ 7.53 (s, 1H, CH = N), 4.02 (s, 2 H, CH ₂ O), 3.57-3.53 (m, approx. 8 H, CH ₂ Si-OCH ₃ and CH ₂ Si-O-Si-OCH ₃ ), 3.35 (m, 2 H, NCH ₂ ), 2.05 (s, 3 H, CH ₃ CO), 1.69 (m, 2 H, CH ₂ CH ₂ N), 1.10 (s, 6 H, C (CH ₃ ) 2-CH2θ), 0.59 (m, 2 H, CH ₂ Si). Example 2 (Aldiminoalkylsilan ALS2) In a round bottom flask under nitrogen atmosphere, 50.0 g 3-aminopropyl-trimethoxysilane (Silquest ^® A-1110, Crompton OSi) dissolved in 40 ml of dry methanol. About 5 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring, 50.4 g of 2,2-dimethyl-3-isobutyroxy-propanal were added from a dropping funnel over the course of 15 minutes, the temperature of the reaction mixture not exceeding 31 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ^° C.). A colorless, clear and fruity-smelling liquid which had a low viscosity at room temperature and an aldimine content, determined as the amine content, of 2.97 mmol NH ₂ / g was obtained.

IR: 2972, 2937, 2876, 2839, 1735 (C = O), 1668 (C = N), 1470, 1410, 1386, 1365, 1341, 1300, 1257, 1190, 1151, 1074, 996sh, 931, 917sh, 874, 816, 795sh, 763sh, 697. ¹ H-NMR (CDCI ₃ , 300 K): δ 7.54 (s, 1 H, CH = N), 4.02 (s, 2 H, CH ₂ O), 3.61-3.53 (m, approx. 8 H, CH ₂ Si-OCH ₃ and CH ₂ Si-O-Si-OCH ₃ ), 3.37 (m, 2 H, NCH ₂ ), 2.55 (gxσ, J = 7.0, 1 H, CH (CH ₃ ) ₂ ), 1.67 (m, 2 H, CH ₂ CH ₂ N), 1.17-1.11 (m, 12 H, CH (CH ₃ ) ₂ and C (CH ₃ ) ₂ -CH ₂ O), 0.60 (m, 2 H, CH ₂ Si). Example 3 (Aldiminoalkylsilane ALS3) 52.7 g of formaldehyde (37% in water, methanol-free), 46.8 g of isobutyraldehyde, 100.0 g of lauric acid and 0.5 g of 4-toluenesulfonic acid were placed in a round-bottom flask with a reflux condenser and water separator (Dean Stark) weighed out and placed under a nitrogen atmosphere. The mixture was heated in an oil bath with vigorous stirring, whereupon water began to separate out. After four hours, the apparatus was evacuated in a water jet vacuum. A total of around 48 ml of distillate collected in the separator. The reaction mixture (aldehyde) was cooled to room temperature. In a second round bottom flask 78.8 g 3-aminopropyl-trimethoxysilane (Silquest ^® A-1110, Crompton OSi) were dissolved in 80 g of anhydrous methanol under nitrogen atmosphere. About 10 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring, the aldehyde described above was added dropwise over a steel cannula over 30 minutes, the temperature of the reaction mixture not exceeding 32 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C.). An amber-colored, clear and completely odor-free oil which had a low viscosity at room temperature and an aldimine content, determined as the amine content, of 2.10 mmol NH ₂ / g was obtained.

IR: 2950sh, 2923, 2852, 1737 (C = O), 1668 (C = N), 1466, 1416, 1394, 1374, 1343, 1301, 1248, 1188, 1156, 1085, 1036sh, 930, 873, 818, 785sh, 721, 698. ¹ H-NMR (CDCI ₃ , 300 K): δ 7.53 (s, 1H, CH = N), 4.02 (s, 2 H, CH ₂ O), 3.56-3.53 (m, approx. 8 H, CH ₂ Si-OCH ₃ and CH ₂ Si-O-Si-OCH ₃ ), 3.37 (m, 2 H, NCH ₂ ), 2.30 (t, J = 7.5, 2 H, CH ₂ CO), 1.62 (m, 4 H, CH ₂ CH ₂ N and CH ₂ CH ₂ CO), 1.26-1.23 (m, 16 H, CH ₃ - (CH ₂ ) ₈ -CH ₂ CH ₂ CO), 1.10 (s, 6 H , C (CH ₃ ) 2-CH ₂ O), 0.88 ("f, 3 H, J * 6.6, CH ₃ - (CH ₂ ) ιo-CO), 0.59 (m, 2 H, CH ₂ Si). Example 4 (Aldiminoalkylsilan ALS) In a round bottom flask under nitrogen atmosphere, 30.0 g (3,3-dimethyl-4-amino) butyl-trimethoxysilane (Silquest ^® A-1637, Crompton OSi) dissolved in 30 ml of dry methanol. About 5 g of activated 4A molecular sieve were added and the flask was placed in a water bath. With vigorous stirring, 24.5 g of 2,2-dimethyl-3-isobutyroxy-propanal were added from a dropping funnel over the course of 15 minutes, the temperature of the reaction mixture not exceeding 28 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C). A colorless, clear and fruity-smelling liquid which had a low viscosity at room temperature and an aldimine content, determined as the amine content, of 2.97 mmol NH ₂ / g was obtained.

