US3517068A

US3517068A - Vinyl ethyl ether or thioether sulfones

Info

Publication number: US3517068A
Application number: US674038A
Authority: US
Inventors: Albert C Perrino
Original assignee: ICI Organics Inc
Current assignee: ICI Organics Inc
Priority date: 1963-05-01
Filing date: 1967-09-11
Publication date: 1970-06-23
Anticipated expiration: 1987-06-23
Also published as: GB1023716A

Description

United States Patent 011cc 3,517,068 VINYL ETHYL ETHER R THIOETHER SULFONES Albert C. Perrin-o, Cranston, R.I., assignor to I.C.I./0r-

gszinicg/lne, Providence, R.I., a corporation of Rhode an No Drawing. Original application May 1, 1963, Ser. No. 277,129. Divided and this application Sept. 11, 1967, Ser. No. 674,038

Int. Cl. C07c 147/04; D06m 13/ 32, 13/38 US. Cl. 260-607 8 Claims ABSTRACT OF THE DISCLOSURE A vinyl ethyl sulfone having one of the formulae:

R0 R0 R0 R0 R X BH H s.o EH in which R is hydrogen, R is a member of the group consisting of straight-chain alkyl groups having -18 carbon atoms, branched alkyl groups having 10-16 carbon atoms and alkyl phenyl groups in which the alkyl group has 9-12 carbon atoms, and X is a member of the group consisting of oxygen and sulfur. The compounds are useful in treating cellulosic textiles to render them permanently water repellent and resistant to water-borne stains and to provide a soft, pleasing hand.

This is a division of my copending application, Ser. No. 277,129, filed May 1, 1963.

The present invention relates to new hydrophobic vinyl sulfone derivatives and related latent vinyl sulfone deriva tives, and to their use in the treatment of textiles. They are particularly useful for treating cellulosic textiles to render them permanently water repellent and resistant to water-borne stains and to provide a soft, pleasing hand. These treatments are effected in such a way that a treating agent is bonded to the textile by a primary chemical bond and is not removed by laundering, dry-cleaning and similar operations during normal use.

The new vinyl sulfone derivatives are vinyl-ethyl sulfones in which the ethyl group is substituted in the beta position with an oxygen, sulfur or nitrogen and have one of the formulae:

R0 R0 R0 R-X--CHGHSO2C=CHR0 and R1 R0 R0 R0 N-( JH-JJHSOziJ=CHRo R2 in which R is hydrogen or methyl, R is a straight-chain saturated or unsaturated alkyl group having 10-18 carbon atoms, a branched alkyl group containing 10-16 carbon atoms or an alkylaryl group such as an alkyl phenyl group in which the alkyl group has a straight chain or is branched and contains 9-12 carbon atoms.

R is a saturated or unsaturated straight-chain alkyl group containing 10-18 carbon atoms.

R is a saturated or unsaturated straight-chain alkyl group containing l-18 carbon atoms.

X is oxygen or sulfur. Latent vinyl sulfones within the scope of the invention have the following formulae:

where R and X are the same as previously described, R -=I-I or methyl and A is a good leaving group for E elimination. More specifically, A refers to three general classes:

Patented June 23, 1970 (l) X is O and A is the cation of weak nitrogen bases, i.e.,

A=ii z R5 R4 where R R and R are alkyl, aryl or alkaryl groups of a tertiary amine having an ionization constant less than 10- and Z is an anion such as chloride, bromide, iodide, sulfate, alkyl sulafte, nitrate, benzenesulfonate, toluenesulfonate, methanesulfonate, borate, phosphate, etc.

(b) A= NEYZ where Y is part of a heterocyclic ring containing the nitrogen atom, such as pyridine, alkyl pyrrolidine, etc. Z is the same as in class 1(a).

(2) X=O or S and A is the anion of a strong acid, i.e.,

where V is SSO 050 etc. M is an alkali metal such as sodium, potassium, lithium, etc.

(3) X=O and A is a sulfonium salt, i.e.,

Rs A=% 2 where R R are saturated or unsaturated alkyl groups such as methyl, ethyl, allyl, etc., and Z has the same meaning as in class 1(a).

Since A is a good leaving group for E type elimination and the hydrogens alpha to the sulfone are rendered acidic by the electron withdrawing characteristics of the sulfone group, these compounds readily revert to the corresponding vinyl sulfone on the fabric when treated with alkaline agents, with concomitant reaction of the vinyl sulfone with the cellulosic hydroxyl groups to form a primary valence bond.

