US2741568A - Water insoluble polymeric quaternary ammonium carboxylate salts and the treatment of textiles therewith - Google Patents

Water insoluble polymeric quaternary ammonium carboxylate salts and the treatment of textiles therewith Download PDF

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US2741568A
US2741568A US26011951A US2741568A US 2741568 A US2741568 A US 2741568A US 26011951 A US26011951 A US 26011951A US 2741568 A US2741568 A US 2741568A
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quaternary ammonium
fabrics
textile
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Hayek Mason
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E I du Pont de Nemours and Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2418Coating or impregnation increases electrical conductivity or anti-static quality
    • Y10T442/2434Linear polyether group chain containing

Description

WATER INSOLUBLE POLYMERIC QUATERNARY AMMONIUM CARBOXYLATE SALTS AND THE TREATMENT F TEXTILES THEREWITH Mason Hayek, Wilmington, DeL, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 5, 1951, Serial No. 260,119

12 Claims. (31.117-1395 This invention relates to new polymeric anti-static agents and to textile materials treated therewith. More particularly it relates to polymeric compounds containing quaternary ammonium salts of long chain carboxylic acids.

Textile fibers and fabrics, particularly the newer synthetic hydrophobic materials, tend to develop a static electrical charge which is objectionable both during manufacture and during use of the textile. During manufacture, the static charge on the fiber or fabric interferes with its convenient handling in the various pieces of equipment for spinning, reeling, weaving and the like. Finished articles made of these materials may cling to the wearer and fail to drape properly.

Although certain surface treating agents have been shown to exert an anti-static effect on textiles of this sort, there have not been known heretofore any such agents which have a suitable degree of effectiveness coupled with durability and which are also resistant to laundering or dry cleaning.

It is an object of this invention to provide a new class of polymeric compounds which may be applied to textiles and which produce a durable anti-static efiect there on. A further object is to provide a process by which such compounds may be formed on the surface of the textile. Further objects will appear from the detailed description of this invention which follows. I

These objects are accomplished by the new anti-static agents of this invention, which are polymers of ethylenically-unsaturated monomeric compounds of which at least 1% contains a vinylidene radical,

in which is present their only non-aromatic carbon-tocarbon unsaturation, said vinylidene radical being attached directly to a carbon atom having a double bond and being attached mediately to a nitrogen-containing group from the class consisting of tertiary amino and quaternary ammonium groups, said nitrogen-containing groups existing in the polymer in the form of quaternary ammonium groups, the anion of a majority of which is the anion of a carboxylic acid containing an acyclic carbon chain of at least 8 carbon atoms.

A typical and preferred member of this class of compounds is a poly-beta-methacrylyloxethyldiethylmethylammonium salt, in which polymer the anion of a majority of the quaternary ammonium groups is the anion of a long chain carboxylic acid such as stearic acid. This product is conveniently prepared by first reacting betadiethylarninoethyl methacrylate with a methyl ester such as dimethylsulfate to form the quaternary ammonium derivative, which is then polymerized. This intermediate polymeric quaternary ammonium salt, e. g. the methylsulfate, is applied to the surface of the textile material, after which the treated surface is brought into contact with the long chain carboxylic acid or its salt in order to form the desired carboxylate salt of the polymer directly on the textile surface. Alternatively, the. inter- 2,741,568 Patented Apr. 10, 1956 mediate polymeric qaternary ammonium salt may be reacted with the long chain carboxylic acid or its salt to form the carboxylate salt prior to application to the textile.

The preparation and application of the new products of this invention are illustrated by the following exarnples, in which parts are by weight unless otherwise stated.

Example 1 The anti-static properties, i. e. the resistance to build up of static electricity, of the various treated fabrics is determined by the following test.

A small piece of fabric (approximately 4 x 5") is treated with the anti-static agent as described in the succeeding examples. The treated fabric is dried.

A strip 3 cm. wide is then cut off, and its electrical resistance at a controlled relative humidity of 25% is measured on a special apparatus which comprises two electrodes separated by a space of 1.25 cm. and having a potential difference of volts. The fabric is held in place between the electrodes so as to provide a conducting area 1.25 cm. long and 3 cm. wide. The reading gives the resistance of this standard area in ohms. .For

The rating of the untreated control in the non cellulosic, hydrophobic fibers herein discussed is usually nil.