IR: 2964, 2837, 1735 (C = O), 1670 (C = N), 1470, 1385, 1364, 1340, 1190, 1151, 1081, 1032, 992, 936, 887, 824, 788, 759, 677.

Example 5 (Aldiminoalkylsilane ALSS) 14.3 g of 2,2-dimethyl-3-isobutyroxy-propanal were dissolved in 20 ml of dry ethanol in a round-bottom flask under a nitrogen atmosphere. About 2 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring from a dropping funnel within 15 minutes 20.0 g of N- (2-aminoethyl) -3-aminopropyl triethoxysilane (Silquest ^® Y-11763, Crompton OSi) was added, keeping the temperature of the reaction mixture 28 ° C is not exceeded. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ^° C.). A colorless, clear and fruity-smelling oil was obtained which was thin at room temperature and had an aldimine content, determined as the amine content, of 4.33 mmol NH ₂ / g. IR: 3337 (NH), 2972, 2929, 2881, 2840sh, 2804sh, 1732 (C = O), 1667 (C = N), 1470, 1408sh, 1389, 1365, 1344, 1305, 1260, 1192, 1156, 1097 , 1074, 995, 954, 898, 789, 774, 690.

Example 6 (aldiminoalkylsilane ALS6) 10.8 g of formaldehyde (37% in water, free of methanol), 9.6 g of isobutyraldehyde, 20.6 g of lauric acid and 0.1 g of 4-toluenesulfonic acid were weighed into a round-bottom flask with a reflux condenser and water separator (Dean Stark) and placed under a nitrogen atmosphere. The mixture was heated in an oil bath with vigorous stirring, whereupon water began to separate out. After four hours, the apparatus was evacuated in a water jet vacuum. A total of around 9.5 ml of distillate collected in the separator. The reaction mixture (aldehyde) was cooled to room temperature. In a second round bottom flask (OSi Silquest Crompton ^® Y-11763,) under nitrogen atmosphere, 22.9 g of N- (2-aminoethyl) -3-aminopropyl triethoxysilane dissolved in 20 g of anhydrous ethanol. About 2 g of activated molecular sieve 4A were added and the flask was placed in a water bath. With vigorous stirring, the aldehyde described above was added dropwise over a steel cannula within 15 minutes, the temperature of the reaction mixture not exceeding 26 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C.). A brown-orange, clear and odorless oil which was viscous at room temperature and had an aldimine content, determined as the amine content, of 3.21 mmol NH ₂ / g was obtained. IR: 3337 (NH), 2951sh, 2921, 2852, 1737 (C = O), 1650, 1466, 1408, 1392, 1365, 1295, 1165, 1092sh, 1076, 953, 840, 784, 721.

Aldiminoalkylsilan ALS7 (Comparative Example) In a round bottom flask under nitrogen atmosphere, 50.0 g 3-aminopropyl-trimethoxysilane (Silquest ^® A-1110, Crompton OSi) dissolved in 100 ml of dry methanol. About 10 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring, 32.6 g were from a dropping funnel within 30 minutes

Benzaldehyde was added, the temperature of the reaction mixture not exceeding 35 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C.). A colorless, clear and intense liquid which was viscous at room temperature was obtained

Bitter almond-smelling liquid that has an aldimine content, determined as

Amine content of 3.73 mmol NH ₂ / g. IR: 3060, 3026, 2938, 2838, 1704, 1645 (C = N), 1580, 1493, 1451, 1411, 1377,

1343, 1310, 1250, 1189, 1076, 916, 881, 814, 753, 692.

