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Publication numberUS3558711 A
Publication typeGrant
Publication dateJan 26, 1971
Filing dateJan 26, 1968
Priority dateFeb 9, 1967
Also published asDE1593894A1
Publication numberUS 3558711 A, US 3558711A, US-A-3558711, US3558711 A, US3558711A
InventorsHeins Arnold
Original AssigneeHenkel & Cie Gmbh
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Tertiary n-alkyl-n-(2-hydroxyalkyl)-polyhydroxy-alkylamines
US 3558711 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Oihce 3,553,711 Patented Jan. 26, 1971 ILS. Cl. 260-584 4 Claims ABSTRACT OF THE DISCLOSURE As a textile softening agent, an N-alkyl-N-(Z-hydroxyalkyl)-polyhydroxyalkylamine and corresponding quaternary compounds, said amines have the formula:

and being characterized by the fact that Z is a polyhydroxyalkyl of 3-6 carbon atoms, R1 is an alkyl of 8-18 carbon atoms, and R2 is an alkyl of 6-18 carbon atoms, R1|R2 having 24-36 carbon atoms in total.

This invention relates to tertiary N-alkylN-(2hydroxy alkyl)-polyhydroxyalkylamines, the quaternary ammonium compounds thereof and to methods for preparing and using the same.

It is known from German Provisional Pat. 1,220,438 that there can be obtained by the addition of higher terminal alkylene oxides to secondary N-methyl-polyhydroxyalkylamines the corresponding tertiary N-methyl- N-(2-hydroxyalkyl)-polyhydroxyalkylamines, for instance, N-methyl-N-(2-hydroxyoctyl)-glucamine can be obtained by reaction of N-methyl glucamine and octylene oxide-1,2. The N-methyl-polyhydroxyalkylamine products thus obtained are intended for use as textile adjuvants, as washing agents and as emulsiers.

In accordance with the invention it has now been found that tertiary N-alkyl-N-(Z-hydroxyalkyl)-polyhydroxyalkylamines adapted for use as textile softeners having the formula:

in which R1 is alkyl having 8-18 carbon atoms, which alkyl may possibly be interrupted by an oxygen atom, R2 is alkyl having 6-18 carbon atoms, the total of the carbon atoms present in R1 and R2 together amounting to 24-36 and preferably 28-32, and Z is polyhydroxyalkyl having 3-6 carbon atoms,the number of hydroxyl groups present in said polyhydroxyalkyl group being at least half the number of carbon atoms, and their corresponding quaternary compounds which in addition contain a further radical having up to 8 carbon atoms bound to the nitrogen atom can be obtained by reacting a secondary N- alkyl -polyhydroxyalkylamine of the formula:

wherein R1 and Z are as above defined, with a terminal alkylene oxide having 8-20 carbon atoms and thereafter if the quaternary compound is desired, quaternizing the resultant tertiary amine by introduction of an organic radical containing at the most 8 carbon atoms.

In the above formulae, the number of hydroxyl groups present in Z is preferably l less than the number of carbon atoms contained therein. Accordingly, there enter into consideration as illustrative of Z the following moieties:

CHQOH CH- C (GB01-Dm or l (CHOHL. CHZOH CHZOH in which m represents a whole number of from 1-4 and n a whole number of from 0-3.

The tertiary or quaternary products having the above formula and prepared in accordance with the invention constitute new hitherto unknown materials.

The secondary amines having the formula Z-NH-R1 which are to be used as starting materials in accordance with the process of the invention can be prepared in the conventional manner, as for instance by reacting a primary amine R1-NH2 with a halohydrin or epoxide of a corresponding structure and which contains hydroxyl groups. Thus for instance starting from a primary alkylamine and glycerin chlorhydrin or glycide there are obtained secondary polyhydoxyalkylamines Z-NH-Rl in which Z can have the above-indicated structure wherein m=1 or 11:0.

Compounds of analogous structure wherein m=3 or 4 or n: 2 or 3 can be obtained by hydrogenating a pentose or hexose or their oligomers by means of Raney nickel in the presence of a higher alkylarnine. Suitable hexoses are in particular, glucose, mannose, galactose, fructose, sorbose or their mixtures, such as, for instance, invert sugar; however, their oligomers, such as maltose, can also be used. Mixtures of different hexoses and mixtures of hexoses and pentoses can also be employed.

