DE10216233A1 - A process for preparation of a hydrosilyated alkene derivatives useful as surfactants, wetting agents or foam stabilizers for polyurethane foams, paints, coating compositions, textile and leather adjuvants, and in plant protection - Google Patents

Abstract

A process for preparation of a hydrosilyated alkene derivatives by reaction of one or more non-adjacent and non-terminal heteroatom groups with silanes, siloxanes, or oligomers having at least one SiH group in the presence of a hydrosilation catalyst is new. A process for preparation of a hydrosilyated alkene derivatives by reaction of alkenal derivatives of formula (I) with siloxanes of formula (II): X = O, S, or NH; R1, R2 = 1-30C alkyl or 1-30C hydroxyalkyl, optionally interrupted by one or more non-adjacent and non-terminal heteroatom groups, selected from O, S, NH, or SO2; or 6-12C aryl, 7-30C alkaryl, or 7-30C aralkyl; or R1 + R2 = (CR3R4)n; R3, R4 = H, or R1; or CR3R4 = C=O; n = 2, 3, or 4; Y = a single bond or 1-30C alkylene; R5 = H, 1-30C alkyl or phenyl; E = Si(R6)3 or Si(R6)2R7; R6 = 1-30C alkyl or phenyl; R7 = 1-30C alkyl or 1-30C hydroxyalkyl optionally substituted by O, S, NH or SO2; R8 = CH2CH(R5)CH(X-R1)2; x = at least0, y = at least 1, and z = 0-100.

Description

The invention relates to hydrosilylated alkene derivatives, processes for their preparation and their use.

The synthesis of acrolein acetals is described in the literature, the Acrolein acetals can be further alkoxylated. EP-A-0 043 966 relates to such a Process for the preparation of polyethers, in which a trivalent or polyvalent Alcohol in which at least two hydroxyl groups are acetalized or ketalized with Implements oxiranes. The acetalization of the alcohol is especially with acrolein carried out. After the reaction with, for example, ethylene oxide, the acetal can can be split, and the product can be used as an emulsifier, demulsifier, leveling agent and Complexing agents can be used.

Similar alkoxylated acetals are described in GB-A 2 020 702, the Acetal structure derived from an aliphatic aldehyde. The ethoxylated obtained Compound is used particularly as a retardant in the coloring of polyesters used.

In US 5,932,667 reactive adducts of vinyl dioxo compounds are described be used in the manufacture of scratch-resistant coatings. The described Compounds have an acrolein acetal that contains a terminal silyl radical. The Compound is used as a binder in curable coating compositions used.

It is also known to produce polyether siloxanes based on allyl alkoxylates, where Siloxanes that contain SiH groups are reacted with allyl alkoxylates, compare US 4,847,398.

The object of the invention is to provide a method for producing hydrosilylated alkene derivatives and such hydrosilylated alkene derivatives which can be used in particular as surfactants. They should preferably be used as a foam stabilizer for polyurethane foams or when used in active ingredients or Effect formulations such as paints, coating compositions, Textile auxiliaries, fiber treatment agents, crop protection formulations or Cosmetics have advantageous properties. The surfactants are particularly preferred be acid-cleavable.

The object is achieved according to the invention by a process for the preparation of hydrosilylated alkene derivative by reaction of alkene derivatives of the general formula (I)


with the meaning
X each independently O, S, NH
R ¹ , R ² independently of one another are C _1-30 alkyl or C _1-30 hydroxyalkyl, optionally interrupted by one or more non-adjacent and non-terminal heteroatom groups, selected from O, S, NH, SO ₂ ;
C _6-12 aryl, C _7-30 alkaryl or C _7-30 aralkyl,
where R ¹ , R ² together can also form a residual (CR ³ R ⁴ -) _n with R ³ , R ⁴ each independently being hydrogen or as defined for R ¹ , R ² , a group CR ³ R ⁴ also having C = O can mean
n 2, 3 or 4,
Y single bond or C _1-30 alkylene,
R ^{5 is} hydrogen, C _1-30 alkyl or phenyl,
with silanes, siloxanes or oligomers or polymers thereof, which have at least one Si-H group, on a hydrosilylation catalyst.