Example 2 To a stirred mixture of 55.5 parts of beta-diethylaminoethyl methacrylate and 55 parts of water are added 38 parts of dimethyl sulfate over a period of 45 minutes, at 30-35 C. The solution is stirred for 30 additional minutes at 3035 C. and is then diluted with a solution of 10 parts of sodium acetate trihydrate in parts of water. The reaction mixture is heated to 50-55 C. and a solution of 0.4 part ammonium persulfate in 27 parts of water is added. The mixture is stirred for 20 minutes at 50-55" C. under a nitrogen atmosphere, during which time polymerization proceeds. At the end of this time, the greatly thickened solution is bottled. The viscosity continues to increase for several hours. After 24 hours from the beginning of the polymerization, a portion of the 30% solution is diluted to give a 1% aqueous solution and the dilute solution is padded onto fabrics of nylon, cellulose acetate, polyacrylonitrile and polyethylene terephthalate. The fabrics are heated for 3 minutes at l40-l60 C. The pick-up of the quaternary salt ranges from 0.25 to 0.5% by weight, based on the weight of the fabric. The treated fabrics are then scoured for 30 minutes at 70-75" C. in an aqueous bath containing about 0.5% of a tallow soap, to convert the quaternary ammonium compounds to their carboxylic acid salts. The fabrics are then rinsed and dried and tested for anti-static action by the procedure described in Example 1. All of the treated fabrics display very good to excellent anti-static properties.

To test the durability of these treatments to washing, the treated fabrics are scoured for an additional 2 hours in the same aqueous soap bath, rinsed, dried and tested as before. The fabrics show very good to excellent antistatic properties as before.

The, durab l y. of. he. reatmept q ry cl an n s termined by tumbling the treated fabrics for 2.5 hours at room temperature in jars containing pebbles and an excess of perchlorethylene. The samples are given three rinses andare then air dried. In each case, the anti-static rating after this treatment is equal or slightly superior to the initial rating.

When samples of the same fabrics are padded with a solution of the methylsulfate salt and thereafter scoured in the soap bath, but without the intermediate 3 minute heat treatment at 140-160 C., the same initial anti-static ratings are obtained. The durability to washing is only slightly impaired, the anti-static ratings being very good.

Example 3 A mixture of 100 parts of beta-diethylaminoethyl methacrylate, 76.6 parts of methyl iodide and 142 par ts of ether is allowed to stand overnight at room tempera.- ture, during Which time a white crystalline solid deposits. The solid quaternary ammonium salt is filtered, washed with etherand air dried. A solution of 70. parts of this monomeric salt and 0.75 part of alpha, alpha-azo-diisobutyronitrile in 70 parts of Water is warmed to 6582 C. and held at this temperature for'2.5 hours. An additional 15 parts of Water are added during the polymerization to keep the mass fluid. The resulting solution is cooled and contains 45% of the polymeric quaternary ammonium salt.

This solution is diluted with water to give a 1% solution, which is applied to test fabrics of nylon, cellulose acetate, polyacrylonitrile and polyethylene terephthalate by padding. After a heat treatment and a soap scour as in Example 2, the fabrics are rinsed, dried and tested for anti-static properties. Both initially and after an additional 2 hour soap scouring, the fabrics rated very good to excellent.

Example 4 To a stirred mixture of 27 parts of .beta-methacrylyloxyethyltrimethylammonium iodide and 54 parts of distilled Water at 42 C. and under a nitrogen atmosphere is added 0.1 part of alpha, alpha'-azo-diisobutyrouitrile. The temperature is raised to 64-76" C. and maintained in this range for 2 hours while polymerization takes place. The resulting polymer solution is diluted to a 1% solution, which is padded onto samples of nylon, polyacrylonitrile and polyethylene terephthalate fabrics. After heat treatment and scouring with soap as in Example 2, the anti-static properties of the treated fabrics are found to be fair to very good. After further scouring in aqueous soap solution for 2 hours, the anti-static ratings are fair to good.

Example 5 A mixture of 60 parts of beta-acrylyloxyethyldiethyl methylammonium iodide, 25 parts of Water and 0.5 part of alpha, alpha-azo-diisobutyronitrile is stirred for 30 minutes in a nitrogen atmosphere at'room temperature. The resulting polymer is diluted with water to give a 1% solution which is applied to test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate. The treated fabrics are heat treated and scoured with soap as in Example 2 to form the carboxylate salts. All of the samples have a good anti-static rating, both initially and after an additional 2 hour scouring.

Example 6 Equal amounts of vinyl acetate and of beta-methacrylyloxyethyltrimethylammonium methylsulfate are copolymerized in aqueous solution. When separate test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate are padded with a 1% aqueous solution of the copolymer, heated at 140160 C. for 3 minutes, scoured for 30 minutes at 7075 C. in an aqueous bath containing 0.5% of a tallow soap, rinsed and dried, the resulting fabrics show fair to very good anti-static properties.

