Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/262—Sulfated compounds thiosulfates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/272—Unsaturated compounds containing sulfur atoms
  • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins

Definitions

• ABSTRACT OF THE DISCLOSURE A process which comprises heating a dry, essentially unswollen cellulosic textile material to an elevated temperature, impregnating the textile material with an acid acting catalyst and the reaction product of a methylol textile resin and an ester of a sulfone or sulfoxide, the reaction product having at least one functional group which is reactive to cellulose under textile resin curing conditions and at least one activated ester group which is substantially inert under such curing conditions but which is reactive to the cellulose in the presence of a strong aqueous base.
• the reaction product is chemically fixed to the textile material and thereafter is impregnated with a strong aqueous base so that the textile material is crosslinked by the reaction product. At least one linkage occurs while the textile material is in a dry, essentially unswollen condition and at least one linkage occurs while the textile material is in a wet, essentially swollen condition.
• This invention relates to methods for treating cellulosic textile materials to improve certain characteristics thereof, to the textile materials thus obtained and to novel compounds and compositions.
• a cellulosic textile material as defined hereinafter, impregnated with a polyfunctional organic compound having both an acid reactive group and a base reactive group is heated under textile resin curing conditions in the presence of a textile resin catalyst, to chemically fix the compound to the cellulosic material by the reaction of the acid reactive group while the textile material is in a dry, unswollen condition, and then contacting the resulting product with strong aqueous base to further chemically fix the compound to the cellulosic material by the reaction of the base reactive group while the textile material is in a wet, swollen condition, thereby producing a product having improved dry and wet resiliency.
• the step employing strong aqueous base can be eliminated while retaining many of the advantages of this invention.
• Another object is to provide novel chemically modified textile materials.
• Still another object is to provide novel compounds and compositions.
• Textile materials which can be treated according to the process of this invention are those in which the anhydroglucose units are chemically substantially unmodified.
• cellulosic textile material when used herein means any textile material comprising fibers within the above definition, e.g., cotton, linen, jute, flax, regenerated cellulose fibers, including viscose rayon, in the form of staple, yarn and fabrics.
• This invention is directed primarily and preferably to cellulosic textile fabrics knitted and preferably woven.
• the advantages of this invention can be achieved by treating the cellulosic fibers, yarns, or threads employed to produce these fabrics.
• the thus treated material when woven or knitted into fabric will produce a fabric having better wet and dry resiliency than identical fabric woven from identical untreated yarn or thread.
• the properties of the staple yarn and thread are modified in a desirable fashion.
• the staple is less prone to compression into hard masses during wet or dry processing. Satisfactory results can be achieved employing cellulosic materials containing both cellulosic and non-cellulosic fibers, especially if the non-cellulosic fibers have minimum care characteristics of their own.
• the wet and dry resiliency of fabrics formed from a mixture of glycolterephthalate, polyacrylic, or nylon filaments or fibers with cotton or rayon can be improved by this process.
• the improved characteristics of the materials treated according to the process of this invention will be more readily apparent when the cellulosic content of the fabric is substantial, e.g., about 40% or more by weight.
• the invention is primarily directed to fabrics, preferably consisting essentially of cellulosic materials, especially cotton. Bleached and usually also commercially mercerized or printed fabric, e.g., printcloth, broadcloth, and oxfordcloth, is usually employed as the starting fabric. Generally, it is preferred to employ starting fabrics having a tensile strength of at least 35 pounds and a tear strength of at least 400 grams in both the filling and Warp.
• the polyfunctional organic compounds employed to impart wet and dry resiliency to the starting textile materials are those having both an acid reactive group and a base reactive group, i.e., compounds which will react with the cellulose under acidic conditions and will also react with the cellulose under basic conditions.
• the purpose of this polyfunctionality is to permit a certain portion of the chemical linkages between the textile material and the polyfunctional organic compound to occur while the textile material is in a dry, unswollen condition and a portion .of the chemical linkages to occur while the textile material is in a wet, swollen condition.
• This polyfunctionality permits achieving the dry resiliency obtained from a comparable resin treatment yet, surprisingly, the concommitant loss of strength of the textile material is often markedly less.
