DE10036533A1 - Production of polyquaternary polysiloxanes, useful as wash-resistant fabric conditioners, comprises reacting hydrogen-terminal dimethylpolysiloxane with olefin-terminal epoxide, and reacting with mixture of tertiary and ditertiary amines - Google Patents

Abstract

Production of polyquaternary polysiloxanes (I) comprises reacting a hydrogen-terminal dimethylpolysiloxane with an olefin-terminal epoxide and reacting the product with a mixture of a tertiary amine and a ditertiary amine in the presence of an acid. Production of polyquaternary polysiloxanes of formula (I) comprises: (a) reacting a hydrogen-terminal dimethylpolysiloxane of formula (II) with 1.0-1.5 moles (per SiH group) of an epoxide having a terminal olefinic bonds and comprising at least 4C atoms and optionally a noncyclic ether group, in the presence of a hydrosilylation catalyst at 50-150 deg C; (b) removing excess epoxide; and (c) reacting the product with a mixture of a tertiary amine (NR<1>R<2>R<5>) and a ditertiary amine (R<1>R<2>N-Y-NR<3>R<4>) in the presence of an acid (HA) at 40-120 deg C, the molar ratio of epoxide groups to tertiary amino groups to HA being 1:1:1. X = a divalent hydrocarbon group with at least 4 C atoms, optionally substituted by OH and/or interrupted by O; Y = a divalent hydrocarbon group with at least 2C atoms, optionally substituted by OH and/or interrupted by O or N; Z<1>, Z<2> = bonds forming a cyclic structure, or Z<1> is H, OH, alkyl, alkoxy, OH-substituted \-4C hydrocarbyl (optionally interrupted by one or more O atoms) or a group of formula (i) or (ii) and Z<2> is a group of formula (iii); R<5> = 1-20C alkyl; R<1>-R<4> = 1-4C alkyl or benzyl, or R<1>+R<3> and/or R<2>+R<4> are alkylene; A<-> = an anion; n = 5-20; and m = 1 or more. An Independent claim is also included for wash-resistant diquaternary polysiloxanes of formula (III): Z = a group of formula (iv)-(vi); R<6>-R<8> = optionally OH-substituted 1-22C alkyl or 2-22C alkenyl, at least one having \-10C atoms; R<9>, R<10>, R<12>, R<14>, R<15> = optionally OH-substituted 1-22C alkyl or 2-22C alkenyl; R<11> = O or NR<13>; R<13> = H, 1-4C alkyl or 1-4C hydroxyalkyl; s = 2-4; M = a group of formula (vii)-(xviii) in which the asterisked bond is attached to the N atoms of Z; r = 0-200; and B = anion.

Description

The invention relates to a method for producing polyquaternary Polysiloxanes and their use as washable hydrophilic plasticizers.

Polysiloxanes containing amino groups and used as textile softeners are already known from EP-A-441 530. U.S. 5,591,880 and U.S. 5,650,529 disclose the introduction of modes by ethylene oxide / propylene oxide units fected amino structures as side chains, which improve the effect as cause textile softener. The alkylene oxide units allow this targeted adjustment of the hydrophilic-hydrophobic balance. A disadvantage of the Making the compounds in the synthesis is the difficult one included Esterification of amino alcohols with siloxane-linked carboxylic acid groups. Additional difficulties arise with the softening Properties due to the general comb structure of the products. US 5,807,956 and US Pat. No. 5,981,681 describe to eliminate these disadvantages that α, ω- epoxy-modified siloxanes with α, ω-amino-functionalized alkylene oxides  to be implemented, and these products as hydrophilic plasticizers use.

