WO2007060089A2

WO2007060089A2 - Alpha-(beta-ketocarbonyl)-functional organo-silicium compounds and the production thereof

Info

Publication number: WO2007060089A2
Application number: PCT/EP2006/068162
Authority: WO
Inventors: Christian Herzig
Original assignee: Wacker Chemie Ag
Priority date: 2005-11-24
Filing date: 2006-11-07
Publication date: 2007-05-31
Also published as: DE102005056050A1; WO2007060089A3

Abstract

The invention relates to novel (-ketocarbonyl)-functional organo-silicium compounds, which contain at least one Si-bound radical B which is selected from the group of general formulae -CR<SUP>1</SUP>

Description

CC- (β-ketocarbonyl) -functional organosilicon compounds and their preparation

The invention relates to OC- (β-ketocarbonyl) -functional organosilicon compounds and a process for their preparation.

US Pat. No. 4,861,839 describes alkoxysilanes which are substituted by acetoacetic (thio) ester or acetoacetamido groups and are used as monomeric chelate ligands for metal catalysts.

Polymeric β-ketoester siloxanes are known from US 4,808,649, as is a process for their preparation and their use as a stabilizer for polyvinyl chloride.

Functional polysiloxanes containing acetoacetate groups are described in US Pat. No. 5,952,443, wherein a part of the functional groups must contain at least two β-ketocarbonyl groups per functional group and the number of dimethylsiloxy units is not higher than 50. The crosslinking with polyamines in coating formulations is widely described.

The modification of carbinol or aminopolysiloxanes with diketene and its derivatives is described in US 6,121,404. The products are in aqueous solution together with

Aminopolysiloxanes used for the production of elastomeric films.

The object was to provide CC- (β-ketocarbonyl) -functional organosilicon compounds which can be prepared selectively by a simple process and without obtaining any reclaimed products. The object is achieved by the invention. The invention provides CC- (β-ketocarbonyl) -functional organosilicon compounds which have at least one Si-bonded radical B selected from the group of the general formulas

-CR ^ -YC (= O) -CHR ³ -C (= O) -CH ₂ R ³ (I) and

-CR 1 -YC (= O) -CR ³ = C (-OH) -CH ₂ R ³ (II)

wherein Y is an oxygen atom or a radical of the formula -NR -, preferably a radical of the formula -NR ² -,

R ^{1 represents} a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 30 carbon atoms, preferably a hydrogen atom, R ^{2 is} a radical R ¹ or an organic radical containing one or more heteroatoms selected from the group of B, N, O, P, S, Si, Ti, F, Cl, Br and J, preferably N, O and Si, R ^{3 is} a radical R ¹ .

The radicals of the formulas (I) and (II) are tautomeric groups. The CC- (β-ketocarbonyl) -functional organosilicon compounds according to the invention preferably contain 1 to 20 radicals of the formulas (I) and / or (II) per molecule, where they are radicals of the formula (I) only radicals of the formula (II) or can contain both together. Since tautomeric groups are interconvertible, their respective content may change depending on external conditions. Their ratio can therefore vary within wide limits and quotients of about 1000: 1 to about 1: 1000 amount.

The organosilicon compounds of the invention may be silanes or oligomeric or polymeric organopolysiloxanes. The organosilicon compounds according to the invention preferably contain 1 to 10 000 Si atoms, preferably 5 to 5000 Si Atoms, more preferably 60 to 3000 Si atoms. The organosilicon compounds of the invention may be linear, branched, dendrimeric or cyclic. Also included in the scope of the organosilicon compounds according to the invention are network structures of arbitrary size, to which neither a specific or average number of Si atoms can be assigned, provided they contain at least one Si-bonded functional group of the formula (I) and / or (II).

The invention further provides a process for the preparation of CC- (β-ketocarbonyl) -functional organosilicon compounds, wherein the diketenes (1) of the general formula

R ^{3 is} -CH = C-CHR ³ -C = O (III),

or their derivatives,

with organosilicon compounds (2) which contain at least one Si-bonded radical A of the general formula

-CR ^ -YH (IV)

contain per molecule,

wherein R ¹ , R ³ and Y have the meaning given above, be implemented.

Alternatively for diketenes (1) are also their derivatives, such as

Acetoacetic acid tert. butyl ester or the diketene-acetone adduct, can be used, wherein the reactive species by heating at temperatures of preferably 80 to 180 ⁰ C, preferably 100 to 150 ⁰ C, released. The reaction can be carried out without addition of further substances, but also diluted in solvents, such as heptane, toluene, xylene, THF, Take ethyl acetate. Conditionally applicable are also alcohols, such as ethanol, isopropanol, tert. Butanol and propylene glycol, especially if Y is a radical of the formula -NR ² -.

