CN100384913C - Amino-functional polysiloxane wax - Google Patents

Abstract

The present invention relates to silicone waxes having plural tertiary or quaternary amino groups, their preparation and their use as softeners in the textile industry. These waxes can be processed into stable aqueous dispersions and lead to products having a pleasant, soft hand.

Description

Amino-functional polysiloxane wax

The present invention relates to a polysiloxane wax with multiple tertiary or quaternary amino groups, its preparation method and its use as a softener in the textile industry.

There is an extensive literature on aminofunctional silicone compounds. These compounds are used, for example, as plasticizers in the textile industry, as surface treatment agents, as thickeners or in the cosmetics industry. Nevertheless, there is still a need in the textile industry for emollient substances which allow to obtain products with a superior hand without the disadvantages of conventional unstable emulsions.

It has now been found that certain polysiloxane waxes with multiple tertiary or quaternary nitrogen atoms can be processed into stable aqueous dispersions and have surprisingly good properties when used as softeners in the textile industry , and a product with a pleasant, soft hand is obtained.

Accordingly, the present invention provides amino-functional polysiloxane waxes having the general formulas (I) to (IV)

in

R is straight-chain or branched C ₁₁ -C ₂₂ -alkyl,

R1 is C ₁ -C ₇ -alkyl or benzyl, preferably methyl or benzyl,

R2 is -OH _{, -CH3} , _-OCH3 , _-OC2H5 ,

A ^- is CH ₃ OSO ₃ ^- , chloride, bromide, iodide, or tosylate, preferably CH ₃ OSO ₃ ^- or chloride,

n is 2 or 3,

p is 10-200, preferably 20-50,

q+z is 10-400, preferably 15-200, and

q/z is 5-50, preferably 10-30.

These waxes, whether in the quaternized forms (II) and (IV) or in the non-quaternized forms (I) and (III), show good performance when used as softeners. An important advantage of this is that they can be used in the form of dispersions which, compared to emulsions, have a higher shear stability.

The present invention further provides a preparation method of the above polysiloxane wax. The initial step is the preparation of fatty acid diamides by condensation of fatty acids such as stearic acid or lauric acid with diethylenetriamine or dipropylenediamine.

Reaction of the resulting fatty acid diamide with a polysiloxane oil of general formula (V)

wherein p has the same meaning as in general formula (I) or (II), to prepare the wax of general formula (I) or (II),

Or subsequently quaternized with common quaternizing agents such as methyl sulfate, ethyl sulfate, methyl halide, benzyl chloride or tosylate, to prepare the compound of general formula (II) wax. Starting materials and methods for their preparation are known to those skilled in the art.

To prepare waxes of general formula (III) or (IV), the fatty acid diamides obtained are reacted with polysiloxane oils of general formula (VI)

wherein R2, (q+z) and q/z have the same meaning as in general formula (III) or (IV),

Furthermore, in order to prepare the waxes of the general formula (IV), the fatty acid diamides obtained are subsequently quaternized with the customary, abovementioned quaternizing agents.

The present invention further provides the use of the above polysiloxane wax as a softener in the textile industry. The polysiloxane waxes obtained can be converted with the aid of dispersants into aqueous dispersions which have a higher shear stability compared to emulsions and are very useful for softening textiles, giving the material a Pleasant soft touch.

Example

1. Preparation of Fatty Acid Diamides

(fatty acid: RCOOH)

1.1 Preparation of R-CONH(CH ₂ ) ₂ NH(CH ₂ ) ₂ NHCO-R

2 moles of fatty acid were heated to 105°C under nitrogen; then 1 mole of diethylenetriamine was added dropwise while raising the temperature to 130°C. Then, condensation was carried out at 130° C. for 24 hours under a slow nitrogen flow using a distillation bridge. The reaction mixture was subsequently discharged. The acid number (mg of KOH required to neutralize 1 gram of product) of the reaction mixture was below 7. The amount of condensation product obtained required less than 1.1 moles of perchloric acid for titration of free amino groups.

1.2 Preparation of R-CONH(CH ₂ ) ₃ NH(CH ₂ ) ₃ NHCO-R

Repeat 1.1 using dipropylenediamine instead of diethylenediamine.

2. Preparation of Polysiloxane Wax

2.1 Silicone wax W1-W6

Make 661.5 parts of silicone oil of the following general formula

Reaction with x parts of diamides D ₁ to D ₆ at 150° C. under nitrogen for 14 hours. A test is then carried out to see if glycidyl groups are no longer present. The following waxes were obtained:

Diamide x (parts)  Silicone Wax D₁D₂D₃D₄D₅D₆ 233.5317.5373.5247.5331.5387.5 W₁W₂W₃W₄W₅W₆

The wax has the following structure:

n=2 or 3, R=C ₁₁ -C ₂₂ alkyl

2.2 Silicone wax W ₇ -W ₁₂

Make 661.5 parts of silicone oil of the following general formula

Reaction with x parts of diamides D ₁ to D ₆ at 150° C. under nitrogen for 14 hours. A test was then carried out to see if the glycidyl groups had reacted quantitatively. The following waxes were obtained:

Diamide x (parts)  Silicone Wax D₁D₂D₃D₄D₅D₆ 230.9313.9369.3244.7327.8383.2 W₇W₈W₉W₁₀W₁₁W₁₂

The wax has the following structure:

n=2 or 3, R=C ₁₁ -C ₂₂ alkyl

3. Preparation of quaternized polysiloxane waxes WQ ₁ -WQ ₁₂

x parts of silicone wax W were melted and allowed to react with 25.2 parts of dimethyl sulfate at about 70-75°C for 2 hours.