• the step employing strong base tends to fix a higher percentage of the base reactive group containing compound to the cellulosic material, thus increasing the efiiciency of utilization of this compound
• the complete structure of the polyfunctional compounds employed herein is not critical so long as it contains at least one acid reactive group and at least one base reactive group as defined herein.
• compounds of relatively simple structure such as N- methylol-N'-(sodium sulfatoethyl sulfonyl-ethyl) urea, which is the reaction product of monomethylol-urea and divinyl sulfone, can be employed.
• the acid reactive groups are generally those found in the textile resins presently employed in the resin treatment of cellulosic fabrics, e.g., methylol, epoxy, acetal, alkylated methylol, aldehyde, etc. These groups are characterized by their ability to combine with the hydroxy groups of the cellulose molecule under textile resin curing conditions.
• the base reactive groups are those which have the capacity of reacting with the hydroxy groups of the cellulose molecule in the presence of strong base and include epoxy and halohydrin groups and carbonyl, acetylenic, sulfone and sulfoxide activated groups, e.g., of the formula wherein R is a carbonyl, sulfone, sulfoxide or acetylenic group and R is sulfatoethyl, alkali-metal sulfatoethyl, phosphatoethyl, alkali-metal phosphatoethyl, thiosulfatoethyl, and alkali-metal thiosulfatoethyl, quaternary ammonium ethyl halides, e.g., yridinium ethyl chloride, vinyl or substituted, e.g., loWer-alkyl substituted, vinyl.
• R is a carbonyl
• Both the acid reactive and the base reactive groups can be epoxy if one of the epoxy groups has a lower order of activity than the other under textile resin curing conditions so that it does not, at that step, react with the cellulose.
• a mild catalyst such as, for example, zinc chloride, magnesium chloride, or an amine hydrochloride will facilitate such a preferential reaction.
• the amount of acid and base reactive group containing compound which can be employed is not critical and the exact amount to be employed depends, in part, on the properties desired in the final product and the efiiciency of the selected compound. For example, amounts in the range of from about 1% to 40%, preferably about 5% to 25%, calculated on the weight of the dry textile material, can be applied to the textile material. As the pickup of solution of the selected compound, if it is supplied as a solution, will range from about 50% to 200% of the weight of the textile material, a solution concentration should be selected which will provide the desired deposition of compound on the selected textile material under the conditions of pick-up.
• a polymethylol textile resin can be mixed with a compound having both an aliphatic hydroxy group and a base reactive group in the molecule The hydroxy group of the latter compound will then react with a reactive group of the textile resin, ordinarily amethylol group, in a manner analogous to the known reaction of lower alkanols with the methylol aminoplast textile resins.
• reaction can also occur in an aqueous solution of a mixture of these compounds, especially if the mixture is heated, in which case the resulting product would fall within the definition of a compound having both acid reactive and base reactive groups in the molecule.
• reaction between the two compounds can occur while the textile material, impregnated with the mixture of compounds, is heated, e.g., when drying the textile material, if the mixture of compounds is applied as an aqueous solution, or while the textile material is being heated under textile resin curing conditions.
• the known polymethylol textile resins constitute a large class of compounds which can be employed to contribute the acid reactive group to the polyfunctional compounds employed in the processes of this invention.
• textile resin as used herein is in conformity with the generally accepted usage in the textile art, i.e., it defines a thermosetting reagent which is applied to a textile fabric and reacted therewith when the dry fabric is heated, usually in the presence of an acidic catalyst, at a temperature usually between about 140- to 200 C. At this temperature, the reagent, even by itself, will ordinarily resinify in the presence of an appropriate catalyst, thus probably contributing to the use of the term resin treatment.
• textile resins are of relatively low molecular weights, are almost always water soluble and are often liquids.
• ureaformaldehyde and the melamine-formaldehydes e.g., dimethylol-urea and tetraand penta-methylol-melamines
• the acrolein-urea-formaldehyde resins the cyclic ethylene urea-formaldehyde resins, e.g., dimethylol cyclic ethylene urea and dimethylol dihydroxy cyclic ethylene urea
• triazones e.g., dimethylol-N-ethyl-triazone, di
• aminoplast textile resins exemplify the wide variety of structures which can be used to contribute an acid reactive group to the polyfunctional compounds employed in the process of this invention.
