WO2008065134A1 - Silanes containing methylol groups - Google Patents

Abstract

The invention relates to compounds (V) of the general formula (1) (R1O)3-aR2aSi-R3-NR4R5 (1), where R4 is a -CH2OR6 radical or a -CH(OH)- group and a, R1, R2, R3, R4, R5 and R6 have the meanings given in claim 1, with the proviso that at least one of the radicals R3 or R5 bears a -(C=O) group directly adjacent to the nitrogen atom to which they are bound. The invention likewise relates to a process for preparing compounds (V) and their use for the condensation of polysiloxanes.

Description

 Methylol-containing silanes

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

Silicone or silicone-containing formulations and composites are known and are used in the form of films, coatings and coatings in large quantities for the modification and equipment of various materials and fibers.

In their range of properties, silicones or silicone-containing formulations are superior to purely organic films, coatings and coatings in many respects. Thus, the use of silicone products leads to a vast improvement in otherwise unavailable, but usually desirable properties, such as flow behavior, gas permeability, abrasion resistance, hydrophobicity, smoothness, feel or gloss of the treated substrate.

A major problem of all coatings, but in particular of limited in their chemistry silicone coatings, is the often lack of adhesion to the respective treated substrate (so-called permanence of the coating). As a result, the coating can either be easily removed mechanically, for example by rubbing or rubbing, or by chemical stress, such as contact with various solvents and / or exposure to certain pH environments (as used, for example, in washing processes occur), again from the substrate can solve.

One approach to solving the problem of lack of permanence is to add the individual silicone polymer chains both to one another and to the substrate to be treated network and thus increase the mechanical and chemical resistance and thus the permanence of the entire system.

Crosslinking and binding to the substrate can be effected both by non-covalent interactions and by covalent bonds.

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 thermoplastic silicone elastomers is described in detail, inter alia, in the publications EP 0 606 532 A1 and EP 0 342 826 A2.

Another noncovalent crosslinking mechanism is based 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, in particular have a positive influence on the hydrophobicity and softness of textiles and, because of their Lewis-basic amino functionalities, have the property of being 'grown up' on the Lewis acidic fibers. Such silicone amine oils and their applications are described for example in EP 1555011 A.

Both mechanisms have in common that their produced permanence is temporary and inadequate and the coating both can be easily removed mechanically as well as chemically.

Significantly better permanence is achieved when the fixation of polymer and substrate or the crosslinking of

Polymer is done to each other by forming covalent bonds.

A covalent crosslinking can for example take place in that the silicone polymers already in the preparation by using z. B. trifunctional building blocks are crosslinked. However, the resulting polymers are thereby adversely affected in their processing properties (eg, melt viscosities, deformability, solubility in an application aid). Also, a fixation to the substrate is usually no longer possible. Subsequent fixation / cross-linking following a successful application is therefore always more useful.

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 described for example in EP 1544223 Al. However, the Si-O-C or Si-OE bonds (E = element of the substrate) formed in the connection to the substrate are as a rule hydrolysis-labile and therefore easily reopened, as a result of which a good permanence, in particular in an aqueous medium, is generally achieved is not given. Forming comparatively stable siloxane bonds Si-O-Si is required however, usually again 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. EP 0 143 175 A utilizes this effect, for example, which uses free-radical emulsion polymerization to produce polymer dispersions which can be post-crosslinked via the methylol mechanism just discussed.

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 Pat. No. 3,461,100 describes condensation products of aldehydes and primary diamines and monoamines. The resulting high polymer condensation products are discussed as protective coatings. DE 10047643 A1 describes polymeric condensation products of aldehydes and silicon amines, which are, however, exclusively high polymer and highly crosslinked. In both documents the product is already highly polymer after conversion. It is thus no longer a reactive form, as it is the monoaddition product of a formaldehyde molecule to an amine, and is therefore no longer available for subsequent reactions on substrates or post-crosslinking reactions with each other.

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 type are again described in WO 0021967 only in the case of primary amines.

The invention relates to compounds (V) of the general formula (1)

(R ¹ O) _a R 3_ 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 ¹ ^ - 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, wherein the carbon chain is replaced by non-adjacent oxygen, sulfur or -NR ¹ ^ - Interrupted groups and may optionally be substituted by -CN or - halogen; a is 0, 1, or 2;

R 1 is a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, the carbon chain being denoted by non-adjacent - (CO) -, -O-,

-S- or -NR ^ - groups may be interrupted and optionally substituted with -CN or -halogen;

R ^{4 is} a -CH ₂ OR ⁶ radical or is a -CH (OH) group covalently linked to R ^ or an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical covalently linked to R c each with 1 to 20 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -0-, -S- or -NR ^ - groups and may optionally be substituted by -CN or -halogen;

R5 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or

- (CO) -NR8R9, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and may optionally be substituted by -CN or -halogen, and optionally by a radical may be SiR ^ _a (OR ¹⁾ _a 3_ terminated;

R ^{6 is} a hydrogen atom, an alkyl, cycloalkyl, alkenyl,

Aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain by non-adjacent - (CO) -, -0-,