4- Example A copolymer of the acetate and methiodide salts of beta-dimethylaminoethyl methacrylate is prepared as follows. To a stirred solution of 50 parts (0.27 mol) of beta-dimethylaminoethyl methacrylate in 132 parts of hexane, held under nitrogen at 65-75 C., is added 0.5 part of alpha, alpha'-azo-isobutyronitrile. As the polymerization proceeds, an additional 33 parts of hexane are added to keep the mass fluid. After no further increase in viscosity is apparent, about 40 minutes after the initial thickening, air is admitted to the reaction vessel and the charge is cooled to 25 C. The solution is agitated and there are added over a 5 minute period 18.5 parts (0.13 mol) of methyl iodide. The solid product is allowed to stand for several hours and is then mixed with 950 parts of water and heated on a steam bath to remove hexane. Finally 8.5 parts of glacial acetic acid are added, causing the solution to thin markedly. A portion of the resulting solution is diluted to a solids content of 1.8% and is applied to fabrics of nylon, polyacrylonitrile and polyethylene terephthalate. The treated fabrics are heat treated and soap scoured by the procedure described in Example 2. Their anti-static properties are fair to good initially, and after 2 hours additional scouring with soap solution fair.

Example 8 To a solution of 29.4 parts of poly-2-methyl-5-vinyl pyridine, which has polymerized spontaneously at room temperature, in parts of methanol and 44 parts of benzene are added 127.8 parts of methyl iodide. The mixture is refluxed for 7 hours. After cooling, the solid polymeric salt is recovered by filtration. When a 1% aqueous solution is applied to test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate, and the fabrics are heat treated, soap scoured, rinsed and dried as in Example 2, very good anti-static effects are produced. The fabrics display good dura bility to further scouring for 2 hours, the anti-static ratings then being good to very good.

Example 9 A copolymer of beta-methacrylyloxyethyldiethylmethylammonium iodide and 1-rnethyl-4-vinylpyridinium iodide is prepared by copolymerizing 20 and 10 parts of the respective monomers in 60 parts of distilled water with the aid of 0.1 part of alpha, alpha-azo-diisobutyronitrile. The polymerization is carried out over a 4.75 hour period under a nitrogen atmosphere at 5863 C. An aqueous solution of this copolymer containing 1% active ingredient is padded onto test fabrics of nylon, polyacrylonitrile and polyethylene terephthalate. The treated fabricsare heat treated, soap scoured, rinsed and dried as in Example 2. They display very good anti-static properties. The anti-static ratings after 2 hours additional scouring with aqueous soap solution are fair to good.

Example 10 A mixture of 20 parts of beta-diethylaminoethyl methacrylate and 6.7 parts of the methacrylate of a fatty alcohol mixture containing approximately 75% lauryl alcohol and 25% mixed C-14, C-16 and C-lS primary alcohol in 26.4 parts of benzene is polymerized with the aid of 0.1 part of alpha, alpha-azo-diisobutyronitrile. The polymerizationis effected under nitrogen at 6070 C. over a period of 4 hours. The tertiary amino groups in the copolymer are then quaternized by the addition of 12.6 parts of dimethyl sulfate over a period of 6 minutes at a maximum temperature of 40 C. During this period 88 parts of benzene are added to keep the mass fluid. At the end of the dimethyl sulfate addition, the polymer separates. Two hundred (200) parts of water are added and the benzene-water azeotrope is distilled until all of the benzene is removed. A portion of the resulting milky Example 11 A mixture of 87 parts of methacrylarnide with 176 parts of ethylene oxide is heated at 120 C. for 2 hours. A solution of parts of the resulting liquid condensation product and 20 parts of betaunethacrylyloxyethyldiethylmethylamrnonium iodide in 60 parts of water is polymerized at 6872 C. in the presence of 0.1 part of alpha, alphaazo-diisobutyronitrile. The polymerization requires 1 hour. The reaction product is diluted to give a 1% aqueous solution which is padded onto test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate. The treated fabrics are heat treated, soap scoured, rinsed and dried as in Example 2. They are then found to have very good to excellent anti-static properties, both initially and after 2 hours additional scouring with soap solution.

Example 12 A mixture of 20 parts of beta-diethylaminoethyl methacrylate, 10 parts of a methacrylamideethylene oxide condensation product (obtained by heating for 1 hour at 100 C. a mixture of 42 parts of methacrylamide and 247.5 parts of ethylene oxide), and 10 parts of vinyl acetate in 10 parts of methanol is polymerized with the aid of alpha, alpha-azo-diisobutyronitrile in a nitrogen atmosphere at 80 C. over a period of several hours. To this mixture are then added 21 parts of Water and 9.7 parts of dimethyl sulfate. Additional Water is added and the methyl alcohol is removed by distillation. A portion of the aqueous solution of the copolymer is diluted to give a 1% solution, which is padded onto separate fabric samples of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate. These fabrics are heated, scoured with soap solution, rinsed and dried according to the procedure of Example 2. The treated fabrics show fair to good anti-static properties. After 2 hours further scouring with soap solution the anti-static ratings are fair.

