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Publication numberUS3849435 A
Publication typeGrant
Publication dateNov 19, 1974
Filing dateMar 1, 1973
Priority dateMar 2, 1972
Also published asCA1001634A1, DE2210087A1, DE2210087B2
Publication numberUS 3849435 A, US 3849435A, US-A-3849435, US3849435 A, US3849435A
InventorsU Cuntze, H Diery, A May, E Milewski
Original AssigneeHoechst Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Imidazolinium salts as softening agents for textiles
US 3849435 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,849,435 IMIDAZOLINIUM SALTS AS SOFTENING AGENTS FOR TEXTILES Helmut Diery, Kelkheim, Taunus, Ulrich Cuntze, Hofheim, Taunus, Adolf May, Diedenbergen, Taunus, and Eckard Milewski, Schwalbach, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing. Filed Mar. 1, 1973, Ser. No. 337,203 Claims priority, application Germany, Mar. 2, 1972, P 22 087.4 Int. Cl. C07d 49/34 US. Cl. 260309.6 2 Claims ABSTRACT OF THE DISCLOSURE Imidazolinium salts of the general formula in which R means alkyl or alkenyl of 7 to 21 carbon atoms, R means alkyl or alkenyl of about 6 to 18 carbon atoms, at least one of the radicals R and R having more than 14 carbon atoms, R means methyl or ethyl, X means oxygen or the rest --NH and A means a saltforming anion, and their use as softening agents for textiles.

It is known that washed textiles, especially those of cellulosic fibers, show a hardening of the handle after drying. This is especially the case when washing has been effected on a washing machine.

It is also known that this undesired hardening of the handle can be avoided by treating the textile materials after Washing with a rinsing bath containing cationic substances that contain at least 2 long chain aliphatic radicals in the molecule. In practice, the dialkyl-dimethyl-ammonium salts which are dispersible in water are used. However, these products have the disadvantage of not being fluid as concentrated solutions, which is the preferred commercial form, but of having a pasty consistency and, in addition, of being usable and workable at elevated temperatures only.

It is known that certain imidazolinium compounds which are fluid as concentrated solutions can be used as softeners for textile materials. These imidazolinium compounds are, for example, l-alkylamido-ethyl-2-alkyl-3- methyl 3 methyl-imidazolinium-methosulfates, whose softening effect is much lower than that of dialkyl-dimethyl-ammonium salts.

Now, we have found that textile softening agents on the basis of imidazolinium salt of the genreal formula I in which R represents alkyl or alkenyl of about 7 to 21 carbon atoms, R represents alkyl or alkenyl of about 6 to 18 carbon atoms, of which radicals R and R at least one contains more than 14 carbon atoms, R represents a methyl or ethyl radical, X represents oxygen or the radical -NH- and (A represents a salt-forming anion, in particular CR or -R OSO do not have the above-described disadvantages.

Thus, the present invention provides imidazolinium compounds of the general formula I in which R represents alkyl or alkenyl of about 7 to 21 carbon atoms, R represents alkyl or alkenyl of about 6 to 18 carbon atoms, of which radicals R and R at least one contains more than 14 carbon atoms, R represents a methyl or ethyl radical, X represents oxygen or the radical -NH and A represents a saft-forming anion, in particular Cl or -R -OSO The present invention furtermore relates to fluid concentrates of softeners for textiles which consist essentially of about to 80% by weight, preferably to by weight, of an imidazolinium salt of the above-specified general formula I in a polar organic solvent.

As such polar organic solvents for the preparation of the concentrates of softeners for textiles, there may be used above all lower aliphatic alcohols or glycols, in particular ethanol, isopropanol, isobutanol, ethylene glycol, propylene glycol or polyethylene glycols which are liquid at room temperature.

The imidazolinium compounds on which the softeners of the invention are based may be prepared by the condensation of 1 mole of a long chain aliphatic carboxylic acid of the formula in which R has the meaning given above, with about 1 to 1.1 mole of diethylene-triamine or N-oxyethyl-ethylene diamine in known manner and further reaction of the condensation product with about 1 to 1.2 moles of a 1,2- epoxy-alkane of the formula CHz-CH-Rr in which R has the formula given above. The reaction is carried out by melting the reaction partners while stirring at temperatures in the range of from about to 180 0, preferably at to C. The reaction is completed after about 1 to 3 hours.

After having been allowed to cool and after addition of about 20 to 50% by weight, suitably 25 to 40% by weight, of a polar organic solvent such as isopropanol or propylene-glycol, the reaction product is combined with 1 to 1.1 mole of dimethylor diethyl sulfate. Instead of which the dialkyl sulfates, quaternization may also be carried with chloro-methyl using super-atmospheric pressure. The concentrates of imidazolinium salts obtained in this manner constitute fluid solutions at concentrations of up to about 80% by weight.

