EP1957503A1

EP1957503A1 - Enamine oils and method for the production thereof

Info

Publication number: EP1957503A1
Application number: EP06819695A
Authority: EP
Inventors: Christian Herzig
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2005-12-08
Filing date: 2006-11-23
Publication date: 2008-08-20
Also published as: US7973120B2; US20080312398A1; DE102005058745A1; CN101296931A; WO2007065798A1; JP2009518348A

Abstract

The invention relates to organosilicon compounds containing at least one Si-bound radical of general formula (E1)xZ-Y-C(O)-CR4=C(CH2R4)-NR2-R1- (I). Said organosilicon compounds can be produced by reacting an amino silicon compound (2) with a compound (3) of general formula (E2)x Z-Y-C(O)-CR4=C(CH2R4)-OH (II) or (E2)x Z-Y-C(O)-CHR4-C(O)-CH2R4 (III), wherein R1 represents an organic radical that can contain one or several N atoms, R2 represents a hydrogen radical or an organic radical comprising 1 to 30 C atoms, R4 represents a hydrogen radical or a hydrocarbon radical comprising 1 to 18 C atoms, Y represents O or NR2, Z represents a bifunctional to hexafunctional organic radical which has a monomer, oligomer, or polymer structure and is provided with a minimum heteroatom moiety of 10 percent by weight that is bound via C atoms, E1 represents a monofunctional terminal group or an Si-C-bound radical of general formula -Y-C(O)-CR4=C(CH2R4)-NR2-R1-, E2 represents a monofunctional terminal group or a radical of general formula -Y-C(O)-CR4=C(CH2R4)-OH or -Y-C(O)-CHR4-C(O)-CH2R4, and x represents a whole number from 1 to 5.

Description

Enamine oils and process for their preparation

The invention relates to enamine oils and processes for their production.

The production of polyacetoacetates and polyacetoacetamides from polyols or polyamines by reaction with diketene or also by transesterification is described in US 3668183. Further information on the derivatization of polycarbinols with diketene can be found in US 3542855. Methods for reacting polymeric compounds such as polyethers, polyacetates, polyether acetals, polyesters, polyester polyols with diketene or acetoacetates are disclosed in GB 1154726 and GB 1218509. The polymers used contain at least one carbinol group, and the products accordingly at least one acetoacetyl group.

US 6121404 describes the production of acetoacetylated silicone polyethoxylates, linear siloxanes with terminal and also lateral propyl polyethoxylates being used. The implementation is done with diketen.

According to EP 603716, acetoacetylated polyols, polyethers or polyesters are used to produce elastomers by crosslinking them by adding aminopolyester or aminopolyether. The latter are synthesized from the former by adding an excess of polyamine.

Coating compositions which cure within several hours are obtained in accordance with EP 481345 if compounds having more than one acetoacetate group are mixed with polyamines which have previously been reacted with aldehydes or ketones in aldimines or ketimines. A comparable methodology is also described in US 3668183, polyacetoacetamides also being able to be used here.

EP 483583 describes the formation of elastomers from polyacetoacetamides or esters after reaction with aminosilanes without the presence of atmospheric moisture.

A special case of filming is described in US Pat. No. 6,121,404: an aqueous solution is prepared from an acetoacetylated silicone polyether. siloxane is dried and forms an elastomer film.

The present invention relates to an organosilicon compound (1) which has at least one Si-bonded radical of the general formula

(E ¹ J _x ZYC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -NR ² -R ^X - (I), obtainable by the reaction of an aminosilicon compound (2), with a compound (3) the general formula

(E ² ) _x ZYC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH (II) or (E ² ) _x ZYC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ (III ) in which

R ^{1 is} an organic radical which can contain one or more N atoms,

R is a hydrogen radical or an organic radical with 1 to 30

Carbon atoms,

R ^{4 is} a hydrogen radical or a hydrocarbon radical with 1 to 18 carbon atoms,

Is YO or NR ² ,

Z is a bi- to hexafunctional organic radical with a monomeric, oligomeric or polymeric structure, which has a weight-based heteroatom content of at least 10%, which is bonded via carbon atoms,

E ^{1 is} a monofunctional end group or an Si-C bond

Rest of the general formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -NR ² -R ^X -,

E ^{2 is} a monofunctional end group or a residue of the general

Formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH or -YC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ is x is an integer from 1 to 5.

