DE1469383A1 - Process for softening textiles - Google Patents

Description

Process for softening l'extiles.

The present invention relates to certain new quaternary ammonium fatty compounds and their use for the calibration of textiles.

A number of quaternary ammonium fatty compounds are used in the calibrating of textiles. For example, the use of quaternary ammonium difatty dimethyl chloride, in which the fatty group is predominantly an saturated C-ng-ii group, is common. These compounds are generally obtained from a starting material which is rich in saturated fatty acids, in particular stearic acid, e.g. ß. aun ¹ yrs. These quaternary ammonium compounds previously used grease are indeed in terms of their softening iiigenschaften satisfactory but have deh disadvantage that they impart! Textiles water repellent properties when used repeatedly, v / ground beispiels-

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wise bath towels repeated with the softening compounds treated, they acquire reduced absorbency and are therefore less suitable than those towels that still have their original absorption capacity.

It has now been found that it is possible to produce quaternary ammonium fatty compounds which have about the same plasticizing properties as the quaternary dimethyl dihydrogen currently used Tallow compounds by using as starting material the monomeric fatty acids that remain as residue after the polymerization of unsaturated fatty acids. These quaternary compounds have about the same softening properties However, like the compounds listed above, "these are" in terms of their rewetting properties far superior.

The new invention. Compounds have the following formula: ■

NR ₂ X "

in the R and BU lower. Alkyl groups with 1 to 4 carbon atoms mean - R., the hydrocarbon radical, which corresponds to the residual fatty acid monomer * which remains after the polymerization of more unsaturated fatty acids with 8 to 24 carbon atoms - and X is a "quaternary" Is ammonium anion. R ₁ and R ₂ can be methyl, ethyl, propyl or butyl groups, which are either straight or branched chain, and preferably R 1 and R _{2 are} both;

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Methyl groups. X can be any quaternary anion, such as a chloride, sulfate, ethysulfate, nitrate and the like. Because of the easy preparation of the compounds by methylation with methyl chi oride the chloride anion is preferred.

As stated above, R is the hydrocarbon group derived from the monomer remaining in the polymerization. Fatty acid polymers of the type described above are commercially available products. They are obtained by simple thermal polymerization of unsaturated fatty acids and also by catalytic polymerization of such fatty acids, for example by means of clay catalysts. In these polymerizations, a mixture of fatty acids having 8 to 24 carbon atoms, usually derived from natural fatty oil, is used as the starting material. V / ground these acids of thermal polymerization, for example at 260 ° to 300 ⁰ G, or a catalytic thermal polymerization, for example in the presence of clay at 180 ° subjected to 25O ⁰ O, then they polymerize. With the thermal. Processes polymerize the polyunsaturated fatty acids the easiest and the remaining monomer consists almost entirely of monounsaturated fatty acids, along with any saturated acids that may have been present in the starting material. In the catalytic process, both the polyunsaturated and the monounsaturated acids polymerize and a correspondingly lower residue of monomers is obtained, but again the unsaturated acids in the monomers are almost completely monounsaturated not polymerized, modified in structure in such a way that it no longer has the physical or chemical properties of the original starting material. Indeed

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it is modified in such a way that it is usually no longer can be used for the same purposes for which the fatty acid is used in its unmodified form can be. Therefore, this residual monomer has so far only had a limited range of uses in industry found and in many cases it was burned as fuel as it was used for this purpose Had greater value for many conventional chemical uses than s ζ v / ecke. Conjectures about possible structures of these residual monomers are in the Journal of the Oil Chemists Society, Vol. 26, No. 6, p. 278 (1949) and in Industrial And Endgineering Chemistry, Vol. 44, P. 1. 113 (1952) reproduced. Although it was difficult to find suitable uses for this monomer To tap into, it was surprisingly found that the monomer, when it becomes a quaternary ammonium fatty compound is transformed, certain unique properties unfold that it is such materials that obtained from more expensive raw materials, make superior. One of those unique properties is that the quaternary ammonium compounds have emollient properties similar to those of others Compounds used industrially are comparable, but that they also have superior rewetting properties as will be shown in more detail below.

In preparing quaternary ammonium compounds from the residual monomer, the monomer is converted to the nitrile by reaction with ammonia in a conventional manner. The nitrile thus obtained is then hydrogenated in the presence of a catalyst to give a secondary fatty amine, (R,) ₂ NH. The preparation of the secondary amine is carried out by methods known in the art. The secondary amine is then converted into the quaternary ammonium compound by reaction with typical alkylation agents such as methyl chloride. Also the alkylation

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is known in the art and does not form part of the present invention.