Example 13 A 1% aqueous solution of poly-betamethacrylyloxyethyldiethyhnethylammonium iodide prepared as in Example 3 is padded onto test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate and the treated fabrics are heated for 3 minutes at 140- 160 C. Each of the fabrics is then cut into three pieces and one piece of each is scoured for 30 minutes at 160 F. in a solution of 1 part lauric acid and 0.67 part of 30% sodium hydroxide in 219 parts of water. Another piece of each fabric is secured in a 0.5% solution of sodium stearate. The third piece of each fabric is scoured in 1 part behenic acid and 0.4 part or" 30% sodium hydroxide in 219 parts of water. The fabrics are rinsed and dried and tested for anti-static properties. All of the fabrics show fair to good anti-static ratings.

Example 14 A 1% aqueous solution of the polymeric methomethyl sulfate salt of beta-diethylaminoethyl methacrylate, prepared as described in Example 2, is padded onto a polyacrylonitrile fabric giving approximately 0.25% of the polymer on the fabric. The sample is held at 160 C. for 3 minutes and is then suspended in an agitated 1% aqueous solution of sodium polymethacrylate for 30 minutes at 70 C., to replace the methylsulfate anion of the quater nary ammonium salt with the polymethacrylate anion. After rinsing and drying, the treated fabric displays excellent anti-static properties.

aft- .6 8

. Example 15 An aqueous solution of 21.8 parts of poly -beta-meth- .acrylyloxyethyldiethylmethylammonium iodide, prepared as in Example. 3, is added gradually to a stirred solution of 15.3 parts of sodium stearate in water. The resulting paste is partially dried by filtration, giving a white, waxy solid consisting of 24% poly-beta-methacrylyloxyethyldiethylmethylammonium stearate in water. Test fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate'are padded with a 1% active ingredient solution of this polymer in isopropyl alcohol, giving 0.25 to 0.5% polymer on the fabrics. After drying, the treated fabrics show good to very good anthstatic properties, both initially and :after 2 hours scouring with aqueous soap solution.

A preferred class of polymers according to this invention consists of those which are derived from nitrogencontaining esters of acrylic or alkacrylic acids and which contain recurring monomeric units having the formula:

R20 0 O;r I R R3 R4 in which R1 is a member of the class consisting of hydrogen, methyl and ethyl radicals, R2 is a radical containing an acryclic carbon chain of at least 8 carbon atoms, R3,

R4 and R5 are aikyl radicals of from 1 to 4 carbon atoms and B is a saturated bivalent hydrocarbon radical of from a l to 4carbon atoms.

Another preferred class of polymers consists of those which are derived from vinylpyridine compounds and which contain recurring monomeric units having the formula;

OHFC

which radical is attached directly to a carbon atom having a double bond and is attached mediately to a tertiary amino or a quaternary ammonium group. The monomers in which the nitrogen is in the form of quaternary ammonium groups are obtained by the quaternization of the corresponding tertiary amino vinylidene compounds by reaction with a lower alkyl ester, the alkyl group of which preferably contains from 1 to 4 carbon atoms. If the polymerization is carried out using a tertiary amino compound, then quaternization with the lower alkyl ester is performed after the polymerization. Exemplary tertiary amine monomers which are usable in the preparation of the products of this invention include the dialkylaminoalkyl acrylates and methacrylates such as beta-diethylaminoethyl acrylate, beta-diethylaminoethyl methacrylate, and beta-dimethylaminoethyl methacrylate and the vinylpyridines such as 4-vii1y1pyridine, Z-methyl-S- 'vinylpyridine' and 2,4 diethyl-5-viriylpyridifie. Ex'emplary quaternary ammonium monomers which are usable 'in- "monium chloride, and the N-alkyl-vinylpyridinium"salts such as 1-ethyl-2-vinylpyridinium bromide, 1-butyl-2- vinyl-S-ethylpyridi nium iodide and pyridinium-p-toluene sulfonate.

It is somewhat preferable to quaternize the tertiary 1-methyl-4-vinylamine prior to polymerization rather than afterward, since it is easier to obtain complete quaternization and also to remove any excess of the quaternizing agent. It is also possible to form the antistatic agents by converting the *monomeric' quaternary ammonium saltsto the long chain carboxylates prior to polymerization but this is less con- 7 venient.