The imidazolinium salts of the formula -I are soluble or dispersible in water. They may be applied as softeners for textiles in known manner by impregnating the material to be treated by immersion or spraying with aqueous solutions or dispersions of these imidazolinium salts. In general, about 0.01 to 0.7%, preferably 0.05 to 0.2%, referred to the weight of the textile material, of compounds of the formula I are applied onto the textile material. In the preferred application of the softeners as additions to the last rinsing water after washing at a goods to liquor ratio of about 1:5 to 1:10 as usual for these purposes, the concentration of the imidazolinium salts amounts to about 0.02 to 1.5 g./l. of rinsing bath.

The aqueous solutions or dispersions of the softeners for textiles of the invention, which in general contain about 1 to 30% by weight, in most cases 4 to by weight, of imidazolinium compounds of the formula I and about 0.3 to 30% by weight of a polar organic solvent, may also contain other components or auxiliary agents which have been admixed either to the concentrates of the imidazolinium salts or have been added separately to the aqueous solutions or dispersions or to the treatment baths destined for utilization, and which may serve, for example, for an additional influence on the handle or on other properties of the textiles to be treated or for an adjustment of the viscosity, of the regulation of the pH- value or of the increase of the stability of the solutions to cold. Such other components may be, for example cationic or non-ionogenic surface-active substances, electrolytes, organic complex formers, optical brighteners or solubilizers.

After impregnation with the baths which contain the softeners for textiles of the invention, the textile material is dried in the usual manner.

The imidazolinium salts of the invention have proved to be particularly good washing after-treatment agents. When used for this purpose, they are added, after the washing of the textile material, to the last rinsing bath.

The imidazolinium salts of the invention confer on any textile materials, especially those of native or regenerated cellulose, wool, cellulose acetate and triacetate, polyamide, polyacrylonitrile, polyester and polypropylene, an agreeable soft handle. The application as washing after-treatment agent to terry towelling and underwear made of cotton is particularly advantageous.

The following Examples illustrate the invention:

Example 1 93 g. of l-hydroxyethyl-Z-tallow fat-alkyl-imidazoline (content of base nitrogen 4.2%) and 5.3 g. of a 1,2-epoxyalkane having a chain length of 11 to 14 carbon atoms were heated for 2 hours to 160 C. A yellowish product was obtained (base nitrogen content 2.9%, acid number 1.5, Epon number 0), which was combined at 80 C. with 55 g. of isopropanol and quaternized at 60 C. with 31.5 g. of dimethyl sulfate. A liquid was obtained which contained 74.5% of solids and which was dispersible in cold water.

Example 2 F 220 g. of 1-hydroxyethyl-2-fat alkyl-imidazoline (the fat alkyl rest constituted a mixture of 62% of tallow fat alkyl and 38% of behenyl alkyl) and 157 g. of a 1,2- epoxy-alkane having a chain length of 15 to 18 carbon atoms, were heated for 2 hours to 170 C. A yellowish product was obtained (content of base nitrogen 2.5%, acid number 1.2, Epon number 0) which was combined at 80 C. with 116 g. of isopropanol and which was quaternized at 60 C. with 77 g. of dimethyl sulfate. A liquid was obtained which was dispersible in cold Water and contained 75% of solids.

Example 3 87 g. of 1-aminoethyl-2-tallow fat alkyl-imidazoline (content of base nitrogen 8.2%) were heated for 2 hours at 170 C. with 53 g. of a 1,2-epoxyalkane having a chain length of 11 to 14 carbon atoms. A yellowish product was obtained (content of base nitrogen 5.3%, acid number 1.0, Epon number 0), which was combined at C. with 60 g. of isopropanol and which was quaternized at 60 C. with 31.5 g. of dimethyl sulfate. A liquid was obtained which was dispersible in cold Water and which contained 73% of solids.

Example 4 44.2 g. of l-aminoethyl-2-heptyl-imidazolne (content of base nitrogen 11.3%) were heated for 3 hours to C. with 53.8 g. of a 1,2-epoxyalkane having a chain length of 15 to 18 carbon atoms. A solid yellowish product was obtained (content of base nitrogen 5.2%, acid number 0.6, Epon number 0) which was combined at 80 C. with 40 g. of isopropanol and which was quaternized at 60 C. with 30.5 g. of diethyl sulfate. A liquid was obtained which was dispersible in cold water and which contained 76% of solids.

Example 5 44.2 g. of 1-hydroxyethyl-2-heptyl-imidazoline (content of base nitrogen 7.0%) were heated for 3 hours to 100 C. with 53.8 g. of a 1,2-epoxyalkane having a chain length of 15 to 18 carbon atoms. A yellowish product was obtained (content of base nitrogen 5.3%, acid number 0, Epon number 0) which was combined at 80 C. with 35 g. of isopropanol and which was quaternized at 120 C. in an autoclave with methyl chloride. A liquid was obtained which was dispersible in cold water and which contained 73% of solids.

Example 6 68.6 g. of 1-hydroxyethyl-Z-heptadecyl-imidazoline (content of base nitrogen 4.4%) were heated for 3 hours to 100 C. with 36.8 g. of 1,2-epoxydodecane. A yellowish product was obtained and content of base nitrogen 2.9%, acid number 0.3, Epon number 0) which was combined at 80 C. with 43 g. of isopropanol and which was quaternized at 60 C. with 25 g. of dimethyl sulfate. A liquid was obtained which was found to be dispersible in cold water and which contained 76% of solids.