A wax with the following structure is obtained:

and

n=2 or 3, R=C ₁₁ -C ₂₁ alkyl.

4. Preparation of the final product

4.1 Silicone-based waxes W ₁ -W ₁₂

Melt 125.0 parts of silicone wax (W). Then add the following compound (Dispersant 1)

70% solution in propylene glycol 25.0 parts and stearyl poly-10-glycol ether (dispersant 2) 37.5 parts. Once a homogeneous melt is obtained, 800.0 parts of water are added in increments with stirring. Finally 12.5 parts of glacial acetic acid are added. This gives 1000.0 parts of a 12.5% silicone wax dispersion (W-E).

4.2 Based on quaternary ammonium polysiloxane waxes WQ ₁ -WQ ₁₂

4.1 was repeated except that silicone wax (WQ) was used instead of silicone wax (W), and finally 12.5 parts of water were added instead of 12.5 parts of glacial acetic acid. This gives 1000.0 parts of a 12.5% silicone wax dispersion (WQ-E).

Products W ₁ -E to W ₁₂ -E and WQ ₁ -E to WQ ₁₂ -E are very stable against shear forces; they can be applied to textile materials in the padding process and in the exhaust process (cotton and synthetic fibers) of both. The final textile material has an excellent, soft, pleasantly smooth hand.

Application example

The following finishing operations were performed:

Empty process

At about 40°C and a liquid ratio of 6:1 to 20:1, in a laboratory injector, the finishing substrate is added to an aqueous solution containing 0.5% to 4.0% of The final product described in the example. After 20 minutes at pH 5.0 to 6.0 (40°C) with continuous agitation of the substrate, the substrate was removed from the solution, centrifuged and dried without tension at 140°C for 70-90 seconds.

padding process

The finishing substrate is padded to 100% dry weight gain at room temperature using an aqueous solution comprising 15 to 60 g/l of the final product W-E or WQ-E. The padded material was then dried at 140°C for 70-90 seconds.

Substrate:

Empty process: Warp knitted fabric, dyed, with or without setting - 100% cotton - polyester (50%)/cotton (50%)   Padding process: Warp knitted or woven fabric, dyed, with or without setting - 100% cotton - polyester (50%) / cotton (50%) - polyester (100%) - polyacrylonitrile (100%) - nylon 6 (100%)

test:

Softness is tested in pairs using a Handle Tester (eg 211-5 Twing Albert). Finished samples were first conditioned (24 hours, 20°C, 65% relative humidity) prior to evaluation.

All finishes showed a clear improvement in softness compared to unfinished fabrics.

Claims (7)

1. Aminofunctional polysiloxane waxes of the following general formulas (I) to (IV)

in R is straight-chain or branched C ₁₁ -C ₂₂ -alkyl, R1 is C ₁ -C ₇ -alkyl or benzyl, R2 is -OH _{, -CH3} , _-OCH3 , _-OC2H5 , A ^- is CH ₃ OSO ₃ ^- , chloride, bromide, iodide, or tosylate, n is 2 or 3, p is 10-200, q+z is 10-400, and q/z is 5-50. 2. The aminofunctional polysiloxane wax of claim 1, wherein R, R2 and n are each as defined above, R1 is methyl or benzyl, A ^- is CH ₃ OSO ₃ ^- or chloride, p is 20-50, q+z is 15-200, and q/z is 10-30. 3. The method for preparing the aminofunctional polysiloxane wax of general formula (I) or (III) in claim 1, it is characterized in that, by fatty acid and diethylenetriamine or dipropylenediamine condensation Preparation of fatty acid diamides followed by reaction with polysiloxane oils of general formula (V) to prepare waxes of general formula (I):

Wherein, p has the same meaning as in general formula (I) or (II), Alternatively react with polysiloxane oils of general formula (VI) to prepare waxes of general formula (III)

wherein R2, (q+z) and q/z have the same meanings as in general formula (III) or (IV). 4. The method according to claim 3, characterized in that the obtained polysiloxane wax of general formula (I) or (III) is quaternized to obtain a compound of general formula (II) or (IV). 5. The method according to claim 3 or 4, characterized in that the fatty acid is stearic acid, behenic acid or lauric acid. 6. Use of the silicone waxes according to claim 1 or 2 as softeners in the textile industry. 7. Use according to claim 6, characterized in that the polysiloxane wax is used in the form of an aqueous dispersion.