The residual material used as the starting material Monomers contains a considerable amount of fatty acids that are still somewhat unsaturated. Generally have quaternary ammonium compounds made from this residual monomer are excellent softening properties and excellent rewetting properties. However, if the fat group in the quaternary compound is substantially unsaturated, the textiles plasticized with these compounds tend to adopt a shade of yellow, which in general is considered undesirable. This tendency to yellowing does not affect the softening properties, but only represents an aesthetic disadvantage. It is therefore preferred to use the degree of unsaturation in the JTett group to such an extent that the quaternary compound obtained has an iodine number of 4-0 or less. This can be done by appropriate hydrogenation of the monomer used as the starting material or can be achieved simultaneously with the formation of the amine from the nitrile. While it is possible that To decrease the iodine value by hydrogenation, however, it is extremely difficult to obtain a value approaching zero To achieve iodine number. The nature of the unsaturation became apparent during the polymerization process modified to some extent so that not all double bonds can be saturated with hydrogen. However, it is possible to hydrogenate the iodine number to a value below 40 and actually you can get the iodine number reduce to 5 or less. These hydrogenated products are less likely to turn yellow.

In the manufacture of softeners for textiles from quaternary compounds, the quaternary compound is usually in an aqueous medium, either alone or with the help of an organic solvent,

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such as a lower aliphatic alcohol, for example isopropanol, dispersed. To achieve a usable distribution of the softener on the textile surface, the softening agent can be used in a concentration of 0.00707% by weight, based on the solution. Conventionally, it is employed at a level of about 0.00125 grams of softening agent per gram of dry fabric. The amount of softener used can vary widely, but is generally between 0.0005 and 0.005 g / g of the dry textile article.

The softening ability of the various compounds were determined in the following test: Rag of white Birdseye cotton (91f5 x 30.5 cm) are a conventional 3 _F 6 kg V / äsehebündel added and at 60 G with a conventional household laundry detergents in the same manner washed as it is with the normal household laundry of the JPaIl. The rags are washed in an automatic washing machine with a 6 minute washing cycle followed by a one minute spray rinse and finally a 4 minute built-in rinse. The flaps are then immersed in solutions of the compounds to be tested.

The immersion is done in a water bath using containers and stirring with a stir bar. In this immersion, the conditions of the last dpülvorganges the automatic washing machine to be repeated, which is 4 minutes of stirring at 38 ⁰ C using a solution having a solid concentration of 0.00707 ° ß> (concentration for normal purposes) and a ratio of solution to dry tissue of 17.7 s 1. This means a usage concentration of 0.00125 g per g of the dry textile article. After stirring, the cloths are left to stand for 1 minute, then the thawing solution is poured off and the cloths are placed in the washing machine.

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machine spun to remove excess immersion solution. The rags are then air dried before being cut up for testing. After drying, each rag is cut into 12 test pieces measuring 10.2 by 10.2 cm. The specimens are marked and stored in a room maintained at 22 ° C. under controlled temperature conditions and with a relative humidity of 50 ° C. until testing.

The group test is carried out with a group of 12 women who test twice each, so that a total of 24 tests are performed. Each test consists of comparing the softness of three pairs of test pieces. These pairs were treated as follows:

(1) Use 1 1/2 times the normal amount Concentration of test compound versus normal concentration of comparison compound.

(2) using the normal concentration of the Test compound versus normal concentration of control compound.

(3) Use the normal concentration of the test compound versus half the normal concentration the comparison compound.

The group is asked to indicate which sample of each pair they think is the softest. The results are statistically

2 V squared method evaluated, where X = y ();

(o = found, e = expected). See: Applied General Statistics, by Groxton and Gowden, Copyright 1939 » Prentice-Hall, Inc.) With the tfert of X is then in A table is looked up to see if the test results are significant, and if so, to what extent they are

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are significant. This can be used to determine whether the connection as good as the comparison compound is, half as good as that Comparison compound, or whether it is between "half as good" and "just as good" in terms of its plasticizing properties lies.

In the above test it was found that the invention Compounds have approximately the same plasticizing properties as the conventional used for comparison Link.

