DE102006056892A1 - Methylol-containing silanes - Google Patents

Abstract

The invention relates to compounds (V) of the general formula (1) (R <SUP> 1 </ SUP> O) <SUB> 3-a </ SUB> R <SUP> 2 </ SUP> <SUB> a < / SUB> Si-R <SUP> 3 </ SUP> -NR <SUP> 4 </ SUP> R <SUP> 5 </ SUP> (1), where R <SUP> 4 </ SUP> a -CH <SUB> 2 </ SUB> OR <SUP> 6 </ SUP> radical or is a -CH (OH) group, and a, R <SUP> 1 </ SUP>, R <SUP> 2 < / SUP>, R <SUP> 3 </ SUP>, R <SUP> 4 </ SUP>, R <SUP> 5 </ SUP> and R <SUP> 6 </ SUP> have the meanings given in claim 1 with the proviso that at least one of the radicals R <SUP> 3 </ SUP> or R <SUP> 5 </ SUP> bears a - (C = O) group in the direct vicinity of its jointly bonded nitrogen atom. The invention likewise provides a process for the preparation of compounds (V) and their use for the condensation to form polysiloxanes.

Description

The The present invention relates to methylolated organofunctional Silanes, their preparation and use for condensation to polysiloxanes.

silicones respectively silicone-containing formulations and composites are known and are in the form of films, coatings and Coatings in large Quantities for modification and equipment of various materials and fibers used. Their range of properties includes silicones or silicone-containing formulations purely organic films, coatings and Superior coatings in many ways. So leads the Use of silicone products to a substantial improvement otherwise not available, but usually more desirable Properties, such as flow behavior, gas permeability, Abrasion resistance, hydrophobicity, smoothness, feel or gloss of treated substrate.

One great Problem of all coatings, but especially in their chemistry limited silicone coatings, is the often lack of adhesion on the respective treated substrate (so-called permanence of the coating). this leads to to simply remove the coating mechanically can be, for example, by rubbing or rubbing, or by chemical Stress, such as contact with various solvents and / or exposure to certain pH environments (such as those found in washing processes), release from the substrate again can.

One Approach to solve the problem of lack of permanence exists therein, the individual silicone polymer chains both with each other as also to crosslink with the substrate to be treated and in this way the mechanical and chemical resistance and thus the permanence of the overall system.

The Networking with each other and the bond to the substrate can thereby both by non-covalent interactions as well as by covalent Bindings take place.

Among the non-covalent interactions, hydrogen bonds in particular have become established. These provide, for example, formed in the form of urethane or urea groups within the group of thermoplastic silicone elastomers with each other for an increased network density and by interaction with hydrogen bond forming groups of the substrate (eg., Hydroxyeinheiten in cellulose surfaces) also for a certain fixation. Production and use of such silicone thermoplastic elastomers is disclosed, inter alia, in the publications EP 0 606 532 A1 and EP 0 342 826 A2 described in detail.

Another noncovalent crosslinking mechanism relies on acid-base interactions between Lewis basic / Lewis acidic groups of the silicone polymer with Lewis acidic / Lewis basic groups of the substrate or polymer. Examples of these are amino-functional silicone oils which, as is known, have a positive influence, in particular, on the hydrophobicity and softness of textiles and, because of their Lewis-basic amino functionalities, have the property of being 'absorbed' onto the Lewis acidic fibers. Such silicone amine oils and their applications are, for example, in EP 1555011 A described.

Both Mechanisms are common that their permanence generated only temporarily and is insufficient and the coating both mechanically as also chemically easily removed.

substantially better permanence is achieved when the fixation of polymer and substrate or crosslinking of polymer with each other the formation of covalent bonds takes place.

A Covalent crosslinking can be effected, for example, by the silicone polymers already in the manufacture by use from Z. B. trifunctional building blocks are crosslinked. The polymers thus obtained However, they are characterized in their processing properties (eg. Melt viscosities Deformability, solubility in an application aid). Also is a fixation to the substrate usually no longer possible. A subsequent Fixation / cross-linking following a successful application therefore always more meaningful.