It has been found according to the invention that alkenal derivatives of the general formula (I) can be reacted with silanes, siloxanes or oligomers or polymers thereof which have at least one Si-H group on a hydrosilylation catalyst, acetal groups being present in the finished product. An example implementation scheme is shown below. It can be seen that acrolein acetals, which are alkoxylated, are bound to the polysiloxanes as the side chain.

The alkoxylated acrolein acetals shown by way of example in the above reaction scheme can be prepared according to the scheme below from acrolein and polyhydric alcohols such as trimethylolpropane (TMP) and subsequent alkoxylation.

In the hydrosilylated alkene alder derivatives according to the invention, the acetal structure can be below acidic, also Lewis acidic, conditions are split, leaving the alkoxylated residue can be separated from the siloxane group. This makes it possible, for example, to deactivate the surfactant according to the invention or the polysiloxane units from the Separate polyether units. It is possible, for example, to separate them Remove polysiloxanes by phase separation. It is also possible, for example, the Introducing polysiloxanes in the form of the surfactant into a material, after cleavage only the siloxane remains in the product while the polyether chains are removed. The property as a cleavable surfactant can be used in particular for textile applications and the formulation of active substances and effect substances.

The above explanation relates, by way of example, to acrolein acetals which Have alkoxide groups. The same applies to the others mentioned above Alkene derivatives of the general formula (I).

In the formulas listed above and below, the same-named residues occur in part multiple times. At each position, each of the residues can be made individually from the specified meanings selected. However, it can also have the same name Residues have the same meaning in the entire molecule. The expressions "each independent "and" independent of each other "express that each of the specified Residues individually and regardless of the meaning of the other residues from the specified meanings can be selected.

In the alkene derivatives of the general formula (I), X each independently denotes O, S. or NH. The two groups X can be identical or different from one another his. The radicals X are each independently O or S. In particular, both are Residues X oxygen atoms.

The radicals R ¹ and R ² can independently have one of the following meanings:
C _1-30 alkyl, preferably C _1-12 alkyl, especially C _1-6 alkyl. The alkyl radicals can be linear or branched. Accordingly, hydroxyalkyl radicals with the same carbon number can also be used. These are, in particular, terminal hydroxyalkyl residues. The alkyl or hydroxyalkyl radicals can optionally be interrupted by one or more non-adjacent and non-terminal heteroatom groups which are selected from O, S, NH, SO ₂ . Several different of the heteroatom groups mentioned can be present in each chain. In particular, there are oxygen atoms that interrupt the alkyl chain. In the radicals R ¹ and R ² , a breakdown of the alkyl chain, for example by oxygen atoms, can give a structure which can be derived from alkylene oxides. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide, particularly preferably ethylene oxide and propylene oxide, particularly preferably ethylene oxide. Different alkylene oxides can be present along the chain. They can be block-like compounds or statistically distributed compounds in which alkylene oxide blocks or individual, different alkylene oxide units are present. This means that the alkylene group can also be branched between two oxygen atoms, as shown above in the reaction scheme. The radicals mentioned can be derived, for example, from hydroxyalkyl groups which are further reacted with one or different alkylene oxides.

In the above formula, m and n can each have values of preferably 0 to 30, preferably have 0 to 20. I to 15 ethylene oxide units are particularly preferably in front.

The radicals R ¹ and R ² can also independently of one another C _6-12 aryl, preferably phenyl, C _7-30 alkaryl, preferably C _7-13 alkaryl or C _7-30 aralkyl, preferably C _7-13 aralkyl mean. An aromatic group is preferably present only in one of the radicals R ¹ or R ² .

The radicals R ¹ and R ² can preferably also form a radical - (CR ³ R ⁴ -) _n together with
R ³ , R ^{4 are} each independently hydrogen or as defined above for R, R ¹ , R ² , where a group CR ³ R ^{4 can} also mean C = O,
n 2, 3 or 4.

In this embodiment, the group - (CR ³ R ⁴ -) _n thus forms a cyclic system, in the case of X = O an acetal. If n has the value 2, a 5-ring is formed, if n has the value 3, a 6-ring and if n has the value 4, a 7-ring, preferably a 6-ring is formed, where n is the value 3 has. R ³ and R ⁴ can have the meanings given at any position independently of one another. The R ³ and R ⁴ radicals are preferably both different from hydrogen at only one position. The - (CR ³ R ⁴ -) _n radical is preferably only a longer alkyl radical which is interrupted by the heteroatom groups mentioned. Such an alkyl radical which is interrupted by the heteroatom groups mentioned is particularly preferably present, and optionally an alkyl radical which is not interrupted by heteroatom groups. For n = 3 there is preferably a group -CH ₂ -CR ³ R ⁴ -CH ₂ -. R ^{3 can} in particular have one of the meanings given, while R ^{4 is} a C _1-30 alkyl radical or C _1-30 hydroxyalkyl radical.

