EP1685175A1 - Polyurethane compositions with nco and silyl reactivity - Google Patents

Abstract

The invention relates to polyurethanes or polyureas, which carry both silyl groups and NCO groups and which can be produced while using asymmetric diisocyanates and substituted alkoxy aminosilanes, to preparations that contain reactive polyurethanes or polyureas that carry silyl groups, to methods for producing these reactive polyurethanes or polyureas that carry silyl groups, and to the use thereof.

Description

 Polyurethane compositions with NCO and silyl reactivity

The present invention relates to compositions containing reactive, silyl group-bearing polyurethanes or polyureas which can be prepared using asymmetric polyisocyanates and substituted alkoxyaminosilanes, to preparations which contain such reactive, silyl group-bearing polyurethanes or polyureas, to processes for producing such reactive, silyl group-bearing polyurethanes or polyureas as well as their use.

Reactive polyurethanes or polyureas have reactive end groups that can react with water or other compounds that have an acidic hydrogen atom. This form of reactivity makes it possible to bring the reactive polyurethanes or polyureas in the processable state (generally thin to highly viscous) to the desired location in the desired manner and by adding water or other compounds that have an acidic hydrogen atom ( in this case referred to as hardener).

With these so-called 2-component systems, the hardener is usually added immediately before use, normally with the help of a mixing and dosing system, with the processor only having a limited processing time after adding the hardener.

However, it is also possible to cure polyurethanes or polyureas with reactive end groups without the addition of hard materials simply by reacting with atmospheric moisture (1K systems). Compared to the 2K systems, such IC systems generally have the advantage that the often tedious mixing of the frequently viscous components before the application is no longer necessary for the user.

The polyurethanes or polyureas with reactive end groups usually used in 1K or 2K systems include, for example, the polyurethanes or polyureas with preferably terminal isocyanate (NCO) groups. In order to obtain polyurethanes or polyureas with terminal NCO groups, it is customary to react polyfunctional alcohols or polyarnines with an excess of monomeric polyisocyanates, usually diisocyanates.

It is known that at the end of the reaction, regardless of the reaction time, a certain amount of the monomeric diisocyanate used remains for statistical reasons. However, such a content of monomeric diisocyanate generally has a disruptive effect, in particular for health reasons, in particular in the manual processing of adhesives, sealants and foams based on such reactive polyurethanes or polyureas.

Even at room temperature, monomeric diisocyanates such as TPDI or TDI can have a vapor pressure that should not be neglected. Due to the vapor pressure, measurable amounts of isocyanates are constantly escaping under normal processing conditions, to which the processor, for example, is exposed unprotected if protective measures are lacking. This noticeable vapor pressure is particularly severe when the polyurethanes or polyureas are sprayed on, since significant amounts of isocyanate vapors can occur in the area around the application site, which are toxic due to their irritating and sensitizing effects and whose occurrence must be avoided in many countries for industrial hygiene reasons ,

In addition, the processing of adhesives often takes place at elevated temperatures. For example, the processing temperatures of hot melt adhesives are between about 100 ° C and about 200 ° C, those of molding adhesives between about 30 ° C and about 150 ° C. At these temperatures and other specific application parameters, e.g. Humidity also form the widespread bicyclic diisocyanates, for example diphenylmethane diisocyanates, gaseous and aerosol emissions. The above-mentioned diisocyanates with a lower molecular weight are even more released into the ambient air at such elevated temperatures.

In many countries, therefore, complex measures to protect the people processing the product, in particular complex measures to keep the breathing air clean, are prescribed by law, which limits the maximum permissible concentration of agents of gas, steam or suspended matter in the workplace and the health of those with Processing of such products should be protected (in Germany, for example, by the annually updated MAK value list of the technical rule TRGS 900 of the Federal Ministry of Labor and Social Affairs).

Since protective and cleaning measures are usually associated with high financial hivestitions, there is a need on the part of users for products that have the lowest possible proportion of monomeric dusocyanates.

It is not only the use of reactive adhesives that still contain monomeric polyisocyanate that leads to problems. The placing on the market of substances and preparations that contain more than 0.1% free MDI or TDI, for example, can be problematic in many countries. Such substances often fall under the relevant hazardous substance regulations in many countries and are often to be labeled accordingly. However, the germ-labeling requirement often involves special measures with regard to packaging and transport, which can significantly increase the total costs for the product.

After all, containers with such adhesives have to be labeled and disposed of separately in many countries. However, such products meet with little acceptance, particularly among end users.

The presence of monomeric, volatile diisocyanate often leads to problems in further processing. For example, monomeric diisocyanates can "migrate" from a coating or bond into the coated or bonded materials. Such migrating components are often referred to as "migrates" in specialist circles. The isocyanate groups of the migrates are continuously converted to amino groups by contact with moisture. However, the resulting compounds are often carcinogenic.

Such migrates are particularly undesirable in integral polyurethane foams such as are used, for example, in the production of steering wheels in motor vehicles, since contact of the A ine formed from the migrated dusocyanates with the skin cannot be ruled out. Migrates are also extremely undesirable in the packaging sector, especially in food packaging. On the one hand, the migration of the migrates through the packaging material can lead to contamination of the packaged goods, on the other hand, depending on the amount of free monomeric diisocyanate capable of migration, long waiting times are necessary before the packaging material is "migration-free" and may be used.

The content of the amines produced by migrated diisocyanates, especially the primary aromatic amines, must, for example in Germany, be below the detection limit of 0.2 μg aniline hydrochloride / 100 ml sample based on aniline hydrochloride (Federal Institute for Consumer Health Protection and Veterinary Medicine, BGVV, according to official collection from Examination procedure according to § 35 LMBG - Examination of food / Determination of primary aromatic amines in aqueous test food).

Another undesirable effect that can be caused by the migration of monomeric diisocyanates is the so-called anti-sealing effect in the production of bags or carrier bags from laminated plastic films: The laminated plastic films are often coated with a lubricant based on fatty acid amides. By reaction of migrated monomeric diisocyanate with the fatty acid amide and / or moisture, urea compounds are formed on the film surface, which may have a melting point above the sealing temperature of the plastic films. This creates an alien layer between the film parts to be sealed, which counteracts a uniform seam formation.

For the reasons mentioned above, the development of reactive polyurethanes or polyureas with a reduced proportion of monomeric diisocyanates is therefore highly desirable.

EPO 316 738 A1 describes a process for the preparation of polyisocyanates containing urethane groups with a maximum proportion of 0.4% by weight of diisocyanate free of urethane groups, by reaction of aromatic diisocyanates with polyhydric alcohols and subsequent removal of the unreacted, excess diisocyanate, wherein the distillative removal of the excess diisocyanate is carried out in the presence of an aliphatic polyisocyanate. EP 0 261 409 A1 describes alkoxysilane-terminated, moisture-curing polyurethanes which are obtainable by a process in which almost all free isocyanate groups are reacted with special alkoxysilanes. A disadvantage of such compositions is the fact that almost no isocyanate groups are present.

DE 38 15 237 AI describes a process for reducing the monomer content of urethane or isocyanurate-modified polyisocyanates based on 2,4-TDI or a mixture thereof with up to 35% by weight of 2,6-TDI or IPDI. The monomer can be reduced by thin-layer distillation and subsequent reaction with water.

EP 0 393 903 A1 describes a process for the preparation of polyurethane prepolymers, in which monomeric diisocyanate is reacted with a polyol in a first step. A sufficient amount of a catalyst is then added so that a substantial proportion of the remaining isocyanate groups are converted into allophanate groups. After the theoretical NCO content has been reached, the reaction is stopped by rapid cooling and the addition of salicylic acid.

WO 01/40342 describes reactive polyurethane adhesive or sealant compositions based on reaction products made from polyols and high molecular weight diisocyanates, a diol component with a stoichiometric excess of monomeric diisocyanate being converted into a high molecular weight diisocyanate in a first stage, and the high molecular weight diisocyanate for example by adding a non-solvent for the high molecular weight diisocyanate from the monomeric diisocyanate from the reaction mixture. In a second step, this high molecular weight diisocyanate is reacted with a polyol to form a reactive prepolymer with isocyanate end groups.