Such subsequent fixation / crosslinking may be effected, for example, by the presence of alkoxysilyl groups in the silicone polymer which provide better permanence by hydrolysis and condensation with hydroxy groups of the substrate or hydroxy groups of other silicone polymers. Such alkoxysilyl-containing silicone polymers are, for example, in EP 1544223 A1 described. The at the on Bonding to the substrate resulting Si-OC or Si-OE bonds (E = element of the substrate) are, however, usually hydrolysis-labile and therefore easy to reopen, whereby a good permanence, especially in an aqueous environment, usually not given , On the other hand, the formation of comparatively stable siloxane bonds Si-O-Si generally requires a previous treatment of the substrate with corresponding silanes.

Another crosslinking mechanism which is already known in the field of purely organic polymers concerns the so-called N-methylol crosslinking. In this case, polymers which carry N-methylolamide groups are produced by copolymerization with suitable monomers. These are known to bind covalently to alcoholic groups even at lower temperatures in the absence of water at elevated temperature or in the presence of acidic catalysts. Likewise, they can react with each other and thus cause a crosslinking of the polymer. In both cases, covalent ether bonds or methylene bridge bonds are formed, which are known to be very strong and are only broken again under extreme physical or chemical stresses. This effect makes itself for example EP 0 143 175 A exploiting the free radical emulsion polymerization polymer dispersions which are nachvernetzbar on the just discussed Methylolmechanismus.

In principle, methylolamide groups can be prepared by reacting amines with formaldehyde, but as a rule, the reaction leads to polymeric condensation products, with the result that polymeric networks ultimately result via imine intermediates. This reaction of amines with formaldehyde has already been described: US 3461100 describes condensation products of aldehydes and primary di- and monoamines. The resulting high polymer condensation products are discussed as protective coatings. DE 100 47 643 A1 describes polymeric condensation products of aldehydes and silicon amines, which are, however, exclusively high polymer and highly crosslinked.

In In both publications, the product is already highly polymer after conversion in front. It is no longer a reactive form, like add the monoaddition product of a formaldehyde molecule Amin, and thus stands for subsequent reactions on substrates or post-crosslinking reactions are no longer available.

The situation is different when the postcrosslinking-capable silicone polymers are synthesized by hydrolysis and condensation from already N-methylolated building blocks. In general, however, these defined monomers, in contrast to the subsequent modification of already existing silicones, must first be prepared under anhydrous conditions, since they have hydrolysis-labile alkoxy groups. Building blocks of this kind are in WO 0021967 again described only in the case of primary amines.

The invention relates to compounds (V) of the general formula (1) (R ¹ O) _3-a R ² _a Si-R ³ -NR ⁴ R ⁵ (1), in which
R ^{1 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR ¹⁰ groups and optionally substituted by -CN or Halogen may be substituted;
R ^{2 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain is interrupted by non-adjacent oxygen, sulfur or -NR 10 - groups and optionally with -CN or -halogen may be substituted;
a is 0, 1, or 2;
R ^{3 is} a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical each having 1 to 20 C atoms, wherein the carbon chain by non-adjacent - (CO) -, -O-, -S- or -NR ⁹ Groups may be interrupted and optionally substituted with -CN or -halogens;
R ^{4 is} a -CH ₂ OR ⁶ radical or is a -CH (OH) group covalently linked to R ⁹ or an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical covalently linked to R ⁸ , respectively 1 to 20 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ⁹ - groups and may optionally be substituted by -CN or -halogen;
R ^{5 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or - (CO) -NR ⁸ R ⁹ , wherein the carbon chain by not adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen and may optionally be terminated by a radical SiR ² _a (OR ¹ ) _3-a ;
R ^{6 is} a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, where the carbon chain may be interrupted by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups and may optionally be substituted by -CN or -halogens;
R ^{7 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups interrupted and optionally substituted with -CN or -halogen and may be terminated by a radical SiR ² _a (OR ¹ ) _3-a ;
R ^{8 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen and may optionally be covalently bonded to R ⁴
R ^{9 is} a radical -CH ₂ OH or a group -CH (OH) - which is covalently linked to R ⁴ ;
R ^{10 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹¹ groups interrupted and optionally substituted with -CN or -halogen;
R ^{11 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms;
where the radicals R ⁴ and R ^{8 can be} covalently bonded with the proviso
in that at least one of the radicals R ³ or R ⁵ bears a - (C = O) group in the direct vicinity of its jointly bonded nitrogen atom.