• Other non-nitrogen containing textile resins can also be employed, e.g., the epoxy and acetal textile resins. It will be obvious to one skilled in the art that the choice of compound employed to contribute the base reactive group will be influenced by the functional groups present in the compound contributing the acid reactive group.
• Compounds which can be employed to contribute the reactive group to the polyfunctional compounds employed in the process of this invention include polyhydroxy compounds, at least one hydroxy group of which is activated and esterified. Esters of activated hydroxy groups can be carried through the heating step under textile resin curing conditions and will then be available to react with the cellulose molecule in the presence of strong aqueous base. The unesterified hydroxy group is available to react with the compound contributing the acid reactive group, e.g. an aminoplast textile resin, thereby producing a polyfunctioial compound having both acid and base reactive groups.
• a novel class of compounds within the above definition are the monoesters of di-B-hydroxyethyl-sulfone and of di-B-hydroxyethyl-sulfoxide.
• the mono-ester can be the sulfate, phosphate, or thiosulfate, preferably in the form of their alkali-metal salts, or an organic ester, e.g., lower alkanoate, or other alkyl, aryl, alkaryl, or arylalkyl ester, preferably hydrocarbon and containing from 1 to 12 carbon atoms. Because of the activated character of the hydroxy groups of the starting compounds, the mono-esters thereof can readily be prepared by employing a mole of the esterifying reagent per mole of the starting dihydroxy compound. Only very mild esterification conditions are required.
• the sulfato mono-ester can be prepared at room temperature with about two molar equivalents of concentrated sulfuric acid.
• the reaction product can be converted to an alkali-metal salt by pouring into ice water and then carefully neutralizing to a pH of about 4 with, e.g., sodium carbonate.
• a method of producing an alkali-metal salt directly involves mixing the starting dihydroxy compound with about a molecular equivalent of sodium or potassium bisulfate and then heating while removing the water of reaction, usually with an azeotropic solvent. These monoesters can then be reacted with an aminoplast polymethylol textile resin either prior to applying the compounds to the selected textile material or subsequent thereto.
• Examples of compounds containing acid and base reactive groups which can be used in the process of this invention are the reaction products of the sodium salt of the sulfato mono-ester of di-B-hydroxyethyl-sulfone with dimethylol urea, dimethylol-N-ethyl-triazone, dimethylol- N-hydroxyethyl-triazone, dimethylol cyclic ethylene urea, or dimethylol-dihydroxy-cyclic ethylene urea, and the reaction products of the corresponding acetic acid monoester with each of the above textile resins.
• reaction product of one of the above-described monoesters of di-/9-hydroxyethyl-sulfone and a polymethylol aminoplast textile resin to provide the acid and base reactive group containing poly'functional compound.
• reaction products therefore constitute a preferred class of compounds to be employed in the process of this invention.
• a reaction temperature of between about and C. is preferred.
• the molar ratio of polymethylol aminoplast textile resin and base reactive group containing compound, used to produce the acid and base reactive group containing polyfunctional compounds employed in the process of this invention is not critical as satisfactory results have been obtained when the molar ratio was varied from as low as 1:2 to as high as 2: 1. This may be due to the fact that the reaction between the two compounds does not proceed to theoretical completion or the resultant compound rearranges to a certain extent to permit fixation of a portion of the resultant mixture to the cellulose during the heating step under textile resin curing conditions. In any event, the fixation occurs at least partially during the heating step and partially during the treatment with strong aqueous base.
• the amount of selected compound containing the acid reactive group and the amount of selected compound containing the base reactive group which should be employed in the process of this invention will depend, of course, on the selected ratio between them which produces optimum results. Generally, from about 2% to about 25% of each compound is employed, calculated on the weight of the dry textile material. If a textile resin is employed to supply the acid reactive group, solution concentrations of between about 3% and 40% of each compound can be employed to apply them to the selected textile material.
• the textile resin catalysts employed during the heating step under textile resin curing conditions are a wellknown class of compounds and include the acid acting compounds, i.e., those acidic in character under the curing conditions.
