US2727004A - Chemical compounds and process of treating textile materials therewith - Google Patents

Description

United States Patent CHEMICAL COMPUUNDS AND PROCESS OF TREATING TEXTILE F/EATERIALS THERE- WITH Oscar P. Cohen, Newton, Mass, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application October 2, 1952, Serial No. 312,867

19 Claims. 01. 252-5375 The present invention relates to processes of finishing textile materials, particularly synthetic staple fibers or yarns, and it more particularly relates to processes of applying a lubricant finish or a lubricant and anti-static finish to such textile materials. The present invention also relates to novel chemical compounds which are especially suitable for use in the textile finishing processes of this invention.

It is one object of this invention to provide processes for treating textile materials, particularly synthetic staple fibers or yarns having low moisture pick up or adsorptivity to render them more amenable to processing operations such as spinning in the case of staple fibers, and weaving in the case of yarns or filaments.

It is a further object of this invention to provide textile materials, particularly synthetic staple fibers or yarns, having a low moisture pick up or adsorptivity, which have a lubricant finish or a lubricant and anti-static finish thereon.

It is a further object of this invention to provide novel textile finishing compositions.

It is a further object of this invention to provide novel chemical compounds which are especially suitable for use in finishing textile materials to provide such materials with a lubricant finish or a lubricant and anti-static finish.

Still further objects and advantages of this invention will become apparent from the following description and the appended claims.

The present invention provides novel chemical compounds having the structural formula:

where R is selected from hydrogen and methyl and ethyl radicals, R is selected from hydrogen and methyl, ethyl,

and

l I! C2114 \O C2H4/, O (L) R groups, R" is selected from saturated and unsaturated aliphatic hydrocarbon radicals consisting of carbon and hydrogen atoms and containing from 5 to 23 carbon atoms, x represents an integer from 1 to 20, y represents an integer from 1 to 19 and x and y taken together represent a whole number not exceeding 20. In general, compounds which are included in the scope of the above formula and which contain 9 and more oxyethylenc {OC2H4} units have relatively low melting points and are normally liquids at room temperature. Moreover, such compounds are soluble or colloidally dispersible in water and thus may be used in aqueous textile finishing compositions. On the other hand, compounds of the above formula which contain one but less than 9 oxy- 2,727,004 Patented Dec. 13, 1955 where x is an integer of 1 to 20; compounds having the structural formula:

C2H4 0CiE[4},0 C n as where x and y are integers which taken together total at least 2 but not more than 20; compounds having the structural formula:

where x is an integer of l to 20; and the like.

The novel compounds of this invention may be prepared by first condensing 2 to 20 mols of ethylene 0xide with 1 mol of a sulfonamide having the structural formula:

R\ i) Ii 3 i where R and R have the same significance as in the structural formula of the novel compounds of this invention, hereinbefore given, preferably in the presence of an alkaline condensing agent such as caustic soda, caustic potash or alkali metal alcoholates such as sodium ethylate. This reaction or condensation is preferably carried out in a closed vessel at temperatures between about 70 and 200 C., and at pressures ranging from atmospheric pressure to about 10 atmospheres. The pressure decreases as the ethylene oxide enters into the reaction. The above reaction or condensation provides compounds having the structural formula:

where R, R and x have the same significance as hereinbefore described. When R in the formula of the sulfonamide is hydrogen and at least 4 mols of ethylene oxide are employed, a mixture of a compound having the structural formula described immediately above and a compound having the structural formula:

where R, x and y have the same significance as hereinbefore given, is obtained. This mixture may be used in preparing the novel compounds of this invention.

As examples of sulfonamides which may be reacted or condensed with ethylene oxide as described above may be mentioned benzene sulfonamide also known as benzene sulfonic amide), toluene sulfonamide (also known as toluene sulfonic amide), including the ortho and para isomers and mixtures thereof, dimethyl benzene sulfonamides, N-ethyl' toluene sulfonamjde and the like. Of these compounds, ortho or para toluene sulfonamide or mixtures thereof and N-ethyl toluene sulfonamide are preferred as starting materials.

