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Publication numberUS2723256 A
Publication typeGrant
Publication dateNov 8, 1955
Filing dateFeb 27, 1953
Priority dateFeb 27, 1953
Publication numberUS 2723256 A, US 2723256A, US-A-2723256, US2723256 A, US2723256A
InventorsHayek Mason
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polymeric alkyl sulfate quaternary ammonium salts of the acrylyloxyethylamine type
US 2723256 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

POLYMERIC ALKYL SULFATE QUATERNARY AMMONIUM SALTS OF THE ACRYLYLOXYETH- YLAMINE TYPE Mason Hayek, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware Application February 27, 1953, Serial No. 339,453

10 Claims. (Cl. 26079.3)

No Drawing.

This invention relates to polymeric anti-static agents and to textile materials treated therewith. More particularly it relates to certain polymeric alkyl sulfate quaternary ammonium salts of the acrylyloxyethylamine type.

One disadvantage of the new textile fibers and fabrics prepared from the recently introduced synthetic hydrophobic. materials, and of all textile fibers treated. with conventional resin finishes, is that they tend to develop a staticv electrical charge. This charge is objectionable during themanufacture of the textile and in the finished garment. During manufacture, the static charge on the fiber or fabric prepared therefrom interferes with their convenient handling during treatment with various pieces.

of equipment, such. as in spinning, reeling, weaving and the like. Finished articles which are designed to drape like cotton or wool articles fail to do this properly, in thatthe fabrics often cling tothe wearer. Furthermore, suchitextiles tend to collect dust and lint, and the electric discharge itself is bothersome.

Many treating agents have been proposed to impart anti-static effects to textiles of this type. However, none of these proposed agents is entirely satisfactory, but all are deficient in effectiveness, either initial or sustained, and are also deficient with respect to resistance to washing and dry cleaning.

It is therefore an object of this invention to provide an effective anti-static agent which is highly resistant to washing and dry cleaning. Another object is the provision of a new clas of polymeric compound which-imparts a durable, anti-static effect to synthetic. textile fibers and fabrics. A still further object is-the treatment of textiles at any stage during the manufacture of textile. fabrics with such polymeric. compounds to produce the substantially permanent anti-static effect. Another object is a simple method for applying'suchpolymeric compounds to the textile material. Other objects will appear as the description of the invention proceeds.

These and other objects are accomplished by a new composition of matter comprising (1) a polymeric salt of the type:

where R i H, CH or Cal-I; R1 is a divalent hydrocarbon radical of 1 to-4 carbon atoms; R2, R3, and R4 arealiphatic hydrocarbon groups of lto 4 carbon atoms; X. is a hydrocarbon sulfate anion of 8. to 20 carbon atoms; and n is greater than and (2) copolymersof these-with less than 75% of another ethylenically unsatu' rated monomer.

In the preferred compositions R is methyl, R1 is ethylene (CHZ-CH2), at least two of R2, R3 and R4 are ethyl. The alkyl substituent on X. is preferably hexadecenyl, and the composition is a homopolymer.

Among the operable comonomers are vinyl ethers of quaternary ethanol amines, vinyl acetate, dodecyi methice acrylate; acrylonitrile, methacrylamide and itsethylene oxide condensates.

These compositions-may be conveniently prepared by a dimethyl'ordiethylisulfatequaternization of the appropriate acrylyloxyalkyldialkylamine in water followedby polymerization, and then reaction with a salt of an alkyl' sulfate having from 8 to 20 carbon atoms in the alkyl' group. This latter reaction may be carried out either ina reaction vessel or onthe textile itself.

Itis somewhat preferable to quaternize the tertiary amine prior to polymerization rather than afterward,

since it is easier to obtain complete quaternization and also to remove any excess of the quaterniziug agent.

The intermediate polymeric quaternary ammonium salt is preferably Water-soluble, since it i conveniently applied to the textile surface from aqueous solution. Its anionis chosen with this property in view.- Suitable quaternizing agents forreaction with thetertiaryamine either before or after polymerization arealkyl halides such as methyl iodide, ethylb'romideand' butyl-chloride; alkyl sulfates such as dimethyl sulfate; alkyl sulfonates' such as ethylp-toluenesulfonate; alkyl phosphatessuch as triethyl phosphate; and alkyl phosphites such as triethyl phosphite. Specifically preferred as the interme diate i the methylsulfate salt of the quaternary ammonium compound which is obtained by reaction of the tertiaryamine'with dimethyl sulfate.