B leell 0N R-X--C5HlH-SOz(BH3HO-Cell These latent sulfone compounds have the advantage over the corresponding vinyl sulfones in that they are soluble or self-dispersing in aqueous systems, thereby eliminating the need for extraneous dispersing or solubilizing agents which might interfere with the water repellency. They can, however, also be applied to the fabrics from organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, etc., if so desired, with the alkali being applied at a later stage.

The following compounds are illustrative of the invention: fl-nonylphenoxyethyl vinyl sulfone, B-dodecyloxyethyl vinyl sulfone, B-tetradecyloxyethyl vinyl sulfone, B-n-hexadecyloxyethyl vinyl sulfone, fi-hexadecyloxyethyl vinyl sulfone (hexaethyl moiety contains chain branching), B-octadecyloxyethyl vinyl sulfone, B-dodecylthioethyl vinyl sulfone, fi-dodecylphenoxyethyl vinyl sulfone and N-methyl-N-dodecyl-fi-aminoethyl vinyl sulfone.

The new vinyl sulfone derivatives compounds may be prepared by reaction of a divinyl sulfone with an alcohol or mercaptan in the presence of a catalyst, or reaction of divinyl sulfone with a secondary amine at room or an elevated temperature. Preferably, the temperature is about 200 C. and anhydrous conditions are used. Suitable catalysts are alkaline materials such as alkali metals and their alkoxides. For example, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium metal, lithium metal and potassium metal may be used. It is also desirable to carry out the reaction under an inert gas since this gives superior results, although this is not essential. This process is illustrated by the following example, in which parts are by Weight.

EXAMPLE 1 Preparation of B-hexadecyloxyethyl vinyl sulfone A branched chain hexadecyl alcohol (60.61 parts), divinyl sulfone (29.54 parts) and 88 parts on anhydrous benzene were charged into a vessel equipped with a stirrer, heating mantle, condenser and thermometer. Sodium methoxide (0.2 part) was added with stirring, the reaction mixture was stirred for 13 minutes and an additional 0.1 part of sodium methoxide was added. After stirring for 12 minutes, the reaction mixture was refluxed for 203 minutes followed by addition of 0.1 part of sodium methoxide. The reaction mixture was then heated at reflux for 73 minutes, cooled, 0.5 part of acetic acid added, and the benzene removed at reduced pressure. A yellow oil remained; weight, 91.1 part, percent OH, 0.82.

Other inert solvents may be used in place of benzene in this example, such as aromatic hydrocarbons. Toluene, xylene, etc. will give satisfactory results.

These latent sulfone derivatives may be prepared by the following types of reactions.

Compounds of the class 1a type (as designated above) can be prepared by treating the ,G-substit-uted ethyl vinyl sulfone derivative with a secondary amine to form the ,B-aminoethyl derivative, followed by quaternization of the tertiary amine with typical alkylating agents such as alkyl halides, sulfates, etc.

Compounds of the class 1b (as designated above) can be prepared by the same technique as above, or by treating the ti-substituted ethyl vinyl sulfone derivative with a mixture of the tertiary amine and in an acid salt of the tertiary amine.

Compounds of the class 2 type (as designated above) for example when A is SSO Na, can be prepared by treating the B-substituted ethyl vinyl sulfone with sodium thiosulfate.

Compounds of the class 3 type can be prepared by treating the B-substituted ethyl vinyl sulfone with an alkyl mercaptan and an alkaline catalyst to form the ,3'-thioether derivative, followed by alkylation of the S atom with typical alkylating agents such as alkyl halides (i.e., methyl iodide, etc.), alkali sulfates (i.e., dimethyl sulfate), etc. to form the sulfonium salt.

EXAMPLE 2 Preparation of fi-hexadeeyloxyethylsulfonylethylmethyldipropyl-ammonium methosulfate p-Hexadecyloxyethyl vinyl sulfone (7.2 parts) was dissolved in parts of dioxane in a vessel equipped with a stirred, heating mantle, condenser and thermometer. Di-n-propylarnine (2 parts) was added and the mixture heated slowly to reflux for 215 minutes. The solvent was then removed by distillation under water vacuum.

Five parts of the above B-hexadecyloxyethyl-,3'-dipropylamino diethyl sulfone and 40 parts of toluene were charged into a vessel and heated to 100 C. A solution of 0.95 part of dimethyl sulfate dissolved in 10 parts of toluene was added slowly with stirring over a minute period and the reaction mixture was then maintained at 100 C. for an additional 60 minutes. The toluene was removed by distillation and a tan low melting solid remained. This solid readily dispersed in water.