The; ethylene oxidersulfonamide condensation products hereinbefore described, are reacted with aliphatic fatty'monocarboxylic acids containingv from 6 to 24 carhon: atoms and having the, structural formula:

where R has the same significance as hereinbefore described to produce the novel compounds of this invention. About 1 mol of fatty acid is employed for each hydroxyl group in the ethylene oxide-sulfonamide condensation product, and depending on whether the monoor diester is desired. This reaction is preferably carried out in the presence of an inert, water-soluble organic solvent as, for example, liquid aromatic hydrocarbons such as benzene, toluene, xylene and the like, and; a small amount of a strong acid esterification catalyst such as; a strong mineral acid as, for example, sulfuric or phosphoric acid or a strong organicsulfonic acid such as toluene monosulfonic acid, naphthalene monosulfonic acid or benzene monosulfonic acid or the like. The esterification reaction is carried out at least at the boiling point of water with the removal of 1 mol of water per mol of fatty acid employed, and at atmospheric or subatniospheric pressure. The acid catalyst in the pr duct thus obtained is preferably neutralized with a base such as sodium hydroxide, or, more preferably, with an organic base which is soluble in the organic solvent as, for example, morpholine, pyridine and quaternary ammonium hydroxides, toprovide a neutral product. The organic. solvent, if used, is then evaporated leaving the desired product as the residue.

As examples of fatty acids which may be used in preparing the novel. esters of this invention maybe mentioned saturated fatty acids suchas caproic acid, capric acid, lauric acid, palmitic acid, stearic acid and the like,

and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and the like.

Various changes may be made in the processes described above. For example, it is possible when the sulfonamide contains two reactive hydrogen atoms to replace one of such hydrogen atoms with one or more oxyethylene -(-OCzH4-} groups and then esterify the resulting mono-alcohol compound with 1 mol, of the fatty acid. This compound may be used as such or it may be further condensed through the remaining active hydrogen with ethylene oxide tointroduce one or more oxyethylene groups. The resulting compound may be used as such or it may be, further esterified with 1 mol of one of the fat y acids. to produce a diester. Other modifications of the processes described above will be apparent to those skilled in the art.

The textile finishing process of this invention comprises applying to a textile material a textile, finishing composition comprising a compound having the following structural formula:

(Hi-R" where R is selected from hydrogen and methyl and ethyl groups, R is selected from hydrogen and methyl, ethyl and groups, R" is selected from saturated and unsaturated aliphatic hydrocarbon radicals consisting of carbon and hydrogen atoms and containing from 5 to 23 carbon atoms, 11 represents 0 and integers from 1 to 20, m represents 0 and integers from 1 to 20, and n and m taken together represent 0 and integers, the total of which does not exceed 20. The compounds represented by the above structural formula include the novel compounds of this invention, and they also. include known chemical compounds such as N, N-di-beta hydroxyethyl benzene sulfonamide distearate and N-beta-hydroxyethyl benzene sulfonamide stearate which have not been suggested heretofore. for use in the finishing of textile materials.

The compounds, defined inthe. preceding paragraph are. preferably applied to, textile materials in an amount sufiicient to lubricate such materials or to lubricate and inhibit the formation of charges of static electricity on such materials. Satisfactory results, for these purposes, are obtained, in general, by applying: about 0.1 to 5% by weight and preferably about 0.2 to 3.5% by weight of these compounds based on the weight of the. textile materials. These compounds per se may be applied directly to the textile, material in the liquid state, using hea t,. if necessary, to melt them prior tov application. However, it is preferred to incorporate these compounds in, a textile finishing composition which contains water, mineral oil or an emulsion of mineral oil and water as the sole or primary liquid other than the compounds per se. When aqueous textile finishing compositions or emulsions of waterand mineral oil are employed it is preferli d' to use those ester compounds which are sol- U 21? OI colloidally dispersible in water, particularly those, ester compounds, as hereinbefore defined, which contain 9 or more oxyethylene +O?C2H4 groups in the, molecule. Compounds which contain less than 9 oxyethylene groups are more soluble in mineral or hydrocarbon oils and are'not generally soluble or colloidally dispersible in water per se. Therefore, these com.- pounds are preferably applied to textile from mineral oil compositions or emulsion of mineral oil and water. However, they may be dispersed in aqueous compositions with the aid of emulsifying agents if necessary, and may thus be applied to textile materials from such compositions.