Aldiminoalkylsilan than 8 (Comparative Example) In a round bottom flask under nitrogen atmosphere, 50.0 g 3-aminopropyl-trimethoxysilane (Silquest ^® A-1110, Crompton OSi) dissolved in 100 ml of dry methanol. About 10 g of activated molecular sieve 4Ä were added and the flask was placed in a water bath. With vigorous stirring, 32.6 g were from a dropping funnel within 45 minutes Isobutyraldehyde was added, the temperature of the reaction mixture not exceeding 35 ° C. The molecular sieve was then filtered off and the volatile constituents were removed in vacuo (10 mbar, 70 ° C.). A colorless, clear and pungent-smelling liquid which had a low viscosity at room temperature and an aldimine content, determined as the amine content, of 4.49 mmol NH ₂ / g was obtained.

IR: 2962, 2936, 2871, 2838, 1735, 1670 (C = N), 1466, 1410, 1386, 1366, 1343, 1302, 1249, 1192, 1082, 952, 872, 814, 695. Example 7 (aldiminoalkylsilane ALS3 in polyaldimine) into a round bottom flask, 10.0 g of alpha, omega-polyoxypropylene diamine (Jeffamine ^® D-230, Huntsman; amine content = 8.29 mmol NH ₂ / g) and 2.8 g of 3-aminopropyl-trimethoxysilane (Silquest ^® a-1110, OSi Crompton) weighed and placed under a nitrogen atmosphere. The flask was placed in the water bath. With vigorous stirring, 30.5 g of freshly distilled 2,2-dimethyl-3-lauroyloxypropanal were added from a dropping funnel over the course of 20 minutes, the temperature of the reaction mixture not exceeding 32 ° C. The volatile constituents were then removed in vacuo (10 mbar, 70 ° C.). A colorless, clear and almost odorless liquid which had a low viscosity at room temperature and an aldimine content, determined as the amine content, of 2.37 mmol NH ₂ / g was obtained.

Analysis by liquid chromatography showed a very low content of condensation products. IR: 2957, 2922, 2852, 1737 (C = O), 1666 (C = N), 1466, 1418, 1374, 1343, 1249, 1156, 1107, 1020, 930, 873, 822, 722.

Production and testing of moisture-curing polyurethane compositions containing aldiminoalkylsilanes Examples 8 to 20 Approx. 50 g of polyurethane polymer PP1, the production of which is described below, were placed in a polypropylene cup with screw cap. weighed and placed under dry nitrogen. In each case 1.0% by weight (based on the polyurethane polymer PP1) of the aldiminoalkylsilanes listed in Table 1 and, if listed in Table 1, further additives were added and homogeneously mixed in using a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc.). To determine the storage stability, the polyurethane compositions were immediately filled into internally coated aluminum tubes, sealed airtight and stored in the oven at 60 ° C. The viscosity of the polyurethane compositions was measured a first time after 12 hours and a second time after 7 days of storage. The storage stability results from the ratio of the two viscosity measurements (relative increase in the viscosity of the sample stored for 7 days compared to the viscosity of the sample stored for 12 hours). The results are shown in Table 2. To test the adhesion, the polyurethane compositions of Examples 8 to 20 described above were freshly prepared again and stored in the tube at room temperature (no oven storage). The procedure for each example was as follows: A glass plate (float glass; Rocholl company, Schönbrunn, Germany) measuring 10 x 15 cm was placed on the air side (test with UV light, wavelength 254 nm) on the long side with spacer tape J (karochemistry ) stuck that three glass sheets of 1.5 x 15 cm were obtained. The sheets were wiped three times each with a hygienic wipe moistened with acetone. After a flash-off time of 5 minutes, the polyurethane composition from the tube was applied to the glass sheets in a layer thickness of 2 to 3 mm, taking care that it did not flow out over the glass edge. The glass plate was stored flat in a standard climate (23 ± 1 ° C, 50 ± 5% relative humidity) for 7 days, the polyurethane composition curing. The first track was then checked for liability. The glass plate was then stored in water at room temperature for 7 days, allowed to dry and the second web checked for adhesion. The glass plate was then stored in cataplasma (70 ° C., 100% atmospheric humidity) for 7 days and the third web was checked for adhesion. The adhesion test was carried out as follows: The web of the cured polyurethane composition ("bead") was cut at one end just above the glass surface (adhesive surface). The cut end of the bead was held by hand and then carefully and slowly, peeling in the direction of the other end of the caterpillar, pulled from the glass surface If the adhesion was so strong that the end of the caterpillar was in danger of being torn off when pulling, a cut was made perpendicular to the direction of the caterpillar pulling down to the bare glass surface and the caterpillar was detached a bit If necessary, cuts were repeated at a distance of 2 to 3 mm during further pulling in. In this way, the entire bead was pulled or cut from the glass sheet. The adhesive properties were assessed on the basis of the cured polyurethane composition remaining on the surface after the bead was pulled off (Cohesion break), and z was by estimating the cohesive portion of the adhesive surface, according to the following scale: 1 = more than 95% cohesive break 2 = 75 - 95% cohesive break 3 = 25 - 75% cohesive break 4 = less than 25% cohesive break 5 = 0% cohesive break (purely adhesive break )

Test results with cohesive failure values of less than 75% are considered insufficient.