DE 41 36 490 AI relates to solvent-free two-component coating, sealing and adhesive systems with low migration values from prepolymers containing polyols and isocyanate groups. The NCO prepolymers are prepared by reacting polyol mixtures with an average functionality of 2.05 to 2.5 with at least 90 mol% of secondary hydroxyl groups and diisocyanates with differently reactive isocyanate groups in a ratio of the isocyanate groups to hydroxyl groups of 1.6 to 1.8 1.Table 1 on page 5 shows that MDI prepolymers produced according to the teaching of DE 4136490 AI have a monomer content of more than 0.3%.

WO 03/006521 AI describes reactive polyurethanes with an NCO content of 4 to 12% NCO and a content of monomeric asymmetric diisocyanates of 0.01 to 0.3%, which are obtained by reacting at least one monomeric asymmetric diisocyanate with a molecular weight of 160 g / mol to 500 g / mol with at least one diol with a molecular weight of 60 g / mol to 2000 g / mol are available, the ratio of the isocyanate groups to hydroxyl groups being from 1.05 to 1 to 2.0 to 1 Production can take place without additional refurbishment and cleaning steps. Such reactive polyurethanes are suitable for the production of reactive one- and two-component adhesives and sealants, assembly foams, casting compounds as well as soft, hard and integral foams, which can optionally contain solvents, and as a component for the production of reactive hotmelt adhesives. More important As an advantage of these reactive polyurethanes over known reactive polyurethanes with a low proportion of monomeric diisocyanates, the freedom from by-products, as is usually the case in the thermal processing of reactive polyurethanes, is mentioned.

Problems often arise when using polyurethanes, which on the one hand require the known good properties of compounds with isocyanate groups, but on the other hand, for example due to insufficient adhesion to certain substrates such as glass or ceramic, the presence of further functional groups which fill to crosslink , especially the presence of silyl groups, may appear desirable. The presence of silyl groups is also frequently required when producing compositions for use in foams.

It is known from the prior art to introduce silyl groups as reactive end groups in polyurethanes. WO 99/48942 AI describes polyurethanes which can be crosslinked or hardened via one or more alkoxysilyl end groups and nevertheless have excellent elasticity, flexibility and tear resistance even at low temperatures. These compounds can be prepared by reacting at least two components, a polyisocyanate or a mixture of two or more polyisocyanates and a polyol or a mixture of two or more polyols, one being, for example, a polyol Polyether with a molecular weight (M _n ) of at least 4000 and a polydispersity PD (M _w / M _n ) of less than 1.5 or an OH functionality of about 1.8 to about 2.0 is used. A problem with the compositions mentioned here, for example, is the fact that during the production on addition of unsubstituted aminosilanes, polymeric compounds are formed which do not carry silyl groups at the chain end but in the middle of the polymer chain.

There is therefore still a need for reactive polyurethanes with a low proportion of monomeric diisocyanates, which are suitable both for use as reactive one- and two-component adhesives and sealants, in particular for reactive hot-melt adhesives or laminating adhesives, and for the production of assembly foams, casting compounds and plasticizers. , Rigid and integral foams are suitable.

The present invention is therefore based on the object of providing polyurethanes which have the advantages of the compositions known from the prior art, the disadvantages of which do not yet show, or at least to a reduced extent. In particular, it was an object of the present invention to provide polyurethanes which have excellent adhesion to a large number of substrates. In particular, it was an object of the invention to provide reactive polyurethanes carrying at least one silyl group for use as adhesives or sealants which are largely free of monomeric diisocyanates or have the lowest possible proportion of monomeric diisocyanates. Ideally, these should be free from mandatory labeling in as many countries as possible.

In order to achieve the low proportion of monomeric diisocyanates, complex and expensive cleaning steps are sometimes carried out according to the prior art. Specific examples are the removal of excess monomeric diisocyanates by selective extraction, for example with supercritical carbon dioxide, thin-film distillation, thin-film evaporation or the precipitation of the reactive polyurethane from the reaction mixture with monomeric diisocyanates. A further object of the present invention was therefore to provide reactive polyurethanes which carry at least one silyl group and which have a low content of monomeric diisocyanates without the complicated work-up steps. Another object of the invention was to provide reactive polyurethanes bearing at least one silyl group, in which the ratio of NCO groups and silane groups can be controlled in a targeted manner in order to provide polyurethanes with desirable properties.

The problems on which the invention is based are solved by polyurethanes bearing silyl groups, as are described in more detail in the context of the text below.

The present invention thus relates to a composition comprising at least one polyurethane bearing at least one isocyanate group and at least one polyurethane bearing a silyl group, the polymers having at least two different types of urethane groups and a silyl group of the general formula I as the silyl group

wherein the radicals R ¹ to R each independently represent a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 C atoms, a saturated or unsaturated cycloalkyl radical having 4 to about 24 C atoms or an aryl radical having 6 to about 24 Are carbon atoms, R ^{7 is} an optionally substituted alkylene radical with 1 to about 44 C atoms, an optionally substituted cycloalenyl radical with 6 to about 24 C atoms or an optionally substituted arylene radical with 6 to about 24 C atoms, n , m and j each represent an integer from 0 to 3, where m + n + j = 3, a an integer from 0 to 3, b an integer from 0 to 2 and c a number from 0 is to 8 and R ⁸ is a linear or branched, saturated or unsaturated Cι _-24 alkyl, cycloalkyl, phenyl, tolyl, mesityl, trityl, or 2,4,6-tri-tert-butylphenyl group, is included and the composition is less than 0.1 wt. -% of monomeric isocyanates and the ratio of isocyanate groups to silyl groups is about 90:10 to about 10:90.

In the context of the present invention, the term “polyurethane” stands for a compound with a polyurethane structure, as can be obtained in the context of a targeted one- or multi-stage polyurethane synthesis. A polyurethane in the sense of the invention has two or more urethane groups. The term also includes all deviations from this structure as they result from the statistical nature of the polyaddition process.

In the context of the present invention, a “silyl group” is understood to mean a functional group of the general formula I described above, in which the radicals R ¹ to R ⁶ each independently of one another represent a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 C - Atoms, a saturated or unsaturated cycloalkyl radical with 4 to about 24 carbon atoms or an aryl radical with 6 to about 24 carbon atoms, R ⁷ for an optionally substituted alkylene radical with 1 to about 44 carbon atoms, an optionally substituted cycloalkylene radical with 6 to about 24 carbon atoms or an optionally substituted arylene radical with 6 to about 24 carbon atoms, n, m and j each represent an integer from 0 to 3, where m + n + j = 3, a is a is an integer from 0 to 3, b is an integer from 0 to 2 and c is a number from 0 to 8 and R ^{8 is} a linear or branched C ₂ alkyl radical, a cycloalkyl, in particular Cyclopentyl or cyclohexyl radical, a phenyl, tolyl, mesityl, trityl or 2,4,6-tri-tert-butylphenyl radical.

In the context of the present invention, the term “composition” relates to a mixture of compounds as are obtained according to a suitable production process for polyurethanes bearing silyl groups. A corresponding composition contains, for example, the above-described polyurethanes carrying silyl groups and, where appropriate, starting materials which have not been reacted in the course of the reaction, and products such as those formed by incomplete conversion of the starting materials.

In the context of a preferred embodiment of the present invention, a composition according to the invention can contain, for example, polyurethanes which have only silyl groups as crosslinkable functional groups. In addition, a composition according to the invention can contain, for example, polyurethanes which have silyl groups and NCO groups as crosslinkable functional groups. In addition, a composition according to the invention can contain, for example, polyurethanes which have only NCO groups as crosslinkable functional groups. It is preferred in the context of the present invention if the ratio of NCO groups to silyl groups in a composition according to the invention is about 90:10 to about 10:90. Particularly suitable ratios are, for example, about 80:20 to about 20:80 or about 70:30 to about 30:70 or about 60:40 to about 40:60.

According to the present invention, a composition according to the invention contains at least one polyurethane which has at least two different types of urethane groups. In the context of the present text, “different types of urethane groups” are understood to mean urethane groups which have a different chemical environment. This means, for example, that different types of urethane groups are covalently linked to different subsequent groups. In practice, different types of urethane groups can be obtained in particular by using polyisocyanates which carry types of urethane groups of different reactivity. In the context of a preferred embodiment of the present invention, the different types of urethane plugs, as are present in a polyurethane in a composition according to the invention, are produced by using at least one asymmetric polyisocyanate. The asymmetry of a corresponding polyisocyanate has a particular effect on the different reactivity of the isocyanate groups in the polyisocyanate.