The textile finishing compositions described above preferably contain from about 0.1 to 10% by weight of the ester compounds hereinbefore defined, and the remainder preferably consists of water, a water-mineral oil emulsion or a mineral oil. However, such compositions may also contain the usual amounts of conventional textile treating agents such as colloidal silica, thermosetting resins, thermoplastic resins, wetting or emulsifying agents or the like.

These textile finishing compositions may be applied to the textile materials in various ways. Thus they may be applied by dipping or immersing the textile materials therein followed, if desired, by squeezing between rolls, centrifuging or the like, or they may be applied to textile materials by spraying or dripping the compositions on the materials. Such compositions may also be applied to textile materials by passing the materials over one or more wicks or rolls which are covered with a film of the composition. Various other procedures tqr applying such compositions to textiles will be apparent to those skilled in the art.

The ester compounds, hereinbefore defined, may be incorporated directly into synthetic textile staple fibers or yarns and filaments during the manufacture of such textiles. For example, in those instances where the synthetic textile staple fiber or yarn or filament is prepared from a spinning dope such as a solution of cellulose acetate in acetone, the ester compound may be incorporated in the spinning dope or solution which is then extruded to form the textile staple fibers or filaments.

The novel compounds or textile finishing compositions of this invention may be applied to a large variety of textile materials, particularly those materials which require a lubricant or which normally acquire static electric charges due to the friction developed during their processing. For example, such compounds or compositions may be applied, prior to spinning, to natural fibers of vegetable origin such as cotton, linen, rann'e or the like or to nautral fibers of animal origin such as wool, alpaca, camels hair or the like, or they may be applied to yarns or-fabrics composed wholly or partly of such natural fibers. The compounds or compositions of this invention may also be applied to regenerated cellulose staple fibers, yarns or fabrics. In such applications the ester compounds serve, primarily, the function of lubricating the fibers, yarns or fabrics, although they also inhibit the formation of static electricity on such textile materials. However, the latter phenomenon is not too marked since the natural fibers pick up and retain moisture quite readily and hence do not accumulate static electricity charges to a marked extent and do not, as a general rule, require the application of compounds having anti-static properties.

The textile finishing compositions or compounds are particularly effective as lubricants and anti-static agents on synthetic staple fibers and yarns or filaments which have low moisture pick up or adsorptivity. The term synthetic textile materials as used herein and in the appended claims is intended to include staple fibers and yarns prepared from fiber-forming synthetic polymers prepared by polymerizing a suitable vinyl or vinylidine monomer per se or a suitable vinyl or vinylidine monomer and an unsaturated organic compound copolymerizable therewith and having at least one -C=C- group in the molecule, for example, polymers such as polyacrylonitrile, copolymers of acrylonitrile and vinyl chloride, copolymers of acrylonitrile and vinyl pyridine, polyvinylidine chloride, copolymers of vinylidine chloride and vinyl chloride and the like, and is also intended to include fiber-forming polymers prepared by condensing an alkylene diamine and an aliphatic dibasic acid, for example, polymers such as polyhexamethyleneadipamide, polyhexamethylene-sebacamide and the like; and is also intended to include fiber-forming polymers prepared by condensing terephthalic acid with polyhydric alcohols such as ethylene glycol, diethylene glycol and the like; and is also intended to include water-insoluble fiber-forming cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrate and the like. The term synthetic textile materials does not, however, include hydrophilic staple fibers or yarns of regenerated cellulose prepared by regenerating cellulose xanthate or cuprammonium solutions or dopes.