A group CR ³ R ⁴ can also mean C = O, so that a carboxyl group can be present in the ring.

The radical Y denotes a single bond or a C _1-30 alkylene radical, preferably a single bond or a C _1-12 alkylene radical, in particular a single bond or a C _1-6 alkylene radical. Y is particularly preferably a single bond.

R ⁵ has the meaning hydrogen. C _1-30 alkyl or phenyl, preferably the alkyl radical is a C _1-12 alkyl radical, in particular a C _1-6 alkyl radical.

In the alkylene derivative of the general formula (I), X is particularly preferably O and R ¹ , R ² together —CH ₂ —CR ³ R ⁴ —CH ₂ -.

Y is particularly preferably a single bond or a C _1-6 alkylene and R ^{5 is} hydrogen.

The siloxanes or oligomers or polymers thereof used in the process according to the invention are preferably those of the general formula (II)

EO- [SiR ⁶ ₂ -O] _x - [SiHR ⁶ -O] _y - [SiR ⁶ R ⁷ -O-] _z -E (II)

with the meaning
E each independently SiR ⁶ ₃ , SiR ⁶ ₂ R ⁷ , where both radicals E together can mean SiR ⁶ ₂ or SiR ⁶ R ⁷ ,
R ^{6 are} each independently C _1-30 alkyl or phenyl,
R ⁷ C _1-30 alkyl or C _1-30 hydroxyalkyl, interrupted by one or more non-adjacent and non-terminal heteroatom groups, selected from O, S, NH, SO ₂ ,
x integer ≥ 0,
y integer ≥ 1,
z integer from 0 to 100,
the basic building blocks can be distributed along the siloxane chains as desired.

Depending on the chain length, these can be monomers, oligomers or polymers with a siloxane backbone. The radicals E, R ⁶ and R ⁷ can have different meanings for each of the positions indicated. Each of the residues on each of the silicon atoms can have a different meaning. However, the radicals E, R ⁶ and R ⁷ each have the same meaning in themselves. If both radicals E together mean SiR ⁶ ₂ or SiR ⁶ R ⁷ , a cyclic siloxane is formed.

R ⁶ is preferably a C _1-12 alkyl radical, particularly preferably a C _1-6 alkyl radical, in particular a C _1-3 alkyl radical.

The radical R ⁷ preferably denotes a radical interrupted by heteroatoms, as described for the radicals R ³ and R ⁴ . It is preferably a C _1-30 alkyl radical or C _1-30 hydroxyalkyl radical which is interrupted by one or more oxygen atoms, so that the structure is derived from polyalkoxides. These can preferably be traced back to ethylene oxide, propylene oxide and / or butylene oxide as monomer units. It can be an alkyl radical which is substituted by one or more alkoxy radicals which are linked to one another.

x is an integer with a minimum value of 0. Preferably x has a value of 0 to 100, particularly preferably from 0 to 50. y means an integer with a Minimum value of 1. Preferably y has a value of 1 to 200, particularly preferably from 1 to 15.

z is an integer from 0 to 100, preferably from 0 to 50.

The individual brackets can be distributed anywhere in the polysiloxane available. For example, they can be in the form of blocks or statistically distributed available.

Siloxanes or oligomers or polymers thereof of the general formula (II) with the meaning are particularly preferred
E SiR ⁶ ₃
R ⁶ C _1-6 alkyl,
x integer from 10 to 100
y integer from 1 to 10
z 0.

The reaction according to the invention leads to an addition of the double bond of the alkenal derivatives of the general formula (I) to the silicon atoms which carry hydrogen atoms. Hydrosilylated alkenal derivatives are thus obtained. The hydrosilylated alkenal derivatives according to the invention preferably have the general formula (III)

EO- [SiR ⁶ ₂ -O] _x - [SiR ⁶ R ⁸ -O] _y - [SiR ⁶ R ⁷ -O] _z -E (III)

with the meaning
E, R ⁶ , R ⁷ , x, y, z as defined above,
R ⁸

with the meanings given above for R ⁵ , X, Y, R ¹ .