Preferably, in the compounds (V) at least one free radical -CH ₂ OH or a group -CH (OH) - present.

The compounds (V) are storage-stable in the appropriate organic solvents and condensable by methods known to those skilled in the art to the methylol -CH ₂ OH and / or -CH (OH) - postcrosslinkable polysiloxanes having excellent permanence on many substrates often do not require pretreatment.

R ¹ is preferably alkyl radicals having in each case 1 to 6 C atoms, preferably n-propyl, i-propyl, ethyl and methyl, in particular the methyl radical.

R ² is preferably an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, preferably n-propyl, i-propyl, ethyl and methyl, in particular the methyl radical; particularly preferably the methyl radical.

R ³ is preferably divalent hydrocarbon radicals, such as -CH ₂ - and - (CH ₂ ) ₃ -; particularly preferably -CH ₂ -.

R ⁵ is preferably alkyl radicals having in each case 1 to 6 C atoms which may be terminated by a radical -SiR ² _a (OR ¹ ) _3-a or by a radical - (CO) -OR ⁷ or - ( CO) -NR ⁸ R ⁹ . Particularly preferred are the methyl radical, the radical - (CH ₂ ) _n -SiR ² _a (OR ¹ ) _3-a with n = 1-3, a radical - (CO) -OR ⁷ or - (CO) -NR ⁸ R ⁹ .

R ⁶ is preferably a hydrogen atom or an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, such as the phenyl radical. Particularly preferred is the hydrogen atom or the methyl radical.

R ⁷ is preferably an alkyl radical having in each case 1 to 6 C atoms, which may be terminated by a -SiR ² _a (OR ¹ ) _3-a unit; particularly preferably the methyl radical, or the - (CH ₂ ) _n -SiR ² _a (OR ¹ ) _3-a radical where n = 1-3.

R ⁸ , R ¹⁰ and R ¹¹ are each preferably an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, such as the phenyl radical. Particularly preferred is the methyl radical.

halogen radicals are preferably fluorine, chlorine and bromine.

The invention likewise provides a process for preparing compounds (V) by reacting compounds (VI) of general formula (2), (R ¹ O) _3-a R ² _a Si-R ³ -NHR ⁵ (2), in which
R ^{1 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR ¹⁰ groups and optionally substituted by -CN or Halogen may be substituted;
R ^{2 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR ¹⁰ groups and optionally substituted by -CN or Halogen may be substituted;
a is 0, 1, or 2;
R ^{3 is} a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, where the carbon chain is protected by non-adjacent - (CO) -, -O-, -S- or -NH- Interrupted groups and may optionally be substituted by -CN or -halogens;
R ^{5 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or - (CO) -NR ⁸ H, wherein the carbon chain by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups interrupted and may optionally be substituted by -CN or -halogen and may optionally be terminated by a radical SiR ² _a (OR ¹ ) _3-a may be terminated;
R ^{6 is} a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, wherein the carbon chain is represented by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen;
R ^{7 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups interrupted and optionally substituted with -CN or -halogen and may be terminated by a radical SiR ² _a (OR ¹ ) _3-a ;
R ^{8 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups interrupted and optionally substituted with -CN or -halogen,
R ^{10 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹¹ groups interrupted and optionally substituted with -CN or -halogen;
R ^{11 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms;
with the proviso
at least one of the radicals R ³ or R ⁵ bears a - (C = O) group in the direct vicinity of its jointly bonded nitrogen atom,
with anhydrous formaldehyde.

The used formaldehyde, for example, in monomeric form of Formaldehyde, such as formaldehyde gas, but also in condensed form, for example as paraformaldehyde, Trioxane or other formaldehyde condensates. Also can one Formaldehyde derivative, such as glyoxal.

The Compounds (V) can in the form of organic solutions as well as in pure form.

The Preparation of the compounds (V) with formaldehyde can be carried out both in Dispersion, in organic solution as well as in solid substance, continuous or discontinuous respectively.

Prefers an optimal and homogeneous mixing of the ingredients takes place under the reaction conditions, with a phase incompatibility between the reaction components optionally by solubilizers is prevented.

Preferably become those leading to the compounds (V) of the general formula (1) precursors (V1) of the general formula (2) in a suitable formaldehyde inert, solvent solved or suspended and then added to the formaldehyde.