Furthermore, the reaction can be carried out with the aid of one or more organic compounds (3) which delay or reversibly prevent the addition of the β-ketocarbonyl compounds to radicals A in (2), preferably amino radicals. Except in cases where too high an exotherm is to be expected due to high concentrations of the reactive groups (III) and (IV), the reaction without the addition of further substances is preferred.

Examples of compounds (3) which can be used in the process according to the invention are those which can form more or less solid adducts with amines, such as aldehydes or ketones. Preferred examples are acetone, butanone, methyl isobutyl ketone and cyclohexanone. Adducts can be thermally split again and thus rest A slowly released.

The dosing order is largely uncritical, so that compound (2) can be dosed to compound (1) or vice versa, the latter being preferred for practical reasons.

Preferred is diketene of the formula

CH ₂ = C-CH ₂ -C = O

^ O -> used.

The organosilicon compounds (2) which can be used in the process according to the invention can be silanes or oligomeric or polymeric organopolysiloxanes. The

Organosilicon compounds (2) can be linear, branched, dendrimer or cyclic. Preparation methods for organosilicon compounds (2) are known to the person skilled in the art. Preference is given in the case of Y = -NR ² - and if the organosilicon compounds (2) are polymers, equilibration and 5 condensation methods, as they correspond to the prior art. Particularly preferred is the condensation of α-amino silanes containing alkoxy groups, with OH-terminated polydimethylsiloxanes, which proceeds under mild conditions autocatalytically with elimination of small amounts of alkanols 0.

In the method according to the invention are preferably as organosilicon compounds (2) organopolysiloxanes from units of the general formula. 5

A _a R _c (OR ⁴ ) _d SiO ₄ - ₍ a ₊ c ₊ d) (V)

wherein 0 A is a radical of the general formula -CR ¹ ^ -YH (IV), wherein R ¹ and Y have the meaning given above, R is a monovalent, optionally substituted

Hydrocarbon radical having 1 to 18 carbon atoms per radical, 5 R ^{4 is} a hydrogen atom or an alkyl radical having 1 to 8

Carbon atoms, preferably a hydrogen atom or a methyl or ethyl radical, a is 0 or 1, c is 0, 1, 2 or 3 and O d is O or 1, with the proviso that the sum a + c + d <_ 3 and on average at least one residue A per molecule is used. Preferred examples of organosilicon compounds (2) are organopolysiloxanes of the general formula

A _g R ₃ - _g S iO (S iR ₂ O) _I (S iRAO) _k S iR ₃ - _g A _g (VI a) and

(R ⁴ O) R ₂ SiO (S iR ₂ O) _n (S iRAO) _m S iR ₂ (OR ⁴ ) (VIb)

wherein A, R and R ^{4 have} the meaning given above, g is 0 or 1, k is 0 or an integer from 1 to 30 and

1 is 0 or an integer from 1 to 1000, m is an integer from 1 to 30 and n is 0 or an integer from 1 to 1000, provided that on average at least one residue A is contained per molecule.

The organosilicon compounds (2) used in the process according to the invention preferably have a viscosity of from 1 mPa.s to 1,000,000 mPa.s at 25 ° C., preferably 100 mPa.s to 50,000 mPa.s at 25 ° C.

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl radicals; Alkynyl radicals, such as the ethynyl, propargyl and 1-propynyl radicals; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and Aralkyl radicals, such as the benzyl radical, the CC and the β-

Phenylethyl radical.

Examples of radicals R ¹ are, in addition to the preferred hydrogen, alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert , Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical,

Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Aryl radicals, such as aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; and aralkyl radicals, such as the benzyl radical, the CC and the β-phenylethyl radicals.

Preferably, R ^{2 is} an alkyl, cycloalkyl, aryl or aralkyl radical of 1 to 30 carbon atoms which may contain one or more heteroatoms selected from the group of N, O and Si, preferably an alkyl, cycloalkyl, aryl or Aralkyl radical having 1 to 30 carbon atoms.

Examples of R ¹ are also fully applicable to Examples R ² . Preferred examples of R ² are the methyl radical and the cyclohexyl radical.

In addition, R ^{2 may} also contain heteroatoms. Further examples of R ² are therefore

-C ₂ H ₄ N (CHs) ₂ -C ₃ H ₆ N (CHs) ₂ -C ₃ H ₆ N (CH ₃₎ C ₃ H ₆ N (CHs) ₂ -C ₂ H ₄ OH -C ₃ H ₆ OH

-C ₃ H ₆ (OC ₃ H ₆ ) TR ¹ with r = 1-100 C ₃ H ₆ Si (CH ₃ ) ₃ where R ^{1 has} the meaning given above,

Examples of R ³ correspond to those for R ¹ , hydrogen being preferred.

