The present invention concerns silicone waxes having plural tertiary or quaternary amino groups, their preparation and their use as softeners in the textile industry.
There is extensive literature on amino-functional silicone compounds. These compounds are used for example as plasticizers in the textile industry, as surface-treating agents, as thickeners or in the cosmetic industry. Nonetheless, there is a demand in the textile industry for softening substances which lead to products having a superior hand and which do not have the disadvantage of unstable emulsions in use.
It has now been found that certain silicone waxes having plural 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 lead to products having a pleasant, soft hand.
The invention accordingly provides amino-functional silicone waxes of the formulae (I) to (IV)
where
These waxes, whether in the quaternized form (II) and (IV) or in the non-quaternized form (I) and (III), exhibit good properties when used as softeners. Their great advantage is that they can be used in the form of dispersions which, compared with emulsions, have a higher shearing force stability.
The present invention further provides for the preparation of the aforementioned silicone waxes. The initial step is to prepare fatty acid diamides by condensation of fatty acids, for example stearic acid or lauric acid, with diethylenetriamine or dipropylenediamine.
The resultant fatty acid diamide is reacted with silicone oils of the general formula (V)
where p has the same meaning as in formula (I) or (II), to prepare the waxes of formula (I) or (II),
or subsequently quaternized with the customary quaternizing agents such as methyl sulfate, ethyl sulfate, methyl halide, benzyl chloride or tosyl sulfate to prepare the waxes of the formula (II). The starting materials and their preparation will be known to one skilled in the art.
To prepare the waxes of the formula (III) or (IV), the resultant fatty acid diamide is reacted with silicone oils of the general formula (VI)
The present invention further provides for the use of the aforementioned silicone waxes as softeners in the textile industry. The silicone waxes obtained can be converted by means of dispersants into aqueous dispersions which have a higher shearing force stability than emulsions and are very useful for softening textiles in that the material acquires a pleasant, soft hand.
1.1 Preparation of R—CONH(CH2)2NH(CH2)2NHCO—R
2 mol of fatty acid are heated to 105° C. under nitrogen; 1 mol of diethylenetriamine is then added dropwise while at the same time the temperature is raised to 130° C. This is followed by 24 hours of condensation at 130° C. under a slow stream of nitrogen using a distillation bridge. The reaction mixture is subsequently discharged. The acid number of the reaction mixture (number of mg of KOH to neutralize 1 g of product) is less than 7. The resultant amount of condensation product requires less than 1.1 mol of perchloric acid to titrate the free amino groups.
1.2 Preparation of R—CONH(CH2)3NH(CH2)3NHCO—R
1.1 is repeated using dipropylenediamine instead of diethylenediamine.
2.1 Silicone Waxes W1-W6
661.5 parts of the silicone oil of the formula
are reacted at 150° C. under nitrogen for 14 hours with x parts of the diamides D1 to D6. A check is subsequently carried out to see that glycidyl groups are no longer present. The following waxes are obtained:
The waxes have the following structure:
2.2 Silicone Waxes W7-W12
661.5 parts of the silicone oil of the formula
are reacted at 150° C. under nitrogen for 14 hours with x parts of the diamides D1 to D6. A check is subsequently carried out to see that glycidyl groups have reacted quantitatively. The following waxes are obtained:
W10
W11
W12
The waxes have the following structure:
x parts of silicone wax W are melted and allowed to react with 25.2 parts of dimethyl sulfate for 2 hours at about 70-75° C.
Waxes having the structures:
are obtained.
4.1 Based on Silicone Waxes W1-W12
125.0 parts of silicone wax (W) are melted. 25.0 parts of a 70% solution of
(dispersant 1) in propylene glycol and also 37.5 parts of stearyl poly-10-glycol ether (dispersant 2) are then added. As soon as there is a homogeneous melt, 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 Silicone Waxes WQ1-WQ12
4.1 is repeated except that the silicone waxes (WQ) are used instead of the silicone waxes (W) and 12.5 parts of water are added at the end instead of 12.5 parts of glacial acetic acid. This gives 1000.0 parts of a 12.5% silicone wax dispersion (WQ-E).
The products W1-E to W12-E and also WQ1-E to WQ12-E are very stable to shearing force; they can be applied to textile material (cotton and synthetic fibres) both in the padding process and in the exhaust process. The finished textile materials possess an excellent, soft, pleasant, smooth hand.
The following finishing operations were carried out:
All the finishes show a distinct improvement in softness compared with unfinished fabric.
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