When solubilizers preferred are ethers, such as tetrahydrofuran and dioxane, hydrocarbons, such as toluene, xylene, chlorinated hydrocarbons, ketones, such as acetone and methyl ethyl ketone and esters, and mixtures thereof. solubilizers with a boiling point or boiling range of up to 120 ° C at 0.1 MPa are preferred.

The compounds (V) present as methylol ethers in which R ^{6 has} a meaning other than hydrogen are readily accessible from the resulting primary ethylols in which R ^{6 is} a hydrogen atom by consecutive etherification methods familiar to the person skilled in the art.

The compounds (V) can be condensed to polysiloxanes. These polysiloxanes are stable on storage and are suitable in pure form or as a constituent of formulations as coating agents, binders and coating compositions for a variety of substrates, especially fibers of any kind, such as textile fibers, cellulose fibers, cotton and paper fibers, as well as plastic fibers, including but not limited are on polyester, polyamide or polyurethane fibers. Also, they are useful for coating moldings and surfaces capable of chemically reacting with methylol functions, for example, wood or wood composites, as well as paper-coated substrates and molded articles. The treatment of the above substrates with the polysiloxanes obtainable by condensation of the compounds (V) imparts to the treated substrate typical silicone properties on its surface, such as, for example, hydrophobicity, anti-blocking effects or softening.

All The above symbols of the above formulas have their meanings each independently on. In all formulas, the silicon atom is tetravalent.

So far Unless otherwise indicated, all quantities and quantities are in the examples Percentages by weight, all pressures 0.10 MPa (abs.) And all Temperatures 20 ° C.

Examples

In Examples 1 to 6 below, the following compounds were used or prepared:

example 1

In A 500 ml three-neck round bottomed flask is 8.01, with exclusion of water g (50.0 mmol) of the amidosilane 1 and 1.50 g (50.0 mmol) of paraformaldehyde suspended in 90 ml of dry toluene at room temperature. The reaction mixture will over 2.5 hours at 70 ° C touched. This in the form of a toluene solution product containing 8.51 g (44.5 mmol, 89%) 1 'is about some Days storage stable.

Example 2

In a procedure analogous to Example 1 are at room temperature 7.50 g (42.3 mmol) of the methylcarbamatosilane 2 and 1.28 g (42.5 mmol) of paraformaldehyde suspended in 150 ml of dry toluene. The Reaction mixture is over 3 h at 80 ° C touched. You get Product 2 'as toluolische solution containing 8.33 g (40.2 mmol, 95%).

Example 3

In for example 1 analogous procedure 8.03 g (45.3 mmol) of amidosilane 3 and 1.38 g (45.5 mmol) of paraformaldehyde in 120 ml of dry xylene at room temperature. The reaction mixture will over 5 h at 90 ° C touched. You get Product 3 'as xylene solution containing 7.69 g (37.1 mmol, 82%).

Example 4

In a procedure analogous to Example 1, 11.37 g (55.4 mmol) of the methylcarbamatosilane 4 and 1.67 g (55.5 mmol) of paraformaldehyde suspended in 120 ml of dry xylene at room temperature. The reaction mixture will over 6 h at 90 ° C touched. You get Product 4 'as xylene solution containing 11.34 g (48.2 mmol, 87%) over some Days storage stable.

Example 5

In a procedure analogous to Example 1, 6.00 g (22.7 mmol) of ureidosilane 5 and 1.36 g (45.4 mmol) of paraformaldehyde suspended in 100 ml of dry xylene at room temperature. The reaction mixture will over 3 h at 75 ° C touched. This in the form of an xylene solution containing 6.78 g (20.9 mmol, 92%) of product 5 'is over several Days storage stable.

Example 6

In In a 500 ml three-neck round bottom flask, add 6.78 g (20.9 mmol) of the bis (N, N'-methylol) ureidosilane 5 'in a two-phase mixture from 100 mL xylene and 15 mL water in the presence of 0.10 mL in NaOH (0.10 mmol) submitted. After a reaction time of 4 h at 60 ° C to obtain a turbid reaction solution, the in addition to higher N-methylolated oligosiloxanes containing product 6 as a main component.