Preferably, the CC (β-ketocarbonyl) functional organosilicon compounds of the invention are

Organopolysiloxanes from units of the general formula

B _a R _c (OR ⁴ ) _d SiO ₄ - (a ₊ c ₊ d) (VII)

2

wherein B, R, R ^4, a, c and d have the meaning given above, with the proviso that the sum a + c + d <_ 3 and on average at least one radical B per molecule is included.

Preferred examples of β-ketocarbonyl-functional organosilicon compounds are organopolysiloxanes of the general formula

B _g R ₃ - _g SiO (SiR ₂ O) _I (SiRBO) _k SiR ₃ - _g B _g (VIIa) and

(R ⁴ O) R ₂ SiO (SiR ₂ O) _n (SiRBO) _m SiR ₂ (OR ⁴ ) (VIIb)

wherein B, R, R ⁴ , g, k, 1, m and n have the meaning given above, with the proviso that on average at least one radical B per molecule is contained.

In the process according to the invention diketene (1) in amounts of preferably 0.5 to 2.0 mol, preferably 0.9 to 1.2 mol, depending Mol radical A of the general formula (IV) used in the organosilicon compound (2).

The reaction of compounds (1) with (2) normally proceeds spontaneously if Y = -NR ² -. For the case Y = oxygen, it is advantageous to use the catalysts commonly used in the production of acetoacetic esters, such as tert. Amines, preferably those with high nucleophilicity, tin or titanium compounds.

The inventive method is preferably carried out at temperatures of 0 to 140 ⁰ C, preferably 20 to 100 ⁰ C, performed. Furthermore, the process of the invention is preferably carried out at the pressure of the surrounding atmosphere, but can also be carried out at higher and lower pressures.

The CC- (β-ketocarbonyl) -functional organosilicon compounds according to the invention preferably have a viscosity of from 5 mPa.s to 1,000,000 mPa.s at 25 ° C., preferably 100 mPa.s to 100,000 mPa.s at 25 ° C.

The β-ketocarbonyl-functional organosilicon compounds of the invention can be used:

a) for the fixation of silicon compounds / siloxanes on amine-containing surfaces, which is controllable due to the pH dependence b) to the polymer structure (linear, branched) by means of amine-containing reactants to

Depending on the functional density, they function as crosslinkers or as polymers to be crosslinked. C) for fixing to substrates containing metal ions, the metal ions reacting under chelation with the compounds according to the invention Bind products, the bond strength depends on the ion type d) for crosslinking with polyacrylates by Michael addition

Example 1:

a) For the preparation of the organosilicon compound (2) the condensation method is used: For this purpose, 1350 g of an α, ω-Dihydroxypolydimethylsiloxans with a viscosity of 67 mm ² / s (25 ° C) with 74g cyclohexylaminomethyl methyldiethoxysilane mixed. The mixture is heated to 80 ⁰ C and stirred for 2 hours and applying a vacuum until a constant viscosity is reached. The split-off ethanol is continuously removed, whereupon a 2940 mm ² / s (25 ° C) aminopolysiloxane is obtained. The colorless, clear oil has an amine value of 0.204 m.quad./g and thus contains on average one sec. Of amino group per 4902 g of polymer. The ¹ H NMR spectrum shows only traces of Si-bonded ethoxy groups: the condensation has gone to 98%. The ²⁹ Si NMR spectrum shows a sharp signal for the cyclohexylaminomethylmethylsiloxy group at -26.0 ppm relative to tetramethylsilane. The total yield deducted from the resulting ethanol is 1390g, which corresponds to 99% of theory.

b) 1216 g of the aminopolysiloxane prepared under a) are mixed at 26.degree. C. with 21.9 g of diketene. With stirring, the internal temperature rises within 15 minutes to 12 ⁰ C at. It is allowed to react for 2 hours without external heating and receives a nearly colorless silicone polymer with a

Viscosity of 3220 mm ² / s (25 ° C) in virtually quantitative yield. In the ²⁹ Si NMR spectrum, the sharp signal of the precursor can no longer be seen at -26.0 ppm (detection limit approx. 1 mol%). Instead, two new signals are available at -31.1 ppm and -32.0 ppm for the

Ketocarbonylprodukt and its tautomeric form formed, which are in the keto / enol ratio of 55/45. Despite the relatively high functionality of on average 5 amino groups per molecule, the viscosity of the aminopolysiloxane used has only increased by about 10%, which practically precludes a secondary reaction by enamine linkage. Enamine, detectable by the CH ₃ C (N) = signal at 1.90 ppm, could not be detected in the ¹ H NMR spectrum either.