R ¹ is preferably a bifunctional hydrocarbon radical which can contain one or more N atoms. In the nitrogen-free form, it corresponds to an alkylene, arylene or aralkylene radical, alkylene radicals being preferred. Examples of these are diradicals of the formulas -CH2-, -C2H4- and —C6H12- •

In the nitrogen-containing form, R ¹ contains the N, preferably isolated from other N atoms and in the form of sec. Or tert. Amino groups. It is therefore particularly preferred that two N atoms are not bonded directly to one another. Examples of this are the groupings of the formulas

-C ₃ H ₆ NHC ₂ H ₄ -, -C ₃ H ₆ N (CH ₃ ) C ₂ H ₄ -, -C ₃ H ₆ NHC ₃ H ₆ -,

-C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ -, -C ₃ H ₆ N (CH ₃ ) C ₂ H ₄ N (CH ₃ ) C ₂ H ₄ - or

-C ₃ H ₆ NHC ₃ H ₆ NHC ₃ H ₆ -.

R ² is preferably a hydrogen radical.

R ⁴ is preferably a hydrogen radical.

Y is preferably an oxygen radical. Z preferably has a heteroatom content by weight of at least 20% and particularly preferably at least 25%. x is preferred 1. The invention further relates to a method for producing an organosilicon compound (1) which is characterized in that an aminosilicon compound (2) with a compound (3) of the general formula (E ² ) _x ZYC (O) - CR ⁴ = C (CH ₂ R ⁴ ) -OH (II) or

(E ² ) _x ZYC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ (III) is reacted, wherein

R ^{1 is} an organic radical which can contain one or more N atoms,

R ^{2 is} a hydrogen radical or an organic radical with 1 to 30 Carbon atoms,

Is YO or NR ² ,

E is a monofunctional end group or a radical of the general formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH or -YC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ , x is an integer from 1 to 5.

The aminosilicon compound (2) is preferably an aminosiloxane which contains primary amino groups. Possibly. the aminosiloxane can also contain sec. amino groups.

The aminosilicon compound (2) is particularly preferably a compound having Si-bonded substituents of the formula

H-NR ² -R ¹ - (IV) where R ¹ and R ^{2 have} the meaning already mentioned.

The aminosilicon compound (2) preferably attaches to the compound (3) with the exclusion of water.

The compounds (2) are preferably used without prior conversion of the amino groups by means of protective group reagents such as aldehydes or ketones. They preferably contain at least one prim. Amino group. Examples of this are the amino methyl or the aminopropyl group. If the aminosilicon compounds (2) from "diamino" -

Monomers such as aminoethylaminopropyl or aminoethylaminoisobutylsilanes produced contain these per prim. Amino group a sec. Amino group bound to the same Si atom. Prefers but the prim reacts. Amino group with compounds (3), whereby sec. Amino groups are retained as basic centers and can therefore also be protonated. The compound (2) preferably contains an amine group concentration in the range from 0.01 to about 10 meq / g, particularly preferably from about 0.05 to 5 meq / g. Preferred viscosities are in the range from approximately 100 to 100,000 mPa's at 25 ° C., the range 500 to 50,000 mPa's being particularly preferred.

The org. Compound (3) can be used as a reactant for the amino silicon compound (2) in two tautomeric forms which correspond to the formulas (II) and (III). This compound is obtained by reacting the basic compounds (E ² ) _x ZY (4) on which the free valences are saturated with hydrogen, with diketene, acetyketene, alkyl diketene, diketene-acetone adduct or also acetoacetate according to reactions known in the literature . The reaction with diketene or its acetone adduct is preferred.

The radical "Z" is an organic radical which, due to its bi- to hexafunctionality, is linked to 2 to 6 further groups. The sum of "E" plus "Y" corresponds in numerical value to this functionality "Z" is bifunctional. In this case, "Z" is bound to either two Y groups or one Y group and a monofunctional end group. Monofunctional end groups can be saturated or unsaturated hydrocarbon radicals, or also acyl radicals such as the acetate, butyrate, palmitate or stearate radical , as well as the acrylate, methacrylate or benzoate residue.