The intermediate polymeric quaternary ammonium salt is preferably water-soluble, since it is conveniently applied to the textile surface from aqueous solution. Its anion is chosen with this property in view. Suitable quaternizing agents for reaction with the tertiary amine either before or after polymerization are the lower alkyl esters of inorganic acids. Examples of such esters are alkyl halides such as methyl iodide, ethyl bromide and butylchloride; alkyl sulfates such as dimethyl sulfate; alkyl sulfonates such as ethyl p-toluene sulfonate; alkyl phosphates such as triethyl phosphate; and alkyl phosphites such as triethyl phosphite. Specificallyv preferred "as the intermediate is the methylsulfate salt of the quaternary ammonium compound which is obtained by reaction of the tertiary amine with dimethyl sulfate.

The'polymerization or copolyrnerization of the monomeric vinylidene compounds is carried out by any of the conventional methods, either with or without a solvent or in an emulsion. In most cases polymerization in aqueous solution is advantageous, though other hydroxylated solvents and particularly the monohydric alcohols containing from 1. to 4 carbon atoms, such as methanol, and tertbutanol, are usable. The time and temperature required for a substantial degree of polymerization to take place depend on the monomeric compounds and the catalyst employed, from one to twenty-four hours and from to 100 C. being customary conditions. The free radical type catalysts are employed. Suitable compound are the peroxygen compounds, e. g. ammonium persulfate, potassium persulfate, and benzoyl peroxide; azo compounds of the type described in U. S. 2,471,959," e. g. alpha, alphaazo-diisobutyronitrile; combinations of thiourea with hydrog'en peroxide, a bromate with a bisulfite, hydrogen peroxide'with atit'anous salt, etc. The amount of the catalyst used is generally small, e. g., 0.01-5 by weight of the polymerizable monomers.

The monomeric vinylidene compounds containing tertiary amino or quaternary amino groups are polymerized by themselves or are copolymerized with other ethylenically-unsaturated compounds such as vinyl acetate, vinyl chloride, vinylidene chloride, methyl'methacrylate, methyl vinyl ketone,'methyl acrylate, styrene, acrylonitrile, ethylone, and methacrylamide or its condensates with ethylene oxide. The properties of the resultingpolymer are "modified according tothe amount and nature of the additionalpolymerizable material. Copolymers in which as little as 1% of the monomeric units are vinylidene compounds containing nitrogen which exists in the copolymer as quaternary ammonium groups exhibit anti-static properties and are within the scope of this invention.

The intermediate polymeric quaternary animonium salt is reacted with a long chain carboxylic acid or a metal salt thereof to formthe anti-static agents of this invention. This longchain carboxylic acid which furnishes the anion V of the polymeric quaternary ammonium salt is any one or a mixture of saturated or unsaturated carboxylic acids containing an acyclic carbon chain of at least 8 'carbon proportion of the anions, it is desirable to use an excess of the long chain carboxylic acid or salt, preferably at least 25 to 50% above the theoretical amount. In this way a majority of the pre-existing anion radicals are displaced and. ordinarily the displacement is more than complete. A small proportion of the intermediate anion, e. g., chloride or methylsulfate, remains in the finished polymer. The amount of these anions is not large enough to affect the properties of the polymer significantly. When the anion exchange is carried out in the presence of water, some hydrolysis may take place, with the formation'of hydroxide anions attached to a small fraction of the quaternary ammonium groups.

It is most convenient to apply the intermediate polymeric quaternary ammonium salt to the textile fiber from a dilute aqueous solution containing 5% or less and preferably about 1% of the salt. The fibers are impregnated with this solution by any conventional method such as padding or exhausting. This application is ordinarily performed after dyeing although it may be done beforehand. The durability of the anti-static effect appears to be somewhat improved if the impregnated fibers are subjected to ashcrt heat treatment, for example, 3 minutes heatat to C., prior to formation of the long chain carboxylate salt. This heat treatment may be omitted however without substantial effect on the antistatic properties or their durability.

Conversion of the polymeric intermediate salts to the carboxylate salts is performed by scouring the treated fabrics with a solution of the carboxylic acid or a metal salt thereof. A convenient and preferred method is to employ an aqueous solution of an alkali metal salt, particularly the sodium salt, of the carboxylic acid. The use of a 0.25 to 0.5% soap solution at 105 to 160 F. for 5 to 30 minutes gives satisfactory results.