The reaction can be carried out in the presence of any suitable hydrosilylation catalysts. Preference is given to using catalysts containing noble metals, in particular catalysts containing platinum, palladium and / or rhodium. In particular, H ₂ PtCl ₆ or a derivative thereof is used as the catalyst.

The reaction can be solvent-free or in the presence of customary solvents be performed. Examples of suitable solvents can be aromatic Solvents such as benzene, toluene or xylene. Cyclic ethers such as Dioxane, diethyl ether, MTB ether or THF or alcohols such as aliphatic Alcohols, petroleum ethers, halogenated, especially chlorinated hydrocarbons or Mixtures of these are used.

The reaction is carried out at any suitable temperature. Preferably the temperature is 20 to 140 ° C, in particular 60 to 100 ° C.

The pressure under which the implementation is carried out is not critical. It can at Overpressure or underpressure can be worked. Preferably at ambient pressure worked.

In addition, a means for adjusting the pH can be used in the reaction become. The reaction should preferably be at a pH in the neutral range occur. If necessary, this pH value can be adjusted in the neutral range using Buffer substances such as salts of organic or inorganic acids can be adjusted. Examples of suitable buffer substances are sodium acetate and sodium benzoate.

It is also possible for stabilizers to be present in the reaction mixture. such Stabilizers can, for example, come from acrolein. Acrolein will usually mixed with a stabilizer to prevent polymerization.

The reaction is preferably carried out so that the pH of the Reaction mixture does not go into the acidic pH range.

The hydrosilylated alkenal derivatives according to the invention can - as already above described - used as a surfactant. In particular, they are used as wetting agents or Foam stabilizers for polyurethane foams, in paints, Coating compositions, textile auxiliaries, leather auxiliaries, Process chemicals in paper manufacture, fiber treatment agents, Plant protection formulations or cosmetics use.

The invention is illustrated below with the aid of reaction schemes and examples explained.

Acrolein acetals which are preferably used can be prepared according to the following scheme:

In the first implementation step, different at least two-valued ones can be used Alcohols or polyols can be used. Examples of suitable alcohols that can be used are Trimethylolmethane, trimethylolethane, trimethylolpropane etc., glycerin, pentaerythritol, Pentite (arabite, adonite, cylitol), hexite (sorbitol, mannitol, dulcite). At least two hydroxyl groups are present in acetalizable form.

The preparation of acrolein acetals and the subsequent alkoxylation can be carried out as in EP-A-0 043 966. In this document there are also suitable ones Reaction conditions and catalysts listed.

Further processes for the preparation of acrolein acetals are in GB-A-2 020 702 and DE-A-21 36 572 described.

The reaction with the siloxane component can be carried out according to the following scheme:


Examples Example 1 (and general procedure) Preparation of the siloxane backbone

73 g of hexamethyldisiloxane, 771 g of octamethylcyclotetrasiloxane and 156 g of polymethylhydrosiloxane are introduced and rendered inert with N ₂ . 0.65 g (376 µL) of trifluoromethanesulfonic acid are added and the mixture is stirred at 70 ° C. for 6 h.

Then allowed to cool to room temperature and stirred for a further 12 h.

7.5 g of finely powdered sodium hydrogen carbonate are added and the mixture is stirred for 2 hours. The precipitate is filtered off. Hydrosilylation of the siloxane backbone with acrolein acetal

60.6 g (0.3 mol) of siloxane backbone, 34.8 (0.2025 mol) of acrolein acetal, 25.3 .mu.L Na benzoate (33% aqueous solution) and 27.2 .mu.L catalyst (7.5% Hexachloroplatinic acid in isopropanol) and inertized with a moderate N ₂ flow. The mixture is then heated to 80 ° C. and stirred for 2 hours. A colorless oil is obtained after filtration. Example 2

67.4 g (0.02 mol) of the siloxane and 18.6 g (0.108 mol) of the acrolein acetal were used. In addition, 22.8 ul sodium benzoate solution and 24.5 ul hexachloroplatinic acid solution were used. Example 3

67.4 g (0.02 mol) of the siloxane component and 15.3 g (0.108 mol) of the acrolein acetal were used. Furthermore, 22.0 ul sodium benzoate solution and 23.6 ul hexachloroplatinic acid solution were used. Example 4

50.5 g (0.015 mol) of the polysiloxane and 51.4 g (0.084 mol) of the alkoxylate were used. 58 μl of hexachloroplatinic acid solution were also added. Example 5

There were 50.5 g (0.015 mol) of the polysiloxane and 32.9 g (0.084 mol) of the alkoxylate used. In addition, 23.8 μl of hexachloroplatinic acid solution were used.