The results of the tests are shown in Table 2.

The polyurethane polymer PP1 was produced as follows: 845 g of Polyol ^Acclaim® 4200 N (Bayer; polypropylene oxide diol, OH number

28.5 mg KOH / g) and 115 g 4,4'-methylenediphenyl diisocyanate (MDI;

Desmodur ^® 44 MC L, Bayer) were reacted to give an NCO-terminated polyurethane polymer by a known method at 80 ° C. The The reaction product had a titrimetrically determined free isocyanate group content of 1.96% by weight and a viscosity at 20 ° C. of 37 Pa s. Table 1: Composition of the polyurethane compositions of Examples 8 to 20.

^a based on the polyurethane polymer PP1 ^b dialdimine from 2,2-dimethyl-3-lauroyloxypropanal and 1,3-xylylenediamine ⁰ reference examples without aldiminoalkylsilane ^d comparative examples according to the prior art

Table 2: Storage stability and adhesion to glass of the polyurethane compositions of Examples 8 to 20

^a = (viscosity after 7 d / viscosity after 12 hours - 1) x 100% ^b Reference examples without aldiminoalkylsilane

⁰ Comparative examples according to the prior art

It can be seen from Table 2 that Examples 8 to 16, which contain aldiminoalkylsilanes according to the invention, have both very good storage stability (slight increase in viscosity) and very good adhesions on glass. Comparative Examples 19 and 20, which contain aldiminoalkylsilanes according to the prior art, also have good adhesions on glass, but the storage stability is not given with viscosity increases of well over 100%. Reference examples 17 and 18 without aldiminoalkylsilanes have no adhesion to glass. Preparation and testing of adhesion promoter compositions Examples 21 to 26 1.0% by weight of the aldiminoalkylsilanes according to the invention were dissolved in methanol (ALS1 to ALS4) or ethanol (ALS5 and ALS6) and used as an adhesion promoter composition for improving the adhesion of the

Polyurethane polymer PP1 tested on glass. The procedure was as follows: As already described for Examples 8 to 20, three glass plates were glued with spacer tape for each example. Each of the three glass sheets per plate was first wiped three times with a hygienic wipe moistened with acetone and then wiped once with the hygienic wipe moistened with the respective adhesion promoter composition according to Examples 21 to 26. After a flash-off time of 15 minutes (1st glass plate) or an open time of 8 hours (2nd glass plate) and 7 days (3rd glass plate), the polyurethane polymer PP1 (= Example 17, reference without aldiminoalkylsilane) was applied, stored and tested in each case and assessed as already described for Examples 8 to 20. The results of these tests are shown in Table 3.

Table 3: Adhesion to glass of the polyurethane polymer PP1 (= Example 17, Ref.), Treated with the adhesion promoter compositions according to Examples 21 to 26, depending on the flash-off time or open time.

Open time 8 hours / 3rd number: glass plate with open time 7 days ^b % by weight The results in Table 3 show that the polyurethane polymer PP1

(= Example 17), which had no adhesion to glass without pretreatment

(see Table 2), after pretreatment with the inventive

Aldiminoalkylsilanen ALS1 to ALS6 has significantly improved adhesions, both with a flash-off time of 15 minutes and at one

Open time of 8 hours or 7 days. Production and Testing of Moisture-Curing Polyurethane Compositions as Adhesives Examples 27 to 31 Examples 27 to 31 demonstrate the production of moisture-curing polyurethane compositions and their use as adhesives on glass.

Preparation of the base material PUR1: In a vacuum mixer, 1750 g of polyurethane polymer PP2, 500 g polyurethane polymer PP3, 800 g of carbon black, 800 g caiciniertes kaolin, 240 g of diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF), 900 g urea thickeners and 10 g p-Tolylsulfonyl isocyanate (additive Tl ^® , Bayer) processed to form a bulb-free, homogeneous paste with exclusion of moisture, this immediately filled into internally coated aluminum cartridges and sealed airtight.