Attempts have been made to improve the substantivity, quaternary Introduce ammonium groups in alkylene oxide-modified siloxanes. branched alkylene oxide-modified quaternary polysiloxanes can by condensation of α, ω-OH-terminated polysiloxanes and trialkoxysilanes can be synthesized. The quaternary ammonium structure is introduced over the silane, the quaternary nitrogen atom is substituted by alkylene oxide units, as in US Pat. No. 5,625,024 disclosed. Strictly comb-like alkylene oxide-modified quaternary poly siloxanes have already been described in US Pat. No. 5,098,979. The hydroxyl groups of Comb polyethersiloxanes substituted with epichlorohydrin in the corresponding chlorohydrin derivatives transferred. This is followed by one Quaternization with tertiary amines. The disadvantage of this synthesis is that Use of epichlorohydrin and the relatively low reactivity of chlorohydrin Grouping during quaternization.

For this reason, the hydroxyl groups are substituted like a comb Alternatively, polyether siloxanes are esterified with chloroacetic acid. Through the The final quaternization can be carried out more easily by carbonony activation as disclosed in US 5,153,294 and US 5,166,297.

DE-OS 32 36 466 discloses a fundamentally different approach. The implementation of OH-terminated siloxanes containing quaternary ammonium structures Alkoxysilanes provides reactive intermediates with suitable crosslinking agents, such as trialkoxysilanes, on the fiber surface to be wash-resistant Network layers. A major disadvantage of this approach is that the The stability of an aqueous equipment bath that is necessary for hours is not guaranteed can be and unforeseen cross-linking reactions in the bathroom before the Textile equipment can occur.

EP-A-0 282 720 describes polyquaternary polysilxane polymers, the manufacturers of which by reaction of α, ω-diepoxides with tertiary amines in the presence of Acids and use in cosmetic preparations as hair treatment agents.

There are no satisfactory solutions to the problem from the prior art have found the soft grip typical of advanced silicones and the  pronounced hydrophilicity even after initial equipping of a textile material ensure if this is attacked by aggressive detergent formulations in the Course of repeated washing processes at an optionally elevated temperature is exposed.

EP-A-0 282 720 describes a process for the preparation of compounds in which the reaction of α, ω-diepoxides with di-tertiary amines takes place in the presence of acids to give polymeric structures. Production via quaternary Z ¹ and Z ² groups has not been disclosed.

The object of the present invention has therefore been to provide an improved one Process for the preparation of polyquaternary polysiloxane polymers and others To provide applications for these connections. This is what it is about the applications on textiles, since silicones give way to a typical silicone Give grip and a pronounced hydrophilicity, whereby this property profile also after exposure to detergent formulations, after repeated Washing processes at a possibly elevated temperature are not lost.

Accordingly, it was an object of the present invention to provide an improved process for the preparation of the di- or polyquaternary polysiloxane polymers of the general formula (I)

and / or linear compounds of the general formula (II)

wherein X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by an oxygen or nitrogen atom, Z ^{1 is} an H, OH, an alkyl or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest

has, where R ^{5 is} a C ₁ -C ₂₀ alkyl radical, Z ² the group

R ¹ , R ² , R ³ and R ^{4 are} identical or different and mean C1-C4-alkyl radicals or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be components of a bridging alkylene radical, A ^- an inorganic one or organic anion, n is 5 to 20 and, m is an integer ≧ 1,
and by the reaction of α, ω-hydrogen polysiloxanes of the general formula

with, based on SiH groups, 1.0 to 1.5 mol of an epoxide, with terminal olefinic bonds, in which the epoxide has at least 4 carbon atoms and may additionally contain a noncyclic ether group, in the presence of a hydrosilylation catalyst at temperatures from 50 to 150 ° C. is implemented, the excess of olefinic epoxide is removed, and the reaction product with a mixture of a tertiary amine of the formula

and a di-tertiary amine of the formula

is reacted in the presence of acids HA at 40 to 120 ° C, the molar Ratio of epoxy groups to tertiary amino groups and to the acids HA 1: 1: 1 is.

In a further embodiment of the present invention, the tertiary and di-tertiary amines in a molar ratio, based on amino groups, of 0.001 to 0.999 to 0.9 to 0.1.

In a further embodiment of the present invention are preferred molar ratios of the amino groups of the tertiary amines to the di-tertiary Amines used from 0.001 to 0.999 to 0.5 to 0.5.

In a preferred embodiment of the present invention, a molar ratio of 0.01 to 0.99 to 0.2 to 0.8 used.