A composition described above and containing at least one silyl group-containing polyurethane or such a polyurea and at least one polyurethane containing at least one NCO-Grappe or such a polyurea is used, for example, as part of a preparation in the context of the present invention.

The present invention therefore also relates to a preparation comprising at least one polyurethane bearing at least one silyl group or at least one polyurea bearing at least one silyl group or a mixture of two or more thereof and at least one polyurethane bearing at least one NCO group or at least one at least one NCO -Grappe-bearing polyurea or a mixture of two or more thereof, which can be prepared by reacting at least three components A, B and C, where a) as component A an asymmetric diisocyanate or a mixture of two or more asymmetric diisocyanates, b) as component B, a silane of the general formula II

(OR ³ ) (OR) R «m 2-b (RO) _, - Si-O- o- -Si- -R '- NHR ° 3-a (π) R 4 j in which the radicals R ¹ to R ⁶ each independently represent a linear or branched, saturated or unsaturated hydrocarbon radical with 1 to about 24 C atoms, a saturated or unsaturated cycloalkyl radical with 4 to about 24 C atoms or an aryl radical with 6 to about 24 C atoms, R ⁷ represents an optionally substituted alkylene radical with 1 to about 44 C atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 C atoms or an optionally substituted arylene radical with 6 to about 24 C atoms, n, m and j each represent a whole Are from 0 to 3, where m + n + j = 3, a is an integer from 0 to 3, b is an integer from 0 to 2 and c is a number from 0 to 8 and R ^{8 is} one linear or branched Ci-io-alkyl radical, cycloalkyl, phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl radical and c) as a component C a polyol or a mixture of two or more polyols or a polyamine or a mixture of two or more polyamines or a polyol and a mixture of two or more polyamines or a mixture of two or more polyols and a polyamine or a mixture of two or more polyols and a mixture of two or more polyols is used, the number ratio of NCO-Grappen to Silylgrappen is 10:90 to 90:10.

In the context of the present invention, component A is a polyisocyanate, for example a diisocyanate, or a mixture of two or more polyisocyanates. Polyisocyanates are understood to mean compounds which carry at least two isocyanate groups (NCO groups). For example, these are compounds of the general structure O = N = CZC = N = O, where Z is an asymmetrical linear or branched aliphatic, alicyclic or aromatic hydrocarbon radical which may optionally have further inert substituents or those which intervene in the reaction. Monomeric asymmetric diisocyanates in the sense of this invention are basically aromatic, aliphatic or cycloaliphatic diisocyanates as can be obtained in the course of the synthesis of isocyanates. For example, in the context of the present invention, monomeric asymmetric diisocyanates can be compounds with a molecular weight of 160 g / mol to 500 g / mol, which have NCO groups with a different reactivity compared to functional groups reactive with NCO groups with the formation of a covalent bond. However, it is also possible in the context of the present invention that monomeric asymmetric isocyanates are compounds with a molecular weight of more than 500 g / mol, for example compounds such as those formed in the course of dimerization, trimerization, oligomerization or polymerization of isocyanates, for example NCO groups load-bearing allophanates or isocyanurates or polymer isocyanates such as polymer MDI.

The different reactivity of the NCO groups of the diisocyanates is fundamentally caused by a different chemical environment in which the NCO groups are located, for example by differently adjacent substituents to the NCO groups on the molecule, which, for example by steric shielding, the reactivity of one NCO - Reduce group compared to the other NCO group and / or by different binding of an NCO group to the rest of the molecule, for example in the form of a primary or secondary NCO group.

Examples of suitable aromatic asymmetric diisocyanates are all isomers of tolylene diisocyanate (TDI) either in isomeric form or as a mixture of several isomers, diphenylmethane-2,4 'diisocyanate (MDI) and mixtures of 4,4'-diphenylmethane diisocyanate with the 2,4' MDI isomers.

Examples of suitable cycloaliphatic asymmetric diisocyanates are, for example, 1-isocyanatomethyl-3-isocyanato-l, 5,5-trimethylcyclohexane (isophorone diisocyanate, PDF), 1-methyl-2,4-diisocyanatocyclohexane or hydrogenation products of the aforementioned aromatic diisocyanates, in particular hydrogenated MDI in isomer-free Form, preferably hydrogenated 2,4'-MDI. Examples of aliphatic asymmetric diisocyanates are 1,6-diisocyanato-2,2,4-trimethylliexane, 1,6-diisocyanato-2,4,4-trimethylhexane and lysine diisocyanate.

In the context of the invention, it is particularly preferred if TDI or 2,4-MDI or TPDI or polymer MDI or a mixture of two or more thereof is used as the monomeric asymmetric diisocyanate.

In the context of a further embodiment of the present invention, the different types of urethane groups or the different types of urea groups are produced by using at least one polyisocyanate which has at least two isocyanate groups, the reactivity of which with an isocyanate-reactive functional group is at least a factor of 1.1, for example at least one Factor of 1.2, 1.3, 1.4, 1.5 or more.

As component B, a silane of the general formula II is used in the preparation of the compositions according to the invention

used, in which the radicals R ¹ to R ⁶ each independently of one another for a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 C atoms, a saturated or unsaturated cycloalkyl radical with 4 to about 24 C atoms or an aryl radical with 6 are up to about 24 carbon atoms, R ^{7 is} an optionally substituted alkylene radical with 1 to about 44 carbon atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 carbon atoms or an optionally substituted aryl radical with 6 to about 24 carbon atoms , n, m and j each represent an integer from 0 to 3, where m + n + j = 3, a for an integer from 0 to 3, b for an integer from 0 to 2 and c for a number from 0 to 8 and R ^{s represents} a linear or branched C _-24 alkyl radical, cycloalkyl, phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl radical. In principle, any compounds of the general formula are suitable for the preparation of the polyurethanes according to the invention. For adequate reactivity of the silyl groups, however, the following compounds have been found to be advantageous, said Verbmdungen on the N atom in each case a substituent selected from the group consisting of a linear or branched Cι _-24 alkyl, cyclopentyl, cyclohexyl, Phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl radical must have, unless this is already apparent from the compound name itself: N- (α-methyldimethoxysilylmethyl) amine, N- (α - Trimethoxysilylmethyl) amine, N- (α-diethylmethoxysilylmethyl) amine, N- (-Ethyldimethoxysilylmethyl) amine, N- (-Methyldiethoxysilylmethyl) amine, N- (α-triethoxysilylmethyl) amine, N- (-Ethylysethylmethyl) amine - (ß-Methyldimethoxysilylethyl) amine, N- (ß-

Trimethoxysilylethyl) amine, N- (ß-ethyldimethoxysilylethyl) amine, N- (ß-methyl-diethoxysilylethyl) amine, N- (ß-triethoxysilylethyl) amine, N- (ß-ethyldiethoxysilylethyl) amine, N- (γ-methyldimethyl) dimethyl , N- (γ-trimethoxysilylpropyl) amine, N- (γ-

Ethyldimethoxysilylpropyl) amine, N- (γ-methyldiethoxysilylpropyl) amine, N- (γ-

Triethoxysilylpropyl) amine, N- (γ-ethyldiethoxysilylpropyl) amine, N- (4-methyldimethoxysilylbutyl) amine, N- (4-trimethoxysilylbutyl) amine, N- (4-triethylsilylbutyl) amine, N- (4-) , N- (4-ethyldimethoxysilylbutyl) amine, N- (4-

Methyldiethoxysilylbutyl) amine, N- (4-triethoxysilylbutyl) amine, N- (4-diethylethoxysilylbutyl) amine, N- (4-ethyldiethoxysilylbutyl) amine, N- (5-methyldimethoxysilylpentyl) amine, N- (5) , N- (5-triethylsilylpentyl) amine, N- (5-

Ethyldimethoxysilylpentyl) amine, N- (5-methyldiethoxysilylpentyl) amine, N- (5-

Triethoxysilylpentyl) amine, N- (5-Diethylethoxysilylpentyl) amine, N- (5-Ethyldiethoxysilylpentyl) amine, N- (6-Methyldimethoxysilylhexyl) amine, N- (6-Trimethoxysilylhexyl) amine, N- (6-Ethyldimethox) , N- (6-methyldiethoxysilylhexyl) amine, N- (6-

