US3047426A

US3047426A - Process for treating a "nitrile alloy" article with a polyphenolic antistatic agent and product obtained thereby

Info

Publication number: US3047426A
Application number: US751656A
Authority: US
Inventors: Stanley A Murdock; Allan R Wirth
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1958-07-29
Filing date: 1958-07-29
Publication date: 1962-07-31
Anticipated expiration: 1979-07-31

Description

July 31, 1962 s. A. MURDOCK ET AL 3,047,426

PROCESS FOR TREATING A "NITRILE ALLOY" ARTICLE WITH A POLYPHENOLIC ANTISTATIC AGENT AND PRODUCT OBTAINED THEREBY Filed July 29, 1958 IN V EN TORS 5/00 /eg ,9. Murdock H TTORNEYS This invention lies primarily in the synthetic textile fiber field and contributes particularly to the art of beneficially treating certain varieties of such manufactures, as well as related shaped articles, to render them nonsusceptive, or at least substantially less propense, to accumulate charges of static electricity when they are in a dry state or condition. More particularly, the present invention has reference to the destaticization of certain of the nitrile alloy types of acrylonitrile polymer fibers and the like and related shaped articles and structures.

Amongst the achievements that crown the progress of the man-made artificial silk and synthetic fiber industry has been the development and attainment of certain of the so-called nitrile alloy varieties of synthetic textile fibers. Such synthetic fibers, as is known and pursuant to the indicated generic description therefor, are based largely and essentially on fiber-forming acrylonitrile polymers, especially those that contain in the polymer molecule at least about 80 percent by weight of acrylonitrile, advantageously polyacrylonitrile, that have been beneficially alloyed or blended with various ameliorative additaments, adjuvants or components that, generally, are polymeric in nature and which are intimately and permanently associated or coupled with the acrylonitrile polymer substrate by either physical or chemical means, or both. Predominantly desirable and advantageous members of the nitrile alloy class of synthetic fibers and the like are those, hereinafter more fully delineated, that are comprised of acrylonitrile polymer substrates and which contain minor integrant proportions of either, or both, various N-vinyl lactam polymers and copolymers or derivatives thereof or various N-vinyl-Z-oxazolidinone polymers and copolymers or derivatives thereof.

Such nitrile alloys, without compromise of the outstanding physical and other properties and characteristics as textile fiber materials and the like that are inherently obtainable in and with acrylonitrile polymers, are most advantageously bestowed with many desirable and peculiar additional features and qualities that are quite foreign to conventional acrylonitrile polymer (or acrylic) fibers. Most noteworthy and remarkable of their repletion, especially in view of their acrylonitrile polymer derivation and extraction, is the most proficuous and felicific capability of the referred-to nitrile alloy fibers to be highly receptive of and excellently dyeable with any of a wide variety of dyestuffs. For example, by conventional procedures and without resort to specialized methods or extraordinary techniques, the described nitrile alloy fibers may be easily and satisfactorily dyed with most acid, vat, acetate, direct, naphthol, sulfur and premetalized dyestuffs.

In common with other synthetic, essentially hydrophobic, polymeric textile fibers and the like articles, however, the above-mentioned types of nitrile alloy fibers, when in the dry state, tend to accumulate charges of static electricity upon being handled. This, of course, and as can be readily appreciated, engenders various difficulties of the widely recognized variety in their handling and use, both in their processing in and through various textile and the like operations and in connection with their application as finished textile articles (including filaments, fibers, yarns, threads, cords and the ts tat ice 3,fi47,42fi ?atented July El, 1962 like and cloth and fabric constructed therefrom) as Well as in other varieties of shaped articles and structures. Such characteristics tend to lessen the otherwise general attractiveness of the nitrile alloy fibers and other articles. For example, besides the difficulty in handling during various manufacturing operations and use applications, many individuals may object to the delitescent electrical shocks that they may be subject to or the sparks that may be discharged when they serve as the effective grounding means for articles comprised of nitrile alloys when there is a considerable accumulation of electrical charges on the articles. Furthermore, electrostatically charged articles of any synthetic polymer, including the nitrile alloys, display great tendencies to collect dust and dirt and to have undesirably high degrees of soil retentivity. As is apparent, such behavior limits their adaptability for being utilized in a completely satisfactory manner for many apparel, upholstery, home furnishing, decorative, and other uses.