The polymerization oncopolymerization of IhE'InODOF meric vinylidene compound is-carried-out by any of theconventional methods, either with orwithout 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'tert-butanol, areusable;

The amount of comonomer may vary from 0 to wt'. per cent, and in some cases to of the] material to be polymerized. The choice depends on'one'or more factors-such as economicsand the desired physical properties ofthe polymer. 'If a comonomeriis used, its amount generallyisin the range of 5% to 75%. The time and temperature required for a substantial, degree of polymerization to take place depend on. the monomeric compounds and the catalyst employed, from 1 to 24'hours and from 20- to C being'customary conditions; Thefreeradical type catalysts are employed. Suitable compounds are. the peroxygen compounds, e. g., ammonium persulfate, potassium persulfate, and benzoyl peroxide; azocompounds: of the: type describedtin U. S. 2,471,959, e. g., alpha,alpha-azo-diisobutyronitrile; corn: binationsofthiourea with hydrogen peroxide, a. bromate' with a bi-sulfite,.. hydr0gen. peroxide with a. titanous. salt; etc. The. amountof the catalyst used is generally small}. e. g., 0.01-5% by weightof thepolymerizable.monomers.

If desired; therateof polymerization carrbe decreased by use of a. small amount of a polymerization inhibitor suchas.p-tert-butylcatechol. Introduction of:a trace of a dithiocarbamatesalt such as sodium. dimethyldithiocarbamate will stop thepolymerization atanydesired stage.

The compositions ofthisa invention are white to creams colored-brittle;waxy-solids, relatively 'insoluble in water but som'ewhatmore:soluble-in common; polar organic.

atoms. The preferred acids are the fatty acids containing from 12 to 22 carbon atoms such as lauric, stearic, oleic, palmitic, myristic, arachidic and behenic acids. Polymeric carboxylic acids such as the polyacrylic and polymethacrylic acids are also suitable.

The formation of the long-chain carboxylate salts results from an anion exchange reaction in which the existing anion associated with the quaternary ammonium group is displaced by the carboxylate. In order to displace a high proportion of the anions, it is desirable to use an excess of the long-chain carboxylic acid or salt, preferably at least to 50% above the theoretical necessary amount. In this way a majority of pre-existing anion radicals are displaced and, ordinarily, the displacement is relatively complete, i. e. 90% or more.

The compositions of this invention are applied to textile materials by (1) padding from their solution in one of the solvents described above; (2) padding from a dilute aqueous solution (about 1% to 5%) of one of the abovedescribed short-chain alkyl sulfate intermediates, followed I by scouring with a long-chain alkyl sulfate; (3) exhaustion of a short-chain intermediate with the aid of a longchain alkyl sulfate, as described in copending application Serial No. 339,482, filed February 27, 1953. The temperature of the treating bath is not particularly critical, but best results are obtained at temperatures above 140 F. for a period of about 'minutes. The textile materials to which the present invention is applicable may be in the form of fibers, filaments, yarns, or fabrics. The compounds produce anti-static effects on any organic textile fiber which has a tendency to accumulate a static charge. Many of the natural fibers and some of the synthetic fibers do not exhibit undesirable static effects and, therefore, the invention is of primary importance to synthetic organic textile materials which have high electrical resistivity and, as a result, accumulate static charges. Among the fabrics which are benefited by treatment according to the present invention are nylon, acrylonitrile fibers, polyethylene terephthalate fibers and similar fibers and textiles. The salts of the present invention may also be applied to wool with advantageous results.

The invention is illustrated by the following examples, although these are given merely by Way of illustration and not limitation, since any polymeric salt or comonomer falling within the above generic definition may be used in the examples in equivalent amount.

The agents of this invention are applied to textiles and tested as described in Examples I and II of our copending application Serial No. 260,119, filed'December 5, 1951.

Example I To a stirred mixture of 55.5 parts of beta-methacrylyloxyethyldiethylamine and 55 parts of water is added 38 parts of dimethyl sulfate over a period of minutes, at

30 to 35 C. The solution is stirred for 30 additional minutes at 30 'to 35 C., and is then diluted with a solution of 10 parts of sodium acetate trihydrate in 125 parts of water. The reaction mixture is heated to to 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 to 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 140 C. to 160 C. The pick-up of the quaternary salt ranges from 0.25 to 0.5% by weight,

based on the weight of the fabric.

These fabrics are scoured with a commercial dodecyl sodium sulfate detergent in about 0.25% aqueous solution .to convert the finish to the corresponding dodecyl sulfate salt. These fabrics have considerably improved anti-static properties over untreated controls.

Example II The polymeric methiodide quaternary of Example III of Hayek Serial No. 260,119 is diluted to give a 1% solution. This is applied to fabrics composed of nylon, polyacrylonitrile and polyethylene terephthalate to give loadings of about 0.25% of the methiodide salt. These treated fabrics are then Washed with a 0.5% solution of the sodium salt of a technical dodecyl sulfate (average carbon chain length C12). The coating on the textiles is thus converted into the corresponding long-chain alkyl sulfate. The anti-static ratings are fair.