Triethoxysilylhexyl) amine, N- (6-ethyldiethoxysilylhexyl) amine, N- [γ-tris-

(Trimethoxysiloxy) silylpropyl] amine, N- [γ-tris- (trimethoxysiloxy) silylpropyl] amine, N- (γ- trimethoxysiloxydimethylsilylpropyl) amine, N- (γ-trimethylsiloxydimethoxysilylpropyl) amine, N- (iet) (γ-triethoxysiloxydiethoxysilylpropyl) amine, N, N-butyl- (γ-trimethoxysilylpropyl) amine, N, N-butyl- (γ-triethoxysilylpropyl) amine, N, N-phenyl- (γ-trimethoxysilylpropyl) amine Phenyl- (γ-triethoxysilylpropyl) amine, N, N-cyclohexyl- (γ-trimethoxysilylpropyl) amine, N, N-ethyl- (γ-trimethoxysilylpropyl) amine, diethyl-N-

(trimethoxysilylpropyl) aspartate, diethyl-N- (triethoxysilylρropyl) aspartate, N, N-ethyl- (γ-dimethoxymethylsilypropyl) amine, N, N-ethyl- (γ-trimethoxysilylisobutyl) amine, N, N-bis- (trimethoxypropyl) amine, N, N-ethyl- (γ-trimethoxsilylisobutyl) amine, N, N-ethyl- (α-trimethoxysilylmethyl) amine, dibutyl-N- (trimethoxysilylpropyl) aspartate, dibutyl-N-

(triethoxysilylpropyl) aspartate, N, N- (ß-aminopropyl) - (γ-trimethoxysilylpropyl) amine, N, N-di- (trimethoxysilylpropyl) ethylenediamine, tetra- (trimethoxysilylpropyl) ethylenediamine and N, N-trimethyl- (ilyl ) amine or N- [γ-tris (trimethylsiloxy) silylpropyl] amine or N, N-cyclohexyl-triethoxysilylmethylamine or N, N-cyclohexyl-α-methyldiethoxysilylmethylamine or N, N-phenyl- -trimethoxysilylmethylamine or N, N-phenyl -methyldimethoxysilylmethylamine or mixtures of two or more thereof.

Compounds B which carry at least one methoxy group or one ethoxy group on the silicon atom are preferably used as component B, particularly preferred are compounds having two or three methoxy groups or two or three ethoxy groups or any mixtures of methoxy and ethoxy groups.

A composition according to the invention can already be obtained, for example, by reacting components A and B in the appropriate proportions. However, it is provided according to the invention and has an advantageous effect with regard to the properties of the compositions and the preparations produced therefrom if at least one compound is used in the preparation of the compositions which is polyfunctional in terms of its reactivity with NCO-Grappa, preferably two or three with one another NCO groups has reactive groups. Suitable groups reactive towards NCO groups are, for example, OH grappes, COOH groups, amino groups or mercapto groups. Polyols or polyamines are particularly suitable in the context of the present invention. It has therefore proven to be advantageous if, in the course of the production of a composition or a preparation according to the invention, as component C a polyol or a mixture of two or more polyols or a polyamine or a mixture of two or more polyamines or a polyol and a mixture of two or more polyamines or a mixture of two or more polyols and a polyamine or a mixture of two or more polyols and a mixture of two or more polyols.

In the context of the present invention, a polyol or a mixture of two or more polyols is therefore used, for example, as component C in the production of the compositions according to the invention. In the context of the present invention, the term “polyol” encompasses a compound which has at least two OH groups, regardless of whether the compound has further functional groups. However, a polyol used in the context of the present invention preferably comprises only OH groups as functional groups, or if further functional groups are present, all other functional groups are at least non-reactive to isocyanates under the conditions prevailing in the reaction of components A and B.

Polyols suitable as component C are, for example, polyester polyols which, for example, are known from Ullmann's Encyclopedia of Technical Chemistry, 4th edition, volume 19, pages 62-65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with polyhydric, preferably dihydric, polycarboxylic acids. The polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally e.g. be substituted by halogen atoms and / or unsaturated. Examples include corkic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, hexahydrophthalic anhydride,

Tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride,

Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid and / or dimeric fatty acids.

The named polycarboxylic acids can either be used individually as the exclusive acid component or in a mixture with one another to form component C. Carboxylic acids of the general formula HOOC- (CH ₂ ) _y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.

Examples of polyhydric alcohols for reaction with the polycarboxylic acid component to build up component C include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol and butyne -1,4-diol, pentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, bis- (hydroxymethyl) cyclohexane, such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1 , 3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycol, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycol are considered. Preferred are neopentyl glycol and alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples include ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1, 8-diol and dodecane-1, 12-diol.

Component C also includes polycarbonate diols, such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.

Also suitable are lactone-based polyester diols, which are homopolymers or copolymers of lactones, preferably hydroxyl-containing addition products of lactone with suitable bifunctional starter molecules. Examples of suitable lactones are ε-caprolactone, ß-propiolactone, γ-butyrolactone and / or methyl-ε-caprolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the structural component for the polyester polyols. Low molecular weight polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactone, the corresponding chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used. The polyester polyols can also be constructed with the aid of minor amounts of mono- and / or higher-functional monomers. Also as polyol component C are polyacrylates bearing OH groups, which are obtainable, for example, by the polymerization of ethylenically unsaturated monomers which carry an OH group. Such monomers can be obtained, for example, by the esterification of ethylenically unsaturated carboxylic acids and bifunctional alcohols, the alcohol usually being in a slight excess. Suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid. Corresponding esters carrying OH groups are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate or 3-hydroxypropyl methacrylate or a mixture of two or more thereof. In addition, component C may be polyether diols. They are in particular by polymerizing propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF ₃ or by addition of these compounds, optionally in a mixture or in succession to starting components with reactive hydrogen atoms, such as water, alcohols or amines, for example propane -l, 2-diol, propane-l, 3-diol, l, 2-bis (4-hydroxydiphenyl) propane or aniline available.

Alcohols with a functionality of more than two can be used in minor amounts both for the production of the polyester polyols and for the production of the polyether polyols. In particular, these compounds, such as, for example, trimethylolpropane, pentaerythritol, glycerol, sugars, such as, for example, glucose, oligomerized polyols, such as, for example, di- or trimeric ethers of trimethylolpropane, glycerol or pentaerythritol, partially esterified polyfunctional alcohols of the formula described above, such as, for example, partially esterified trimethylolpropane, partially esterified glycerine partially esterified pentaerythritol, partially esterified polyglycerol and the like, preferably monofunctional aliphatic carboxylic acids being used for the esterification. If appropriate, the hydroxyl groups of the polyols can be etherified by reaction with alkylene oxides. The above compounds are also suitable as starter components for building up the polyether polyols. The polyol compounds with a functionality> 2 are preferably used only in minor amounts to build up the polyesterpolyols or polyetherpolyols.

Also suitable as component C are polyhydroxy olefms, preferably those with two terminal hydroxyl groups, e.g. α, ω-dihydroxypolybutadiene, α, ω-

Dihydroxypolymethacrylic ester or α, ω-dihydroxypolyacrylic ester.

The above-mentioned short-chain alkanediols are also used as further polyols, with neopentyl glycol and the unbranched diols having 2 to 12 carbon atoms, for example propylene glycol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, being preferred. The polyols listed so far can also be used as a mixture in any ratio.

Divalent or polyvalent compounds which have at least one primary or secondary or, insofar as more than one amino group is present per molecule, can also have primary and secondary amino groups at the same time as polyols. In addition to the amino groups, the corresponding amm compounds of component C have further functional groups, in particular grappes reactive towards isocyanates. These include in particular the hydroxyl group or the mercapto group. The compounds which can be used as polyol for the purposes of the invention include, for example, monoamionic alcohols having an aliphatic hydroxyl group, such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-cyclohyxylethanolamine, N-tert-butylethanolamine, leucinol, isoleukinol, valinol, proline , Hydroxyethylaniline, 2- (hydroxymethyl) piperidine, 3- (hydroxymethyl) piperidine, 2- (2-hydroxyethyl) piperidine, 2-amino-2-phenylethanol, 2-amino-l-phenylethanol, ephedrine, p-hydroxyyephedrine, norephedrine, Adrenaline, noradrenaline, serine, isoserine, phenylserine, 1,2-diphenyl-2-aminoethanol, 3-amino-l-propanol, 2-amino-l-propanol, 2-amino-2-methyl-l-propanol, isopropanolamine, N-ethylsopropanolamine, 2-amino-3-phenylpropanol, 4-amino-l-butanol, 2-amino-l-butanol, 2-aminoisobutanol, neopentanolamine, 2-amino-l-pentanol, 5-amino-l-pentanol, 2-ethyl-2-butyl-5-aminopentanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 2- (2-aminoethoxy) ethanol, 3- (aminomethyl) -3,5,5-trimethylcycloh exanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 3-amino-5-methylbenzyl alcohol, 2-amino-3-mefhylbenzyl alcohol.