Instead of forming the final carboxylate salt on the textile material, it may be formed separately and applied to the textile in a one-step operation. When this is done,

the polymeric quaternary ammonium carboxylate is applied to the fabric from an organic solvent solution or from an aqueous emulsion. This is ordinarily somewhat less convenient than application of the Water-soluble intermediate salt followed by anion exchange.

The textile materials which are to be treated maybe in any desired form, e. g., that of fibers, filaments, yarns, sheets or fabrics. Application of the new compounds produces anti-static effects on any organic textile fibers, but the greatest utility is obtained with those fibers having high electrical resistivity and hence having the greatest tendency to accumulate a static charge, such as wool and the various synthetic hydrophobic fibers, e. g, nylon, polyacrylonitrile, polyethylene terephthalate,

The polymeric anti-static agents of this invention are high melting, waxy solids and are generally White in color. In addition to their anti static properties, they are also useful as textile softeners and as anti-soiling agents for W001.

What is claimed is:

l. A water-insoluble polymer of ethylenically-unsaturated monomers each of which contains a vinylidene radical in which is present its only non-aromatic carbon-tocarbon unsaturation, the vinylidene radical in at least 1% of said monomers being attached directly to a carbon atom having a double bond and being attached mediately to a nitrogen-containing group from the class consisting of tertiary amino and quaternary ammonium groups, said nitrogen-containing groups existing in the polymer in the form of quaternary ammonium groups, the anion of a majority of which is the anion of a carboxylic acid con taining an acyclic carbon chain of at least 8 carbon atoms, said polymer being characterized by becoming water-soluble When its long-chain carboxylate anions are replaced by methylsulfate radicals.

2. A water-insoluble poly-methacrylyloxyethyltrialkylammonium salt in which the alkyl radicals contain from 1 to 4 carbon atoms, the anion of a majority of the quater,

nary ammonium groups in the polymer being the anion of a fatty acid containing from 12 to 22 carbon atoms.

3. A water-insoluble poly-vinylpyridinium salt, the anion of a majority of the quaternary ammonium groups being the anion of a fatty acid containing from 12 to 22 carbon atoms.

4. A water-insoluble copolymer of ethylenically-unsaturated monomers each of which contains a vinylidene radical in which is present its only non-aromatic carbonto-carbon unsaturation, from 1 to 99% of the monomeric units being methacrylyloxyethyltrialkylammonium salts in which the alkyl radicals contain from 1 to 4 carbon atoms, the anion of a majority of the quaternary ammonium groups in the polymer being the anion of a fatty acid containing from 12 to 22 carbon atoms.

5. A water-insoluble poly-methacrylyloxyethyltrialkylammonium salt in which the alkyl radicals contain from 1 to 4 carbon atoms, the anion of a majority of the quaternary ammonium groups in the polymer being a polymethacrylate radical.

6. A method of imparting durable anti-static properties to textile fibers and fabrics which comprises applying to the surface of the textile a water-soluble polymer of ethylenically-unsaturated monomers, each of which contains a vinylidene radical in which is present its only non-aromatic carbon-to-carbon unsaturation, the vinylidene radical in at least 1% of said monomers being attached directly to a carbon atom having a double bond and being attached immediately to a nitrogen-containing group from the class consisting of tertiary amino and quaternary ammonium groups, said nitrogen-containing groups existing in the polymer in the form of quaternary ammonium groups, and thereafter contacting the surface of the textile with a member of the class consisting of caranswers boxylic acids containing an acyclic carbon chain of at least 8 carbon atoms and their alkali metal salts so as to form a water-insoluble salt.

7. A method of imparting durable anti-static properties to textile fibers and fabrics which comprises applying to the surface of the textile a water-soluble poly-betamethacrylyloxyethyltrialkylammonium salt in which the alkyl radicals contain from 1 to 4 carbon atoms, and thereafter contacting the surface of the textile with an alkali metal salt of a fatty acid containing from 12 to 22 carbon atoms so as to form a water-insoluble salt.

8. A method of imparting durable anti-static properties to textile fibers and fabrics which comprises applying to the surface of the textile water-soluble poly-betamethacrylyloxyethyldiethyhnethylammonium methylsulfate and thereafter contacting the surface of the textile with sodium stearate so as to form a water-insoluble salt.

9. A surface treated textile material having antistatic properties produced according to the process of claim 6.

10. A surface treated textile material having anti static properties produced according to the process of claim 7.

11. An organic textile material, the surface of which is impregnated with the polymer of claim 1, said textile being characterized by a reduced tendency toward the development of a static electrical charge.