It would be advantageous, therefore, to provide an effective and eificient means for destaticizing synthetic textile fibers and the like and related articles comprised of the indicated varieties of nitrile alloys.

Pursuant to the accomplishment of this and related desiderations, it is the primary object of the present invention to advance the art and technology of synthetic textile fibers by providing an improved method for destaticizing and benefitting the indicated varieties of nitrile alloy fibers and the like and related shaped articles as well as the destaticized products resulting from practice of the method.

To this end, nitrile alloy fibers and other shaped articles that are comprised of acrylonitrile polymer substrates, and especially those which contain minor proportions of either, or both, N-vinyl lactam polymers and copolymers or derivatives thereof or N-vinyl-2-oxazolidinone polymers and copolymers or derivatives thereof, may advantageously and most effectively be destaticized by finishing them with certain varieties of polyphenolic polymers or condensation products which contain in their structure either polyethylene glycol or sulfonate groups or both and in which there are available a plurality of free phenolic hydroxyl substituents, as hereinafter more fully described. The antistatic agents that are employed in the practice of the present invention have the ability to complex with the nitrile alloy base or substrate, such as a filamentary article, over which they are applied by both physical and chemical means so as to become attached to the substrate in a very durable and difficult-to-remove manner. As a consequence of their remarkable substantivity, the antistatic agents used in the practice of the present invention secure an efiicient and literally permanent destaticizing effect on the nitrile alloy articles with which they are combined. in addition to destaticizing the fiber, the antistatic agents used in the practice of the invention tend to increase the washfastness of the treated article when the application has been made subsequent to dyeing. Conversely, regardless of when the application is made with respect to coloration of the nitrile alloy article, the antistatic agents improve its resistance to becoming stained with many dyestuffs and coloring agents. This may be highly advantageous when it is desired for the nitrile alloy article to remain in a naturally uncolored or white condition. Application of the antistatic agents of the present invention exerts no deleterious influence or other interfering effect upon the general utility and properties of the treated fiber. A destaticized nitrile alloy filamentous article in accordance with the present invention is illustrated in the sole FIG- URE of the hereto attached drawing.

Without being limited to or by the specific embodiments and modes of operation set forth, the invention is illustrated in and by the following didactic examples, wherein, unless otherwise indicated, all parts and percentages are to be taken on a weight basis.

EXAMPLE A A phenol-formaldehyde-novolak type of condensation product of the soluble, low molecular weight variety was prepared and subsequently esterified with about 1.8 moles of ethylene oxide added per unit of phenol in the condensation product. The novolak product that was esterified was obtained by refluxing about 898 grams of the common, trifunctional phenol with about 464 grams of a 37 percent aqueous solution of formaldehyde (to provide about 0.6 moles of HCHO per mole of C H OH) in the presence of about 4.5 grams (10.3 ml. of 12 N) hydrochloric acid. The preparation was accomplished in the conventional manner. After phase separation, the resulting resinous condensation product was removed, washed free of chloride with water, and devolatilized by heating it to a temperature of about 130 C. under an absolute pressure of about 2 millimeters of mercury. About 729 grams of novolak product was thereby obtained, having a molecular weight of about 322 (as determined by cryoscopic methods) in which the mole ratio of phenol to formaldehyde was about 1:05, respectively. The product contained an average of about 4 phenolic units per molecule.