4 EXAMPLE 3 Preparation of fl-hexadecyloxyethylsulfonylethylbutylmethyl-sulfonium methosulfate ,B-Hexadecyloxyethyl vinyl sulfone (21.6 parts) was dissolved in parts of benzene in a vessel equipped with a stirrer, heating mantle, condenser and thermometer. n-Butyl mercaptan (6.0 parts) was added followed by 0.05 part of sodium methoxide, and the mixture was stirred at 75 C. for one hour. The reaction mixture was then cooled to room temperature and neutralized with ethereal hydrogen chloride. A solution of 2.6 parts of dimethyl sulfate dissolved in 30 parts of benzene was added slowly over a 60-minute period and the reaction mixture maintained at reflux for 60 minutes. The benzene was then removed by distillation and a low melting solid remained which was readily dispersible in water.

EXAMPLE 4 Preparation of aqueous dispersion of sodium fi-dodecylthioethylsulfonylethyl thiosulfate B-Dodecylthioethyl vinyl sulfone (32 parts), sodium thiosulfate pentahydrate (50 parts) and sodium bicarbonate (8.4 parts) were heated with rapid stirring at 70 C. in 250 parts of dimethylacetamide for 30 minutes. Water parts) was added, the raction mixture stirred at 70 C. for 15 minutes and then added with stirring to 510 parts of water.

The procedure of Example 1 has also been employed in the production of the following compounds: p-dodecyloxyethyl vinyl sulfone, fl-tetradecyloxyethyl vinyl sulfone, ,B-hexadecyloxyethyl vinyl sulfone (straight chain), fi-octadecyloxyethyl vinyl sulfone, p-dodecylthioethyl vinyl sulfone, fi-nonylphenoxyethyl vinyl sulfone, fi-dodecylphenoxyethyl vinyl sulfone.

Cellulosic textiles may be treated with these agents to cause the formation of a primary chemical bond by applying the treating agent to the fabric and curing it by heating to an elevated temperature in the presence of an acid binding agent. A reaction occurs between the vinyl group of the sulfone and the hydroxyl function of the cellulosic to produce the corresponding ether derivative of cellulose in accordance with the following equation:

The hydrophobic sulfone is attached to the cellulosic by a primary valence bond. Hence, it is not removed by the solvents used for dry-cleaning or soap or detergent solutions normally employed for washing in ordinary use.

The sulfones and latent sulfones may be dispersed or emulsified in an aqueous medium and the textile is immersed to soak up an adequate quantity. Aternatively, the treating agent may be dissolved in organic solvent such as xylene, benzene, toluene, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, etc. in which the vinyl sulfone derivative or latent vinyl sulfone is soluble, but which do not contain hydrogen sufliciently reactive that the solvent will react with the sulfone under alkaline conditions more readily than the cellulosic textile reacts with the sulfone. An acid binding agent may be dissolved in the same aqeous medium or it may be applied by immersing the textile in a separate aqueous solution containing it before or after applying the sulfone treating agent. Preferably, when the organic solvent is used, the acid binding agent is in a separate solution in water, and the textile is dried between soaking with the sulfone treating agent and with the acid binding agent so that the repelling effect of water against the organic solvent does not interfere with application of both the acid binding agent and the sulfone treating agent to the textile. Suitable acid binding agents are the carbonates, hydroxides and bicarbonates of most metals such as alkali and alkaline earth metals. They include sodium carbonate, sodium hydroxide, potassium bicarbonate, potassium carbonate, and potassium hydroxide. They should have a pK below about 9.2.

The curing step is carried out at an elevated temperature, usually after the fabric has dried, of about 30 to 200 C. for about 24 hours to 30 seconds. Generally, the treatments time varies inversely with the temperature so that shorter times will be employed as the temperature increases.

The textiles to which the present treating agents may be applied are cellulosic textiles. This term refers to texiles composed of cellulose or modified cellulose, such as cotton, rayon, linen, etc., and mixtures thereof either with each other or non-cellulosics such as nylon (polyhexmethylene adipamide) or Perlon (polycaproamide) Dacron (polyethylene terephthalate) or Acrilan (an acrylic).

It has also been found that natural and synthetic waxes may be incorporated in the treating bath from which the vinyl sulfone is applied to the textile and that a higher initial water repellency is obtained.

The following examples illustrate the use of the above sulfone compounds in the treatment of cellulosic textiles. The spray test ratings were rated in accordance with AATCC Standard Test Method 22-52, which is described on pages 164166 of volume 35 of the Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists.

EXAMPLE Application of fi-nonylphenoxyethyl vinyl sulfone to cotton A piece of 80 x 80 cotton print fabric was immersed in a 2% aqueous sodium hydroxide solution for 30 minutes, squeezed to 120% pickup and immersed in 4% xylene solution of B-nonylphenoxyethyl vinyl sulfone for minutes. The fabric was air dried, heated at 100-103 C. for 10 minutes, rinsed and washed (0.1% Na CO 0.1 nonionic surfactant prepared from oxo-tridecyl alcohol and 7 moles of ethylene oxide). This fabric was water repellent. Extraction of the fabric with boiling ethanol, carbon tetrachloride and perchloroethylene did not reduce the water repellency.