• the most common are the metal salts, e.g.,
• the amounts of catalyst to be employed are the same as those employed when using the usual textile resins, e.g., up to about 20% by weight of the polyfunctional compound employed, with the preferred range being from about 0.5% to about
• Other additives commonly employed when using the usual textile resins can be employed in the process of this invention. For example, a small amount of a surfactant can be added to insure uniform and satisfactory wetting out of the fabric, if an aqueous solution is employed.
• Softeners e.g., the dispersible polyethylenes, can be added to improve tear strengths if the textile material being treated is fabric.
• the strong aqueous bases employed in the second ste of process of this invention are those having a pH of at least 10 as a 1% aqueous solution.
• the bases most commonly employed are the alkali-metal hydroxides, although other compounds such as sodium silicate, sodium carbonate, and potassium carbonate can also be employed. These bases are usually employed as about 0.2% to about 16% solutions, preferably about 2% to about 16%.
• concentration while not critical, will affect the results obtained. The concentration which gives the optimum result will depend, in part, on the percent pick-up of the base by the textile material, the temperature at which the reaction is conducted, and the amount of base consumed in the reaction.
• the amount of base applied to the textile material should be at least the amount that will be consumed by that group. Generally, a 3% to 10% aqueous solution of base is preferred when the pick-up is between about 30% to 130%, calculated on the weight of the dry textile material.
• the cellulosic material uniformly impregnated with a polyfunctional organic compound having at least one acid reactive group and at least one base reactive group is heated under textile resin curing conditions in the presence of an acidic catalyst.
• this acid and base reactive compound can be that which is initially applied to the textile material or can be the product of an in situ reaction of an acid reactive group containing compound and a base reactive group containing compound.
• this step employs conditions identical to that of a conventional resin treatment.
• the selected reagents can be applied to the textile material by padding, spraying, or applicator roll and then passed through squeeze rolls, if necessary, to achieve the desired pick-up of the reagents.
• the textile material is dried and then heated to the appropriate temperature, e.g., about 100 to 200 C., preferably about 140 to 190 C., to fix the compound to the textile material.
• the appropriate temperature e.g., about 100 to 200 C., preferably about 140 to 190 C.
• these steps of drying and curing are conducted while the fabric is free from extraneous wrinkles, usually in a smooth, open width condition.
• Conventional curing equipment is suitable for this operation.
• the reagents can be applied with the usual equipment and then passed through squeeze rolls and dried, e.g., at room temperature or while the fabric passes through a hot air oven or over heated cans. In production it is preferred to conduct the heating operations in a tender frame to maintain the desired dimensions.
• the step of contacting the textile material with strong aqueous base employs conditions generally employed in the textile trade, and the necessary techniques will be apparent to those skilled in the art.
• impregnating the textile material with the selected reagents can be accomplished in a manner similar to those employed in the previous step.
• the material can be moistened by dipping in an aqueous solution of the selected base, squeezed through rollers to achieve the desired pick-up of the base and then maintained at the selected temperature for a time suflicient to insure complete reaction.
• It is ordinarily not preferred to maintain the textile material in the presence of a large excess of the aqueous base solution because of the tendency of large excesses of base and water to sometimes interfere with the desired reaction.
• the textile material is ordinarily maintained with a pick-up of from about 30% to 130%, calculated on the weight of the dry textile material.
• the preferred pick-up is from about 50% to 100%.
• the temperature at which the reaction with the strong aqueous base is conducted can be varied over a fairly wide range, e.g., from about 20 to 100 C., preferably to C. Room temperature is preferred for its convenience.
• the thus treated textile material is ordinarily then given a thorough wash to insure removal of any excess base and any byproducts of the reaction.
• the physical properties of the fabrics treated according to the process of this invention were determined according to accepted standard methods. Tear strength was determined by A.S.T.M. Test designation D-1424-59. Tensile strength was determined by A.S.T.M. Test designation D-39-59 (No. 10). Crease recovery angle was determined by A.S.T.M. Test designation D1295-53T. See A.S.T.M. Standards for Committee D-13 on Textiles (1959). Flat dry ratings were by A.A.T.C.C. Test designation T-88-l958.