12. An organic textile material, the surface of which is impregnated with the polymer of claim. 2, said textile be ing characterized by a reduced tendency toward development of a static electrical charge.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,763 Graves Nov. 29, 1938 2,390,235 Barnard Dec. 4, 1945 2,487,829 Richards Nov. 15, 1949 2,540,985 Jackson Feb. 6, 1951 2,563,506 Werntz Aug. 7, 1951 2,591,573 McBurney Apr. 1, 1952 2,595,225 Cofiman May 6, 1952 2,636,851

OTHER REFERENCES Rohm & Haas Co., Preliminary Data Sheet, Adsorption of Organic Acids by Amberlite IRA-400, Sept. 1949,

3 pgs.

Juda et a1. Apr. 28, 1953

Claims (1)

  1. 6. A METHOD OF IMPARTING DURABLE ANTI-STATIC PROPERTIES TO TEXTILE FIBERS AND FABRICS WHICH COMPRISES APPLYING TO THE SURFACE OF THE TEXTILE A WATER-SOLUBLE POLYMER OF ETHYLENICALLY-UNSATURATED MONOMERS, EACH OF WHICH CONTAINS A VINYLIDENE RADICAL IN WHICH IS PRESENT ITS ONLY NON-AROMATIC CARBON-TO-CARBON UNSATURATION, THE VINYLIDENE RADICAL IN AT LEAST 1% OF SAID MONOMERS BEING ATTACHED DIRECTLY TO A CARBON ATOM HAVING A DOUBLE BOND AND BEING ATTACHED IMMEDIATELY TO A NITROGEN-CONTAINING GROUP FROM THE CLASS CONSISTING OF TERTIARY AMINO AND QUATERNARY AMMONIM GROUPS, SAID NITROGEN-CONTAINING GROUPS EXISTING IN THE POLYMER IN THE FORM OF QUATERNARY AMMONIUM GROUPS, AND THEREAFTER CONTACTING THE SURFACE OF THE TEXTILE WITH A MEMBER OF THE CLASS CONSISTING OF CARBOXYLIC ACIDS CONTAINING AN ACYCLIC CARBON CHAIN OF AT LEAST 8 CARBON ATOMS AND THEIR ALKALI METAL SALTS SO AS TO FORM A WATER-INSOLUBLE SALT.
US2741568A 1951-12-05 1951-12-05 Water insoluble polymeric quaternary ammonium carboxylate salts and the treatment of textiles therewith Expired - Lifetime US2741568A (en)

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Cited By (22)

* Cited by examiner, † Cited by third party
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US2810713A (en) * 1955-03-21 1957-10-22 Rohm & Haas Quaternary ammonium compounds and methods of producing them
US2909445A (en) * 1954-01-25 1959-10-20 American Enka Corp Process for treating polyamide fibers
US2921869A (en) * 1956-05-22 1960-01-19 Du Pont Coated polymeric thermoplastic dielectric film
US2936249A (en) * 1954-07-01 1960-05-10 American Enka Corp Process for conferring antistatic properties to synthetic textile fibers
US2946758A (en) * 1955-10-07 1960-07-26 Ici Ltd Anion exchange resins from esters of acrylic acids with polyhydroxy substituted quaternary ammonium salts
US2958682A (en) * 1955-04-27 1960-11-01 American Cyanamid Co Method of preparing a polymeric betaine
US2964445A (en) * 1955-11-23 1960-12-13 American Cyanamid Co Method of sizing paper and resulting product
US2972536A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Anti-static quaternary salts of c-vinylpyridine polymers with haloacetone cyanohydrins
US2976184A (en) * 1955-11-28 1961-03-21 Du Pont Method of coating a polymeric thermoplastic dielectric film and article produced thereby
US3008851A (en) * 1955-03-21 1961-11-14 Rohm & Haas Novel quaternary ammonium compounds and methods of producing them
US3055749A (en) * 1959-04-16 1962-09-25 Exxon Research Engineering Co Additives for modifying the electrical properties of combustible organic liquids
US3226373A (en) * 1959-12-28 1965-12-28 Gulf Research Development Co Oil-soluble copolymers of acrylic acid esters and quaternary ammonium salts of acrylic acids
US3251794A (en) * 1962-07-13 1966-05-17 Celanese Corp Treating vehicle for polyester filamentary material and method of improving the properties of such material
US3251782A (en) * 1963-06-28 1966-05-17 Du Pont Process for inhibiting foam formation in aqueous talc dispersions
US3313734A (en) * 1963-05-01 1967-04-11 Procter & Gamble Detergent composition
US3361718A (en) * 1963-09-23 1968-01-02 Sanyo Chemical Industry Compan Antistatic agents for textile materials
US3864317A (en) * 1971-09-01 1975-02-04 Kao Corp Durable antistatic agent, hydrophobic fibers and fibrous structures having durable antistatic property and method of making same
JPS5080378A (en) * 1973-11-20 1975-06-30
US4180519A (en) * 1974-06-13 1979-12-25 Rhone-Poulenc Industries Process for obtaining and product acrylic monomers useful in the preparation of cationic flocculants
US4239876A (en) * 1978-11-09 1980-12-16 Rohm Gmbh Method of making polymerizable liquid mixtures
EP0153146A1 (en) * 1984-02-15 1985-08-28 Unilever N.V. Article suitable for wiping surfaces
US4614827A (en) * 1983-07-20 1986-09-30 Rohm Gmbh Method for isolating vinyl salt compounds from aqueous solutions