Since the compounds or compositions of this invention exhibit anti-static properties they are particularly effective in this respect when they are applied to staple fibers or unspun fibers prior to processing such fibers into Webs, slivers, yarns or the like, and they are also particularly effective when applied to yarns or filaments immediately after the formation of such yarns or filaments and prior to further processing thereof such as twisting, coning, weaving or the like. The compounds or compositions of this invention are most etfective as lubricants and anti-static agents when they are applied to staple fibers or yarn containing from about to 100% by weight of the synthetic fiber-forming materials, which term includes the cellulose esters but ex- G cludes regenerated cellulose, defined in the preceding paragraph, and the treatment of such textile materials is preferred.

The particular composition used will depend on the particular textile material which is to be treated and the form of the textile material, that is, whether it is in the form of fibers, yarns or fabrics. For example, in treating cellulose acetate fibers and blends of cellulose acetate fibers and other synthetic staple fibers, as hereinbefore defined, it is customary in most cases to use mineral oil or hydrocarbon oil compositions, and hence such compositions containing the ester compounds are preferably employed on such fibers. On the other hand, in treating animal fibers, vegetable fibers, regenerated cellulose staple fibers and polyhexamethylene-adipamide staple fibers or blends thereof, it is desirable to use aqueous compositions or emulsions of water and mineral oil or vegetable oil. Similar compositions are used in treating yarns or fabrics of these textile materials.

The preferred ester compounds for use in aqueous compositions or emulsion of water and mineral oil are those having the following structural formula:

groups, R is the hydrocarbon chain of oleic acid, x represents an integer from 9 to 20 and x and y taken together represent integers totalling at least 9 but not exceeding 20.

The preferred ester compounds for use in mineral oil compositions are those having the following structural formula:

i l r EXAMPLE I (a) Preparation of ester compound One mol of a mixture of o-toluene sulfonamide and p-toluene sulfonamide was condensed with 4 mols of ethylene oxide at atmospheric pressure and at a temperature of 70 C. The temperature of the reaction mass soon rose to C. due to the heat of reaction and the reaction mass was maintained at this temperature until substantially all of the ethylene oxide had reacted. The resulting product was dispersed in xylene. One mol of lauric acid was then added to the resulting dispersion along with 0.02 mol of p-toluene sulfonic acid which was employed as an esterification catalyst. The resulting mixture was heated to C., and the Water formed during the reaction was removed by distillation at atmospheric pressure into a water trap until no more water was evolved. The resulting product in the solutioncon- 7 'pi'hnsnly of a mixture of a compound having These compounds, after evaporation of the Xylene, are recovered a wax-like materials at room temperature (about 70 F.) and-they are ins luble in water, but soluin mineral or hydrocarbon oils;

(b) Treatment-f textile material Five parts of the mixture "of compounds prepared as described above were dissolved in I00 parts of low' viscosity mineral; oil. Wicks were dipped into the resulting solution and filaments of cellulose acetate, as obtained directly by dry spinning a cellulose acetate-acetone dope, were passed over these wicks and in contact therewith. The amount of ester compounds depositedon the filament was about 1% based on the dry filament weight. The resulting yarn was well lubricated and did not accumulate static electrical charges during subsequent processing operations such as coming or Weaving.

EXAMPLE II (a) Preparation of ester compound One mol of 'p toliren'e "sulfonaniide was condensed with two mols of ethylene oxide at atmospheric pressure and i at a temperature of 70 C. The temperature of the reaction mass soon rose to 130. Qt due to heat of reaction andthe reaction mass was maintained atthis temperature until substantially all of the ethylene oxide had reacted. The resultingproduct consists primarily of a compound "having the formula:

This compound, which has a melting point of 72 C., was separated from other compounds in the product by fractional distillation and was then esterified with 1 mol of acid using 0;02 mol of p-toluene 'sulfonic acid as the esterification catalyst. The esterificatio'n was carried out in xylene at a temperature of 140 C., and the water formed during the 'esterification was removed by distillation into a water trap until no more water was evolved. The resulting product in the solution consisted primarily of a compound having the formula:

this compound, which was a liquid at room temperature,

oils;

(b) Treatment of textile materials;

One part of the compound describedimmediately above was dissolved in parts of water and the resulting solution was placed in a container in which a partially submerged roller was slowly and continuously rotating; The surface of the roller was thus provided with a continuous film of the solution. Filaments of viscose (regenerated cellulose) rayon were coustant;ly brought into contact with the top surface of the roller. About of the compound, based on the dry filament weight, was :deposited on the filaments in this manner. The compound was an e'fiective lubricant for the filaments.