For example, because the use of component C is intended to generate chain branches, e.g. Monoaminopolyols with two aliphatically bound hydroxyl groups such as l-amino-2,3-propanediol, 2-amino-l, 3-ρropanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-l , 3-propanediol, 2-amino-l-phenyl-l, 3-propanediol,

Use diethanolamine, diisopropanolamine, 3- (2-hydroxyethylamino) propanol and N- (3-hydroxypropyl) -3-hydroxy-2,2-dimethyl-1-amino groups.

It is also possible to use polyamines as component C. These include, for example, compounds such as hydrazine, ethylenediamine, 1,2- and 1,3-propylenediamine, butylenediamines, pentamethylenediamines, hexamethylenediamines such as, for example, 1,6-hexamethylenediamine, alkylhexamethylenediamines such as, for example, the second , 4-dimethylhexamethylene diamine, general alkylene diamines with up to about 44 carbon atoms, it also being possible to use cyclic or polycyclic alkylene diamines, such as can be obtained in a known manner from the dimerization products of unsaturated fatty acids. Aromatic diamines, such as, for example, 1,2-phenylenediamine, 1,3-phenylenediamine or 1,4-phenylenediamine, can also be used, but are not preferred. In the context of the invention, higher amines such as diethylenetriamine, aminomethyldiaminooctane-1,8 and triethylenetetramine can also be used. It is critical in the context of the present invention that the polyurethanes present in a composition according to the invention or in a preparation according to the invention have both NCO groups and silyl groups. The advantages according to the invention can only be achieved by functional groups in the presence of both types.

The ratio of NCO groups to silyl groups is within a range from 90:10 to 10:90, these numbers relating to the number ratio of the functional groups. In a further embodiment, it is also possible for the numbers mentioned to relate to the weight ratio of the functional grappa.

In the context of a further preferred embodiment of the present invention, the ratio of NCO groups to silyl groups is within a range from about 90:10 to about 60:40 or about 80:20 to about 70:30.

The present invention also relates to preparations which contain a composition according to the invention, as described in the context of the present text, and at least one further additive. A preparation according to the invention therefore contains a composition according to the invention and one or more compounds selected from the group consisting of plasticizers, reactive thinners, antioxidants, catalysts, hard materials, fillers, tackifiers, drying agents and UV stabilizers.

A composition according to the invention can already be used in the previously described film in the context of the proposed uses according to the invention. As a rule, however, it is advantageous if the composition according to the invention is used in a preparation which contains further compounds, for example for regulating the viscosity or the material properties.

For example, it is possible that the viscosity of the composition according to the invention is too high for certain applications. However, it has been found that the viscosity of the polyurethane according to the invention can generally be reduced in a simple and expedient manner by using a "reactive dimmer" without the material properties of the cured composition suffering significantly. The reactive diluent preferably has at least one functional group which, under the influence of moisture, is able to react with a reactive group of the first polyurethane according to the invention with chain extension or crosslinking (reactive diluent). The at least one functional group can be any functional group which reacts under the influence of moisture with crosslinking or chain extension.

Suitable as real thinners are all polymeric compounds which are miscible with the first polyurethane according to the invention while reducing the viscosity and which largely leave the material properties of the product formed after curing or crosslinking unaffected or at least not so adversely as to result in the unusability of the product. For example, polyesters, polyethers, polymers of compounds with olefinically unsaturated double bonds or polyurethanes are suitable, provided the above-mentioned requirements are met.

However, the reactive diluents are preferably polyurethanes with at least one alkoxysilane group as the reactive group.

The reactive diluents can have one or more functional groups, but the number of functional groups is preferably from 1 to about 6, in particular from about 2 to about 4, for example about 3.

In a preferred embodiment, the viscosity of the real thinners is less than about 20,000 mPas, in particular about 1,000 to about 10,000, for example about 3,000 to about 6,000 mPas (Brookfield RVT, 23 ° C., spindle 7, 2.5 rpm).

The reactive diluents which can be used in the process according to the invention can have any molecular weight distribution (PD) and can therefore be prepared by the customary methods of polymer chemistry.

The reactive diluents used are preferably polyurethanes which can be prepared from a polyol component and an isocyanate component and subsequent functionalization with one or more alkoxysilyl groups. The term “polyol component” in the context of the present text encompasses a single polyol or a mixture of two or more polyols which can be used to produce polyurethanes. A polyol is understood to be a polyfunctional alcohol, ie a compound with more than one OH group in the molecule, as has already been described as component C in the context of the present text.

A large number of polyols can be used as the polyol component for producing the reactive diluents. For example, these are aliphatic alcohols with two to four OH groups per molecule. The OH groups can be either primary or secondary. Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol and the like, polyfunctional alcohols as have already been mentioned in the context of the present text.

Also suitable for use as a polyol component are polyethers which have been modified by vinyl polymers. Products of this type can be obtained, for example, by polymerizing styrene and / or acrylonitrile in the presence of polyethers.

Also suitable as a polyol component for the production of the reactive diluent are polyester polyols with a molecular weight of about 200 to about 5,000. For example, polyester polyols can be used which are formed by the reaction of low molecular weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone, as described above. Also suitable as polyfunctional alcohols for the production of polyester polyols are, as already mentioned, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 1,2-butanediol, triethylene glycol, tetraefhylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.

As already described above, other suitable polyester polyols can be prepared by polycondensation. For example, difunctional and / or trifunctional alcohols can be condensed to give polyester polyols with a deficit of dicarboxylic acids and / or tricarboxylic acids or their reactive derivatives. Suitable dicarboxylic acids and tricarboxylic acids and suitable alcohols have already been mentioned above. In the context of the present invention, polyols used particularly preferably as polyol components for the preparation of the reactive diluents are, for example, dipropylene glycol and / or polypropylene glycol with a molecular weight of approximately 400 to approximately 2500 and polyester polyols, preferably polyester polyols, obtainable by polycondensation of hexanediol, ethylene glycol, diethylene glycol or neopentyl glycol or Mixtures of two or more thereof and isophthalic acid or adipic acid or mixtures thereof.

Polyacetals are also suitable as polyol components for the production of the real thinners. Polyacetals are understood to mean compounds such as are obtainable from glycols, for example diethylene glycol or hexanediol with fomialdehyde. Polyacetals which can be used in the context of the invention can likewise be obtained by the polymerization of cyclic acetals.

Polycarbonates are also suitable as polyol for the preparation of the reactive diluents. Polycarbonates can be obtained, for example, by the reaction of diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate or phosgene.

Polyacrylates bearing OH groups are also suitable as the polyol component for producing the reactive diluents. These polyacrylates can be obtained, for example, by polymerizing ethylenically unsaturated monomers which carry an OH group. Such monomers can be obtained, for example, by the esterification of ethylenically unsaturated carboxylic acids and bifunctional alcohols, the alcohol usually being in a slight excess. Suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid. Corresponding esters carrying OH groups are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate or 3-hydroxypropyl ethacrylate or mixtures of two or more thereof.

To produce the reactive diluents preferred according to the invention, the corresponding polyol component is in each case reacted with an at least difunctional isocyanate. In principle, any isocyanate with at least two isocyanate groups can be used as the at least difunctional isocyanate, but compounds with two to four isocyanate groups, in particular with two isocyanate groups, are generally within the scope of the present invention prefers. The polyisocyanates already mentioned above are particularly suitable for producing the reactive diluents.

The compound present as a real thinner in the context of the present invention preferably has at least one alkoxysilane group, di- and trialkoxysilane groups being preferred among the alkoxysilane groups.

Under certain conditions of use, it can be advantageous if the functional groups of the reactive diluent have a different reactivity to moisture or the hardener used in each case than the functional groups of the first polyurethane with the higher molecular weight.

The preparation according to the invention generally contains the polyurethane according to the invention or a mixture of two or more polyurethanes according to the invention and the reactive diluents or a mixture of two or more reactive diluents in such a ratio that the preparation has a viscosity of at most 200,000 mPas (Brookfield RVT, 23 ° C, spindle 7, 2.5 rpm). For this purpose, as a rule, a proportion of reactive diluents (which also includes a mixture of two or more reactive diluents), based on the total preparation, is from about 1% by weight to about 70% by weight, in particular from about 5% by weight. % up to about 25% by weight.