The structure of the tertiary amines results from the definitions for R ¹ , R ² and R ⁵ . In a preferred embodiment, trimethylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine are used.

Preferably used as anion B ^- physiologically acceptable inorganic residues from the group consisting of chloride, bromide, hydrogen sulfate or sulfate, or organic residues from the group consisting of acetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate or oleate.

In a further variant of the present production process, preference is given to the compounds of the formula (I) and (II) for the radical X

used, which have already been described in EP-A-0 282 720. In a further embodiment, Y is used for Y - (CH ₂ ) _o -, with a value o preferably from 2 to 6. Methyl is particularly preferably used for the radicals R ¹ , R ² , R ³ , R ⁴ .

The present invention further provides diquarternary polysiloxanes of the general formula (III)

where Z

R ⁶ , R ⁷ , R ^{8 are} C ₁ -C ₂₂ alkyl radicals or C ₂ -C ₂₂ alkylene radicals, and the alkyl or alkylene radicals can have hydroxyl groups and at least one of the radicals R ⁶ , R ⁷ , R ^{8 has} at least 10 carbon atoms , R ⁹ _, R ¹⁰ , R ¹² , R ¹⁴ , R ¹⁵ C ₁ -C ₂₂ alkyl radicals or C ₂ -C ₂₂ alkylene radicals, and the alkyl or alkylene radicals can have hydroxyl groups, R ¹¹ -O- or -NR ¹³ - Radical, R ¹³ C ₁ -C ₄ alkyl or hydroxyalkyl radical or hydrogen radical, S 2 to 4, M is a divalent radical selected from the group

The radicals R ⁶ , R ⁷ , R ⁸ and the radicals R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ and R ¹⁵ can be the same or different in the molecule. Preferred compounds are those in which two of the radicals R ⁶ , R ⁷ , R ^{8 are} lower alkyl radicals having 1 to 4 carbon atoms and the remaining third radical is a long-chain hydrocarbon radical with at least 10 carbon atoms. Among the long-chain hydrocarbon radicals, particularly preferred are saturated and unsaturated branched or unbranched hydrocarbon radicals which are derived from the naturally occurring fatty acids.

If the radicals R ⁹ , R ¹⁰ and R ^{12 are} adjacent to one another, preference is given to those compounds in which R ⁹ and R ^{10 are} a lower hydrocarbon radical having 1 to 4 carbon atoms and the radical R ^{12 is derived} from a fatty acid R ¹² COOH which has at least 8 carbon atoms.

EP-A-0 282 720 and DE-PS 37 19 086 describe the use of each disclosed compounds in cosmetic formulations, especially in the Hair care described. The advantages are generally improved combability, good gloss, high antistatic effectiveness and preferred in EP-A-0 282 720 called improved washout resistance.

The latter property is not in with a wash resistance equate the inventive sense. While the washout resistance from hair on the short-term attack of primarily water and very mild, non-irritating surfactants, have wash-resistant, hydrophilic Softener for textiles to attack concentrated surfactant solutions with high Resist fat and dirt dissolving ability. These surfactant systems are in modern detergents strongly alkaline complexing agents, oxidizing Bleach and complex enzyme systems added. The action takes place often for hours at elevated temperatures. For these reasons, one is Transfer of experience from the cosmetics sector to the field of wash-resistant fabric softener not possible. DE-OS 32 36 466 discloses that to achieve washable textile equipment on cross-linkable Systems would have been resorted to.

Furthermore, it could not be derived that the compounds according to EP-A-0 282 720 and DE-PS 37 19 086 in an advantageous manner as an internal plasticizer Formulations based on anionic / nonionic surfactants for washing Textiles and fibers can be used. In this case, too apply the aggressive detergent systems, the elevated temperatures and long Considerations made.

Another object of the present invention is the use of polyquaternary polysiloxane polymers according to the general formulas (I) to (III) as a softener after washing textiles with nonionic or anionic / nonionic detergent formulations, as plasticizers in from formulations based on nonionic or anionic / nonionic surfactants been to textile washing.