• Surfonic N- refers to an ethylene oxde condensation product of nine parts ethylene oxide and one part nonyl phenol
• Mercerol GV refers to an anionic ether derivative free of cresylic acid.
• Moropol 700 refers to a nitrogen-free nonionic polyethylene emulsion used in conjunction with thermosetting resins (Technical Manual of AATCC, vol. 36, page 527, copyright 1960, AATCC, Lowell, Mass); Aerotex Resin 23 refers to a triazineformaldehyde condensate (Technical Manual of AATCC; vol. 36, page 452); Rhonite N-17 refers to a liquid monomeric thermosetting resin (Technical Manual of AATCC, vol.
• Surfonic N-95 refers to a nonionic alkyl aryl polyethylene glycol ether (Detergents and Emu1sifiers-up to date-1960, page 104, copyright 1960, John W. McCutchen, Inc.); Mercerol GV refers to a mixture of anionic surfactants free of cresylic acid, sold by Sandoz, see 1960 product bulletins.
• EXAMPLE 1 1.0 mole (154 g.) of di-B-hydroxyethyl-sulfone was mixed with 1.0 mole g.) of sodium bisulfate at least partially dissolved in about 50 ml. of water. The mixture was heated with about 220 ml. of toluene in a 3-necked flask fitted with a stirrer and condenser having a Stark- Dean trap. The added water and water of reaction was removed azetropically with the refluxing toluene. When the added water and the theoretical amount of water of reaction had been removed, the mass was poured into cold water. The toluene was separated and the pH of the aqueous solution was adjusted to 4 with about 6.5 g.
• EXAMPLE 2 1.0 mole (154 g.) of di-fi-hydroxyethyl-sulfone was melted in a reaction flask. To the melt was slowly added 1.0 mole (102 g.) of acetic anhydride. The acetic acid formed was removed under vacuum. There was thus obtained di-B-hydroxyethyl-sulfone monoacetate as a viscous oil. Hydrolysis studies indicated that the purity was at least 85%.
• esters of difihydroxyethyl-sulfone are prepared by reaction with the selected anhydride, to produce the propionate, butyrate, succinate, octanoate, chloroacetate, phenylacetate, phenylpropionate, benzoate, chlorobenzoate, or other alkyl, aryl, alkaryl or arylalkyl ester, particularly those containing up to twelve carbon atoms.
• the formate mono-ester is readily prepared from concentrated formic acid.
• the monoacetate can also be prepared from glacial acetic acid, preferably in the presence of an esterification catalyst, e.g., ptoluenesulfonic acid, and preferably also with removal of the water of reaction by 'azeotropic distillation.
• an esterification catalyst e.g., ptoluenesulfonic acid
• This compound can be isolated by dissolving in water to make up a concentrated solution and then chilling the resulting solution.
• EXAMPLE 4 770 g. (5.0 moles of di-B-hydroxyethyl-sulfone was melted (45 C.) in a 3-necked round bottom flask. 550 mls. (10.0 moles) of 96.6% H 50 was then added slowly, with cooling, so that temperature did not rise above 50 C. The reaction mass was then held at room temperature overnight.
• EXAMPLE 5 1.0 mole (256 g.) of dimethylol-N-hydroxyethyltriazone textile resin as a aqueous solution was mixed with 1.0 mole (256 g.) of sodium B-hydroxyethyl-;3'- sulfatoethyl sulfone as a 40% aqueous solution. The mixture was refluxed for about 2 hours. There was thus produced an aqueous solution of the reaction product of the resin and the sulfone. The thus produced reaction product can also be conducted at between about 80 and 190 C.
• resin mixtures were prepared in which the ratio of textile resin to sulfone were 2:1 and 1:2.
• the dimethylol-N-hydroxyethyltriazone textile resin and sulfone aqueous reaction products prepared according to the procedure of Example 1 were made up to an aqueous solution of the following composition: about 22% textile resin-sulfone reaction product (solid), 1% zinc nitrate, 6% polyethylene softener (Moropol 700), and 0.5% surfactant (Surfonic N-95).