About 580 grams of the resulting novolak product was dissolved in 290 grams of dioxane. In this solution there was incorporated about 1.74 grams of sodium hydroxide (obtained by addition of about 3.5 grams of a 50 percent aqueous solution of NaOH). The ingredients were charged into an Aminco rocking-type reactor wherein they were heated until a temperature of about 130 C. was attained. At this point, ethylene oxide was admitted under pressure until a total of about 608 grams (13.8 moles) was charged over a 20 minute period. This quantity of ethylene oxide constituted about 2.5 moles of alkylene oxide per phenolic OH in the novolak resin, Upon addition of the ethylene oxide, a rapid exothermic reaction ensued. This elevated the temperature of the reaction mass to about 200 C. Within about 30 minutes after the addition of the alkylene oxide, the reaction mass returned to a temperature of about 130 C., whereat it was synthermally maintained for an additional two hour period. The etherified novolak product was then recovered from the reaction mass and, upon devolatilization, was found to have a weight of about 1018 grams. This corresponded to a weight gain on the modified novolak resin of about 438 grams and indicated that an average of about 1.8 moles of ethylene oxide had actually been added on per phenolic OH of the starting novolak. The resulting composition, upon the basis of reasonable information and belief, was presumed to have a general structure corresponding to the following formula:

(C2H4O)7..2 Ion CH2 l\ CH2 on About 20 grams of the etherified novolak was dissolved in about 80 grams of acetone to form a cloudy solution. Upon the addition of 100 grams of water, a clear, light yellow solution was obtained. The resulting solution contained about percent of the dissolved, solid, novolakethylene oxide reaction product or adduct. About 100 grams of the resulting 10 percent etherified novolak solution was diluted with an additional 100 grams of a mixture of about equal proportions by volume of acetone and water in order to form an applicating solution of the antistatic agent for a nitrile alloy fiber.

A sample of about 17 grams of a poly-N-vinyl-2-pyrrolidone-impregnated polyacrylonitrile nitrile alloy fiber 4% was immersed in the applicating solution of the etherified novolak antistatic agent for about 30 seconds at room temperature. After this, it was removed and the excess solution squeezed out. About 9 percent of the antistatic agent, based on the weight of the fiber, was thus picked-up on the fiber structure. The treated fiber was then dried at about C. to form the destaticized article.

The nitrile alloy fiber sample that was treated had been prepared by impregnating filamentary structures that were in aquagel condition after having been salt-spun and wet-stretched in and with an aqueous solution of poly-N- vinyl-2-pyrrolidone that contained about 3 percent of the dissolved vinyl lactam polymer. The polyacrylonitrile aquagel fiber that was so-employed had been obtained by extruding a spinning solution of fiber-forming polyacrylonitrile comprised of about 10 parts of the polymer dissolved in 90 parts of a 60 percent aqueous solution of Zinc chloride through a spinnerette having 750 individual 6 mil diameter orifices into an aqueous coagulating bath that contained about 42 percent of dissolved zinc chloride to form a multiple filament tow. After being spun, the tow bundle of coagulated polyacrylonitrile aquagel fiber was washed substantially free from salt from the coagulating bath. It was then wet-stretched for orientation to a total stretched length that was about 12 times its original extruded length. The aquagel fiber was then passed through the mentioned aqueous impregnating bath of the dissolved polyvinylpyrrolidone adjuvant so as to become impregnated with about 8 percent, based on the dry weight of the resulting nitrile alloy fiber, of the poly-N-vinyl-Z-pyrrolidone. Following the impregnation, the aquagel fiber was irreversibly dried at C. to destroy the Water hydrated structure and convert it to a finished fiber form. The finally obtained, three denier, nitrile alloy fiber product had a tenacity of about 4 grams per denier, an elongation of about 30 percent and a wet yield strength of about 0.8 gram per denier. After application of the etherified novolak antistatic agent in the above-indicated manner, the physical properties of the fiber remained substantially unchanged. Likewise, other of its characteristics, including its hand (or feel to the touch) and general visual appearance were unaltered.

