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Publication numberUS2878273 A
Publication typeGrant
Publication dateMar 17, 1959
Filing dateSep 6, 1956
Priority dateSep 6, 1956
Publication numberUS 2878273 A, US 2878273A, US-A-2878273, US2878273 A, US2878273A
InventorsConbere John P, Perry Edward M
Original AssigneeArnold Hoffman & Co Inc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium salts
US 2878273 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent QUATERNARY AMMONIUM SALTS John P. Conbere and Edward M. Perry, Barrington, R. 1., assignors to Arnold, Hoffman & 'Co., Incorporated, Providence, R. I., a corporation of Rhode Island No Drawing. Application September 6, 1956 Serial No. 608,187

Claims. (Cl. 260-4045) The present invention relates to novel quaternary ammonium compounds and methods of preparing the same.

An object of the invention is to provide novel quaternary ammonium salts of fatty acid esters of a polyhydroxypolyamine.

An additional object is to prepare novel compounds useful to impart softening and lubricating characteristics to textiles.

A further object is to prepare novel textile softeners having increased stability to heat. i,

Yet another object is to prepare novel anti-static agents for textiles.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent. to those skilled in the art from this detailed description.

It has been discovered that these objects can be attained by the preparation of quaternary ammonium salts of fatty acid esters of N,N,N',N'-tetrakis(2 hydroxyethyl)ethylenediamine having the formula 110011.011: crnomon z or the formula where R is an aliphatic acyl radical having :12 to 18 carbon atoms or hydrogen, at least one R being an aliphatic acyl radical, M is a monovalent hydrocarbon group containing 1 to 4 carbon atoms, X is ananion and Z is the valence of X.

R can be lauroyl, stearoyl, oleoyl, myristoyl, palmitoyl, ricinoleoyl, etc. M can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. X can be a sulfate ion, a halide ion, e. g., chloride, bromide, iodide, benzene sulfonate ion, toluenesulfonate ion, borate ion, phosphate ion, etc. When there are 2 M groups, they can be alike or different. Similarly, when more than one R is an acyl group, the acyl groups can be alike or different.

The compounds of the present invention are valuable as softening and anti-static agents for textile fabrics such as cellulose acetate, nylon, vinyl resins, e. g., vinyl chloride resins, etc. I a I The compounds of the present invention lend valuable softening and lubricity to textile fabric and also prevent the undesirable physical manifestation of static electrical charges which tend to accumulate on many fibers. The compounds are water dispersible which results in easy and low cost application. The compounds also are unique "ice in that they afford a means of binding three or four long fatty acid chains, which when quaternized possess unexpected solubility and compatability in conventional aqueous textile resin treating baths with internal pH buifering. Such buffering is necessary for urea and melamine formaldehyde resin bath stability.

The present products also haveinherent stability to heat (non-scorching) which is superior to the nonquaternized acetate salts of the same starting compound, for example.

The compounds of the present invention are made by reacting the appropriate tertiary amine with a quaternizing agent. As quaternizing agents, there can be employed alkyl halides, e. g., methyl bromide, methyl chloride, methyl iodide, ethyl bromide, propyl chloride, n-butyl chloride, dimethyl sulfate, diethyl. sulfate, di-npropyl sulfate, di-n-butyl sulfate, methyl benzene sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, trimethyl phosphate, tributyl phosphate, dimethyl butyl phosphate, trimethyl borate, allyl chloride, allyl bromide, crotyl chloride, etc.

Whether the mono or diquaternary ammonium salt is formed depends on the proportions of the tertiary amine and the quaternizing agent. Two equivalents of quaternizing agent are required to form the diquaternary compound and only one equivalent to form the monoquaternary compound.