Furthermore, the compounds of the general formulas (I) to (III) for the initial equipment of fibers and textiles, in polishes for treatment and  Hard surface finishing, in formulations for drying automobiles and other hard surfaces after machine washing.  

Examples

The following examples are intended to explain the invention in greater detail, but without it limit.

example 1

1a) 28 g of water and 12.2 g (0.14 mol of amino groups) of N, N, N ', N'-tetramethyl-1,6-hexanediamine were placed in a 1 liter three-necked flask at room temperature. 56.1 g (0.14 mol) of dodecanoic acid were added in the form of a 50% solution in 2-propanol within 5 minutes. After the batch had been heated to 50 ° C., 313.5 g (0.14 mol epoxy groups) of an epoxysiloxane of the average composition were added dropwise within 25 minutes

and 35 ml of 2-propanol. The cloudy mixture was heated under reflux for 6 hours. After removal of all components volatile up to 100 ° C. and at 2 mm Hg in vacuum, 346.7 g of a light brown, clear and flowable material of the structure were obtained

Example 2

The procedure was as in Example 1, with the difference that a mixture of 10.96 g (0.126 mol amino groups) N, N, N ', N'-tetramethyl-1,6-hexanediamine and 2.06 g (0.014 mol of amino groups) of a 40% by weight solution of trimethylamine in water. After removal of the volatile constituents, 351.4 g of a yellow-light brown, viscous and slightly slightly cloudy substance of the average composition

receive.

Example 3

To demonstrate suitability as a wash-resistant, hydrophilic plasticizer, white cotton jersey was subjected to the treatment described below with formulations based on the quaternary ammonium salts according to Examples 1 and 2. For comparison, a commercially available hydrophilic plasticizer based on patents US 5,807,956 and US 5,981,681 was used. The following clear base formulations were first produced:

20 g of these base formulations were dissolved in 980 g of distilled water. This is followed by effectively containing 0.4% active siloxane Formulations an equipment of 60 cm × 90 cm and 87 g heavy Cotton jersey pieces in the foulard process. For this, the cotton material 5 completely immersed in the respective formulation for up to 10 seconds, after Forced application spun and dried at 120 ° C, 3 minutes.

The flaps were then divided and one half five by machine Washing cycles in the presence of a mild detergent (1.7 g detergent / liter Wash liquor). Each wash cycle lasted 25 minutes Washing temperature was 40 ° C.

The hydrophilicity became apparent on the unwashed and washed textile pieces (this is the pull-in time of a drop of water in seconds) determined and additionally rated the grip by 10 test persons.

The results showed that the textile materials finished according to the invention also after 5 washing cycles, you still have the desired combination of properties Hydrophilicity, expressed by a very short drop-in time, and that typical silicone grip.

Example 4

To prove the softening properties as an internal softener during the washing process, bleached and on the surface were no further equipped cotton strips a washing process in the presence of Ariel Futur®, Dash 2 in 1® containing bentonite and the silicone quat described in Example 2 subjected.

The following boundary conditions were observed.

The water was heated to 60 ° C, the detergents and in the case of Cotton stripe 1 additionally dissolved the compound according to Example 2. The cotton strips were then washed in these solutions for 30 minutes rule. The strips were then rinsed 5 times with 600 ml of water and finally dried at 120 ° C for 30 minutes.

13 test persons evaluated the three cotton strips for softness of the handle, where grade 1 is the softest stripe and grade 3 is the hardest stripe was allocated.  

As a result of the evaluation, cotton stripe 1 received an average grade of 1.6. The cotton strip 2 was treated with an average of 2.4 and the bentonite Strip 3 rated 2.0.