The alkyl groups of the primary Rl-NH2 amines which may be used in the preparation of the Z-NH--R1 starting materials may be saturated or unsaturated, straight or branched chain, synthetic or of natural origin. The R1 groups present in the amines can be derived from octyl, decyl-, dodecyl, tetradecyl, cetyl, stearylor oleyl-amine. There can also be used amines whose carbon chains are interrupted by an ether oxygen atom in the vicinity of the NH2 group and particularly where the oxygen atom is located between the 2 and 3 or 3 and 4 carbon atoms (counted from the NH2 group). Amines, in which the NH2 group and ether oxygen atom are separated from each other by 3 carbon atoms, are obtained, for instance, by the addition of acrylonitrile to a fatty alcohol of corresponding chain length followed by reduction of the nitrile group.

This reduction is also suitable for conversion of the nitriles obtained from fatty acids or fatty acid mixtures into the corresponding primary amines. Accordingly, the alkyl groups of these amines can be present as mixtures of homologs, such as can be obtained, for example, from fats of natural origin, as for instance, from plants or land or sea animals. Instances of such natural materials are palm oil, linseed oil, cottonseed oil, peanut oil, rape oil, etc., lard, tallow, iish and Walrus oil. Fractions of the fatty acids contained in all these fats can also be used for the preparation of the amines.

The amines which are to be used are preferably not too highly unsaturated, i.e. the iodine numbers of the starting fatty acids should preferably not be more than 50 and in particular not more than 30'. Amines of substantially completely hydrogenated fatty acids having iodine numbers of less than and preferably less than 5 can also be used.

For the preparation of the terminal epoxides which are to be reacted in accordance with the invention with the secondary N-alkyl-N-polyhydroxyalkylamines it is necessary only to carry out an epoxidation of a terminal olen which itself can be prepared by various known methods, as for instance, by the cracking of petroleum parains.

`In carrying out the alkoxylation of the N-alkyl-N- polyhydroxyalkylamines, a mixture of the starting materials is heated to a temperature at which no water is split olf from the polyhydroxyalkylamine and preferably to a temperature within the range of 1Z0-170 C. The starting materials are preferably employed in equimolar quantities, but small excesses of one component amounting to, for instance, up to 30 mol percent can also be used. The reaction proceeds even in the absence of any catalyst at an industrially acceptable velocity. Solvents are not required, although it is possible to operate, particularly in the case of small batches, in the presence of inert solvents. In industrial operation, the use of solvents are dispensed with or they are used in such small quantities that they constitute at most 50% by weight of the total reaction mixture.

The crude products obtained are generally of yellowish color. Their consistency depends to a great degree on the nature of the two groups R1 and R2. In the case where R1 and R2 are of straight-chain nature and uniform with respect to their chain lengths, the products produced by the method of the invention constitute solids and are readily crystallizable. With an increase in the number of the isomers of different chain lengths present in the product, the products become waxlike or pasty. The presence of chain branchings also result in products of a pasty consistency.

In the case where it is desired to convert the tertiary N alkyl N (2 hydroxyalkyl) polyhydroxyalkyl amines thus obtained into their corresponding quaternary compounds, a group containing at most 8 carbon atoms is introduced into the polyhydroxalkylamine in the conventional manner by reacting the tertiary polyhydroxyalkylamine with a known quaternizing agent. Suitable quaternizing agents include, for instance, dimethlsulfate, diethylsulfate and other dialkylsulfates, alkyl halides, such as methylor ethyl bromide, alkylene halohydrins, such as ethylene bromhydrin, propylene bromhydrin, glycerin chlorhydrin, epichlorhydrin, etc. Alkyl aromatic compounds, such as benzyl chloride and benzyl bromide, can also be used as quaternizing agent. `In the case of aliphatic quaternizing agents, the preferred agents are those having alkyl groups containing 1-4 carbon atoms. Quaternizing agents which contain hydoxyl groups or epoxide groups are of particular interest insofar as the solubility of the resultant quaternary compounds and their salts is improved by the presence of the oxygen function.

The tertiary and quaternary N-alkyl-N-(Z-hydroxyalkyl)-polyhydroxyalkylamine products of the invention are obtained as crude materials and can be used as such as textile softeners. If desired, the products and the tertiary compounds in particular can be purified by recrystallization or redissolving from suitable organic solvents.