Following application of the antistatic agent, a portion of the treated fiber sample was scoured for about one hour at the boil using 0.5 percent detergent on the weight of the goods contained in a bath having a 30:1 water volume to fiber weight ratio, respectively. The detergent that was employed was 'Igepal CA-630 (an alkylphenoxypolyoxy alkylene glycol, non-ionic detergent obtained from General Aniline and Film Corporation).

The antistatic properties of the destaticized and scoured nitrile alloy fiber were then determined by measuring the electrical conductance of the fiber product at various humidities. As will be appreciated by those skilled in the art, the basis for such a test is that all fibers have a tendency to generate static electricity upon being handled in the dry state. Only those that are possessed of sufficient electrical conductance to dissipate the charge as quickly as it forms are not hampered by the bothersome effects of static electricity. Thus, a measure of the electrical conductance of a fiber is a good indication of its ability to dissipate static electricity. The conductivity of the fiber sample that was tested, along with the conductivities of various other samples determined for purposes of comparison, was found by measuring its electrical resistance. Resistance, of course, is the reciprocal quantity of conductivity. In order to permit various fiber samples to be compared on a common basis, the conductivities of the samples tested were actually measured as volume resistivities according to the following formula:

Volume resistivity (Resistance) (Cross-sectional area) U YAA on a dry weight basis).

The units of volume resistivity are ohm-c1n. /cm. The actual resistivity of each sample was determined after the sample being tested was conditioned for 72 hours at the particular temperature and relative humidity conditions involved by tautly connecting a web-like sample of the yarn between two electrodes, each of which were 9 cms. long, spaced parallel 13.5 ems. apart, and across which three was applied a 900 volt direct current potential. For purposes of comparison, the volume resistivities of cotton, wool, the undestaticized nitrile alloy fiber, and an ordinary unmodified polyacrylonitrile fiber (obtained in the same general way as the nitrile alloy fiber but without having the poly-N-vinyl-Z-pyrrolidone incorporated therein) were also tested in the indicated manner with the destaticized fiber sample that had been prepared in accordance with the present invention. The results are set forth in the following tabulation which indicates the volume resistivity obtained at various relative humidities (RH) at 24 C. of each of the samples tested.

TABLE I Volume Resistivity of Various Fiber Samples Compared to Nitrile Alloy Fibers Destaticized With Ethylene Oxide Etherified Novolak Antistatic Agent As is apparent from the foregoing, the destaticized fiber sample, even after being severely scoured, had electrical conductance properties much superior to the nitrile alloy fiber that had not been treated or to ordinary unmodified polyacrylonitrile and even to wool. Its static properties were only slightly poorer than cotton. Thus, a very practical and significant increase in electrical conductivity and resulting decrease in propensity to accumulate static electricity Was obtained in the treated nitrile alloy fiber.

When the destaticizing agent was attempted to be ap plied to the ordinary polyacrylonitrile fiber, it was found to have very poor adherence thereon and very little substantivity thereto. This, of course, precluded the realization of satisfactory results in such operation.