-S- or -NR ¹⁰ - may be interrupted groups and optionally substituted with -CN or -halogen;

R 'is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain by non-adjacent - (CO) -, -0-, -S- or -NR ¹⁰ - groups may be interrupted and optionally substituted with -CN or -halogen and may be terminated by a residue SiR ^ _a (OR ¹ ) 3_ _a ;

R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and optionally substituted with -CN or -halogen and may optionally be covalently bonded to R ^

R ^ is a radical -CH 2 OH or a group -CH (OH) - which is covalently linked to R 1;

R ^{10 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 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 1 and R 2 can be covalently bonded, with the proviso that

that at least one of R ^ or R ^ 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 stable in storage in the suitable organic solvents and, using methods known to those skilled in the art, to the methylol groups -CH 2 OH and / or

-CH (OH) - postcrosslinkable polysiloxanes condensable, which have excellent permanence on many substrates, which often require no pretreatment.

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

R 1 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 1 is preferably a divalent hydrocarbon radical, such as --CH 2 - and - (- 2) 3 -; particularly preferably -CH2-.

It is preferable that when R ^ alkyl radicals each having 1 to 6 carbon atoms, which may be terminated by a radical -SiR ^ _a (OR ^) 3_ _a or a radical - (CO) -OR ⁷ or - (CO ) -NR ⁸ R ⁹ . Particularly preferred are the methyl radical, the radical - (Cf ^) _n "

SiR ² _a (OR ¹⁾ _a 3_ with n = 1 - 3, a radical - (CO) -OR ⁷ or - (CO) - NR ⁸ R. ⁹ R 1 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 '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 with 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-R3-NHR 5 (2)

in which

R ^{1 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 ¹ ^ - groups and optionally with -CN or - Halogen may be substituted; 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; a is 0, 1, or 2;

R 1 is a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, the carbon chain being denoted by non-adjacent - (CO) -, -O-, -S- or -NH- Interrupted groups and optionally with - CN or -halogen may be substituted;

R5 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 may be interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and may optionally be substituted by -CN or -halogen and optionally by a residue SiR ^ _a (OR ¹ ) 3-a may be terminated;

R ° is a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being replaced by non-adjacent - (CO) -, -O-,

-S- or -NR ¹⁰ - may be interrupted groups and optionally substituted with -CN or -halogen;

R 'is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, said 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 be terminated by a radical SiR ^ _a (OR ¹ ) 3- _a ; R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and optionally substituted with -CN or -halogen,

R ^{10 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 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

that at least one of R ^ or R ^ in the direct vicinity of its jointly bonded nitrogen carries a - (C = O) group with anhydrous formaldehyde.

The formaldehyde used can be present for example in monomeric form of formaldehyde, such as, for example

Formaldehyde gas, but also in condensed form, such as paraformaldehyde, trioxane or others

Formaldehyde condensates. Also, a formaldehyde derivative such as glyoxal can be used.

The compounds (V) can be prepared in the form of organic solutions as well as in pure form.

The preparation of compounds (V) with formaldehyde can be carried out both in dispersion, in organic solution and in

Solid substance, carried out continuously or discontinuously. An optimal and homogeneous mixing of the constituents under the reaction conditions is preferably carried out, wherein a phase incompatibility between the reaction components is optionally prevented by solubilizers.

The precursor compounds (VI) of the general formula (2) leading to the compounds (V) of the general formula (1) are preferably dissolved or suspended in a suitable solvent which is inert with respect to formaldehyde, and the formaldehyde is subsequently metered in.

Preferred solubilizers 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 having 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 1 has a meaning other than hydrogen, are easily accessible from the resulting primary ethylols in which R ° is a hydrogen atom by consecutive etherification according to methods familiar to the person skilled in the art.

The compounds (V) can be condensed to polysiloxanes. These polysiloxanes are storage-stable and are suitable in pure form or as a constituent of formulations as coating agents, binders and coating agents 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 suitable 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 moldings. The treatment of the above substrates with the polysiloxanes obtainable by condensation of the compounds (V) gives 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 each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

Unless otherwise indicated, all are in the examples

Quantities and percentages by weight, all pressures 0.10 MPa (abs.) And all temperatures 20 ⁰ C.

Examples

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

R = H 1 R = H 2

R = CH ₂ OH 1 ¹ R = CH, OH 2 '

R = H 3 R = H 4 R = H 5

R = CH ₂ OH 3 ¹ R = CH, OH 4 ¹ R = CH, OH 5 ¹

example 1

In a 500 ml three-necked round bottom flask, 8.01 g (50.0 mmol) of the amidosilane 1 and 1.50 g (50.0 mmol) of paraformaldehyde in 90 ml of dry toluene are suspended at room temperature with exclusion of water. The reaction mixture is stirred for 2.5 h at 70 ⁰ C. The product 1 'obtained in the form of a toluene solution with a content of 8.51 g (44.5 mmol, 89%) is storage-stable over a few days.