Example 111 The composition of Example I is also prepared in benzene, Stoddard solvent and without any solvent. In these cases, the reaction with dimethyl sulfate is followed by the addition of water and sodium bicarbonate, with which the product is agitated for 17 to 18 hours (Stoddard solvent and benzene runs) and 7 hours (without solvent) at 50 C., to destroy the excess dimethyl sulfate. During these heating periods polymerization takes place. In the benzene and Stoddard solvent runs thesolvent is decanted.

The products are viscous, pourable pastes to rubber-like masses difficultly soluble in Water. They are evaluated by diluting to 1% active ingredient with water and applying, scouring with a 20-carbon alkyl sodium sulfate and testing as described in Example I. The anti-static rating of each of the four fabrics is improved, and the effect is durable to washing in each case.

Example IV A mixture of 15 parts of beta-methacrylyloxyethyldiethylamine and 15 parts of beta-vinyloxydimethylamine is made in 25 parts of benzene, containing 0.05 part of the catalyst alpha,alpha-azo-diisobutyronitrile. This mixture is stirred under nitrogen at to 83 C., for 2.3 hours, during which time 0.2 part additional catalyst is added.

Then 25.2 parts of dimethyl sulfate is added over 0.5 hour at 25 to 54 C. with stirring. The quaternized polymer separates. Water (200 parts) is added and the benzene is removed by azeotropic distillation.

A 2.0% active ingredient solution in Water is padded onto fabrics of nylon, polyacrylonitrile, polyethylene terephthalate and cellulose acetate at 0.5% loadings. The treated fabrics are scoured with a 0.25 solution of the sodium salt of a technical hexadecenyl alkyl sulfate, and found to have markedly improved anti-static properties when tested as described above. The anti-static eflect is very durable to soap scouring.

Example V Example I is repeated using a :25 copolymer of betamethacrylyloxyethyltrimethyl ammonium methylsulfate with vinyl acetate as the polymer. Markedly improved anti-static properties are obtained. The elfect is durable to washing.

Example VI A copolymer of beta-methacrylyloxyethyldiethylamine (20 parts) with 6.7 parts of the methacrylate of technical lauryl acohol is made by mixing them in the absence of air in 25 parts of benzene containing 0.1 part of alpha,alpha-azo-diisobutyronitrile and heating 4 hours at 60 to 70 C. Then 12.6 parts of dimethyl sulfate is added with stirring over 6 minutes. An additional parts of benzene is also added during this period to keep the reaction mass fluid enough to stir. The benzene is removed by azeotropic distillation with Water.

As a 1% active ingredient solution in Water this product is padded onto fabrics of cellulose acetate, nylon, polyacrylonitrile and polyethylene terephthalate. When the fabric are secured with a dilute aqueous solution of sodium hexadecenyl sulfate, a durable anti-static effect of satisfactory quality is produced.

Example VII A 75 :25 copolymer of beta-methacrylyloxyethyldiethylamine and vinyl acetate is prepared by the procedure of Example IV, except that the benzene is omitted until the quaternization step. Application of the product and conversion to the dodecyl sulfate salt gives satisfactory results as in Example VI.

Example VIII A 50:50 copolymer is made of the methiodide of betamethacrylyloxyethyldiethylamine (20 parts) with 20 parts of 4-vinyl-pyridine, using the procedure of Example VII. About 75 parts of ethanol is added to maintain a stirrable reaction mass.

Then 21.6 parts of dimethyl sulfate is added over 12 minutes at 26 to 34 0., together with 100 parts of water, to quaternize the vinyl-pyridine portion.

The polymer is then converted to the dodecyl sulfate salt by addition of a molar equivalent of sodium dodecyl sulfate with agitation.

Example IX A solution of 12.5 parts of the polymeric methylsulfate salt of Example I in 129 parts of water is added dropwise at room temperature to a stirred solution of 11.6 parts of octanol sodium sulfate in 150 parts of water. The white waxy solid which separates is removed, washed several times with water and dried under vacuum. The resultant poly-beta-methacrylyloxyethyldiethylmethyl ammonium octyl sulfate is a white amorphous solid containing 8.88% S. (theory 7.82). When a 2.0% alcoholic solution of the product is padded onto nylon and polyacrylonitrile fabrics, good anti-static properties, which are durable to washing, are obtained.

Example X Poly beta methacrylyloxyethyldiethylmethyl ammonium dodecyl sulfate is prepared by the method of Example IX, using 14.4 parts of dodecyl sodium sulfate. The white solid product contains 7.38% S. (theory 6.88). The corresponding solid products are obtained when polybeta-acrylyloxyethyldiethylmethyl ammonium methyl sulfate and poly-beta-ethacrylyloxyethyldiethylmethyl ammonium methyl sulfate are used as starting material.

Nylon and polyacrylonitrile fabrics treated with these products, according to Example 1X, show marked antistatic properties which are durable to washing.