Claims (10)

1. Process for the preparation of hydrosilylated alkene derivatives by reaction of alkene derivatives of the general formula (I)


with the meaning
X each independently O, S, NH
R ¹ , R ² independently of one another are C _1-30 -alkyl or C _1-30 -Hydroxyalkyl, optionally interrupted by one or more non-adjacent and non-terminal heteroatom groups, selected from O, S, NH, SO ₂ ;
C _6-12 aryl, C _7-30 alkaryl or C _7-30 aralkyl,
where R ¹ , R ² together can also form a residual (CR ³ R ⁴ -) _n with R ³ , R ⁴ each independently being hydrogen or as defined for R ¹ , R ² , a group CR ³ R ⁴ also having C = O can mean
n 2, 3 or 4,
Y single bond or C _1-30 alkylene,
R ^{5 is} hydrogen, C _1-30 alkyl or phenyl,
with silanes, siloxanes or oligomers or polymers thereof, which have at least one Si-H group, on a hydrosilylation catalyst. 2. The method according to claim 1, characterized in that in the alkene derivative of the general formula (I)
X each O and
R ¹ , R ² together -CH ₂ -CR ³ R ⁴ -CH ₂ - mean. 3. The method according to claim 1 or 2, characterized in that in the alkene derivative of the general formula (I) Y is a single bond or C _1-6 alkylene and R ^{5 is} hydrogen. 4. The method according to any one of claims 1 to 3, characterized in that the siloxanes or oligomers or polymers thereof have the general formula (II)

EO- [SiR ⁶ ₂ -O] _x - [SiHR ⁶ -O] _y - [SiR ⁶ R ⁷ -O-] _z -E (II)

with the meaning
E each independently SiR ⁶ ₃ , SiR ⁶ ₂ R ⁷ , where both radicals E together can mean SiR ⁶ ₂ or SiR ⁶ R ⁷ ,
R ^{6 are} each independently C _1-30 alkyl or phenyl,
R ⁷ C _1-30 alkyl or C _1-30 hydroxyalkyl, interrupted by one or more non-adjacent and non-terminal heteroatom groups, selected from O, S, NH, SO ₂ ,
x integer ≥ 0,
y integer ≥ 1,
z integer from 0 to 100,
the basic building blocks can be distributed along the siloxane chains as desired. 5. The method according to claim 4, characterized in that in the siloxane or oligomer or polymer thereof of the general formula (II)
E SiR ⁶ ₃
R ⁶ C _1-6 alkyl,
x integer from 10 to 100
y integer from 1 to 10
z mean 0. 6. The method according to any one of claims 1 to 5, characterized in that H ₂ PtCl ₆ or a derivative thereof is used as catalyst. 7. Hydrosilylated alkene derivative, obtainable by a process according to one of the Claims 1 to 6. 8. Hydrosilylated alkene derivative of the general formula (III)

EO- [SiR ⁶ ₂ -O] _x - [SiR ⁶ R ⁸ -O] _y - [SiR ⁶ R ⁷ -O] _z -E (III)

with the meaning
E, R ⁶ , R ⁷ , x, y, z as defined in claim 4 or 5,
R ⁸

with the meanings given in claim 1 or 2 for R ⁵ , X, Y, R ¹ . 9. Use of hydrosilylated alkene derivatives according to claim 7 or 8 as fissile surfactant in which the polysiloxane units from the polyether units can be split off under acidic conditions. 10. Use according to claim 9 as a wetting agent or as a foam stabilizer for Polyurethane foams, in paints, coating compositions, Textile auxiliaries, leather auxiliaries, process chemicals in paper production, Fiber treatment agents, crop protection formulations or cosmetics.