The polyurethane polymer PP2 was prepared as follows: 1,290 g of polyol Acclaim ^® 4200 N (polypropylene oxide diol having an OH number of 28.5 mg KOH / g; Bayer), 2580 g of polyol Caradol ^® MD34-02 (polypropylene oxide-polyethylene triol, OH number 35.0 mg KOH / g; Shell), 630 g of 4,4'-methylene diphenyl diisocyanate (MDI; Desmodur ^® 44 MC L, Bayer) and 500 g

Diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF) were according to the known

Process at 80 ° C to an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined free isocyanate group content of 2.07% by weight.

The polyurethane polymer PP3 was prepared as follows: 590 g of polyol Acclaim ^® 4200 N (polypropylene oxide diol having an OH number of 28.5 mg KOH / g; Bayer), 1180 g of polyol Caradol ^® MD34-02 (polypropylene oxide-polyethylene triol, OH number 35.0 mg KOH / g; Shell) and 230 g

Isophorone diisocyanate (IPDI; Vestanat ^® IPDI, Degussa) were terminated NCO according to a known method at 80 ° C to a Implemented polyurethane polymers. The reaction product had a titrimetrically determined free isocyanate group content of 2.12% by weight. The urea-thickener was prepared as follows: In a vacuum mixer, 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 and gently heated. Then 270 g of monobutylamine were slowly added dropwise with vigorous stirring. The resulting paste was further stirred under vacuum and cooling for one hour.

Production of the polyurethane compositions: 300 g of the above-described basic mass PUR1 with the additives listed in Table 4 were added in a vacuum mixer

Exclusion of moisture processed into a lump-free, homogeneous paste, this immediately filled into internally coated aluminum cartridges and sealed airtight.

Table 4: Composition of Examples 27 to 31.

^a Reference examples without aldiminoalkylsilane

° di-n-butyltin dichloride (1.8% by weight in DIDP) ^c dialdimine from 2,2-dimethyl-3-isobutyroxy-propanal and 1,3-xylylenediamine ^d salicylic acid (5% by weight in dioctyl adipate) The freshly prepared polyurethane compositions of Examples 27 to 31 were then applied to a cleaned glass plate. The procedure for each of the examples was as follows: A glass plate (float glass; Rocholl company, Schönbrunn, Germany) measuring 10 x 15 cm was three times on the air side (test with UV light, wavelength 254 nm) with one moistened with acetone Hygiene wipe wiped. After a flash-off time of 5 minutes, the polyurethane composition from the cartridge was applied to the glass plate along the long side as beads of about 7 mm in diameter (15 cm bead length; 3 beads), the distance between two beads being at least 20 mm. Immediately after application, the beads were each covered with an LDPE strip on the long side and evenly pressed to a width of approx. 10 mm and a layer thickness of approx. 2 mm using a second glass plate. The glued glass plate was stored for 7 days in a standard atmosphere (23 ± 1 ° C, 50 ± 5% relative air humidity), whereby the polyurethane composition hardened. The first caterpillar was then checked for liability. The glass plate was then stored in water at room temperature for 7 days, left to dry and the second bead checked for adhesion. The glass plate was then stored in cataplasma (70 ° C., 100% atmospheric humidity) for 7 days and the third bead was checked for adhesion. The test for adhesion was carried out as follows: The pressed bead of the cured polyurethane composition was cut at one end just above the glass surface (adhesive surface). The incised end of the caterpillar was held with a pair of pliers and, by slowly rolling up the caterpillar, peeling it in the direction of the other end of the caterpillar from the glass surface. If the adhesion was so strong that the end of the caterpillar threatened to tear off when pulled, a cut was made perpendicular to the direction of the caterpillar pulling down to the bare glass surface and the caterpillar was detached a little. Such cuts were repeated, if necessary, at a distance of 2 to 3 mm when moving on. In this way, the entire caterpillar was pulled or cut from the glass sheet. The The adhesive properties were assessed on the basis of the cured polyurethane composition (cohesive fracture) remaining on the surface after the caterpillar had been removed, namely by estimating the cohesive proportion of the adhesive surface, according to the following scale:

1 = more than 95% cohesive break 2 = 75 - 95% cohesive break 3 = 25 - 75% cohesive break 4 = less than 25% cohesive break 5 = 0% cohesive break (purely adhesive break)

The results of the tests are shown in Table 5.

Table 5: Adhesion to glass of the polyurethane compositions of Examples 27 to 31.

Reference examples without aldiminoalkylsilane

The results of Table 5 show that reference examples 27 and 30 have no adhesion to glass without aldiminoalkylsilanes, while examples 28, 29 and 31 show good adhesion. Examples 32 to 34 Examples 32 to 34 demonstrate the production of moisture-curing polyurethane compositions and their use as adhesives on aluminum.