Example 7 68.8 g. of 1-aminoethyl-2-heptadecyl-imidazoline (content of base nitrogen 8.0% were heated for 3 hours to C. with 25.6 g. of 1,2-epoxyoctane. A yellowish product was obtained (content of base nitrogen 5.3%, acid number 0.9, Epon number 0) which was combined at 80 C. with 42 g. of isopropanol and then quaternized at 60 C. with 26 g. of dimethyl sulfate. A liquid was obtained which was dispersible in cold water and which contained 75% of solids.

For determining the softening action of the compounds specified in Examples 1 to 7, textile materials that had been treated in corresponding manner were tested by several persons with regard to handle. These persons gave marks on the degree of softeness of the tissue samples ranging between 1 (very hard handle) and 5 (optimum soft handle). The tests were carried out as follows: marked test tissues (terry towelling specimen each having a weight of about 20 g.) were at first washed at 80 C. and at a goods to liquor ratio of 1:10 with 6 g./l. of a commercial detergent and rinsed 5 times with cold water (about 15 hardness (German Hardness)). The treatment of the textiles was effected with the last rinsing bath to which the aqueous dispersions of the compounds of the invention had been added. The concentration of the respective active substance was 0.1 g./ 1., the goods to liquor ratio was 1:10. After an action period of 5 minutes, the test samples were taken out from the bath, centrifuged and dried at 70 to 80 C. in a drying cabinet. The evaluation of the handle by the judging persons was effected after storage of the test samples for 24 hours in a climate chamber at a temperature of 20 C. and a relative air humidity of 60%.

age values obtained from 5 parallel tests.

TABLE Treating agent Mark of handle Example 1 3.9 Example 2 4.1 Example 3 3.5 Example 4 3.7 Example 5 3.5 Example 6 v 4.0 Example 7 4.1 Untreated sample 1.0 Comparison 1 3.0

Commercial softener 0n the basis of l-tallow fat-alkylnmid0-ethy1-2-tallow fat a1kyl-3 methyl-imidazolinium-methosulfate.

We claim: 1. A compound of the formula N--CH3 R-C\ CH:CHzXCH2(.| H-R1 in which R represents alkyl or alkenyl of 7 to 21 carbon atoms, R represents alkyl or alkenyl of 6 to 18 carbon 6 atoms, of which radicals R and R at least one contains more than 14 carbon atoms, R represents methyl or ethyl, X represents oxygen or NH and A represents Cl or R -OSO 2. A compound of the formula in which R represents alkyl of 9 to 12 carbon atoms and R represents the alkyl radical of the tallow fatty acid.

CHJO S O Kamezawa, Chem. Abst., vol. 66, No. 19191X (1967). Negoro et al., Chem. Abst., v01. 72, No. 66867f (1970).

NATALIE TROUSOF, Primary Examiner US. Cl. X.R. 117139.5 CQ; 2528.75, 8.8; 260348 R

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4109094 *Jun 27, 1977Aug 22, 1978Ashland Oil, Inc.Method for quaternizing imidazolines
US4127489 *Jul 27, 1976Nov 28, 1978The Procter & Gamble CompanyProcess for making imidazolinium salts, fabric conditioning compositions and methods
US4140641 *Mar 17, 1978Feb 20, 1979Colgate-Palmolive CompanyConcentrated liquid detergent with fabric softener
US4233451 *Oct 20, 1978Nov 11, 1980The Procter & Gamble CompanyProcess for making imidazolinium salts
US4544756 *Nov 17, 1983Oct 1, 1985Dresser Industries, Inc.Zwiterionic 2-alkyl imidazolines as emulsifying agents for oil based drilling fluids
US6121457 *Oct 30, 1998Sep 19, 2000Megabios CorporationCompositions and methods using novel substituted imidazolium lipids
US6245520Jul 25, 2000Jun 12, 2001Megabios CorporationMethods for introducing nucleic acids into mammalian cells using imidazolium lipids
WO1999025342A1 *Nov 13, 1998May 27, 1999Megabios CorpHeterocyclic cationic lipids
WO2008020418A2Aug 17, 2007Feb 21, 2008Procter & GambleDryer-added fabric care articles imparting malodor absorption benefits
WO2011014641A1Jul 29, 2010Feb 3, 2011The Procter & Gamble CompanyFabric conditioning fabric care articles comprising a particulate lubricant agent
Classifications
U.S. Classification548/350.1, 510/522, 549/512, 548/349.1
International ClassificationC11D3/00, D06M13/322, C07D233/14, D06M13/02, D06M13/47, D06M13/473, C11D1/62, D06M13/46, C07D233/16
Cooperative ClassificationC07D233/16, C11D1/62, C07D233/14, C11D3/001
European ClassificationC07D233/16, C11D3/00B3, C11D1/62, C07D233/14