As illustrative compounds of the present invention, there can be mentioned the monoquaternary ammonium salt prepared from N,N,N',N-tetrakis(Z-hydroxyethyl) ethylenedia-mine -monostearate and dimethyl sulfate, the corresponding salt from diethyl sulfate, the corresponding salt from methyl bromide, the corresponding salt from di-nbutylsulfate, the corresponding salt from di-n-propyl sulfate, the corresponding salt from metyl chloride, the corresponding salt from methyl bromide, the corresponding salt from methyl iodide, the corresponding salt from ethyl bromide, the corresponding salt from n-propyl bromide, the corresponding salt from n-butyl bromide, the corresponding salt from isobutyl chloride, the corresponding salt from tributyl phosphate, the corresponding salt from trimethyl phosphate, the corresponding salt from trimethyl borate, the corresponding salt from methyl benzenesulfonate, the corresponding salt from methyl p-toluenesulfonate. In place of the monoquaternary ammonium salt, there can be prepared the corresponding diquaternary compound, e. g., the diquaternary ammonium salt prepared from N,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine monostearate and dimethyl sulfate. Similarly, there can be made the monoquaternary ammonium salt prepared from N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine distearate and. dimethyl sulfate, as well as of the other quaternizing agents set forth supra. The diquaternary salt of this compound, e. g., with dimethyl sulfate, also can be made. Likewise, there can be made the monoquartenary ammonium salt prepared from N,N,N,N-tetrakis(Z-hydroxyethyl)ethylenediarnine tristearate and dimethyl sulfate, as well as of the other quaternizing agents set forth supra. The diquaternary stalt of this compound, e. g., with dimethyl sulfate, also can be made. Additionally, there can be made the monoquaternary ammonium salt prepared from N,N,N',N-tetrakis (Z-hydroxyethyl)ethylenediamine tetrastearate and dimethyl sulfate, :as well as of the other quaternizing' agents set forth supra. The diquaternary salt of this compound, e. g., with dimethyl sulfate, also can be made.

In place of the stearate compounds, compounds containing any of the acyl groups previously set forth can be made. Additionally, mixed acyl group containing compounds can be prepared.

amine fatty acid ester productsare oils or waxes. Increas ing the number of acyl'groups in the molecule gives a harder wax.

Illustrative examples showingthe preparation of the starting materials for the present invention are-given.

below.

EXAMPLE 1 N ,N ,N ',N '-letrakis(Z-Izydroxyethyl ethylenediam ine monostearate A mixture of 472 g. of N,N,N',N-tetrakis(2-hydroxy ethyl)ethylenediamine, 680 g. n-butyl stearate and 2.9 g. sodium hydroxide was stirred and heated to 110 C. at 70 mm. pressure. n-Butyl alcohol began to distill from the reaction mixture. The temperature was raised to 140 C. during an hour. The pressure was then reduced to 17 mm. and the charge stirred at 140/ 17 mm. for one hour and fifteen minutes to remove the last' traces of n-butyl alcohol. A total of 151 g. of butyl alcohol was collected (theory 148 g.). The product was a softtan wax which contained 2.95 atoms of active hydrogen per mol.

EXAMPLE 2 N ',N ,N ',N -tetrakis(Z-hydroxyethyl ethylened famine distearate' A stirred mixture of 78.6 g. of N,N,N.,N'.-tetrakis (2-hydroxyethyl)ethylenediamine, 204 g. of n-butyl stean ate and 0.7 g. of sodium hydroxide was heated to 120 C. at 70 mm. n-Butyl alcohol began to distill from the reaction mixture. The temperature was raised to 140 C. during one hour. The pressure was then reduced to 20 mm. and the charge stirred at 140 C. for one-half hour. A quantitative yield of product containing 2.0 atoms .of active hydrogen per mol was obtained.

EXAMPLE 3 N,N,N,N'-tetrakis(ZrhydrOxyethyZ) ethylenediamine tristearate A stirred mixture-of .236 g." N,N,N.',N'-tetrakis::(2-hydroxyethyl)ethylenediamine; 1020 g. of n-butyl stearate and 3.1 g; of sodium hydroxide was heated at 70 mm.

until n-butyl alcohol began to distill at 106 C. Thetemperature was maintained at 110 C. and the presssure at 70 mm. for one hour while n-butyl alcohol was collected. The temperature was gradually raised to 140 C. and then the pressure was reduced to 20 mm. Thereaction mixture was stirred at these conditions for one and one-half hours. The product was obtained as a wax on cooling.