Claims (8)

Compounds (V) of the general formula (1) (R ¹ O) _3-a R ² _a Si-R ³ -NR ⁴ R ⁵ (1), wherein R ^{1 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain interrupted by non-adjacent oxygen, sulfur or -NR ¹⁰ groups and optionally with -CN or -Halogen may be substituted; R ^{2 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR ¹⁰ groups and optionally substituted by -CN or Halogen may be substituted; a is 0, 1, or 2; R ^{3 is} a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical each having 1 to 20 C atoms, wherein the carbon chain by non-adjacent - (CO) -, -O-, -S- or -NR ⁹ Groups may be interrupted and optionally substituted with -CN or -halogens; R ^{4 is} a -CH ₂ OR ⁶ radical or is a -CH (OH) group covalently linked to R ⁹ or an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical covalently linked to R ⁸ , respectively 1 to 20 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ⁹ - groups and may optionally be substituted by -CN or -halogen; R ^{5 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or - (CO) -NR ⁸ R ⁹ , wherein the carbon chain by not adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen and may optionally be terminated by a radical SiR ² _a (OR ¹ ) _3-a ; R ^{6 is} a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, wherein the carbon chain is represented by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen; R ^{7 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups interrupted and optionally substituted with -CN or -halogen and may be terminated by a radical SiR ² _a (OR ¹ ) _3-a ; R ^{8 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups and may optionally be substituted by -CN or -halogen and may optionally be covalently bonded to R ⁴ R ^{9 is} a radical -CH ₂ OH or a group -CH (OH) - which is covalently linked to R ⁴ ; R ^{10 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹¹ groups interrupted and optionally substituted with -CN or -halogen; R ^{11 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms; where the radicals R ⁴ and R ^{8 can be} covalently bonded with the proviso that at least one of the radicals R ³ or R ⁵ in the direct vicinity of their jointly bonded nitrogen atom carries a - (C = O) group. Compounds (V) according to claim 1, wherein at least one free radical -CH ₂ OH or a group -CH (OH) - is present. Compounds (V) according to claim 1 or 2, in which R ¹ denotes an alkyl radical having 1 to 6 C atoms. Compounds (V) according to claim 1 to 3, in which R ² is an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms. Compounds (V) according to Claims 1 to 4, in which R ^{3 is} -CH ₂ - or - (CH ₂ ) ₃ -. Compounds (V) according to Claims 1 to 5, in which R ^{5 is} a methyl radical, a radical - (CH ₂ ) _n -SiR ² _a (OR ¹ ) _3-a with n = 1-3, a radical - (CO) - OR ⁷ or a residue - (CO) -NR ⁸ R ⁹ . Process for the preparation of compounds (V) by reacting compounds (V1) of general formula (2), (R ¹ O) _3-a R ² _a Si-R ³ -NHR ⁵ (2). wherein R ^{1 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain interrupted by non-adjacent oxygen, sulfur or -NR ¹⁰ groups and optionally with -CN or -Halogen may be substituted; R ^{2 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR ¹⁰ groups and optionally substituted by -CN or Halogen may be substituted; a is 0, 1, or 2; R ^{3 is} a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, where the carbon chain is protected by non-adjacent - (CO) -, -O-, -S- or -NH- Interrupted groups and may optionally be substituted by -CN or -halogens; R ^{5 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or - (CO) -NR ⁸ H, wherein the carbon chain by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups interrupted and may optionally be substituted by -CN or -halogen and may optionally be terminated by a radical SiR ² _a (OR ¹ ) _3-a may be terminated; R ^{6 is} a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, wherein the carbon chain is represented by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ groups may be interrupted and optionally substituted with -CN or -halogen; R ^{7 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups interrupted and optionally substituted with -CN or -halogen and may be terminated by a radical SiR ² _a (OR ¹ ) _3-a ; R ^{8 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR ¹⁰ groups R ^{10 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms, wherein the carbon chain by non-adjacent - (CO) -, -O-, -S- or -NR ¹¹ groups may be interrupted and optionally substituted with -CN or -halogen; R ^{11 is} an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms; with the proviso that at least one of R ³ or R ⁵ bears a - (C = O) group in the direct vicinity of its jointly bonded nitrogen atom, with anhydrous formaldehyde. Use of the compounds (V) according to claim 1 to 6 for condensation to polysiloxanes.