EXAMPLE 6 Application of B-hexadecyloxyethyl vinyl sulfone to cotton B-Hexadecyloxyethyl vinyl sulfone (5.0 g.) was heated to 60 C. and added with rapid stirring to a solution of 2.0 g. of Duponol LS (sodium salt of sulfated oleyl alcohol) and 48 g. of water at 50 'C. The dispersion was allowed to cool with stirring. A piece of 80 x 80 cotton print fabric was immersed in a bath containing a dispersion as above to which was added an equal volume of water as well as 1.25% sodium carbonate. The swatch was squeezed to 120% pickup,, air dried, heated at 150 C. for 5 minutes, rinsed and washed. The fabric was water repellent and this repellency was not reduced by extraction with boiling ethanol, carbon tetrachloride and perchloroethylene.

EXAMPLE 7 Application of B-hexadecyloxyethyl vinyl sulfone and methylene-bis-stearamide to cotton A bath containing the following was prepared:

Percent Dispersion containing 10% B-hexadecyloxyethyl vinyl sulfone (similar to that in Example '6) 45.0 Dispersion containing methylene-bisstearamide 9.0 Sodium carbonate 2.2 Water 43.8

A piece of x 80 cotton print fabric was immersed,v

squeezed to pickup, air dried, heated 5 minutes at 150 C. and washed with an aqueous bath containing 0.1% Na CO and 0.1% nonionic surfactant prepared from oxo-tridecyl alcohol and 7 moles of ethylene oxide. This fabric exhibited excellent water repellency (100 spray rating).

The following compounds have been applied to 80 x 80 cotton print fabrics:

B-dodecyloxyethyl vinyl sulfone (a) fl-tetradecyloxyethyl vinyl sulfone (a) fl-hexadecyloxyethyl vinyl sulfone (a) (b) B-octadecyloxyethyl vinyl sulfone (a) (b) B-hexadecyloxyethyl vinyl sulfone (hexadecyl moiety contains chain branching) (b) fl-dodecylthioethyl vinyl sulfone (b) B-nonylphenoxyethyl vinyl sulfone (a) fi-dodecylphenoxyethyl vinyl sulfone (a) N-methyl-N-dodecyl-fl-aminoethyl vinyl sulfone (a) (a) Application by xylene technique as in Example 5. (b) Application from aqueous emulsion as in Exam plc 7.

EXAMPLE 8 Application of sodium S-dodecythioethylsulfonylethyl thiosulfate to cotton A piece of 80 x 80 cotton print fabric was immersed in the dispersion described in Example 4, squeezed to 100% pickup, immersed in a 2% solution of potassium hydroxide, air dried, and heated at C. for 20 minutes. The fabric was then rinsed free of alkali, and after drying was water repellent. The water repellency remained after extraction of the fabric with boiling ethanol, carbon tetrachloride and perchloroethylene EXAMPLE 9 Application of ,B-hexadecyloxyethylsulfonylethylmethyldipropyl-ammonium methosulfate to cotton 5 Hexadecyloxyethylsulfonylethylmethyldipropylammonium methosulfate (3 parts) was added to 96 parts of water at 40 C. and the mixture stirred until homogeneous. A piece of 80 x 80 cotton print fabric was immersed in the dispersion, squeezed to 120% pickup, air dried, immersed in a 2% solution of sodium carbonate, air dried and heated at C. for 5 minutes. After rinsing free from alkali and then drying the fabric was water repellent (50 spray rating) and the water repellency was unaffected by extraction of the fabric with boiling ethanol, carbon tetrachloride and perchloroethylene.

The invention has been illustrated by specific examples, but it will be appreciated that various changes may be made in the nature of the treating agents and in the manner in which they are applied without departing from the scope of the invention, as this is defined in the claims.

What is claimed is:

1. A vinyl ethyl sulfone having the formula:

GUI-BUN 8. B-Hexadecyloxyethyl vinyl sulfone in which the CHARLES B. PARKER, Primary Examiner hexadecyl moiety contains alkyl chain branching.

D. R. PHILLIPS, Asslstant Examiner References Cited UNITED STATES PATENTS 5 3,359,061 12/1967 Welch 260--607 XR 8-115.5, 116.2, 116; 2528.7, 8.75; 260326.82, 567.6, 3,396,198 8/1968 Welch 260-607 294.8, 583, 501.15, 567.6