The remainder "Z" has a heteroatom content of at least 10% by weight. The heteroatoms are selected from the group of 0, N, B, P and S atoms; preferably 0- / N atoms, especially O - Atoms. The remainder "Z" has the task of adding higher polarity and thus a higher degree of hydrophilicity to the compounds (1) to introduce, which is why a higher content of heteroatoms is preferred. The radical "Z" is particularly preferably a polyether or polyester. Examples of polyethers are polyethylene oxide, polypropylene oxide or polybutylene oxide (also poly-THF) and also copolymers of the general formula (C _a H ₂ O) _n C _a H2 _a with a = 2, 3 or 4 and n is an integer from 1 to 500, preferably from 1 to 100.

Tri- to hexafunctional residues "Z" are normally started by alcohols which are as functional as by amines. Trimethylolpropane or ammonia with ethylene oxide provides base compounds (4) with "Z" of the general formula C ₂ H ₅ C (CH ₂ (OC ₂ H ₄ ) _{n / 3} ) ₃ or N (C ₂ H ₄ (OC ₂ H ₄ ) _n _ _3/3 ) ₃ , the free valences of which are linked to oxygen atoms (Y), which in turn are saturated with hydrogen. The correspondingly more highly functionalized carbinol or amino compounds are usually used to prepare compounds (4) with higher functionality: tetrafunctionality from pentaerythritol or ethylenediamine, hexafunctionality from sorbitol or tris (aminoethyl) amine.

Corresponding polyesters can be prepared from the same or similar starter compounds by ring-opening polymerization of cyclic esters (lactones) by generally known methods. Preferred base compounds (4) are polyethylene glycol, polypropylene glycol and their copolymers, and their monoalkyl ethers. The latter are a special case with "Y" being oxygen and "E" being an alkyl group (methyl, alkyl, butyl). With regard to the conversion to compounds (3), these compounds (4) are monofunctional. Compared to the aminosilicon compounds (2), the compounds (3) produced therefrom are also monofunctional and accordingly serve to saturate amino groups with polar polymers.

In contrast to this, polyalkylene glycols also give the reaction partners (3), which are also bifunctional to the compounds (2) and thus act to extend the chain. In this way, branched products (1) can also be obtained if the compounds (2) have at least three amino groups per mo lekul included. An alternating siloxane-polyether structure is created.

The reaction of the compounds (3) with (primary) aminosilicon compounds (2) to give the β-ketoenamines (1) according to the invention proceeds spontaneously even without external heating, but the addition of heat has an accelerating effect on the synthesis of (1).

In principle, the compounds (2) and (3) can be combined with one another and reacted within wide limits. A stochiometric excess of β-ketocarbonyl groups (or their enol tautomer) in relation to amino groups naturally leads to products which contain excess β-ketocarbonyl groups and vice versa. To avoid this case, a stochiometric ratio of β-ketocarbonyl groups to prim is preferred. Amino groups from 0.8 to 1.2, particularly preferably from 0.9 to 1.1, are used.

If compounds (3) with more than just one β-ketocarbonyl group (or their enol tautomer) are used per molecule, it may be necessary to deviate from these MoI ratios, depending on the synthesis goal, be it to determine the molecular weights of

Discontinue products or simply avoid gelling effects. In such cases, the molar ratio of the reacting groups can vary from about 0.1 to about 10.

The reaction temperature amounts to preferably from 0 to approximately 140 ⁰ C, particularly preferably 20 to 100 ⁰ C.

The surrounding pressure is not critical. The reaction under normal pressure or vacuum is preferred. If the water of reaction is removed in vacuo, this usually leads to an increase in the reaction rate. Even in cases in which the reaction water is not completely soluble in the product, it is advantageous to remove it, since clear products are obtained.