The products of the invention are of poor solubility in water. For their recrystallization or redissolving, there are therefore employed suitable water-soluble organic solvents, such as monohydric or polyhydric alcohols having 1-4 carbon atoms, or ether alcohols, such as, for instance, the monoethers of the said monohydric alcohols, with ethylene glycol, ethylene diglycol, propylene glycol, butylene glycol or the monoor diethers of the said monohydric alcohols with glycerin. The tertiary products are soluble in these solvents, as well as in lower water-soluble ketones. Of these solvents, those having boiling points of up to C. are particularly suitable for the recrystallization or redissolving. The purified products separate from the solvent employed in crystalline or amorphous condition, depending on the nature of the alkyl groups.

The following examples will further illustrate this invention, but the invention is not restricted to these examples.

EXAMPLES For the preparation of the N-alkyl-N-(Z-hydroxyalkyl)glucamines described in Examples 1-6, equimolar quantities of N-alkyl-glucamine were heated for 8 hours in an autoclave to about C., with the specific epoxide which was to be processed, the air within the autoclave having first of all been displaced by nitrogen. Following the cooling of the autoclave, the yellowish reaction product which formed was removed and in this condition used without further purification for the tests described below. When the crude product was purified by redissolving from acetone, there was obtained a colorless, partially crystalline and partially wax-like mass.

The advantageous effects which are obtained when these products are used were demonstrated on samples of cotton terrycloth.

The terrycloth samples were washed l5 times in succession in a drum washing machine using a commercial detergent intended for use in such Washing machines. The wash-active substance of the 4washing agent used consisted essentially of a combination of capillary-active sulfonates and soaps. The highest temperature obtained during the boil washing was between 95 and 100 C.

Some of the samples of terrycloth fabric were, for comparison purposes, rinsed without the addition of a softener to the rinse water and dried, while in other tests, a solution of the softener to be used in isopropanol was added to the last rinse water, being added in such amount that the concentration of active substance in the rinse bath wasl 0.2 g./l. The rinsing process in each case took 5 minutes. Thereupon the fabric was dried, conditioned and then subjected to the tests described below.

(l) Manual judging of the hand Several persons in each instance judged the softness of the treated terrycloth samples by manually examining the same, each person indicating for each sample a grade in accordance with the following scale:

Grade 1: Hand is full and very soft Grade 2: Hand is soft Grade 3: Hand is of medium hardness Grade 4: Hand is hard Insofar as the grades given by the individual testers did not agree, an average was obtained based on the individual grades.

(2) Determination of the compressibility In order to obtain an objective measure of the softness obtained, the compressibility of the washed terrycloth was determined. This test was based on the fact that the individual bers in soft textiles are loosened, take up more space and can shift more easily than in textiles which have become hardened by washing. Accordingly, the soft textiles can be more strongly compressed when using the same load than in the case of hard textiles.

The principle of the design of the apparatus used for the measurement can be noted from the accompanying drawing. The material to be tested is allowed to rest on the base plate 1 and was compressed by the feeler which is movable vertically thereover. The feeler consists of the feeler plate 2, the vertical shaft 3 and the bearing surface 4 and is guided by the vertical shaft 3 which, however, rests completely without friction on the base during the measurement. ln the extension of the feeler axis there is contained the feeler of a measuring dial 6 on the scale of which 0.01 mm. can be read off as the smallest unit. For the adjustment of the zero point, the feeler plate 2 was lowered onto the base plate 1 and the feeler 5 was moved downward until it just contacts the bearing surface 4 of the feeler. In order to alect the measurement as little as possible by the measurement pressure of the dial, the moment of contact between feeler 5 and bearing surface 4 is indicated in the case of the apparatus employed through a glow lamp.

When the zero point of the measurement dial has been ascertained, the sample of fabric to be tested was placed on the base plate 1, the fabric completely covering the base plate and extending beyond it at its edges. The feeler (area 25 cm?, weight 50 g.) was then lowered onto the piece of fabric to be` tested and its thickness measured after a waiting time of one minute. The process was repeated a further two times on the same piece of fabric, the measuring pressure being increased by applying weights onto the feeler plate 2 to 10 times (500 g.) and 25 times (1250 g.) the initial value.

If the fabric thicknesses measured with the initial load (2 p./cm.2), with the 10-x load (20 p./cm.2) and with the 25-x load (50 p./cm.2) are designated as d2, d20 and d50, respectively, then the relative compressibility of the soft-rinsed fabric ZW is calculated in accordance with the formulae:

There is furthermore indicated the value:

the same expressing the percentage improvement of the 5 compressibility by the soft-rinsing process.