Polyhexamethylene-adipamide filaments were treatedin the same manner as the viscose rayon filaments in preceding paragraph. The treatedfilaments werenot only lubricated, but also did not accumulate static electrical charges during subsequent processing of the filaments. I

(a) Preparation of ester compound One mol of p-toluene sulfon'amide was condensed four mols of the ethylene oxide using the procedure scribed in the first paragraph of Example I. Thematiing product was then esterified with 1- mail o'f olei'c acid using the procedure set forth in the firstaragraph of Example I. Xylene was evaporated from thfresultiflg solution and the product thus obtained was the'ii densed with 5 mols of ethylene oxide at atmospheric.

pressure in the presence of 1%- of sodium ethylafe and at a temperature of 70 C. The temperature soon rose to C. and "the reaction mass was maintained at this temperature ninil substantially all of ethylene oxide had reacted. This product was then esterifie'uwith '1 mol of oleic acid in the presence of 0.0211161 'of-p toluene sulfonic acid as an esterific'ation catalyst. The s'terifi'ation was carried out in xylene at atmospheric pressure and at a temperature of Q,- and the water tonnes during the reaction was removed by distillation into a water trap until substantially no more water was evorvea. The product consisted primarily of a having the formula:

This compound is water-dispersible.

When the compound is dispersed in an aqueous tion containing about 8% by weight of a water-soluble melamine formaldehyde or urea-formaldehydepl'ecolr densate in an 'amount of about 10 to 20% onjthe of the precondensate, the resulting dispersion is-e spec ia1ly suitable for use in preparing glazed textile fabrics the compound provides good lubrication during the 51:2- ing operation.

This compound when dispersed in a 15% siliea-aquasol in amounts of 0.5 to 3% by weight and then applied to cotton fibers prior to spinning, imparts some-lubricating and anti-static effects to the fibers and also reduces tendency of the silica to dust from the fibers dry weight of the filament, thus depositingabout 033915 of the compound onthe 'filament'weight. ThgTCSl-lhifi soluble in water and onl slightly soluble in 1% filaments were not only lubricated, but also did not accumulate static charges during subsequent processing.

EXAMPLE V The palmitate ester of N-hydroxyethyl toluene sulfonamide was dissolved in a spinning solution of cellulose acetate in acetone in an amount of 2% based on the weight of cellulose acetate. The spinning solution was then extruded through a spinneret into warm dry air. After all of the acetone had evaporated from the resulting filaments, the filaments were free of static electrical charges during subsequent processing of the filaments.

Various changes may be made in the compositions and processes described herein as will be apparent to those skilled in the art to which this invention appertains without departing from the spirit and intent of this invention. Accordingly, it is intended that this invention is not to be restricted except by the scope of the appended claims' What is claimed is:

l. A chemical compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl and ethyl radicals, R is selected from the group consisting of hydrogen and methyl, ethyl,

and

where x is an integer of l to 7.

3. A chemical compound having the structural formula:

where x and y represent integers of at least 1 and which when taken together represent a whole number not exceeding 20.

4. A chemical compound having the structural formula:

where x and y represent integers of at least 1 and which when taken together represent a whole number not exceeding 20.

1o 5. A chemical compound having the structural formula:

o o olmoogn, O iL-GUHa where x and y represent integers of at least 1 and which when taken together represent a whole number not exceeding 20.