The rewet properties were determined as follows: Birdseye cotton rags (60.9 x 30.5 cm) are washed in an automatic washing machine using conventional household detergent, but removed before the final intensive rinse. The swabs are immersed in a solution having a normal concentration of the conventional compound and two swabs are immersed in a solution having twice the normal concentration of the compound to be tested. The immersion procedure is the same as the plasticizer test described above. One of the rags dipped in the normal concentration of the conventional compound and one of the rags dipped in twice the normal concentration of the residual compound is then passed through an identical wash so that the rewet test is performed on samples dipped in normal and double normal levels of plasticizer both after one and after two washes. After immersion, the flaps are air dried and each flap is cut into two 24.5 x 24.5 cm samples. The samples are marked and stored in a room at a regulated temperature and a relative humidity of 50 # at 22 ⁰ O for conditioning. The test was carried out under these temperature and humidity conditions.

The rewetting test consists of dripping of water on a sample of the treated cloth from a burette and in the determination of the average

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- 9 - ■. '■■■

the time required for the drop to be absorbed in the cloth is required. The burette becomes about 9> 5 mm held away from the sample and adjusted so that it releases a drop of water about every 5 seconds.

The sample is held over a 12.75 x 12.75 cm metal frame so that all parts of the cloth are underneath equal tension. The sample is stretched taut over the hanger by means of a weight of 137 g Stapled on each side by 12.75 cm staples.

A drop of vifaser is dropped on the fabric and the time until the drop disappears is given as the rewetting time. Ten of them Tests are carried out on each specimen, for a total of 20 tests on both specimens. The mean rewetting time results from the average of these 20 tests.

EXAMPLE:

Tall oil fatty acids were heated to 200-230 ° for 4 hours at atmospheric pressure in the presence of 10 % montmorillonite clay. The reaction mixture was then filtered to remove the clay and the filtrate was vacuum distilled to recover the residual monomer.

This monomer was then converted to the Mitril by heating in a reactor at 250-300 ° C. for 5 to 10 hours while ammonia was bubbled through the reaction mixture. The reaction is completed in the usual we sea when acid value less than 1 and the amide content is decreased to less than 2 "/ Ό. At this time, the reaction mixture is vacuum distilled to obtain the nitrile.

The nitrile was hydrogenated with Raney nickel at 14 kg / cm pressure and about 225 ° 0 under periodic Removal of the ammonia formed during the reaction

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. converted into the secondary amine. After completion of the reaction was the lieaktionsgemisch cooled to 100 ⁰ G and then filtered to give-a fo product with a total amine content of 99 »0, a content of secondary and tertiary amine of 93» $ 3> and a tertiary amine content of 3 > $ 7 was received.

During the hydrogenation, the iodine number fell to 12.3. This secondary amine was then quaternized with methyl chloride in the presence of isopropanol and alkali. The reaction was carried out for about 15 hours at 70 ° to 80 ° 0, after which time the product was cooled and filtered to give a product consisting of 69.1% solids and 68.0 % quaternary compounds.

This quaternary compound was then dispersed in water to give a solution with a solids content of 0.00707 β> and this solution was used to treat textiles in the manner described above. As stated, the product had essentially the same softening properties but decidedly improved rewet properties. The compound showed in the general re-wetting times of 5-18 seconds, compared to Wiederbenetzun _t; szeiten 100-300 admission of conventional compounds that have been used for comparison, and where it came to dimethyl-dihydrogenated tallow ammonium chloride, the currently used in large quantities to soften textiles.

Similar results were obtained with the quaternäreii Ammonium chloride obtained from the residual monomers of the thermal polymerization of fatty acids was produced.

In the invention, specific examples were given; however, it is obvious that variations of the invention may come within the scope of the following claims possible are.

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Claims (2)

Patent claims: 1. Process for softening textiles, thereby characterized in that a compound of the following formula is distributed on the surface of the fibers: R ₁ ⁺ KR ₂ X in which R and R «are lower alkyl groups with 1 to 4 carbon atoms mean, R ~ is the hydrocarbon residue, the one remaining after the polymerization of more highly unsaturated fatty acids with 8 to 24 carbon atoms Corresponds to fatty acid monomers and X is a quaternary ammonium anion, where R-. and Rp methyl, ethyl, Propyl or butyl groups, either straight or branched chain, and preferably methyl groups, and X is conventional quaternary anion such as a chloride, sulphate, ethsulphate, nitrate or the like and where the chloride anion because of the ready availability of the compounds by methylation with methyl chloride is preferred. BATH ORIGINAL 9 098 24/123 0 2. The method according to claim 1, characterized in that the compound in an amount of 0.0005 to 0.005 g per g of dry textiles is used. For General Mills, Ine, Re c BATH ORIGINAL 909824/1230