In addition to or instead of a reactive diluent, a plasticizer can also be used to reduce the viscosity of the polyurethanes according to the invention.

In the context of the present invention, plasticizers are compounds which generally reduce the viscosity of a preparation which contains a polyurethane according to the invention or a mixture of two or more polyurethanes according to the invention.

Examples of plasticizers are esters such as abietic acid esters, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetic acid esters, esters of higher fatty acids with about 8 to about 44 carbon atoms, esters with OH groups or epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphoric acid esters, phthalic acid esters, linear or branched alcohols containing 1 to 12 carbon atoms, propionic acid esters, sebacic acid esters, sulfonic acid esters, thiobutyric acid esters, trimellitic acid esters, Citric acid esters and esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof. The asymmetric esters of difunctional, aliphatic dicarboxylic acids are particularly suitable, for example the esterification product of monooctyl adipate with 2-ethylhexanol (Edenol DOA, Henkel, Dusseldorf).

Also suitable as plasticizers are the pure or mixed ethers of monofunctional, linear or branched C _4-1 β alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, FA. Henkel, Düsseldorf).

Further examples of plasticizers are end-capped polyethylene glycols such as polyethylene or polypropylene glycol di-C _1-4 alkyl ethers, in particular the dimethyl or diethyl ether of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.

Also suitable as plasticizers in the context of the present invention are diurethanes which can be prepared, for example, by reacting diols with OH end groups with monofunctional isocyanates by selecting the stoichiometry in such a way that essentially all free OH groups react. Any excess isocyanate can then be removed from the reaction mixture, for example by distillation. Another method for the production of diurethanes consists in the reaction of monofunctional alcohols with diisocyanates, all of the NCO grapples reacting as far as possible.

As a rule, the plasticizer is added in an amount of about 1 to about 20% by weight, based on the preparation. 3-15% by weight is preferred and 8-12% by weight is very particularly preferred.

In addition to the plasticizers, the preparation can also contain other additives which generally serve to modify certain material properties of the preparation before or after processing or which promote the stability of the preparation before or after processing.

The invention therefore furthermore relates to a preparation comprising a silanized polyurethane according to the invention or a mixture of two or more thereof and a plasticizer and one or more compounds selected from the grapple, consisting of antioxidants, catalysts, tackifiers, fillers and UV stabilizers.

The amine oxidants are used in an amount of up to 7% by weight, in particular about 2-5% by weight.

The preparation according to the invention can furthermore contain up to 5% by weight of catalysts for controlling the curing rate. Suitable catalysts are, for example, organometallic compounds such as iron or tin compounds, in particular the 1,3-dicarbonyl compounds of iron or of tetravalent or tetravalent tin, in particular the Sn (II) carboxylates or the dialkyl-Sn- (IV ) Dicarboxylates or the corresponding dialkoxylates, for example dibutyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin maleate, tin (II) octoate, tin (II) phenolate or the acetylacetonates of tetravalent or tetravalent tin.

If use as an adhesive is intended, the preparation according to the invention can contain up to about 30% by weight of conventional tackifiers. Suitable tackifiers are, for example, resins, terpene oligomers, coumarone / hide resins, aliphatic, petrochemical resins and modified phenolic resins.

Furthermore, the preparation according to the invention can contain up to about 80% by weight of fillers. Suitable fillers are, for example, inert inorganic compounds such as chalk, callum flour, precipitated silica, pyrogenic silica, zeolites, bentonites, ground minerals, glass balls, glass powder, glass fibers and glass fiber short cuts as well as other inorganic and organic fillers known to the person skilled in the art, in particular fiber short cuts or hollow plastic spheres. If necessary, fillers can be used which impart thixotropy to the preparation, for example swellable plastics such as PVC.

The preparation according to the invention can contain up to about 2% by weight and preferably about 1% by weight of UV stabilizers. The so-called hindered amine light stabilizers (HALS) are suitable as UV stabilizers. In the context of the present invention, it is preferred if a UV stabilizer is used which carries a silane cluster and is incorporated into the end product during crosslinking or curing. The products Lowilite 75 and Lowilite 77 (Great Lakes, USA) are particularly suitable.

It is often sensible to further stabilize the preparations according to the invention against the penetration of moisture by means of drying agents in order to increase the shelf life even further.

Such an improvement in shelf life can be calibrated, for example, by using desiccants. Suitable as desiccants are all compounds which react with water to form a group which is inert to the reactive grapples present in the preparation and which undergo changes in their molecular weight which are as small as possible. Furthermore, the reactivity of the desiccants towards moisture which has penetrated into the preparation must be higher than the reactivity of the end groups of the polyurethane or polyurea according to the invention present in the preparation or the mixture of two or more polyurethanes or two or more polyureas or the mixture of one polyurethane and two or more polyureas or the mixture of two or more polyurethanes and one polyurea or the mixture of two or more polyurethanes and two or more polyureas.

Isocyanates, for example, are suitable as dry agents.

In a preferred embodiment, however, silanes are used as drying agents. For example, vinyl silanes such as 3-vinyl propyltri-ethoxysilane, oxime silanes such as methyl-0, O ', 0 "- butan-2-one-trioximosilane or 0.0', 0", 0 '"- butan-2-ontetraoximosilane (CAS no. 022984-54-9 and 034206-40-l or benzamidosilanes such as bis (N-methylbenzamido) methylethoxysilane (CAS No. 16230-35-6) or carbamatosilanes such as carbamatomethyltrimethoxysilane.

The above-mentioned reactive additives are also suitable as drying agents, provided that they have a molecular weight (M _n of less than about 5,000 and have end groups, the reactivity of which to moisture penetration is at least as great, preferably greater, than the reactivity of the reactive groups of the polyurethane according to the invention ,

The preparation according to the invention generally contains about 0 to about 6% by weight of drying agent. In principle, the compositions according to the invention can be prepared in any manner known to those skilled in the art. However, the methods described below are particularly suitable.

The present invention relates to a process for the production of compositions which comprise at least one polyurethane carrying at least one silyl group. Reaction of a) at least one asymmetric diisocyanate as component A with b) at least one silane of the general formula II

, wherein the radicals R ¹ to R each independently of one another are a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 C atoms, a saturated or unsaturated cycloalkyl radical having 4 to about 24 C atoms or an aryl radical having 6 to about 24 C atoms, R ^{7 represents} an optionally substituted alkylene radical with 1 to about 44 C atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 C atoms or an optionally substituted arylene radical with 6 to about 24 C atoms, n , m and j each represent an integer from 0 to 3, where m + n + j = 3, a an integer from 0 to 3, b an integer from 0 to 2 and c a number from 0 stands to 8, and R ⁸ represents a linear or branched C _{1- 4} alkyl, Cycloallcyl-, phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl, as component B, and c) optionally a polyol or a mixture of two or more poly olen or a polyamine or a mixture of two or more polyamines or a polyol and a mixture of two or more polyamines or a mixture of two or more polyols and a polyamine or a mixture of two or more polyols and a mixture of two or more polyols as component C, the number ratio of NCO grappa to silane grapple in the finished one

Composition is 90:10 to 10:90. The implementation can basically be carried out in one step. However, it is particularly advantageous in the context of the present invention if the reaction is carried out in at least two steps.

In a first step, preferably at least one monomeric asymmetric diisocyanate is reacted with at least one polyol or a polyamine or a mixture thereof, as was described in more detail above as component C, in such a way that a compound with at least one isocyanate group or a mixture of two or more such compounds are formed and this compound is reacted in a subsequent step with at least one silane of the general formula II.

The reaction of component C with component A can be carried out in any manner known to the person skilled in the art according to the general rules of polyurethane production. The reaction can take place, for example, in the presence of solvents. All solvents commonly used in polyurethane chemistry can be used as solvents, in particular esters, ketones, halogenated hydrocarbons, allcans, alkenes and aromatic hydrocarbons. Examples of such solvents are methylene chloride, trichlorethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, Methlisobutylketon, methoxybutyl acetate, cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, diisobutyl ketone, dioxane, ethyl acetate, Ethylenglylcolmonobutyletheracetat, ethylene glycol monoethyl acetate, 2-ethylhexyl acetate, Glylcoldiacetat, heptane, hexane , Isobutyl acetate, isooctane, isopropyl acetate, methyl ethyl ketone, tetrahydrofuran or tetrachlorethylene or mixtures of two or more of the solvents mentioned.