EXAMPLE B Following the procedure of Example A, about 8 percent of the same antistatic agent was padded onto the same nitrile alloy fiber from a 5 percent applicating solution of the antisatic agent that had been prepared using the half-acetone, half-water diluent for the initially obtained percent solution of the etherified novolak adduct that was described in the first example. After the padding, the fiber sample was dried at 60 C. for about an hour. It was then constructed into a knit cloth which was divided into 3 separate portions (of about 5 grams each Each of the portions were subjected to various washing and scouring treatments, after which the electrical conductances of each of the samples was measured in the above-indicated manner and compared to wool, cotton and an undestaticized nitrile alloy fiber sample. The first portion of the destaticized sample was scoured for minutes at 60 C. and a 1 percent aqueous solution of Tergitol NPX (an alkylphenylpolyethylene glycol ether, non-ionic detergent obtained from Union Carbide Chemical Company). The second sample was subjected to a single wash test which consisted of placing the sample into a one quart stainless steel vessel that contained about 100 one-quarter inch steel balls and TABLE II Volume Resistivity of Various Fiber Samples Compared to Several Washed and Seoul-ed Samples of Destaticized Nitrile Alloy" Fibers Volume resistivity, ohm-cmfi/cm. Sample 47 percent 66 percent RH RH Secured portion of destatieized Nitrile Alloy yarn 8. 3X10 9 3. 6X10 9 Single wash tested portion of dest-aticized Nitrile Alloy yarn 1.7)(10 W 5. 7X10 9 Five times washed tested portion of destaticized Nitrile Alloy yarn 2. 9X10 8. 0X10 9 Undestaticized Nitrile Alloy yarn 2. 7X10 13 1. 2X10 12 2. 7X10 5 5. 4X10 0 2X10 3.3)(10 EXAMPLE C Results similar .to those in the foregoing examples may be obtained when the antistatic agent that is employed is of the following structure:

wherein n is a whole integer having an average value of at least 2, preferably between 2 and 8; and at least about A of the R substituents are hydrogen with the requirement that at least three substituent hydroxyl groups are present in each molecule and the remainder of the R substituents are polyethylene oxide groups containing an average of about 2 to 20, advantageously 2 to 10, ethylene oxide units per etherified substituent. As is apparent, and as will be appreciated by those who are skilled in the art, the exact location of the phenyl alkoxy groups relative to the alkylenic bridges are not necessarily in the same positions on each of the rings, but may be either orthoor para-relative to one another as may randomly occur in the preparation of the novolak. Likewise, as is indicated in the foregoing, at least three hydroxyl substituents must be contained in each molecule of the compound so that at least a portion of the phenolic hydroxyl in the novolak remains free and unsubstituted with ethylene glycol groups. This ensures that the antistatic agent will have the desired complexing ability with and substantivity for the nitrile alloy article upon which it is applied.

EXAMPLE D Results similar to those obtained in the first two examples may be realized when the antistatic agent, prepared and utilized in a manner analogous to that set forth in the foregoing, is comprised of the ethylene oxide etherified reaction product of a polyphenolic polymer similar to that set forth in Example C, with the exception that the bridging units are comprised of such difunctional radicals as those derived from vinyl compounds, isopropenyl compounds, divinyl benzene compounds or diisopropenyl compounds so that the resulting structures have the following formula:

wherein R is selected from the group consisting of oxyethylene units and mixed oxyethylene-oxypropylene units; R is hydrogen or methyl with the limitation that not more than one R is hydrogen in any one linkage; R" is selected from the group consisting of the same members as for R and hydrogen with the additional characterization that n is 2 and greater to about 8 when R is hydrogen and n is 3 and greater to 8 when R is the same as R; x is a number having an average value from 2 to 10 and y is a number having an average value from to with the limitation that the sum total of x-i-y is from 2 to 2().

EXAMPLE E Results commensurate with those set forth in the first example may be obtained when the antistatic agent that is utilized is an ethylene oxide ethen'fied polyphenolic polymer derived from such bis-phenol type phenolic monomers as bis-phenol A (para,para-isopropylidene diphenol), bis-phenol sulfone (para,para-sulfonyl diphenol) or bis-phenol sulfoxide (para,para'-sulfinyl diphenol) that have been condensed with such bridging agents as methylene, vinyl, isopropenyl radicals or by means of difunctional radicals from divinyl benzene or diisopropenyl benzene so that the resulting product has a structure represented by the following generic formula:

or propylene (CHCH -CH B is isopropylidene [C(CH sulfonyl (SO and sulfinyl (SO), 11 is 2 or more to 8 when R'=H; n is 3 or more to 8 when R=R; R or R is H or C H and in which at least 30H groups are adjacent per molecule and at least one R is (C H O) per molecule when the value of x is 2 to 10.