Preparation of the base material PUR2: 2100 g of polyurethane polymer PP4, 1500 g of caicinated kaolin, 650 g of carbon black, 740 g of diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF) and 10 g of p-tolylsulfonyl isocyanate (additive Tl ^® , Bayer) were placed in a vacuum mixer with the exclusion of moisture processed into a lump-free, homogeneous paste, immediately filled into internally lacquered aluminum cartridges and sealed airtight.

The polyurethane polymer PP4 was prepared as follows: 1125 g of polyol Acclaim ^® 4200 N (polypropylene oxide diol having an OH number of 28.5 mg KOH / g; Bayer), 2250 g of polyol Caradol ^® MD34-02 (polypropylene oxide-polyethylene triol, OH number 35.0 mg KOH / g; Shell), 375 g poly (hexamethylene carbonate) diol (OH number 130; Aldrich No. 46.117-2), 750 g 4,4'-methylene diphenyl diisocyanate (MDI; Desmodur ^® 44 MC L, Bayer) and 500. g of diisodecyl phthalate (DIDP; Palatinol ^® Z, BASF) were reacted by a known method at 80 ° C to give an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined free isocyanate group content of 2.55% by weight. Production of the polyurethane compositions: In a vacuum mixer, 300 g of the above-described base mass PUR2 with the additives listed in Table 6 were processed with the exclusion of moisture to form a lump-free, homogeneous paste, which was immediately filled into internally coated aluminum cartridges and sealed airtight. ^a Reference example without aldiminoalkylsilane ^b Di-n-butyltin dichloride (1.8% by weight in DIDP) The freshly prepared polyurethane compositions of the examples

32 to 34 were then applied to cleaned aluminum plates. The procedure for each of the examples was as follows: a raw aluminum plate with a low Si content (type AIMg3; Rocholl, Schönbrunn, Germany) or with a high Si content (type AlMgSM; Rocholl) with a size of 30 x 20 cm was thoroughly sanded on one side with abrasive wool and the sanded side wiped three times with a hygienic cloth moistened with isopropanol. After a flash-off time of 5 minutes, the sanded side was pretreated with Sika ^® activator (available from Sika Schweiz AG) and then, after a further flash-off time of 15 minutes, the polyurethane composition was applied as beads of approx. 7 mm diameter (15 cm bead length; 3 beads) , the distance between two caterpillars was at least 20 mm. Immediately after application, the beads were each covered with an LDPE strip on the long side and pressed evenly to a width of approx. 10 mm and a layer thickness of approx. 2 mm using a glass plate. The aluminum plate was stored for 7 days in a standard climate (23 ± 1 ° C, 50 ± 5% relative humidity), the polyurethane composition curing. The first caterpillar was then checked for liability. The aluminum plate was then stored in water at room temperature for 7 days, left to dry and the second bead checked for adhesion. The aluminum plate was then stored in the cataplasma (70 ° C., 100% humidity) for 7 days and the third bead was checked for adhesion. The test for adhesion and the evaluation of the adhesive properties were carried out as described in Examples 27 to 31. The results of the tests are shown in Table 7.

Table 7: Adhesion to aluminum of the polyurethane compositions of Examples 32 to 34.

^a Reference example without aldiminoalkylsilane

The results of Table 7 show that Examples 33 and 34 with aldiminoalkylsilanes according to the invention show significantly better adhesion to aluminum than Reference Example 32 without aldiminoalkylsilane.

Claims

Patent claims

1. Aldiminoalkylsilane ALS, prepared from the reaction of at least one aminoalkylsilane AS of the formula (I) and at least one aldehyde ALD of the formula (II), O ³ 00 Y ^1' V where R ¹ is a linear or branched, optionally cyclic, alkylene group with 1 to 20 carbon atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms, especially nitrogen atoms; R ² represents an alkyl group with 1 to 5 carbon atoms; R ³ represents an alkyl group with 1 to 8 carbon atoms; a represents 0, 1 or 2, especially 0; Y ¹ and Y ² either, independently of one another, each represent an organic radical; or together form a carbocyclic or heterocyclic ring which has a ring size between 5 and 8, preferably 6, atoms; and Y ³ represents either a substituted or unsubstituted alkyl group having at least one heteroatom; or represents a branched or unbranched alkyl or alkylene group with at least 10 carbon atoms; or represents a substituted or unsubstituted aryl or arylalkyl group; or OOO 4 II 4 II 4 II 4 represents OR or OCR or COR or CR, where R is an alkyl, arylalkyl or aryl group with at least 3 carbon atoms and is each substituted or unsubstituted.