• the resin mixture was applied to 80 x 80, 4.0 yds./lb. (in the greige) bleached and mercerized cotton printcloth by padding and then squeezing through nip rolls at lbs./ square inch pressure to provide a pick-up of about based on the weight of the dry fabric.
• the fabric was dried over hot cans and then cured by passing through a curing oven at about 175 C. for 1.5 minutes.
• the cured favric was passed into a 3% aqueous sodium hydroxide solution containing 0.5 of a non-ionic surfactant (Mercerol GV) and then through squeeze rolls to provide a pick-up of about 60%, based on the weight of the dry fabric.
• the fabric was rolled up into a smooth roll and maintained at room temperature for about 15 minutes.
• the fabric was then rinsed in 1% acetic acid, rinsed with water and dried.
• Table I The properties of the thus treated fabric are shown in Table I below.
• various textile resins can be combined with the sodium B-hydroxyethyl-H- sulfatoethyl sulfone, e.g., dimethylol-N-ethyltriazone, dimethylol-N-hydroxyethyltriazone and the corresponding dimethyl ether, dimethylol-cyclic ethylene urea, dimethylol-4,S-dihydroxy-cyclic ethylene urea, pentamethylol melamine, and urea-formaldehyde textile resins to provide novel cellulosic cross-linking agents and cross linked fabric.
• sodium B-hydroxyethyl-H- sulfatoethyl sulfone e.g., dimethylol-N-ethyltriazone, dimethylol-N-hydroxyethyltriazone and the corresponding dimethyl ether, dimethylol-cyclic ethylene urea, dimethylol-4,S-dihydroxy-cyclic
• Example 6 The procedure of Example 4 was followed employing resin-sulfone mixtures and the bases shown in Table H below. The heating step was omitted, thereby permitting the reaction between the resin and sulfone to occur primarily on the dry cans as the fabric was dried. The prop erties of the thus treated fabrics are shown in Table II.
• Resin A Mixture Percent EXAMPLE 8 Modlfied melamme resm (Aerotex 23 (sohds)' 5 Samples of bleached and mercerized 80 x 80, 4.00 yd./
• Triazone resin (Rhonite N-17) (solids) 2.5 Sodium fl-hydroxyethyl-fi-sulfatoethyl-sulfone 10
• Polyethylene softener (Moropol 700) 6
• Catalyst (zinc nitrate) 1
• Surfactant (Surfonic N-95) 0.5 Resin B Mixture:
• Triazone resin (Rhonite R-l) (solids) 5 Modified melamine resin (Aerotex 23) (solids) 2 Sodium B-hydroxyethyl-fi-sulfatoethyl-sulfone 10 Polyethylene softener (Moropol 700) 6 Catalyst (zinc nitrate) l Surfactant (Surfonic N-95) 0.5 Resin D Mixture:
• Triazone resin (Rhonite N-17) (solids) 7.5
• Example 7 The procedure of Example 4 was followed employing a resin mixture consisting of 4.5% (solids) of a modified melamine textile resin (Aerotex 23), 2.5% of a triazone textile resin (Rhonite N-17), 10% monoacetate of di-fihydroxyethyl-sulfone, 1% Zinc nitrate catalyst, 6% polyethylene softener (Moropol 700) and 0.5% surfactant (Surfonic N-95 Pick-up of the solution was substantially the same as in Example 4. The fabric was dried and cured for 1.5 minutes in a curing oven at 177 C. Samples identified as A were then tested for physical properties.
• a resin mixture consisting of 4.5% (solids) of a modified melamine textile resin (Aerotex 23), 2.5% of a triazone textile resin (Rhonite N-17), 10% monoacetate of di-fihydroxyethyl-sulfone, 1% Zinc nitrate catalyst, 6% polyethylene softener (Moropol
• aqueous sodium hydroxide containing 1% surfactant Mercerol GV
• the thus treated fabrics had the following properties:
• the fabric was passed through nip rolls set at p.s.i. to provide a pick-up of the solution of about of the weight of the dry fabric, dried on dry cans and then cured while smooth at 176 C. for 1.5 minutes in a curing oven. A portion of each of these samples was tested for physical properties and the remaining portion passed into 4% aqueous sodium hydroxide containing 0.5% of a surfactant (Mercerol GV) and then I through nip rolls to provide a pick-up of about 60%,
• the sample containing 10% sodium fl-hydroxyethyl-B'- sulfatoethyl-sulfone but no textile resin did not have flat drying properties.