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US2138763A (en) * 1938-03-30 1938-11-29 Du Pont Amino alcohol esters of the alpha substituted acrylic acids
US2390235A (en) * 1945-04-23 1945-12-04 Pacific Mills Textile treatment
US2487829A (en) * 1946-01-25 1949-11-15 Du Pont Polyvinylpyridinium halides
US2591573A (en) * 1947-07-05 1952-04-01 Rohm & Haas Resinous insoluble reaction products of tertiary amines with haloalkylated vinyl aromatic hydrocarbon copolymers
US2636851A (en) * 1949-07-09 1953-04-28 Ionics Ion-exchange materials and method of making and using the same
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909445A (en) * 1954-01-25 1959-10-20 American Enka Corp Process for treating polyamide fibers
US2936249A (en) * 1954-07-01 1960-05-10 American Enka Corp Process for conferring antistatic properties to synthetic textile fibers
US2810713A (en) * 1955-03-21 1957-10-22 Rohm & Haas Quaternary ammonium compounds and methods of producing them
US3008851A (en) * 1955-03-21 1961-11-14 Rohm & Haas Novel quaternary ammonium compounds and methods of producing them
US2958682A (en) * 1955-04-27 1960-11-01 American Cyanamid Co Method of preparing a polymeric betaine
US2946758A (en) * 1955-10-07 1960-07-26 Ici Ltd Anion exchange resins from esters of acrylic acids with polyhydroxy substituted quaternary ammonium salts
US2964445A (en) * 1955-11-23 1960-12-13 American Cyanamid Co Method of sizing paper and resulting product
US2976184A (en) * 1955-11-28 1961-03-21 Du Pont Method of coating a polymeric thermoplastic dielectric film and article produced thereby
US2921869A (en) * 1956-05-22 1960-01-19 Du Pont Coated polymeric thermoplastic dielectric film
US2972536A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Anti-static quaternary salts of c-vinylpyridine polymers with haloacetone cyanohydrins
US3055749A (en) * 1959-04-16 1962-09-25 Exxon Research Engineering Co Additives for modifying the electrical properties of combustible organic liquids
US3226373A (en) * 1959-12-28 1965-12-28 Gulf Research Development Co Oil-soluble copolymers of acrylic acid esters and quaternary ammonium salts of acrylic acids
US3251794A (en) * 1962-07-13 1966-05-17 Celanese Corp Treating vehicle for polyester filamentary material and method of improving the properties of such material
US3313734A (en) * 1963-05-01 1967-04-11 Procter & Gamble Detergent composition
US3251782A (en) * 1963-06-28 1966-05-17 Du Pont Process for inhibiting foam formation in aqueous talc dispersions
US3361718A (en) * 1963-09-23 1968-01-02 Sanyo Chemical Industry Compan Antistatic agents for textile materials
US3864317A (en) * 1971-09-01 1975-02-04 Kao Corp Durable antistatic agent, hydrophobic fibers and fibrous structures having durable antistatic property and method of making same
JPS5080378A (en) * 1973-11-20 1975-06-30
JPS548394B2 (en) * 1973-11-20 1979-04-14
US4180519A (en) * 1974-06-13 1979-12-25 Rhone-Poulenc Industries Process for obtaining and product acrylic monomers useful in the preparation of cationic flocculants
US4239876A (en) * 1978-11-09 1980-12-16 Rohm Gmbh Method of making polymerizable liquid mixtures
US4614827A (en) * 1983-07-20 1986-09-30 Rohm Gmbh Method for isolating vinyl salt compounds from aqueous solutions
EP0153146A1 (en) * 1984-02-15 1985-08-28 Unilever N.V. Article suitable for wiping surfaces
WO1985003722A1 (en) * 1984-02-15 1985-08-29 Unilever Plc Article suitable for wiping surfaces
US4624890A (en) * 1984-02-15 1986-11-25 Lever Brothers Company Article suitable for wiping surfaces

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