The following products were prepared and tested with respect to their softening action:

EXAMPLE 1 Z: polyhydroxyalkyl radical derived from glucose R1: octylf t R2: alkyl mixture C13-C16 Crude product: yellow paste Purified product: yellowish-white paste Hand: 1.5 Compressibility:

Zz: 139% AZyg: 39%

EXAMPLE 2 Z: polyhydroxyalkyl radical derived from glucose R1: dodecyl- R2: alkyl mixture C13-C16 Crude product: yellowish brown paste Puritied product: yellowish-white paste Hand: 1.5 Compressibility:

Zz: 135% AZ: 35%

EXAMPLE 3 Z: polyhydroxyalkyl radical derived from glucose R1: hexadecy1- R2: alkyl mixture C13-C16 Crude product: yellowish brown, solid Recrystallized product: white crystals M.P.=4143 C. Hand: 1.5 Compressibility:

AZg: 37%

EXAMPLE 4 Z: polyhydroxyalkyl radical derived from glucose R1: octadecyl- R2: alkyl mixture C13-C16 Crude product: yellowish brown, solid Recrystallized product: white crystals M.P.=43-45 C. Hand: 2.0 Compressibility:

AZZ: 33%

EXAMPLE 5 Z: polyhydroxyalkyl radical derived from glucose R1: alkyl mixture derived from coconut fatty acid C12-C18,

R2: alkyl mixture C13-C16 Crude product: yellowish brown paste Purilied product: yellowish paste Hand: 1.5 Compressibility:

ZZ: 139% AZZ: 39%

EXAMPLE 6 Z: polyhydroxyalkyl radical derived from invert sugar R1: lkyl mixture derived from coconut fatty acid C12-C13,

R2: alkyl mixture C13-C16 Crude product: yellowish brown paste Purified product: yellowish paste Hand: 2.0 Compressibility:

Zyt: 133% AZg: 33%

Comparison Test A Without softener Hand: 4.0 Compressibility:

2%: 100% AZZ: 0%

Comparison Test B N-methyl-N-(2-hydroxyocty1)glucamine, in accordance with German Provisional Patent 1,220,438, Example 2 Hand: 4.0 Compressibility:

Zz: 102% Ag: 2%

As can be noted from the numerical values determined for the hand and the compressibility, the hardness of the terrycloth treated is in no way inuenced by the known products. In contarast, the use of the products in accordance with the invention results in a softness of the terrycloth sample which can be observed both subjectively and objectively.

What is claimed is:

1. As a textile softening agent adopted to addition to the rinse water in a fabric washing cycle:

N alkyl N (2 hydroxyalkyl) polyhydroxyalkylamines of the formula:

wherein R1 is a member selected from the group consisting of alkyl having 8-18 carbon atoms and alkyl having 8-18 carbon atoms interrupted by an oxygen atom, R2 is alkyl having 6-18 carbon atoms, the total number of carbon atoms present in R1 and R2 tor CH- CHZOH oHzoH (CHOHLl CHzoI-I wherein m is a whole number of from 1-4 and n is a whole number of from O-3, and R1 and R2 together have a total of 28-32 Carbon atoms.

3. The agent of claim 2 wherein R1 is alkyl interrupted by an ether oxygen atom, said oxygen atom being located between carbon atoms 2 and 3.

4. The agent of claim 2 wherein R1 is alkyl interrupted by an ether oxygen atom, said oxygen atom being located between carbon atoms 3 and 4.

References Cited FOREIGN PATENTS 1,220,438 7/1966 Germany 260-584 JOSEPH P. BRUST, Primary Examiner R. L. RAYMOND, Assistant Examiner U.S. C1. XR.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4281201 *Dec 10, 1979Jul 28, 1981Quad Chemical CorporationTertiary amines for use in water base hair care compositions
US4311692 *Aug 25, 1980Jan 19, 1982Quad Chemical CorporationTertiary amine personal care composition
US4389526 *Aug 3, 1981Jun 21, 1983The Regents Of The University Of CaliforniaIntermediates and synthesis of 2-amino-2-deoxytetritols
US4696771 *Dec 3, 1985Sep 29, 1987Henkel CorporationAminopolyols and polyurethanes prepared therefrom
U.S. Classification564/507, 510/525, 510/521, 564/475, 564/165, 564/490, 564/292, 564/497, 564/508
International ClassificationD06M13/322, D06M13/385, D06M13/463, D06M13/368, C07C215/40, C07C215/10, D06M13/00, C07C217/28, C07C213/00, C07C67/00, D06M13/02, C07C217/00, D06M13/46, C07C215/00
Cooperative ClassificationD06M13/463, D06M13/46
European ClassificationD06M13/46, D06M13/463