EXAMPLE 4 N ,N ,N ,N '-tetrakis(2-hydroxyethyl ethylenediamine tetrastearate EXAMPLE 5 N ,N ,N ',N '-tetrakis( Z-hydroxyethyl ethylenediamine dioleate In a similar manner to' Example -3, 11.8 g. of

N,N,N,N tetrakis Z-hydroxyethyl ethylenediamine :was

4 treated with 33.8 g. of n-butyl oleate and 0.2 g. of sodium hydroxide to yield N,N,N,N-tetral is(2-hydroxyethyl) ethylenediamine dioleate as a dark viscous liquid.

EXAMPLE 6 N ,N ,N 'N -tetrakis (Z-hydroxyethyl ethylenediamine dilaurate- In a similar manner to Example 3, 236 g. of N,N,N',N- tetrakis(2-hydroxyethyl)ethylenediamine was treated with 512g. n-butyl laurate and 1.9 g. of sodium hydroxide to. yield N,N,N',N-tetrakis,(2-hydroxyethyl) ethylenediamine dilaurate as a low melting wax.

The compounds ofthe present invention are. prepared as follows:

EXAMPLE 7 Monoquaternary ammonium salt prepared from N,N,

N ,N -tetrakis( Z-hydroxyethyl ethylenediamine monostearate and dimethyl sulfate N,N,N',N' tetrakis(2 hydroxyethyl)ethylenediamine monostearate (150.6 g.) was heated to C. and 37.8 g. of dimethyl sulfate added slowly with stirring. The temperature was maintained between 100 C. and C. and held there for two hours. A soft wax, easily dispersible in water, was obtained.

EXAMPLE 8 Monoqualemary ammonium salt prepared from N,N,

N ,N -tetrakis(Z-hydroxyethyl) ethylenediamine monostearate and dimethyl sulfate in aqueous solution A stirred mixture of 72 g. of N,N,N,N'-tetrakis(2- hydroxyethyl)ethylenediamine monostearate and 150 ml. of water was heated to 100 C. and 18 g.'of dimethyl sulfate was slowly added. The mixture was heated at 100 C. forfive hours and then cooled to room temperature to yield a water dispersible product.

EXAMPLE 9 Monoquaternary ammonium salt prepared from N,N;

N ,N -tetrakis(Z-hydroxyethyl ethylenediamine monostearate and methyl toluenesulfonate N,N,N,N' tetrakis(2 hydroxyethyl)ethylenediamine monostearate (150.6 g.) was heated to 110 C. and 55.8 g. of methyl toluenesulfonatewas slowly added with stirring. The temperature was increased to and maintained at C. for four hours, A water dispersible product was. obtained.

EXAMPLE 10 Monoquaternaryammonium salt prepared. from N,N,

N,N'-tetrakis(2 hydroxyethyl)ethylenediamine distearate and dimethyl sulfate N,N,N',N"- tetrakis(2 hydroxyethyl) ethylenediamine distearate (153.6 g.) was heated to 130 C. and 25.2 g. ofdimethyl'sulfate was slowly added. After the addition was complete, the whole was maintained at 130 C. for an additional hour anda half. The product was a water dispersible wax.

EXAMPLE 11 D'iquaternary ammonium salt prepared from N,N,N',N-

tetrakis(2-hydroxyethyl) ethylenediamine distearate and dimethyl sulfate Dimethyl sulfate (50.4 g.) was added slowly with stirring to 153.6 g. of N,N,N,N'-tetrakis(2-hydroxyethyl) ethylenediamine distearate at 130 C. The. heating was continued after the addition-was complete for an additional-:two hours. The-product was a hard wax and may be dispersed in water.