2. Aldiminoalkylsilane ALS according to claim 1, characterized in that R ¹ represents a methylene, propylene, methylpropylene, butylene or dimethylbutylene group, in particular a propylene group.

3. Aldiminoalkylsilane ALS according to claim 1 or 2, characterized in that R ² represents a methyl group or an ethyl group or an isopropyl group, in particular a methyl group or an ethyl group.

4. Aldiminoalkylsilane ALS according to one of claims 1 - 3, characterized in that R ³ represents a methyl or an ethyl group, in particular a methyl group.

5. Aldiminoalkylsilane ALS according to one of the preceding claims, characterized in that the aminoalkylsilane AS of the formula (I) is 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane or N-(2-aminoethyl)-3-aminopropyltriethoxysilane, in particular 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.

6. Aldiminoalkylsilane ALS according to one of the preceding claims, characterized in that the aldehyde ALD is a compound of the formula (III), where R ⁵ represents a hydrogen atom or an alkyl or arylalkyl or aryl group; and Y ⁴ represents an alkyl or arylalkyl or aryl group.

7. Aldiminoalkylsilane ALS according to one of claims 1 - 5, characterized in that the aldehyde ALD is a compound of the formula (IV), OR ⁵ O ^l ₀ A _γ5 (IV) where R ⁵ represents a hydrogen atom or an alkyl or Arylalkyl or aryl group stands; and Y ⁵ represents either a hydrogen atom; or represents an alkyl or arylalkyl or aryl group which optionally has at least one heteroatom, in particular an ether oxygen, optionally contains at least one carboxyl group, and optionally contains at least one ester group; or represents a mono- or polyunsaturated, linear or branched hydrocarbon chain. Aldiminoalkylsilane ALS according to claim 7, characterized in that R ⁵ represents a hydrogen atom; and that Y ⁵ represents either a linear or branched alkyl chain with 11 to 30 carbon atoms, optionally with at least one heteroatom, in particular with at least one ether oxygen; or represents a mono- or polyunsaturated linear or branched hydrocarbon chain with 11 to 30 carbon atoms; or represents a residue of the formula (V) or (VI),

O - R ₆ ⁶ <OR 7 ^{7 (Vl)} where R ⁶ represents either a linear or branched or cyclic alkyl chain with 2 to 16 carbon atoms, optionally with at least one heteroatom, in particular with at least one ether oxygen; or represents a mono- or polyunsaturated, linear or branched or cyclic hydrocarbon chain with 2 to 16 carbon atoms; and R ⁷ represents a linear or branched alkyl chain with 1 to 8 carbon atoms.

. Aldiminoalkylsilane ALS according to one of the preceding claims, characterized in that Y ¹ = Y ² = methyl.

10. Aldiminoalkylsilane ALS according to claim 7 or 8, characterized in that the aldehyde ALD used for the production of the aldiminoalkylsilane ALS is obtainable by an esterification reaction of a ß-hydroxyaldehyde with a carboxylic acid, in particular without the use of a solvent, the ß-hydroxyaldehyde , optionally in situ, from formaldehyde, or paraformaldehyde, and a second aldehyde.

11. Aldiminoalkylsilane ALS according to claim 10, characterized in that the aldehyde ALD used for the production of the aldiminoalkylsilane ALS is obtainable by an esterification reaction of 3-hydroxypivalaldehyde with a carboxylic acid, in particular without the use of a solvent, with 3-hydroxypivalaldehyde optionally in situ is produced from formaldehyde, or paraformaldehyde, and isobutyraldehyde.

12. Aldiminoalkylsilane ALS according to one of claims 10 or 11, characterized in that the carboxylic acid used for the production of the aldehyde ALD is selected from the group comprising lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, succinic acid, adipic acid, azelaic acid and sebacic acid, their mixtures and their technical mixtures with fatty acids.

3. Aldiminoalkylsilane ALS according to one of the preceding claims, characterized in that the aldiminoalkylsilane ALS has the formula (VII) or (VIII),

where R ⁶ represents either a linear or branched or cyclic alkylene chain with 2 to 16 carbon atoms, optionally with at least one heteroatom, in particular with at least one ether oxygen; or represents a mono- or polyunsaturated, linear or branched or cyclic hydrocarbon chain with 2 to 16 carbon atoms; and R ⁷ represents a linear or branched alkyl chain with 1 to 8 carbon atoms.