EXAMPLE F Excellent antistatic agents are obtained when the procedures of Examples A and B are repeated excepting to employ as the destaticizing substance that is applied to the nitrile alloy fiber, a homopolymer of such difunctional monomers as vinyl or isopropenyl phenols that has been reacted with ethylene oxide so that the antistatic etherified polyphenolic polymer product is of the formula:

on on OR" nca= (2-011 7 c-cn a R R wherein R and R are hydrogen or oxyethylene (C H O); R is hydrogen or methyl; and n is 2 or more to about 8 and provided that at least three hydroxyl substituents are present in each molecule.

EXAMPLE G Results similar to those obtained in Examples A and B may be realized when the antistatic agent employed is a phosphorous-containing polyphenolic polymer that is a condensation product of such phenolic monomers as hydroquinone, bis-phenol A, bis-phenol sulfone, or bisphenol sulfoxide with difunctional bridging radicals derived from phosphorous oxyhalides, such as phosphorous oxychloride (POCI wherein the mole ratio of difunctional phenol to phosphorous is between about 3:1 and 1:1, respectively, preferably about 5:2, etherified with an average of 2 to 20 moles of ethylene oxide per phenol unit in the condensed polymer so that the resulting antistatic resinous product has a structural formula according to the following:

R n (V) in which, when n is 2, R is hydrogen or para hydroxyphenyl and R is a polyoxyethylene unit, i.e., ((1 1-1 0), in which x is a plural integer to 20, preferably from about 2 to 10,

and when n is 3 and greater to 8 at least 3 of the R units must be hydroxyphenyl and the remaining R may be hydroxyphenyl, an alkali metal (lithium, sodium or potassium) or hydrogen; and R is polyoxyethylene.

XAMPLE H Poly(p-hydroxyphenol) substituted alkanes of the general formula:

/i -o- R wherein n is an integer having a value from 2 to 6 and R, R and R" are hydrogen or para hydroxyphenyl groups with a total of from 3 to 6 of the latter groups in the substituted alkane molecule, wherein at least one or more in excess of 2 of the substituted para hydroxyphenyl groups have been etherified with an average of from 2 to 20 moles of ethylene oxide per phenol unit in the molecule causing part of the hydroxyls to be substituted with polyethylene oxide units in the following manner:

wherein in has the indicated numerical value between 2 and 20, preferably up to about 10, so that the resulting ethylene oxide adduct has the general formula:

H uR

R (VI) wherein n is 2 or more to 8 and at least 2 of the R units must be para hydroxyphenyl and at least one R must be polyoxyethylated oxyphenyl in which in is a plural integer up to 20.

As is apparent from the foregoing, nitrile alloy articles treated in accordance with the present invention, one of which is illustrated in the accompanying drawing, retain the antistatic agent in a substantially permanent manner through the normal usage of the material. They have excellent antistatic properties and may be handled and employed readily without difiiculties due to accumulations of antistatic electricity. Furthermore, articles in accordance with the present invention retain their essential characteristics, including hand, and have no undesirable infiuence on the other aesthetic characteristics of the fiber or other article. As a matter of fact, as has been indicated, the treatment of the present invention improves the resistance to staining or discoloration of the treated article and generally benefits the washfastness of an article that has been dyed when the application of the antistatic agent is made on the colored material. In this connection, it is generally beneficial to treat articles intended to be dyed with the antistatic agent after they have been dyed to a desired shade of color in order to avoid dilficulties with dyeing procedures that may be involved if the destaticization is performed prior to dyeing.

Any desired amount of the antistatic, etherified polyphenolic resins may be employed on a nitrile alloy fiber or other shaped article. Usually it is beneficial to apply an amount between about 0.5 and 10 percent by weight of the antistatic agent, based on the dry weight of the shaped article being treated. In many cases, it may be more advantageous for the amount that is used to be between about l.0 and 2.0 percent by weight.