Example XI Example 1X when repeated, using 17.2 parts of n-hexadecyl sodium sulfate in 450 parts of water, yields the corresponding polymeric ammonium hexadecyl sulfate salt, which contains 5.97% S. (theory 6.15). This white salt shows marked anti-static properties and durability to washing when applied to fabrics as described in Example IX.

Example XII Poly beta methacrylyloxyethyltrimethyl ammonium octyl sulfate is prepared by the procedure of Example IX, using 11.3 parts of the corresponding polymeric methyl sulfate salt in 126 parts of water. The white solid contains 8.99% S. (theory 8.40). When applied to nylon and polyacrylonitrile from a 2% alcoholic solution, it gives good anti-static properties and durability to washmg.

6 Example XIII Poly beta methacrylyloxyethyltrimethyl ammonium hexadecenyl sulfate is prepared by the procedure of Example XII, using 14.4 parts of hexadecenyl sodium sulfate. The cream-colored product contains 7.52% S. (theory 7.33) and shows pronounced anti-static properties and good durability on fabrics.

The present invention offers the advantage that the compositions herein described produce a durable antistatic effect on textile materials which is durable to many washings with soap and synthetic detergents. Another advantage is that by the selection of the proper anion, various properties may be imparted to the textile treated with the composition containing it. Another advantage is that the products of the present invention may be applied to the textile materials together with other resinous materials normally used for crease-resistance, dimensional stability and other purposes.

It will be apparent that many widely different embodiments of this invention may be made without departing from the spirit and scope thereof, and therefore it is not intended to be limited except as indicated in the appended claims.

I claim:

1. As new anti-static agents for synthetic fibers, polymeric salts having at least 10 groups per molecule of the in which R is selected from the group consisting of hydrogen, methyl and ethyl; R1 is a divalent hydrocarbon radical having from 1 to 4 carbon atoms; R2, R3 and R4 are monovalent aliphatic hydrocarbon groups having from 1 to 4 carbon atoms and X is a hydrocarbon sulfate anion having from 8 to 20 carbon atoms.

2. The composition of claim 1 in which the polymer is a copolymer with less than of another ethylenically unsaturated monomer.

3. The composition of claim 1 in which R is methyl; R1 is an ethylene group; at least two of R2, R3 and R4 are ethyl; and X is hexadecenyl sulfate.

4. The composition of claim 1 in which the polymer is one of beta-methacrylyloxyethyldiethylmethyl ammonium hexadecenyl sulfate.

5. A textile material having a surface film of the composition of claim 1.

6. The composition of claim 3 in which the polymer is a homopolymer.

7. The composition of claim 3 in which the polymer is a homopolymer of the reaction product of sodium hexadecenyl sulfate and beta-methacrylyloxyethyldiethylmethyl ammonium methylsulfate.

8. A textile material having a surface film of the composition of claim 3.

9. A textile material having a surface film of the composition of claim 7.

10. Poly beta-methacrylyloxyethyldiethylmethyl ammonium hexadecenyl sulfate.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,763 Graves Nov. 29, 1938

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2138763 *Mar 30, 1938Nov 29, 1938Du PontAmino alcohol esters of the alpha substituted acrylic acids
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3026250 *Sep 10, 1957Mar 20, 1962Du PontAerosol hair-treating composition
US3213053 *Feb 23, 1962Oct 19, 1965Du PontAntistatic composition and treatment of synthetic linear polymer texiles therewith
US3239496 *Sep 24, 1962Mar 8, 1966Nalco Chemical CoMethod for producing polymeric salts of aminoalkylacrylates
US3313734 *May 1, 1963Apr 11, 1967Procter & GambleDetergent composition
US3549360 *Sep 29, 1966Dec 22, 1970Rowland Products IncFilm for xerographic production of transparencies and process of making same
US3948866 *Feb 18, 1971Apr 6, 1976Rohm GmbhPolymerization with the aid of macromolecule having both a monomer soluble portion and suspension soluble portion
US4486554 *Aug 19, 1983Dec 4, 1984The Dow Chemical CompanyPreparation of anionic and cationic polymers from 2-oxazolines
US6251276Dec 30, 1999Jun 26, 2001Terumo Kabushiki KaishaLeukocyte eliminating filter and method for manufacturing the same
EP1018346A2 *Dec 29, 1999Jul 12, 2000Terumo Kabushiki KaishaLeucocyte filter and method for manufacturing same
EP1018346A3 *Dec 29, 1999Nov 20, 2002Terumo Kabushiki KaishaLeucocyte filter and method for manufacturing same
U.S. Classification526/287, 526/307, 524/239, 526/923, 260/DIG.180, 526/312, 526/225, 526/292.2, 525/353
International ClassificationD06M15/285
Cooperative ClassificationY10S260/18, Y10S526/923, D06M15/285
European ClassificationD06M15/285