14. A process for producing an aldiminoalkylsilane ALS according to one of claims 1 - 13, comprising a reaction of an aminoalkylsilane AS of the formula (I) with at least one aldehyde ALD of the formula (II),

wherein the water formed in the reaction is essentially completely removed from the reaction mixture.

15. A process for producing an aldiminoalkylsilane ALS according to claim 14, characterized in that for the production of the aldiminoalkylsilane ALS, the aldehyde groups of the aldehyde ALD are used stoichiometrically or in a stoichiometric excess in relation to the primary amino groups of the aminoalkylsilane AS.

16. A process for producing an aldiminoalkylsilane ALS according to claim 14, characterized in that the aminoalkylsilane AS is present in a mixture with at least one polyamine with primary aliphatic amino groups and the aldehyde groups of the aldehyde ALD are stoichiometric or in a stoichiometric excess based on the totality of the primary amino groups are used, which results in a mixture after the reaction containing both the aldiminoalkylsilane ALS and the polyaldimine formed in accordance with the aldehyde ALD used.

17. Use of an aldiminoalkylsilane ALS according to one of claims 1 - 13 in compositions which contain compounds which are reactive towards amines, in particular compounds which have isocyanate groups, particularly preferably compounds which have aromatic isocyanate groups.

18. Use of an aldiminoalkylsilane ALS according to claim 17, characterized in that the composition is used as an adhesive, sealant, coating or covering.

19. Use of an aldiminoalkylsilane ALS according to one of claims 1 - 13 in adhesion promoter compositions.

20. Hydrolysis process, characterized in that an aldiminoalkylsilane ALS according to one of claims 1 - 13 is brought into contact with water, in particular in a gaseous state, preferably in the form of atmospheric moisture, whereby an aldehyde ALD of the formula (II) is released.

21. Hydrolysis process, characterized in that an aldiminoalkylsilane ALS according to one of claims 1 - 13 is brought into contact with water in the form of a water-containing component or a water-releasing component, whereby an aldehyde ALD of the formula (II) is released.

22. Moisture-curing polymer composition comprising at least one polymer containing isocyanate groups and/or silane groups and at least one aldiminoalkylsilane ALS according to one of claims 1-13.

23. Moisture-curing polymer composition according to claim 22, characterized in that the polymer containing isocyanate groups and / or silane groups is a polyurethane polymer containing isocyanate groups, made from at least one polyisocyanate and at least one polyol, and the moisture-curing polymer composition is a moisture-curing polyurethane composition.

24. Moisture-curing polymer composition according to claim 23, characterized in that the polyisocyanate for the production of the polyurethane polymer is a diisocyanate, in particular selected from the group comprising MDI, TDI, HDI, IPDI and mixtures thereof, particularly preferably MDI and TDI and mixtures thereof.

25. Moisture-curing polymer composition according to claim 23, characterized in that the polyol for the production of the polyurethane polymer has an average molecular weight of 1,000 to 30,000 g / mol and an average OH functionality of 1.6 to 3 and is in particular a polyoxyalkylene polyol or a polyester polyol .

26. Moisture-curing polymer composition according to one of claims 22 - 25, characterized in that the aldiminoalkylsilane ALS is present in the polymer composition in an amount of 0.01 - 10% by weight, preferably 0.1 - 5% by weight, in particular 0.25 - 2.5% by weight .

27. Moisture-curing polymer composition according to one of claims 22 - 26, characterized in that a polyaldimine is present in addition to the aldiminoalkylsilane ALS.

28. Moisture-curing polymer composition according to one of claims 22 - 27, characterized in that an aldehyde ALD of the formula (II) is released during the hydrolysis of the polyaldimine.

29. Method of applying a moisture-curing polymer composition according to one of claims 22 - 28, characterized in that it is brought into contact with atmospheric moisture or with water in the form of a water-containing component or water-releasing component during or after the application of the composition to a substrate and subsequently cures, releasing an aldehyde ALD of the formula (II), which preferably remains essentially completely in the cured polymer composition.

30. The method according to claim 29, characterized in that the substrate consists of glass, glass ceramic, concrete, natural stone, aluminum or automotive topcoat, at least in the area of application of the moisture-curing polymer composition.

31. Adhesion promoter composition, characterized in that it contains or consists of at least one aldiminoalkylsilane ALS according to one of claims 1 - 13, in particular characterized in that it additionally contains an aminoalkylsilane AS of the formula (I).

32. Method of applying an adhesion promoter composition according to claim 31, characterized in that it is brought into contact with water or atmospheric moisture during or after application to a substrate, in particular glass, glass ceramic, concrete, natural stone, aluminum or automotive top coat, before an adhesive , a sealant, a coating or a covering is applied to it.