If the reaction components themselves are liquid or at least one or more of the reaction components form a solution or dispersion of further, insufficiently liquid reaction components, the use of solvents can be dispensed with entirely. Such a solvent-free reaction is preferred in the context of the present invention.

To carry out the process according to the invention, component C, if appropriate together with a suitable solvent, is placed in a suitable vessel and dried. The asymmetric diisocyanate is then added. In order to accelerate the reaction, the temperature is usually raised to about 40-80 ° C. Such a reaction is usually carried out using a catalyst, in particular when a polyol or a mixture of two or more polyols is used as the reaction partner.

The catalysts usually used in the production of such a polyurethane include, for example, strongly basic amides such as 2,3-dimethyl-3,4,5,6-tetrahydropyriimdin, tris- (dialkylaminoalkyl) -s-hexahydrotriazines, e.g. B. tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine or the usual tertiary amines, e.g. B. triethylamine, tributylamine, dimethylbenzylamine, N-ethyl-, N-methyl-, N-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodiethyl ether, 2- (dimethylaminoethoxy) ethanol, 1,4-diazabicyclo [2,2,2] octane, 1- Azabicyclo [3,3,0] octane, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine-1,6,

Pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, N, N'-dimethylpiperazine, 1,2-dimethylimidazole, di- (4-N, N-dimethylaminocyclohexyl) methane and the like, and also organic metal compounds such as titanium acid esters, iron compounds such as, for , B. iron (III) acetylacetonate, tin compounds, for. B. tin (ιI) salts of organic carboxylic acids, for example tin (II) diacetate, the tin (II) salt of 2-ethylhexanoic acid (tin (II) octoate), tin (II) - dilaurate or the Dialkylziιm- (IV) salts of organic carboxylic acids, such as. B. dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (rV) maleate or dioctyltin (IV) diacetate or the like, and dibutyltin (IV) dimercaptide or mixtures of two or more of the catalysts mentioned and synergistic combinations of strongly basic amines and organic metal compounds are used. The catalysts can be used in customary amounts, for example about 0.002 to about 5% by weight, based on the polyalcohols.

If it is desired to use a catalyst, the catalyst is generally added to the reaction mixture in an amount of from about 0.005% by weight or from about 0.01% to about 0.2% by weight, based on the overall batch ,

The reaction time depends on the polyol components used, on the isocyanate component used, on the reaction temperature and on the catalyst which may be present. The total reaction time is usually about 30 minutes to about 20 hours. The reaction is felt in such a way that the ratio of NCO groups to functional groups which are reactive towards NCO groups, for example OH groups or amino groups, is selected such that a prepolymer is formed which has at least one NCO group.

The reaction with the amines carrying silyl groups then takes place in a manner known to the person skilled in the art. For this purpose, an NCO prepolymer is reacted, for example with an aminosilane, optionally together with a suitable solvent in a suitable vessel. The temperature is increased, for example, to about 40 to about 80 ° C. Catalysts can optionally be added to accelerate the reaction.

The ratio of NCO groups to silyl groups in the starting materials is chosen so that the desired ratio of isocyanate groups to silyl groups is obtained after the reaction.

Another object of the invention is the use of the compositions according to the invention or the preparations according to the invention for the production of reactive one- or two-component surface coating compositions, in particular reactive one- or two-component adhesives or sealants, for the production of reactive hot-melt adhesives and solvent-free or solvent-containing laminating adhesives and for the production of assembly foams , Casting compounds as well as soft, hard and integral foams.

It is particularly advantageous here that a higher foam yield can be achieved in assembly foams than with conventional silane foams. Less foaming is also observed than in pure PU adhesives.

The invention will now be explained in more detail by examples. EXAMPLES:

Example 1 (not of the invention ^'):

97 g of polypropylene glycol 400 and 40.0 g of tris (monochlorisopropyl) phosphate (flame retardant) were placed in a 500 ml reaction flask with stirring, cooling and heating options, and 0.1 g of dibutyltin laurate was added and the mixture was heated to 50 ° C. with stirring. 63.0 g of 2,4-TDI were added dropwise with stirring at 50 ° C. and the mixture was stirred at 50 ° C. for 20 hours. The low-viscosity product was stored moisture-tightly under nitrogen in an atmospheric sphere in a glass vessel. A free TDI monomer content of 0.3% was determined by means of GPC analysis.

Example 2:

In a 500 ml reaction flask with stirring. Cooling and heating options were provided with 97 g of 400 polypropylene glycol and 40.0 g of tris (monochlorisopropyl) phosphate (flame retardant) and mixed with 0.1 g of dibutyltin laurate and heated to 50 ° C. with stirring. 63.0 g of 2,4-TDI were added dropwise with stirring at 50 ° C. and the mixture was stirred at 50 ° C. for 20 hours. 2.8 g of N-phenylaminomethyldimethoxymethylsilane were then added at room temperature and the mixture was heated at 60 ° C. for a further hour. The low-viscosity product was stored moisture-tight under nitrogen atmospheric sphere in a glass vessel. A content of free TDI monomer of <0.05% (detection limit) was determined by means of GPC analysis.

Example 3:

In one. 500 ml of reaction flask with stirring, cooling and heating options were placed in 97 g of 400 polypropylene glycol and 40.0 g of tris (monochloroisopropyl) phosphate (flame retardant) and mixed with 0.1 g of dibutyltin laurate and heated to 50 ° C. with stirring. 63.0 g of 2,4-TDI were added dropwise with stirring at 50 ° C. and the mixture was stirred at 50 ° C. for 20 hours. Then 6.7 g of N-phenylaminomethyldimethoxymethylsilane were added at room temperature and the mixture was stirred at 60 ° C. for a further hour. The medium-viscosity product became moisture-proof under Nitrogen atmospheres stored in a glass jar. A free TDI monomer content of <0.05% (detection limit) was determined by means of GPC analysis.

Example 4:

97 g of polypropylene glycol 400 and 40.0 g of tris (monochlorisopropyl) phosphate (flame retardant) were placed in a 500 ml reaction flask with stirring, cooling and heating options, and 0.1 g of dibutyltin laurate was added and the mixture was heated to 50 ° C. with stirring. 63.0 g of 2,4-TDI were added dropwise with stirring at 50 ° C. and the mixture was stirred at 50 ° C. for 20 hours. Then 8.5 g of N-phenylaminomethyldimethoxymethylsilane were added at room temperature and the mixture was stirred at 80 ° C. for a further hour. The highly viscous product was stored moisture-tight under nitrogen atmospheres in a glass vessel. A free TDI monomer content of <0.05% (detection limit) was determined by means of GPC analysis.

Example 5 (foam from composition according to Example 3):

82 g of the prepolymer mixture from Example 3 were mixed at room temperature with 1.6 g Tegostab B 8465 (foam stabilizer) and 1.6 g PC Cat. DMDEE (N, N-dimorpholinodiethyl ether) was added and mixed with 22.7 9 blowing agent 152a in an aerosol can and foamed. The result was a white, fine-celled, soft, elastic foam with a tack-free time of 27 minutes.

Example 6 (not according to the invention):

36.8 g of polypropylene glycol 400 and 92.2 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating options and mixed with 0.04 g of dibutyltin laurate and heated to 50 ° C. with stirring. 71.8 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. The low-viscosity product was stored moisture-tight in a glass vessel under nitrogen atmospheres. A free MDI monomer content of 2.8% was determined by means of GPC analysis. Example 7:

36.8 g of polypropylene glycol 400 and 92.2 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating options and mixed with 0.04 g of dibutyltin dilaurate and heated to 50 ° C. with stirring. 71.8 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. Then 2.3 g of N-phenylaminomethyldimethoxymethylsilane were added and the mixture was stirred at 80 ° C. for a further 3 h. The low-viscosity product was stored moisture-tight in a glass vessel under a nitrogen atmosphere. A free MDI monomer content of 0.08% was determined by means of GPC analysis.