EXAMPLE 12 M onoquaternary ammonium salt prepared from .N,N.

N. .,N '-tetrakis(2.- hydroxyethyl) ethylenea'iamine distearate and methyl toluenesulfonate N,N,N ,N.' tetrakis(2 hydroxyethyDethylenediamine idi'stearate (153.64g) was-heatedto 130 C., and 37.2 g.

of methyl toluenesulfonate was slowly added with stirring. After the addition was complete, the mixture was heated for four hours at 130 C. The product was a water dispersible wax.

EXAMPLE 13 Monoquaternary ammonium salt prepared from N,N,

N,N-tetrakis(2 hydroxyethyl)ethylenediamine distearate and methyl bromide Monoquaternary ammonium salt prepared from N,N,

N,N-tetrakis(2 hydroxyethyl)ethylenediamine tristearate and dimethyl sulfate 206.8 g. of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine tristearate was heated to 127 C., and 25.2 g. of dimethyl sulfate slowly added with stirring. After the addition was complete, the temperature was maintained at 125 to 130 C. for three and one-half hours. The product was a hard wax that dispersed in water. The product calculated for C64H125N207: N, 2.41.

Found: N, 2.3. Quaternary ammonium salt 98%; free dimethyl sulfate, none detectable.

EXAMPLE 15 Monoquaternary ammonium salt prepared from N,N,

N ',N-tetrakis(2 hydroxyethyl)ethylenediamine dilaurate and dimethyl sulfate 120 g. of N,N,N,N'-tetrakis(2-hydroxyethyl)ethylenediamine dilaurate was heated to 65 C. and 25.2 g. of dimethyl sulfate was slowly added with stirring. After all of the dimethyl sulfate had been added, the mixture was heated to 130 C. for three hours. The product was a low melting wax that formed a dispersion with water.

EXAMPLE 16 Monoquaternary ammonium salt prepared from N,N, N ,N -tetrakis(Z-hydroxyethyl )ethylenediamine dioleate and dimethyl sulfate 152.8 g. of N,N,N',N-tetrakis(2-hydroxyethyl)ethylenediamine dioleate was heated to 65 C., and 25.2 g. of dimethyl sulfate slowly added with stirring. After the addition was complete, the temperature was increased to and maintained at 130 C. for three hours. The product was a viscous liquid that formed a dispersion in water.

EXAMPLE 17 Monoquaternary ammonium salt prepared from N,N,

N',N' tetrakis(2 hydroxyethyl)ethylenediamine distearate and allyl chloride Allyl chloride (15.2 g.) was slowly added to 153 g. of N,N,N',N'-tetrakis(2 hydroxyethyl)ethylenediamine distearate which had been warmed to 60 C. After the addition was complete, the whole was heated at 100 C. for one hour to yield the product as a soft, water dispersible wax.

EXAMPLE 18 Monoquaternary ammonium salt prepared from nbutyl bromide and N,N,N,N'-tetraki (Z-hydroxyethyl) ethylenediamine distearate n-Butyl bromide (27.4 g.) was "added slowly to a stirred melt of 153 g. of N,N,N,N'-tetrakis (Z-hydroxyethyl)ethylenediamine distearate at 100 C. When the addition was complete, the reaction mixture was stirred and heated at 120 C. for an additional three hours and thirty minutes. The product was a water dispersible wax.

EXAMPLE l9 Monoquaternary ammonium salt prepared from N,N,

N',N' tetrakis (2 hydroxyethyl)ethylenediamine tetrastearate and dimethyl sulfate Dimethyl sulfate (6.3 g.) was slowly added to 65 g. of N,N,N,N' tetrakis(2-hydroxyethyl)ethylenediamine tetrastearate at C. After the addition was complete, the whole was stirred and heated at 100 C. for one hour to yield a water dispersible wax.