Claims (8)

1. Process for the preparation of polyquaternary polysiloxane polymers according to the general formula (I) or (II)
and / or linear compounds of the general formula (II)
wherein X is a divalent hydrocarbon radical with at least 4 carbon atoms, which has a hydroxyl group and which can be interrupted by an oxygen atom, Y is a divalent hydrocarbon radical with at least 2 carbon atoms, which have a hydroxyl group and which can be interrupted by an oxygen or nitrogen atom, Z ^{1 is} an H, OH, an alkyl or an alkoxy radical, or has the meaning of a hydrocarbon radical with at least 4 carbon atoms, which has one or more hydroxyl group (s) and can be interrupted by one or more oxygen atoms, or the meaning of the rest
where R ^{5 is} an alkyl radical having 1 to 20 carbon atoms, Z ^{2 is} the group
R ¹ , R ² , R ³ and R ^{4 are} identical or different and mean C1-C4-alkyl radicals or benzyl radicals or the radicals R ¹ and R ³ or R ² and R ⁴ can each be components of a bridging alkylene radical, A ^- an inorganic one or is organic anion, n is 5 to 20 and, m is an integer ≧ 1, characterized in that for synthesis α, ω-hydrogen polysiloxanes of the general formula
with, based on SiH groups, 1.0 to 1.5 mol of an epoxide, with terminal olefinic bond, in which the epoxide has at least 4 carbon atoms and may additionally contain a noncyclic ether group, in the presence of a hydrosilylation catalyst at temperatures from 50 to 150 ° C. is implemented, the excess of olefinic epoxide is removed, and the reaction product with a mixture of a tertiary amine of the formula
and a di-tertiary amine of the formula
in the presence of acids HA at 40 to 120 ° C, and the molar ratio of epoxy groups to tertiary amino groups and to the acids HA is 1: 1: 1. 2. Process for the preparation of polyquaternary polysiloxane polymers according to Claim 1, characterized in that the mixture of tertiary and di- tertiary amine based on the amino groups, in a molar ratio from 0.001: 0.999 to 0.9: 0.1 can be used with each other. 3. Process for the preparation of polyquaternary polysiloxane polymers according to Claims 1 to 2, characterized in that the molar ratio of Amino groups from tertiary amines to di-tertiary amines 0.001: 0.999 bis 0.5: 0.5 and preferably 0.01: 0.99 to 0.2: 0.8. 4. Process for the preparation of polyquaternary polysiloxane polymers according to claim 1, characterized in that preferred as the tertiary amine those from the group consisting of trimethylamine, dimethylethylamine, Dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, Dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, Dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine be used. 5. wash-resistant diquarternary polysiloxanes of the general formula (III),
where Z is the rest
R ⁶ , R ⁷ , R ^{8 are} C ₁ -C ₂₂ alkyl radicals or C ₂ -C ₂₂ alkylene radicals, in which the alkyl or alkylene radicals can have hydroxyl groups and at least one of the radicals R ⁶ , R ⁷ , R ^{8 has} at least 10 carbon atoms , R ⁹ , R ¹⁰ , R ¹² , R ¹⁴ _, R ¹⁵ C ₁ -C ₂₂ alkyl radicals or C ₂ -C ₂₂ alkylene radicals, in which the alkyl or alkylene radicals can have hydroxyl groups, R ¹ -O- or -NR ¹³ - Radical, R ¹³ C ₁ -C ₄ alkyl or hydroxyalkyl radical or hydrogen radical, S 2 to 4, M is a divalent radical selected from the group
wherein the N atom of the radical Z is connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M, r is a number from 0 to 200 and B is an inorganic or organic anion. 6. Use of the wash-resistant hydrophilic plasticizers based polyquaternary polysiloxane polymers according to claim 1 or 3 as Softener after washing textiles with non-ionic or anionic / nonionic detergent formulations, as plasticizers in based on nonionic or anionic / nonionic surfactants Textile laundry formulations. 7. Use of the wash-resistant hydrophilic plasticizers based polyquaternary polysiloxane polymers according to claim 1 or 3 for Initial equipment of fibers and textiles.   8. Use of the washable hydrophilic plasticizers based polyquaternary polysiloxane polymers according to one of the foregoing Claims hard in polishes for treatment and finishing Surfaces, in formulations for drying automobiles and others hard surfaces after machine washing, as separate plasticizers after washing textiles with nonionic or anionic / nonionic detergent formulations.