Example 8:

36.8 g of polypropylene glycol 400 and 92.2 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating possibilities and mixed with 0.04 g of dibutyltin dilaurate and heated to 50 ° C. under tubes. 71.8 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. Then 4.5 g of N-phenylaminomethyldimethoxymethylsilane were added and the mixture was stirred at 50 ° C. for a further 3 h. The medium-viscosity product was stored moisture-tight in a glass vessel under a nitrogen atmosphere. A free MDI monomer content of 0.06% was determined by means of GPC analysis,

Example 9:

36.13 g of polypropylene glycol 400 and 92.2 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating possibilities and mixed with 0.04 g of dibutyltin laurate and heated to 50 ° C. with stirring. 71.8 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. 6.8 g of N-phenylaminomethyldimethoxymethylsilane were then added and the mixture was stirred at 80 ° C. for a further 3 h. The highly viscous product was stored moisture-tight in a glass vessel under a nitrogen atmosphere. A free MDI monomer content of <0.05% (detection limit) was determined by means of GPC analysis. Example 10 (foam from composition according to Example 8 ^" ):

81.4 g of the prepolymer mixture from Example 8 were mixed at room temperature with 1.6 g Tegostab B 8485 (foam stabilizer) and 1.6 g PC Cat. DMDEE (N, N-dimorpholinodiethyl ether) was added and mixed with 21.1 g of propellant 152a in an aerosol can and foamed. The result was a white, fine-celled, elastic, semi-hard foam with an adhesive free time of 12 minutes. The bulk density was 48 g / l.

Example 11 (not according to the invention):

41.6 g of polypropylene glycol 400 and 104.1 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating options, and 0.1 g of dibutyltin laurate was added and the mixture was heated to 50 ° C. with stirring. 104.1 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. The product was stored moisture-tight in a glass vessel under a nitrogen atmosphere. A free MDI monomer content of 4.7% was determined by means of GPC analysis.

Example 12:

41.6 g of polypropylene glycol 400 and 104.1 g of polypropylene glycol 1000 were placed in a 500 ml reaction flask with stirring, cooling and heating facilities, and 0.1 g of dibutyltin laurate was added and the mixture was heated to 50 ° C. with stirring. 104.1 g of 2,4'-MDI were added with stirring. The mixture was stirred at 50 ° C for 20 hours. Then 75.8 g of N-phenylaminomethyldimethoxymethylsilane were added and the mixture was stirred at 80 ° C. for a further 3 h. The product was stored moisture-tight in a glass vessel under a nitrogen atmosphere. A free MDI monomer content of <0.05% (detection limit) was determined by means of GPC analysis.

Example 13:

Adhesives were prepared with the polymers from Examples 11 and 12 with the addition of 0.2% DBU (1,8-diazabicyclo- [5.4.0] -undec-7-ene) and 0.2% DMDEE (N, N-dimorpholinodiethyl ether) and wood-wood bonding. The tensile shear strengths were determined after 7 days of storage. They also drilled into a block of wood Holes (diameter = 10 mm, depth = 10 mm) filled with the respective adhesives and the expansion of the adhesives determined during curing.

Claims

claims

1. Composition comprising at least one polyurethane bearing at least one isocyanate group and at least one polyurethane bearing a silyl group, the polymers having at least two different types of urethane groups and a silyl group of the general formula I as the silyl group

wherein the radicals R ¹ to R ⁶ each independently represent a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 carbon atoms, a saturated or unsaturated cycloalkyl radical having 4 to about 24 carbon atoms or an aryl radical having 6 to about 24 C atoms, R ^{7 represents} an optionally substituted alkylene radical with 1 to about 44 C atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 C atoms or an optionally substituted arylene radical with 6 to about 24 C atoms, n , m and j each represent an integer from 0 to 3, where m + n + j = 3, a an integer from 0 to 3, b an integer from 0 to 2 and c a number from 0 to 8 and R ^{8 represents} a linear or branched, saturated or unsaturated C _1-24 -alkyl cyclyl, cycloalkyl, phenyl, tolyl, mesityl, trityl or 2,4,6-tri-tert-butylphenyl radical , is included and the composition is less than 0.1 % By weight of monomeric isocyanates and the ratio of isocyanate groups to silyl groups is about 90:10 to about 10:90.

2. Composition according spoke 1, characterized in that the different types of urethane stacks were generated by using at least one asymmetric polyisocyanate. 3. The composition according to claim 1 or 2, characterized in that the different types of urethane groups or urea groups were produced by using at least one polyisocyanate which has at least two isocyanate groups, the reactivity of which to a functional group reactive with isocyanates differs by at least a factor of 1.1 ,

4. Composition according to one of claims 1 to 3, characterized in that the different urethane group types or urea group types were prepared by using asymmetric MDI or IPDI or TDI or a mixture of two or more thereof.

5. Preparation comprising at least one polyurethane carrying at least one silyl group or at least one polyurea bearing at least one silyl group, which can be prepared by reacting at least three components A, B and C, where a) as component A an asymmetric polyisocyanate or a mixture of two or more asymmetric polyisocyanates, b) as component B a silane of the general formula II

, wherein the radicals R ¹ to R ^δ each independently of one another for a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 C atoms, a saturated or unsaturated cycloalkyl radical with 4 to about 24 C atoms or an aryl radical with 6 to about 24 carbon atoms, R ^{7 represents} an optionally substituted alkylene radical with 1 to about 44 carbon atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 carbon atoms or an optionally substituted arylene radical with 6 to about 24 carbon atoms, n, m and j each represent an integer from 0 to 3, where m + n + j = 3, a an integer from 0 to 3, b an integer from 0 to 2 and c a number from 0 to 8 and R ^{8 represents} a linear or branched Ci-io-alkyl radical, cyclohexyl, phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl radical and c) as component C a polyol or a mixture of two or more polyols or a polyamine or a mixture of two or more polyamines or a polyol and a mixture of two or more polyamines or a mixture of two or more polyols and a polyamine or a mixture of two or more polyols and a mixture of two or more polyols is used, the number ratio of NCO groups to silyl groups being 10:90 to 90:10.

6. Preparation according to claim 5, characterized in that it contains one or more additives.

7. Preparation according spoke 5 or 6, characterized in that it contains, as additives, compounds selected from the group consisting of desiccants, plasticizers, reactive diluents, antioxidants, catalysts, hard materials, fillers and UV stabilizers.

8. Preparation according to one of claims 5 to 7, characterized in that it contains less than 0.1 wt .-% of monomeric isocyanates.

9. A process for the preparation of compositions which comprise at least one polyurethane bearing a silyl group or at least one polyurea bearing a silyl group and at least one polyurethane bearing an NCO group or at least one polyurea bearing an NCO group, by reacting a) at least one asymmetrical one Diisocyanate with b) at least one polyol or a mixture of two or more polyols or a polyamine or a mixture of two or more polyamines or a polyol and a mixture of two or more polyamines or a mixture of two or more polyols and a polyamine or one Mixture of two or more polyols and a mixture of two or more polyols and c) at least one silane of the general formula II

OD , wherein the radicals R ¹ to R each independently represent a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to about 24 carbon atoms, a saturated or unsaturated cycloalkyl radical having 4 to about 24 carbon atoms or an aryl radical having 6 to about 24 C atoms, R ^{7 represents} an optionally substituted alkylene radical with 1 to about 44 C atoms, an optionally substituted cycloalkenyl radical with 6 to about 24 C atoms or an optionally substituted arylene radical with 6 to about 24 C atoms, n , m and j each represent an integer from 0 to 3, where m + n + j = 3, a an integer from 0 to 3, b an integer from 0 to 2 and c a number from 0 to 8 and R ^{8 represents} a linear or branched Ci-io-alkyl radical, cycloalkyl, phenyl, tolyl, mesityl, trityl, 2,4,6-tri-tert-butylphenyl radical, the weight ratio of NCO -Grappen to silane stacks in the composition 90:10 to 10: 90 is.

10. The method according spoke 9, characterized in that the implementation is carried out in at least two steps.

11. The method according spoke 9 or 10, characterized in that in a first step at least one monomeric asymmetric diisocyanate is reacted with at least one polyol or polyamine or a mixture thereof such that a compound with at least one isocyanate group or a mixture of two or more of these Compounds are formed and this compound is reacted in a subsequent step with at least one silane of the general formula II.

2. Use of a composition according to one of claims 1 to 4 or a preparation according to one of claims 5 to 8 or a polyurethane or polyurea carrying silyl groups prepared according to one of claims 9 to 11 for the production of surface coating agents, adhesives, assembly foams, casting compounds and plasticizers , Rigid and integral foams.