The quaternary ammonium salts of the present invention are water dispersible and possess surface active properties. They are easily applied to fabrics by the usual padding methods from aqueous dispersions. A typical example illustrating this use is as follows:

EXAMPLE 20 A 0.30% dispersion of the monoquaternary ammonium salt prepared from N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine distearate and dimethyl sulfate was applied to Nylon 200 taffeta by standard padding techniques, i. e., a conventional padding machine, at F. in such a manner as to result in 50% pickup of the dispersion by the fabric. The fabric was dried at 225 F. Nylon 200 taffeta treated in this manner possessed improved softness to the hand, increased lubricity, and superior anti-scorch and anti-static properties. Nylon 200 is a synthetic linear superpolyamide of the hexamethyleneadipamide type.

Unless otherwise stated, all parts and percentages are by weight.

We claim:

1. A compound selected from the group consisting of ROCHzCHr CHzCHzOR Z where R is selected from the group consisting of aliphatic acyl radicals containing from 12 to 18 carbon atoms and hydrogen, at least one R being said aliphatic acyl radical, M is a monovalent hydrocarbon group containing l to 4 carbon atoms, X is an anion and Z is the valence of X.

2. A compound as recited in claim 1 wherein at least one R is a stearoyl radical.

3. A compound as recited in claim 1 wherein at least one R is lauroyl.

4. A compound as in claim 1 wherein M is a saturated hydrocarbon group.

5. A compound as in claim 1 wherein M is an ethylenically unsaturated hydrocarbon group.

6. A compound as in claim 1 wherein X is the sulfate ion.

7. A compound as in claim 1 wherein X is the toluenesulfonate ion. 1

8. A compound as in claim 1 wherein X is a halide ion. 9. A compound as in claim 1 wherein X is a chloride ion. 10. A compound as in claim 1 wherein X is a bromide 1011.

and

References Cited in the file of this patent UNITED STATES PATENTS 2,719,156 De Benneirille et al Sept. 17, 1955 FOREIGN PATENTS 678,604 Great Britain Sept. 3, 1952 Notice of Adverse Deeisien in Interference In Interference N0. 903% involving Patent No. 2,878,273, J. P. Conlbere and E. M. Perry, Quaternary ammonium salts, final judgment adverse to the patentees was rendered Apr. 20, 1962, as to claims 14 and 6-10.

[Ofiiaz'al Gazette June 12,1962]

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2719156 *Dec 4, 1953Sep 27, 1955Rohm & HaasMethylolated quaternary ammonium compounds
GB678604A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3072690 *Feb 1, 1961Jan 8, 1963Nalco Chemical CoWater-dispersible amido-quaternary ammonium salts
US3168416 *May 15, 1962Feb 2, 1965Atlas Chem IndTextile yarn coated with cationic surfactant
US3342630 *Sep 13, 1963Sep 19, 1967Colgate Palmolive CoSilicate and titanate orthoesters and soil-proofed textile materials
US3350218 *Sep 13, 1963Oct 31, 1967Colgate Palmolive CoSoilproofing with quaternary ammonium derivatives of highly fluorinated carboxylic acids
US4812263 *Mar 28, 1988Mar 14, 1989Ppg Industries, Inc.Bis-quaternary ammonium compounds
US9027757 *Oct 6, 2009May 12, 2015Clariant Finance (Bvi) LimitedMixture of an amine alkoxylate ester and a quaternary ammonium compound as a collector for minerals containing silicate
US20110203975 *Oct 6, 2009Aug 25, 2011Clariant Finance (Bvi) LimitedMixture of an Amine Alkoxylate Ester and a Quaternary Ammonium Compound as a Collector for Minerals Containing Silicate
EP0643038A2 *Jul 6, 1994Mar 15, 1995Aranor, S.A.Novel polyfunctional cationic surface active agents, compositions comprised thereof, process for the preparation thereof and uses
Classifications
U.S. Classification554/91, 554/107, 554/105
International ClassificationD06M13/467, D06M13/00
Cooperative ClassificationD06M13/467
European ClassificationD06M13/467