Comparative experiment according to US 6,121,404:

From a silicone oil with the viscosity of 3000 mm ² / s (25 ° C) and a hydrolyzate of Aminopropylmethyldimethoxysilan a methyl-terminated amine oil was prepared with Aminopropylmethyl- siloxyeinheiten having an amine value of 0.201 meq / g and a viscosity of 2895 mm ² / s (25 ° C). This polymer corresponds to the aminosiloxane polymers described in column 6 in US 6,121,404 with Q = -C 3 H 6 NH 2, z = O, s = about 300, t = 4.6. At 25 ⁰ C in 500 g of this polymer are metered 9g diketene with good stirring. Under rapid warming to about 10 ⁰ C, the viscosity increases very much, whereupon the entire approach triggers. A viscosity is not measurable, the product is not soluble in toluene. Consequently, the derivatization of amine oils described in US 6,121,404 with diketene in this form is not possible, while the inventive method provides liquid, and thus usable products with correct analysis.

Claims

claims

1. OC- (β-ketocarbonyl) -functional organosilicon compounds containing at least one Si-bonded radical B selected from the group of the general formulas

-CR ^ -YC (= O) -CHR ³ -C (= O) -CH ₂ R ³ (I) and -CR ^ -YC (= O) -CR ³ = C (-OH) -CH ₂ R ³ (II)

contain, where

Y is an oxygen atom or a radical of the formula -NR -,

R ^{1 represents} a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 30 carbon atoms,

R ^{2 is} a radical R ¹ or an organic radical which may contain one or more heteroatoms selected from the group consisting of B, N, O, P, S, Si, Ti, F, Cl, Br and J,

R ^{3 is} a radical R ¹ .

2. CC- (β-ketocarbonyl) -functional organosilicon compounds according to claim 1, characterized in that Y is a radical of the formula -NR ² -, wherein R ^{2 has} the meaning given in claim 1.

3. CC- (β-ketocarbonyl) -functional organosilicon compounds according to claim 1 or 2, characterized in that R ^{1 is} a hydrogen atom.

4. CC- (β-ketocarbonyl) -functional organosilicon compounds according to claim 1, 2 or 3, characterized in that R ^{2 represents} an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 30 carbon atoms.

5. CC- (β-ketocarbonyl) -functional organosilicon compounds according to one of claims 1 to 4, characterized in that R ^{3 is} a hydrogen atom.

6. CC- (β-ketocarbonyl) -functional organosilicon compounds according to one of claims 1 to 5, characterized in that it organopolysiloxanes from units of the general formula

B _a R _c (OR ⁴ ) _d SiO ₄ - ₍ a ₊ c ₊ d) (VII)

2

in which

B has the meaning given in claim 1, R is a monovalent, optionally substituted

Hydrocarbon radical having 1 to 18 carbon atoms per radical, R ^{4 is} a hydrogen atom or an alkyl radical having 1 to 8

Carbon atoms, a is 0 or 1, c is 0, 1, 2 or 3 and d is 0 or 1, with the proviso that the sum is a + c + d <_ 3 and contains on average at least one radical B per molecule, are.

7. A process for the preparation of CC- (β-ketocarbonyl) - functional organosilicon compounds, wherein the diketenes (1) of the general formula

R ^{3 is} -CH = C-CHR ³ -C = O (III),

or their derivatives,

with organosilicon compounds (2) containing at least one Si-bonded radical A of the general formula

-CR ^ -YH (IV)

contain per molecule, where

Y is an oxygen atom or a radical of the formula -NR -, R ^{1 is} a hydrogen atom or an alkyl, cycloalkyl,

Aryl or aralkyl radical having 1 to 30 carbon atoms,

R ^{2 is} a radical R ¹ or an organic radical which may contain one or more heteroatoms selected from the group consisting of B, N, O, P, S, Si, Ti, F, Cl, Br and J, R ³ a radical R ¹ is optionally reacted in the presence of one or more organic compounds (3) which retard or prevent the reaction of the radical A in (2) with β-ketocarbonyl compounds.

8. The method according to claim 7, characterized in that Y is a radical of the formula -NR ² -, wherein R ^{2 has} the meaning given in claim 7.

9. The method according to claim 7 or 8, characterized in that R ^{1 is} a hydrogen atom.

10. The method of claim 7, 8 or 9, characterized in that R ^{2 is} an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 30 carbon atoms.

11. The method according to any one of claims 7 to 10, characterized in that R ^{3 is} a hydrogen atom.

12. The method according to any one of claims 7 to 11, characterized in that as derivatives of diketenes (1) of acetoacetic tert. butyl ester or the diketene-acetone adduct are used.

13. The method according to any one of claims 7 to 12, characterized in that as compounds (3) those selected from the group of acetone, butanone, methyl isobutyl ketone and cyclohexanone are used.