The following examples serve to further explain the invention. Example 1 :

At 25 ° C., 125 g of a commercially available aminosiloxane consisting of 3- (aminoethylamino) propyl-methylsiloxy and dimethylsiloxy units and with a viscosity of 980 mm ² / s

(25 ° C) has an amine content of 0.293 meq / g. 10.2 g of a methylpolyethylene glycol acetoacetate with an average degree of polymerization of 10.4 are metered in without external heating. The milky, cloudy mixture warms up somewhat and becomes more viscous. The mixture is stirred until a clear, yellowish siloxane polyether copolymer is obtained. The ¹ H-NMR spectrum shows the complete conversion of the acetoacetate to the enamine, since the signal of the acetyl group at 2.3 ppm is no longer detectable and instead the methyl group of the enamine is visible as a singlet at 1.9 ppm. The copolymer contains the structural element (polyether) -O ₂ C-CH = C (CH ₃ ) - NH-C ₂ H ₄ -NH-C ₃ H ₆ - (siloxane).

Example 2:

Carried out analogously to Example 1, but instead of the 125 g of the aminosiloxane from Example 1, 47 g of a telechelic aminosiloxane consisting of 3- (aminoethylamino) propyldimethylsiloxy and dimethylsiloxy units with the amine number 0.78 are used. The mixture with an identical amount of the acetoacetate is also initially very cloudy, but it clears towards the end in the case of a weakly exothermic reaction. The reaction is complete after about 24 hours without external heating, which is confirmed by the ¹ H-NMR spectrum. The structural element between polyether and siloxane corresponds to that of the copolymer from Example 1.

Example 3:

47 g of the telechelic aminosiloxane from Example 2 are mixed with 35.5 g of butyl (polyethylene) - (polypropylene) - at 25 ° C. glycolacetoacetate mixed with equal molar ethylene and propylene and an average molar mass of 1970 g, whereby the starting materials are completely incompatible. With good stirring the mixture clears up at 50 ⁰ C after about 4 hours and one obtains a highly viscous yellowish oil. In the ¹ H NMR spectrum, the product is, but the absence of Acetylpeaks (2.3 ppm) on the new singlet CH ₃ group of enamine can be seen at 1.9 ppm. The structural element between polyether and SiIoxan corresponds to that of the copolymer from Example 1.

Example 4:

35.5 g of the polyether acetoacetate from Example 3 are reacted with an aminosiloxane which is exclusively prim. Amino groups and no combination of prim./sec. Contains amino groups. 95 g of a telechelic aminopropyl PDMS with an amine group content of 0.38 meq / g are metered in with vigorous stirring. After the reaction mixture has cleared, the mixture is left to stir at 50 ^° C. for a further 2 hours. A clear, yellowish oil is obtained, which in turn shows the CH ₃ peak of the enamine at 1.9 ppm in the ¹ H-NMR spectrum: the structure of the end groups corresponds to the structural element:

(Polyether) -O ₂ C-CH = C (CH ₃ ) -NH-C ₃ H ₆ - (siloxane).

Example 5:

195.4 g of a entwasserten polyethylene glycol having an average of 44 ethyleneoxy units are reacted with 18.0 g of diketene at 80 ⁰ C for Bisacetoacetat (catalyst 0.1 g zabicyclooctan slide), and the excess diketene then removed in vacuo. After cooling to 25 ° C., a total of 192.5 g of a silicone oil telechelium with 3-aminopropyl end groups and an amine concentration of 0.52 meq / g are metered in. With good stirring, the initially milky mixture clears when warmed slightly. Thereafter, let at 50 ⁰ C for 2 hours to react further and maintaining a yellowish, viscous oil having a .beta. Ketoenamine concentration of approx.0.25 mEqu./g. No free aminopropyl (Si) groups are detectable in the ¹ H-NMR spectrum, but the same structural element as in the product of Example 4. The polymer is dispersible in water without the addition of an emulsifier.

Example 6: The product from Example 5 contains final β-

Ketoester groups which can be reacted further: 202 g of this product (50 mEqu. Acetoacetate) are mixed with 5.2 g of dimethylaminopropylamine at 25 ° C. after dilution with 50 g of THF. With a slightly exothermic reaction, a telechelic PDMS-polyether copolymer is obtained after 2 hours, which contains polymer segments connected via ß-ketoenamine groups and contains tert. Amine groups is stopped. The concentration of the tert. Amine groups are 0.24 mEqu./g. The same structural elements as in the product of Example 4 are confirmed in the ¹ H-NMR spectrum.