6. A chemical compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl and ethyl radicals, R is selected from the group consisting of hydrogen and methyl, ethyl,

and

radicals, R is selected from the group consisting of saturated and'unsaturated aliphatic hydrocarbon radicals con sisting of carbon and hydrogen atoms and containing from 5 to 23 carbon atoms, x represents an integer from 1 to 7, 3' represents an integer of at least 1 and x and y taken together represent integers totalling from 2 to 8, said compound being soluble in said mineral oil,,but being insoluble and non-dispersible in water.

8. A process of finishing textile materials which comprises applying to said textile materials a compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl and ethyl radicals, R is selected from the class consisting of hydrogen and methyl, ethyl,

and

groups, R" is selected from the group consisting of saturated and unsaturated aliphatic hydrocarbon radicals consisting of carbon and hydrogen atoms and containing from 5 to 23 carbon atoms, n represents 0 and integers from 1 to 7, m represents 0 and an integer of at least 1 and n and m taken together represent 0 and integers the total of which does not exceed 8, said compound being soluble in mineral oil, but being insoluble and non-dispersible in water.

9. A process as in claim 8, but further characterized in that said compound is applied from a textile finishing composition comprising said compound and mineral oil.

t- A prewa as in claim: 8. but further. char c riz in that the textile materials are composed of from about 20 to 100% by weight of synthetic textile materials.

11. A process as in claim 8, but further characterized in thatthe textile materialsarecomposed of. from about 20 to 100% by weight of celluloseacetate textile materials.

12. A process as inclaim 8, but further characterized in that the textile materials are composed of from about 2.0. to 100% by weight of polyhexamethylene-adipamide textile materials;

13. A process as" in claim- 8', but further characterized in that the textile materials are composed of from about 20' to 100% by weight of'polyacrylonitrile;

14. A process of lubricating textile materials which comprises applying to said textile materials.v an aqueous composition comprising from about 0.1 to 10% by weight of a water-soluble: to colloi'dally dispersed compound having the structural' formulaz 'where Z is. selected from the group consisting of hydrogen and methyl, ethyi,

and

O walw-mmLoJLnv groups, R" is selected from the group consisting of .satw rated and unsaturated aliphatic hydrocarbon radicals consisting of carbon and hydrogen atoms and containing from to 23 carbon atoms, x is an integer from 9 to 20 and x and y taken together are integers totallingat least 9 but notexceeding 20, said composition. being supplied in an amount sutficient to: deposit from about 0.1 to, 5% of said compound based on the-dry textile materials.

15. A. processas in. claim. 14,. but. further characterized in that R in the formula; of said compound is the hydrocarbonchain of oleieacid.

16. A.- process-of: lubricating textile materials which comprises applying to' said textile materials-a mineral. oil solution of from about 0:1 to; 10% by weight of a compound: havingthe; formula:

where Z is selected from the group consisting of hydrogen methyl; ethyl,

and

l C2H -O.C -@O-- -R 4 r34! 7 I groups, R is selected from the. group consisting of saturated and unsaturated aliphatic hydrocarbon radicals consisting of carbon and hydrogen atoms and coutainingfrom 5 to 23, carbon atoms, x is an integer from 1; to 7 and: and8 y taken together represent integers totalling from 2 to 17. A process, according to claim 16, but filrther characterized in that the R" in the formula of said compound is' the hydrocarbon chain of oleic acid,

18. An article of manufacture comprising a-textile ma terial having thereon a compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl and ethyl groups, R" is selected from the group consisting of hydrogen, methyl, ethyl,

and

R" is selected from the group consisting of saturated and unsaturated aliphatic hydrocarbon radicals consisting of hydrogen and carbon atoms and containing from 5 to 23 References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoelleret a1 Aug. 21, 1934 2,002,613 Orthner et al May 23, 1935 2,353,694 De Groote et a1 July 18, 1944 2,496,650 Aelony Feb. 7,1950

2,496,651 Aelony ...Feb. I, 1250- FOREIGN PATENTS 380,851 Great Britain Sept. 12, 1932

Claims (1)

1. 7. A TEXTILE FINISHING COMPOSITION COMPRISING A MINERAL OIL AND A COMPOUND HAVING THE STRUCTURAL FORMULA: