US3492316A - Difunctional sulfones - Google Patents

Description

United States Patent Office 3,492,316 DIFUNCTIQNAL SULFONES Joe T. Adams, St. Albans, and Herman F. Lykins, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. ()riginal application July 10, 1963, Ser. No. 294,161, now Patent No. 3,312,522, dated Am. 4, 1967. Divided and 610,747

lnt. Cl.

C07d 1/00; D0611! 13/10 US. Cl. 26t)-348 Claims ABSTRACT OF THE DISCLOSURE This is a division of application Ser. No. 294,161, filed July 10, 1963, now Patent No. 3,312,522, issued Apr. 4, 1967.

The present invention relates to sulfone compounds which are new compositions of matter and specifically to certain novel difunctional sulfones which are useful in the treatment of cellulosic fabrics to impart shrink resistance and wash-and-wear properties thereto.

It is well known that cotton and other cellulosic fabrics can be treated with various polyfunctional cross-linking agents, resins and the like to provide a fabric which is wrinkle and shrink resistant and which will maintain a crease for applications such as mens trousers, pleated skirts and the like. However, many of these methods have been found unsuitable because of their lack of permanence. For example, fabrics treated with polyhydroxy urea resins, such as dimethylol ethylene urea, are subject to degradation under the conditions present in many commercial laundering processes, and lose their wrinkle resistance and ability to retain a sharp crease after only a few launderings. Other resinous materials, which coat the cellulosic fibers, impart an undesirable harsh and boardy hand to the fabric. In addition, because the treatments of the prior art generally comprise the addition of the treating agent to the fabric followed by a one-step cure, usually accomplished at temperatures employed in pressing garments made from the treated fabric, the treatment must be effected by the garment manufacturer when a creased garment is desired. Finally, because the curing occurs during the pressing of the garment, errors in pressing cannot be easily rectified by repressing.

It has been found by this invention, however, that when a cellulosic fabric is impregnated with certain difunctional sulfones, as hereinafter defined, one functional group of which reacts with cellulose under acid conditions and the other functional group of which reacts With cellulose under basic conditions, many of the foregoing disadvantages are obviated. Because the sulfones employed in accordance with this invention contain no nitrogen they aer not subject to degradation during laundering as are the nitrogen-containing resins. Because the sulfones react with the cellulose rather than forming a resin coating, the treated fabric does not have a harsh and boardy hand, but rather, it retains the hand of the untreated fabric.

this application Jan. 23, 1967, Ser. No.v

3,492,316 Patented Jan. 27, 1970 Moreover, because the sulfone can be permanently incorporated in the cellulosic fabric without also crosslinking the fabric, the treatment of this invention, except for the final cross-linking, can be conducted by the textile manufacturer. Finally, because the fabric can be pressed without also causing the final cross-linking, any errors in pressing can be easily rectified.

The difunctional sulfones which are employed in accordance with this invention have the general formula ASO B wherein A is a functional group which will react with a hydroxyl group under acidic conditions (a pH of about 6 or less), such as a group containing a vie-epoxy group; and B is a functional group which will react with a hydroxyl group under basic conditions (a pH of about 8 or higher), such as a vinyl group, a fi-hydroxalkyl group or a B-(alkoxy)alkyl group. More specifically, the compounds employed in this invention have the formula RSO CH (R O),,R wherein R is a vinyl group, a B- hydroxyalkyl grou of from 2 to about 4 carbon atoms, inclusive, or a ,B-(alkoxy)alkyl group having from 1 to about 4 carbons, inclusive, in the alkoxy group thereof and from 2 to about 4 carbons, inclusive, in the alkylene group thereof; R is a divalent alkylene group of from 1 to about 3 carbons, inclusive; R is a vic.-epoxyalkyl group of from 2 to 8 carbons, inclusive; and n is an integer having a value of 0 or 1. As examples of suitable difunctional sulfones one can mention epoxyalkyl vinyl sulfones such as 2,3-epoxypropyl vinyl sulfone, 3,4-epoxybutyl vinyl sulfone, 2,3-epoxybutyl vinyl sulfone, 2-methyl-2,3- epoxypropyl vinyl sulfone, 2,3-epoxyhexyl vinyl sulfone 5,6-epoxyhexyl vinyl sulfone and the like; (epoxyalkoxy)alkyl vinyl sulfones such as 2 (epoxyethoxy) ethyl vinyl sulfone, 2-(epoxyethoxy)propyl vinyl sulfone, Z-(epoxyethoxy)-l-methylpropyl vonyl sulfone, 2 (2,3- epoxypropoxy)ethyl vinyl sulfone, 2 (5,6-epoxyhexoxy) ethyl vinyl sulfone; epoxyalkyl and (epoxyalkoxy)alkyl fi-hydroxyalkyl sulfones such as 2,3-epoxypropyl 2-hydroxyethyl sulfone, 2,3-epoxypropyl 2-hydroxypropyl sulfone, 2,3-epoxy propyl 2-hydroxy-1-methylpropyl sulfone, 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone and the like; and epoxyalkyl and (epoxyalkoxy)alkyl p-(alkoxy)alkyl sulfones such as 2,3-epoxypropyl 2- (methoxy)ethyl sulfone, 2,3-epoxypropyl 2- (ethoxy)ethyl sulfone, 2,3-epoxypropyl 2-(butoxy)ethyl sulfone, 2-(2,3- epoxyethoxy)ethyl 2-(methoxy)ethyl sulfone, and the like; et cetera. The preferred sulfones for use in the treatment of this invention are those wherein the acid-reacting group is a terminal vie-epoxy group and the base-reacting group is a ,B-hydroxyalkyl group because of their greater reactivity in the cross-linking treatment.

These difunctional sulfones are produced by the reaction of organic peracids with olefinically unsaturated compounds of the formula RXCH (R O),,R wherein R, R and n are as defined above; R is an alkenyl radi cal of from 2 to about 8 carbons, inclusive; and X is a divalent thio (S), sulfinyl (-SO) or sulfonyl (SO group. As examples of suitable compounds of this type one can mention allyl vinyl sulfide, 3-butenyl vinyl sulfide, crotyl vinyl sulfide, 2-hexenyl vinyl sufide, S-hexenyl vinyl sulfide, 2-(vinyloxy)ethyl vinyl sulfide, 2-(vinylo-xy) propyl vinyl sufide, 2-(vinyloxy)-1-methylpropyl vinyl sulfide, 2-(vinyloxy)-l-methylpropyl vinyl sulfide, 2- (allyloxy)ethyl vinyl sulfide, 2-(5-hexenyloxy)ethyl vinyl sulfide, allyl 2-hydroxyethy1 sufide, allyl Z-hydroxypropyl sulfide, allyl 2-hydroxy-1-methylpropyl sulfide, 2-(allyloxy)ethyl 2-hydroxyethyl sulfide, allyl Z-(methyloxy) ethyl sulfide, allyl 2-(ethoxy)ethyl sulfide, allyl 2-(butoxy)ethyl sulfide, 2-(alloxy)ethyl 2-(methoxy)ethyl sulfide and the like, as well as the corresponding sulfoxides and sulfones. These unsaturated precursors are readily prepared by reacting a mercaptoalcoh-ol, for example, mercaptoethanol, with a monoolefinic halide, for example allyl chloride, to produce a hydroxyalkyl alkenyl sulfide, for example 2-hydroxyethyl allyl sulfide; divinyl sulfide is reacted with water to produce vinyl Z-hydroxyethyl sulfide, which is reacted with an alkenyl halide to produce a vinyl (alkenyloxy)ethyl sulfide; and the like.

The peracids which are employed to produce the sulfones are aliphatic, cycloaliphatic and aromatic peracids, including peracetic acid, perpropionic acid, perbutyric acid, perhexanoic acid, perdodecanoic acid, perbenzoic acid, monoperphthalic acid and the like. The lower aliphatic hydrocarbon peracids having from 2 to 4 carbon atoms are highly suitable, with peracetic acid being the most preferred.

The reaction is conducted by adding a 10 to 50 weight percent, preferably 20 to 40 weight percent, solution of the peracid in a solvent such as ethyl acetate, butyl acetate or acetone to the olefinically unsaturated compound at a temperature of from C. or lower to about 100 C. or higher; preferably from about 25 C. to about 75 C. The amount of peracid employed should be in excess of the stoichiometric amount required to oxidize the thio or sulfinyl group, if present, to the sulfonyl group, and to epoxidize the olefinic double bond. When a sulfide or sulfoxide is employed as the precursor it is preferred that a portion of the peracid be added at a temperature of from about 15 C. to about 35 C. for the oxidation of the thio or sulfinyl group to the sulfonyl group, and that the balance of the peracid be added at a temperature of from about 40 C. to about 70 C. to epoxidize the double bond. Under these conditions the vinyl group attached to the sulfonyl group will not epoxidize. The difunctional sulfone is separated from the mixture by known techniques.

The fabric teratment of this invention essentially comprises reacting the sulfone with the cellulosic fabric under either acidic or basic conditions to produce a presensitized fabric having properties similar to the untreated fabric. The presensitized fabric is then heated under basic or acidic conditions to cross-link the cellulose and produce a wrinkle-resistant, wash-and-Wear cotton fabric.

The first step of the process of this invention consists of impregnating the fabric with the sulfone and curing catalyst and curing the impregnating fabric to obtain a fabric having from about 2 to about 15, preferably from 3 to about 12, weight percent reacted difunctional sulfone, based on the weight of the untreated fabric. The impregnation is readily accomplished by conventional techniques wherein the fabric is immersed in an aqueous solution of sulfone and either a basic or an acidic curing catalyst.

The concentration of the sulfone in the aqueous bath is not critical, and can vary from as low as 3 percent or less up to about 25 percent or more. When the sulfone is present in such concentrations the desired degree of addon can be obtained by padding the fabric to about 100 percent Wet pick-up, based on the weight of the fabric, and then drying and curing the fabric.

When an acid catalyst is employed in the first step, the reaction on curing occurs between the epoxy group of the sulfone and a hydroxyl group of the cellulosic fabric to provide cellulosic molecules having pendant vinylsulfonyl, ,B-hydroxyalkylsulfonyl or B-alkoxyalkylsulfonyl groups. This product can be represented by the general formula ZHUOHtOR CH SO R] wherein R, R and n are as defined above; Z represents the gellulgsic fabric; and y is an integer,

The acid catalysts which are employed in efiecting this reaction are latent acid catalysts; i.e., compounds which liberate acidic components at temperatures of from about C. to about 200 C. As examples of suitable latent acid catalysts one can mention Lewis acids such as stannic chloride, zinc chloride, aluminum chloride, ferric chloride and the like; Lewis acid complexes, such as etherates and amine complexes, including piperadine-boron trifiuoride, monoethylamine-boron trifluoride, boron trifluoride etherates and the like; fiuoroborate salts of metals such as magnesium fluoroborate, tin fluoroborate, cadmium fiuoroborate, sodium fiuoroborate, zinc fiuoroborate, and the like; stannous and stannic acylates; stannous alkoxides; et cetera, as well as acid catalysts which have been encapsulated with materials melting at 100200 C., such as in disclosed in US. Patent No. 3,018,258.

The amount of acid catalyst in the bath is not critical provided a solution having a pH of about 6 or below is obtained. However, amounts of from about 1 to about 10, preferably from about 2 to about 5, weight percent, are generally suitable. At low pH (3 or less), the epoxy group of the sulfone is susceptible to hydrolysis, thus reducing the efficiency of the cross-linking. For this reason it is desirable to include a buffering agent in the acid bath to maintain a pH of from about 5 to about 6. As examples of suitable buffers one can mention zinc oxide, magnesium oxide, ammonium hydroxide, Zinc acetate and the like.

When a basic catalyst is employed in the first step, the reaction on curing occurs between the vinyl, hydroxyalkyl or alkoxyalkyl group of the sulfone and a hydroxy group of the cellulosic fabric. The product of this step can be represented by the formula [ZOR S() CI-l (OR R wherein Z, R R n and y are as defined above and R is a divalent a,fl-alkylene group of from 2 to 4 carbons.

The basic catalysts which are employed are strong bases such as hydroxides of sodium or potassium, or quaternary ammonium hydroxides such as tetramethylammonium hydroxide, benzyl trimethylammonium hydroxide and the like; or sodium or potassium salts of inorganic acids having a dissociation constant of less than 5 10 such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, tripotassium phosphate and the like.

The amount of basic catalyst in the aqueous bath is not critical, provided the bath has a pH of at least about 8, and preferably at least about 10. In general, amounts of base of from about 1 to about 10, preferably from about 2 to about 5 weight percent are sufficient.

The curing of the impregnated fabric is achieved by heating at from about C. to about 200 C. If desired, the fabric can be dried at lower temperatures such as 50 C. to 100 C. to remove the water prior to curing. After curing the fabric, the treated fabric is then scoured to remove unreacted difunctional sulfone and curing catalyst. The scouring is effected by Washing the fabric in hot (about F.) water containing a small quantity of detergent. The resulting presensitized fabric can be stored for extended periods of time or can be immediately subjected to the final cross-linking step.

The final cross-linking is accomplished by impregnating the treated fabric with a curing catalyst which is acidic if the catalyst employed in the first step was basic, or is baisc if the catalyst in the first step was acidic. The impregnation is accomplished in a manner similar to that employed in the first step; i.e., padding the fabric to about 100 weight percent wet pick-up in an aqueous solution containing from about 1 to about 10, preferably from about 2 to about 5, weight percent dissolved catalyst. After drying, the fabric can be stored or can be immedis ately heated to a temperature of from about 120 C. to about 200 C. to ef ect the. final c oss-link ng. c u e the rate of reaction, in the absence of any catalyst, is relatively slow at temperatures of less than about 170 180 C., the fabric without catalyst can be pressed at temperatures of from 100 C. to 170 C. for up to five minutes without obtaining a high degree of cross-linking. Thus, if errors are made in pressing, the garment can be readily repressed before the final cure.

Although the first step can be either the acid-catalyzed or base-catalyzed reaction, it is preferred to employ the acid-catalyzed step first, particularly if the resulting presensitized fabric is to be stored for extended periods of time. If the base-catalyzed process is employed first, the treated fabric must be thoroughly washed to ensure that all of the catalyst, which would neutralize the latent acid catalyst, is removed from the fabric. In addition, the pendant vinyl, alkoxy or hydroxyl groups in the treated fabric resulting from the acid-catalyzed first step are more stable than the pendant epoxide groups resulting from a base-catalyzed first step, permitting longer storage times of the presensitized fabric produced by the acid-catalyzed first step.

By the term cellulosic fabric is meant a fabric containing at least 40 weight percent cellulose, including cotton, regenerated cellulose, rayon, linen and the like.

The following examples are illustrative. In the evaluation of the treated fabrics the following tests were employed:

(A) Crease recovery-ASTM D-1295053T (warp direction only).

(B) Wash and wear index.A sample of the fabric is washed and either spun dried or tumble dried, and then evaluated as follows:

See Textile Res. 1., 26, 974 (1956) and Amer. Dye Rep, 48, 37 (1959); ASTM Method 88-1960.

(C) Crease rating.A creased fabric was washed and the appearance of the crease rated on a scale of from 1, indicating no crease, to 5, indicating full retention of the crease.

See 1963 Technical Manual of AATCC, pages A37, A38, Report No. RA-61 on Wash and Wear.

EXAMPLE 1 2(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone A mixture of 345 grams of allyl chloride and 200 grams of benzene was fed dropwise over a period of /2 hour to a solution of 312 grams of potassium hydroxide in 1830 grams of thiodiglycol at 100 C. During this period, water of reaction was removed as an azeotrope with benzene by distillation. The resulting mixture was heated at 110-115 C. for an additional hours, at which time all of the water of reaction had been removed. After cooling to room temperature and filtering to remove the potassium chloride formed during the reaction, the reaction mixture was distilled to recover 341 grams of 2-(allyloxy)ethyl Z-hydroxyethyl sulfide as a fraction boiling at 9095 C. and 1.0 mm. The 2-(allyloxy)ethyl Z-hydroxyethyl sulfide had a purity of 99 percent, as determined by analysis for olefinic unsaturation with bromine, and a purity of 94.2 percent, as determined by analysis for the hydroxyl group with acetic anhydride in pyridine catalyzed with perchloric acid. The 2-(all'yloxy)ethyl 2-hydroxyethyl sulfide had a refractive index, n of 1.4936 and a molecular weight of 170 (theory 162) as determined by the modified Menzies-Wright method employing acetone.

To 290 grams of 2-(allyloxy)ethyl Z-hydroxyethyl sulfide there were added dropwise 2470 grams of a 20 percent solution of peracetic acid in ethyl acetate. Two thirds of the solution was added at 25 C. over two hours to oxidize the sulfide to the sulfone, at which time the mixture was heated to 5060 C. and the remainder of the solution was added over one hour to epoxidize the double bond. After heating the resulting mixture at 50-60 C. for an additional 10 hours the mixture was fed dropwise to refluxing ethylbenzene at 50 mm. pressure, while continuously removing acetic acid as an azeotrope with the ethylbenzene. Distillation was continued to a kettle temperature of 60 C. at 3 mm. pressure. The colorless residue remaining in the kettle was 278 grams of 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone having a purity of 84% as determined by epoxide analysis using the pyridine hydrochloride method. The 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone had a refractive index, r1 of 1.4879 and a molecular weight of 217 (theory 210).

Analysis.Calcu1ated for C H O S: C, 39.99%; H 6.71%; S, 15.2%.

Found: C, 40.3%; H, 6.6%; S, 14.9%.

EXAMPLE 2 A sample of mercerized cotton print cloth was immersed in a solution of 10 weight percent 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone, 2.0 Weight percent zinc fiuoroborate and 0.3 weight percent magnesium oxide in Water, padded to about weight percent wet pick-up, dried for 3 minutes at 5 C. in a forced-air oven, and cured for 3 minutes at C. The fabric was then laundered with a 0.1 Weight percent solution of a built detergent in water to remove residual reagents and tumble dried. The dry add-0n after laundering was 5.5 weight percent. The crease recovery and the wash and wear index of the treated fabric were unchanged from the untreated fabric, being about 35 percent and 1, respectively.

A portion of the treated fabric was immersed in a 5 weight percent solution of sodium carbonate in water, padded to about 100 weight percent wet pick-up, creased and dried on a tailors press at 96 pounds steam pressure for 5 minutes to a maximum fabric temperature of 140 C., and then cured for 2 minutes at C. After Washing and tumble drying the treated fabric was found to have a crease recovery of 67 percent and a wash and Wear index of 4.0.

EXAMPLE 3 Employing apparatus, materials and procedures similar to those described in Example 2, except that after padding with the sodium carbonate solution, the fabric was stored for 4 weeks at 70 F. and 65% relative humidity, and then creased and cured, there was obtained a fabric having a crease recovery of 66 percent and a wash and wear index of 4.0.

EXAMPLE 4 In a manner similar to that described in Example 2, a sample of mercerized cotton print cloth is immersed in an aqueous solution of 2,3-epoxypropyl vinyl sulfone, zinc fiuoroborate and magnesium oxide, dried and cured. The treated fabric is then immersed in an aqueous solution of sodium carbonate, dried and cured, to produce a fabric having good wrinkle and shrink resistance and good crease retention properties.

EXAMPLE 5 In a manner similar to Example 2, except that 2-(2,3- epoxypropyl)ethy1 2-(ethoxy)ethy1 sulfone is substituted for the 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone, there is produced a treated cotton fabric having good wrinkle and shrink resistance and good crease retention properties.

EXAMPLE 6 Twelve samples of mercerized cotton print cloth were immersed in a solution of 10 weight percent 2-(2,3- epoxypropoxy)ethyl Z-hydroxyethyl sulfone, 2 weight percent zinc fiuoroborate, and 0.3 weight percent magnesium oxide in water, padded to about 100 weight percent wet pick-up, dried for 10 minutes at 40 C. and cured for 3 minutes at 150 C. Ten of the treated samples were immersed in a 5 weight percent solution of sodium carbonate in water and dried for 10 minutes at 40 C. The samples were then treated as follows:

(A) Two were cured for 2 minutes at 180 C.

(B) Two were stored for 4 weeks at 70 F. and 65% relative humidity and then cured for 2 minutes at 180 C.

(C) Two were creased for 5 minutes on a tailers press at 96 pounds steam pressure to a maximum fabric temperature of 140 C.

(D) Two were creased for 5 minutes on a tailors press at 96 pounds steam pressure to a maximum fabric temperature of 140 C. and then cured for 2 minutes at 180 C.

(E) Two were stored for 4 weeks at 70 F. and 65% relative humidity, creased for 5 minutes on a tailors press at 96 pounds steam pressure to a maximum fabric temperature of 140 C. and then cured for 2 minutes at 180 C.

Wash-Wear Index Dry Crease Add-on, Recovery, Tumble Spin Crease Wt. Percent Percent Dry Dry Rating Treatment:

8 What is claimed is: 1. A difunctional sulfone of the formula RSO CH (R 0 R wherein R is a member selected from the group consisting of Bhydroxyalkyl of 2 to 4 carbons and B-(alkoxy)-alkyl of 1 to 4 carbons in the alkoxy group thereof and 2 to 4 carbons in the aikylene group thereof; R is a divalent alkylene group Of 1 to 3 carbons; R is a vic.-epoxyalkyl group of from 2 to 8 carbons; and n is an integer having a value of from 0 to 1.

2. A difunctional sulfone as described in claim 1 wherein R is fl-hydroxyalkyl of 2 to 4 carbons, R is a divalent alkylene group of 1 to 3 carbons, R is a terminal-vie.- epoxyalkyl group of 2 to 8 carbons, and n is l.

3. A difunctional sulfone as described in claim 1 wherein R is fi-hydroxyalkyl of 2 to 4 carbons, R is a terminalvic.-epoxyalkyl group of 2 to 8 carbons, and n is 0.

4. A difunctional sulfone as described in claim 1 wherein R is fl-hydroxyethyl, R is a methylene group, R is a terminal-vic.-epoxyalkyl group of 2 to 8 carbons, and n is 1.

5. Z-hydroxyethyl 2-(2,3-epoxypropoxy)ethyl sulfone.

References Cited UNITED STATES PATENTS 3,220,981 11/1965 MacPeek et a1. 260348 X OTHER REFERENCES Tesoro, G. C. et al., Textile Research Journal, vol. 33,

" No. 2, pp. 93-107 (1963).

NORMA S. MILESTONE, Primary Examiner US. Cl. X.R.