Example 7: As in Example 5, bisacetoacetate is prepared from 97.7 g of dewatered polyethylene glycols with an average of 44 ethyleneoxy units and 9.0 g of diketene and excess diketene is removed. 385 g of the aminopropyl PDMS (200 mEqu.NH2) used there are metered in with vigorous stirring. After 2 hours at 50 ⁰ C is obtained from the milky mixture only a slightly cloudy, yellowish oil, whose ¹ H-NMR spectrum shows no signal for the acetoacetate more. Instead, the structural element identical to the product from Example 6 can be confirmed using the CH3 peak.

The copolymer contains excess aminopropylene end groups in a concentration of 0.20 mEqu./g. Example 8:

The preparation of the polyether bisacetoacetate according to Example 5 is repeated. 10.6 g of the product obtained are mixed with 68 g of the commercially available aminosiloxane from Example 1 with vigorous stirring. With slight warming, the viscosity increases slowly, then increases more and more. The still cloudy mixture is poured into a Teflon mold. The copolymer solidifies to a pale yellowish elastomer, the polyether and siloxane components of which have elements of the structure -O ₂ C-CH = C (CH ₃ ) - NH-C ₂ H ₄ -NH-C ₃ H ₆ - are connected.

Claims

Claims:

1. Organosilicon compound, the at least one Si-bonded radical of the general formula

(E ¹ J _x ZYC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -NR ² -R ^X - (I) contains, producible by the reaction of an aminosilicon compound (2), with a compound (3) the general formula

(E ² ) _x ZYC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH (II) or

(E ² ) _x ZYC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ (III) where

R ^{1 is} an organic radical containing one or more N-

Can contain atoms

R is a hydrogen radical or an organic radical with 1 to 30 C atoms,

Is YO or NR ² ,

Z is a bi- to hexafunctional organic radical with a monomeric, oligomeric or polymeric structure, which has a weight-based heteroatom content of at least

Has 10%, which is bound via carbon atoms,

E ^{1 is} a monofunctional end group or a Si-C-bonded radical of the general formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -NR ² - R ¹ -,

E is a monofunctional end group or a radical of the general formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH or -YC (O) -CHR ⁴ -

C (O) -CH ₂ R ⁴

x is an integer from 1 to 5.

2. Organosilicon compound according to claim 1, characterized in that R ^{1 is} a bifunctional hydrocarbon radical containing one or more N atoms can

R ² and R ^{4 are} each a hydrogen residue,

Y is an oxygen residue,

Z has a heteroatom content by weight of at least 20% and particularly preferably at least 25% and x is 1.

3. Organosilicon compound according to claim 1 or 2, characterized in that the heteroatoms are selected from the group of O, N, B, P and S atoms, preferably the O and N atoms, especially the O- Atoms.

4. A process for the preparation of an organosilicon compound according to claim 1, 2 or 3, which is characterized in that an aminosilicon compound (2) with a compound (3) of the general formula

(E ² ) _x ZYC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH (II) or (E ² ) _x ZYC (O) -CHR ⁴ -C (O) -CH ₂ R ⁴ (III ) is implemented, whereby

R ^{1 is} an organic radical which can contain one or more N atoms,

R is a hydrogen radical or an organic radical with 1 to 30 C atoms,

Is YO or NR ² ,

E ^{2 is} a monofunctional end group or a radical of the general formula -YC (O) -CR ⁴ = C (CH ₂ R ⁴ ) -OH or -YC (O) -CHR ⁴ - C (O) -CH ₂ R ⁴ is

x is an integer from 1 to 5.

5. The method according to claim 4, characterized in that the aminosilicon compound (2) is an aminosiloxane which contains at least one primary amino group.

6. The method according to claim 5, characterized in that the compounds (2) per prim. Amino group contains a sec. Amino group bound to the same Si atom.

7. The method according to claim 5 or 6, characterized in that the compound (2) has an amine group concentration in

Range from 0.01 to about 10 meq / g, particularly preferably from about 0.05 to 5 meq / g.

8. The method according to claim 5, 6 or 7, characterized in that the compound (2) has a viscosity in the range of approximately 100 to 100,000 mPa's at 25 ° C, the range 500 to 50,000 mPa's being preferred .