Example 2

In a procedure analogous to Example 1, 7.50 g (42.3 mmol) of methylcarbamatosilane 2 and 1.28 g (42.5 mmol) of paraformaldehyde in 150 ml of dry at room temperature

Suspended toluene. The reaction mixture is stirred at 80 ^° C. for 3 hours. Product 2 'is obtained as a toluene solution containing 8.33 g (40.2 mmol, 95%). Example 3

In example 1 analogous procedure, 8.03 g (45.3 mmol) of the amidosilane 3 and 1.38 g (45.5 mmol) of paraformaldehyde are suspended in 120 ml of dry xylene at room temperature. The reaction mixture is stirred for 5 h at 90 ⁰ C. Product 3 'is obtained as a 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 are suspended in 120 ml of dry xylene at room temperature. The reaction mixture is stirred at 90 ^° C. for 6 hours. Product 4 'is obtained as a xylene solution containing 11.34 g (48.2 mmol, 87%) which is stable on storage for several days.

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) are added.

Paraformaldehyde suspended in 100 ml of dry xylene at room temperature. The reaction mixture is stirred for 3 h at 75 ° C. The product 5 'obtained in the form of a xylene solution containing 6.78 g (20.9 mmol, 92%) is storage-stable over several days.

Example 6

In a 500 ml three-neck round bottom flask, 6.78 g (20.9 mmol) of bis (N, N'-methylol) ureidosilans 5 'in a two-phase mixture of 100 mL of xylene and 15 ml of water in

Present 0.10 ml in NaOH (0.10 mmol). After a reaction time of 4 h at 60 ⁰ C gives a cloudy Reaction solution containing product 6 as the main component in addition to higher W-methylolated oligosiloxanes.

Claims

Claims:

1. Compounds (V) of the general formula (1)

(R ¹ O) _a R 3_ 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, wherein the carbon chain is interrupted by non-adjacent oxygen, sulfur or -NR ¹ ^ - 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, wherein the carbon chain is interrupted by non-adjacent oxygen, sulfur or -NR ¹ ^ - groups and optionally with -CN or - Halogen may be substituted; a is 0, 1, or 2;

R 1 is a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, the carbon chain being denoted by non-adjacent - (CO) -, -O-,

-S- or -NR ^ - groups may be interrupted and optionally substituted with -CN or -halogen;

R ^{4 is} a -CH ₂ OR ⁶ radical or is a -CH (OH) group covalently linked to R ^ or an R- covalently linked alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical, respectively 1 to 20 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -0-, -S- or -NR ^ - groups and may optionally be substituted by -CN or -halogen; R5 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR ⁷ or

- (CO) -NR8R9, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and may optionally be substituted by -CN or -halogen, and optionally by a radical SiR ^ _a (OR ¹ ) 3-a may be terminated;

R ° is a hydrogen atom, an alkyl, cycloalkyl, alkenyl,

Aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain by non-adjacent - (CO) -, -0-,

-S- or -NR ¹⁰ - may be interrupted groups and optionally substituted with -CN or -halogen;

R 'is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, said 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 be terminated by a radical SiR ^ _a (OR ¹ ) 3- _a ;

R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and optionally substituted with -CN or -halogen and may optionally be covalently bonded to R ^

R ^{9 is} a radical -CH ₂ OH or a group -CH (OH) - which is covalently linked to R ^;

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), -0-, -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;

where the radicals R 1 and R 2 can be covalently bonded, with the proviso that

that at least one of R ^ or R ^ bears a - (C = O) group in the direct vicinity of its jointly bonded nitrogen atom.

2. Compounds (V) according to claim 1, wherein at least one free radical -CH2OH or a group -CH (OH) - is present.

3. Compounds (V) according to claim 1 or 2, in which R ¹ denotes an alkyl radical having 1 to 6 C atoms.

4. Compounds (V) according to claim 1 to 3, in which R ^ is an alkyl radical having 1 to 6 carbon atoms or an aryl radical mi t 5 bi s 1 0 carbon atoms.

5. Compounds (V) according to claim 1 to 4, wherein R ^ -CH ₂ - or - (CH ₂ ^ - means.

6. Compounds (V) according to claim 1 to 5, wherein R ^ 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 radical - (CO) -NR ^ R9 means.

7. A process for the preparation of compounds (V), by

Reaction of compounds (VI) of the 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, the carbon chain being denoted by non-adjacent - (CO) -, -O-,

-S- or -NH- groups may be interrupted and optionally substituted with -CN or -halogen;

R5 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 interrupted by non-adjacent - (CO) -, -0-, -S- or -NR ¹⁰ - groups and optionally with -CN or -halogen may be substituted and optionally terminated by a radical SiR ^ _a (OR ¹ ) 3_ _a may be terminated;

R ° is a hydrogen atom, an alkyl, cycloalkyl, alkenyl,

Aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain by non-adjacent - (CO) -, -0-,

-S- or -NR ¹⁰ - may be interrupted groups and optionally substituted with -CN or -halogen;

R 'is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, said 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 be terminated by a radical SiR ^ _a (OR ¹ ) 3- _a ;

R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR ¹⁰ - groups and optionally substituted with -CN or -halogen,

R ^{10 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 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 1 or R 4 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 claims 1 to 6 for the condensation to polysiloxanes.