• the samples containing only the regular textile resin had low levels of performance whereas the samples containing the same amount of textile resin plus 10% of the sulfone compound had markedly improved performance both before and after the treatment with base, while retaining about the same or greater residual strength.
• Percent Modified melamine resin blend (Aerotex A-44) (solids) 7.5 Sodium B-hydroxyethyl-p?'-sulfatoethyl-sulfone or Magnesium chloride type resin catalyst (Catalyst MX) 3 or 4.5 Polyethylene softener (Moropol 700) 6 Surfactant (Surfonic N-95) 0.33
• Percent Cyclic ethylene urea resin Permafresh LF (solids) 6 Monoacetate of di-fi-hydroxyethyl-sulfone 0 or 10 Zinc nitrate type resin catalyst (Catalyst X-4) 2 or 3 Polyethylene softener (Moropol 700) 6 Surfactant (Surfonic N-95) 0.33
• Percent Cyclic ethylene urea resin Permafresh LF (solids) 6 or 7.5 Sodium fl-hydroxyethyl-B'-sulfatoethyl-sulfone Zinc nitrate type catalyst (Catalyst X-4) 1.8 Polyethylene softener (Moropol 700) 6 Surfactant (Surfonic N-) 0.25
• the process which comprises the steps of (1) heating under textile resin curing conditions a dry, essentially unswollen cellulosic fabric whose anhydroglucose units are substantially unmodified and which is uniformly impregnated with an acid catalyst and a chemically reactive system selected from the group consisting of (a) a water soluble polymethylol aminoplast textile resin and a water soluble polyfunctional organic monoester represented by the formula HOCH CH S (o) CH -CH -OR wherein x is an integer from 1 to 2 and R is the residue of an organic carboxylic acid or an inorganic acid in alkali metal salt form and (b) the reaction product produced by refluxing said textile resin and said polyfunctional monoester at a temperature of from 80 C. to 190 C.
• a chemically reactive system selected from the group consisting of (a) a water soluble polymethylol aminoplast textile resin and a water soluble polyfunctional organic monoester represented by the formula HOCH CH S (o) CH -CH -OR wherein
• the textile resin is selected from the group consisting of dimethylol urea, dimethylol triazones, polymethylol melamines and dimethylol cyclic ethylene ureas.
• polymethylol aminoplast textile resin is selected from the group consisting of dimethylol urea, dimethylol triazones, polymethylol melamines and dimethylol cyclic ethyleen ureas and the strong base is an aqueous alkali-metal hydroxide of a concentration between about 2% and 16%.
• the textile resin is selected from the group consisting of dimethylol urea, dimethylol triazones, polymethylol melamines and dimethylol cyclic ethylene ureas.
• polymethylol aminoplast textile resin is selected from the group consisting of dimethylol urea, dimethylol triazones, polymethylol melamines and dimethylol cyclic ethylene ureas and the strong base is an aqueous alkali-metal hydroxide of a concentration between about .2 and 16%.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Paper (AREA)

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• 0
  • BE BE615318D patent/BE615318A/xx unknown
  • NL NL276161D patent/NL276161A/xx unknown
• 1962
  • 1962-03-15 GB GB10004/62A patent/GB997821A/en not_active Expired
  • 1962-03-15 FR FR891139A patent/FR1318939A/fr not_active Expired
  • 1962-03-15 GB GB4050/65A patent/GB997822A/en not_active Expired
  • 1962-03-17 ES ES275579A patent/ES275579A1/es not_active Expired
  • 1962-03-19 DK DK125062AA patent/DK109134C/da active
  • 1962-03-20 DE DE19621419427 patent/DE1419427A1/de active Pending
  • 1962-03-20 CH CH331362A patent/CH467898A/fr unknown
• 1966
  • 1966-09-28 US US582757A patent/US3418067A/en not_active Expired - Lifetime

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