Various techniques may be utilized for the application of the etherified antistatic agents of the invention which, if sufficiently oxyalkylated, are often water soluble. As has been illustrated, they may frequently be applied from solution using a suitable solvent for the purpose such as various mixtures of acetone and water or water or acetone alone. Any polar solvents may be used such as alcohol, lower ketones including methyl ethyl ketone and methyl isobutyl ketone, dioxane, cyclohexanol, etc. In an analogous manner, it is oftentimes possible for the application of the antistatic agent to be made from a dispersion using water or some other inert medium as a dispersant vehicle. Frequently, to percent of a dispersing agent on the weight of the dispersion may be effectively employed. Thus, in the manner of conventional textile finish application, applicating formulations of the antistatic agent may be applied directly to a running strand of a nitrile alloy fiber or other shaped article using a liquid jet or spray of the formulation. If desired, applicating rollers and equivalent devices may be utilized for the purpose. It may frequently be more convenient, however, particularly when dyed textile materials are being treated, to employ the applicating formulation as a treating bath in which the nitrile alloy fiber article, including an article in the form of cloth or fabric, during any stage of manufacture or subsequent thereto, is immersed in order to pickup or become impregnated with the desired quantity of the antistatic agent. When cloth and fabric are being treated, it may be most convenient for the application to be made in a manner analogous to conventional padding treatments.

The quantity of dissolved or dispersed solids that is present in the applicating formulations of the antistatic agents may vary, depending upon whether a solution or suspension is being employed. Ordinarily, it is suitable for the applicating solution or dispersion to contain between about one-half and fifteen percent by weight, preferably between about two and five percent of the antistatic agent, based on the weight of the solution or dispersion of applicating liquid. The application may be made at normal room temperatures or at any other desired and practical temperature. After its application on the nitrile alloy fiber or other shaped article, the antistatic agent is dried thereon to provide the desired, destaticized product.

As has been indicated in the foregoing, the nitrile alloy fibers are comprised essentially of the mentioned acrylonitrile polymer base which has been modified or alloyed with beneficial additaments or constituents which are adapted and calculated to provide the fiber product with its peculiar and unusually advantageous properties. Various beneficial additaments or constituents that are capable of securing the desirable characteristics of which the nitrile alloy fiber is possessed may be any of several diverse types. For example, the beneficial constituent may be derived from and originate with a monomer or mixture of monomers, capable of being converted to a dye-receptive and possibly otherwise functional polymer product, which is graft or block copolymerized to and upon the already formed (and, with advantage, already fabricated) acrylonitrile polymer base. Alternatively, and with equal advantage, the beneficial constituent may be a dye-receptive and possibly otherwise functional, polymeric product with which the essential acrylonitrile base is graft or block copolymerized by graft copolymerization of acrylonitrile or an acrylonitrile monomer mixture on or with the already formed functional polymer in order to furnish the fiber-forming polymer product of which the nitrile alloy fiber is composed. Or, as a suitable and frequently quite satisfactory alternative, the already formed beneficial additaments or constituents in the nitrile alloy fiber may be in the nature of polymeric adjuvants that are physically blended and intimately incorporated by any of several suitable procedures with the essential acrylonitrile polymer base. Such adjuvants may be homopolymeric, copolymeric or graft copolymeric substances which serve to augment at least the dyeability of the normally difiicult (if not impossible) to dye acrylonitrile polymer base.

Amongst the most beneficial and advantageous of the nitrile alloy fibers are those that are comprised of the essential acrylonitrile polymer base, particularly polyacrylonitrile, in which there has been intimately and permanently or substantially permanently incorporated minor proportions of up to about 20 or so percent by weight, based on the weight of the nitrile alloy composition, of any of the beneficial additaments or constituents adapted to serve the desired purpose and provide the beneficial result. Generally, such beneficial additaments are employed primarily as dye-assisting adjuvants or components. Advantageously, they may be the polymerized products of such azotic monomers, or mixtures thereof, as the several N-vinyl lactams including such broadly related products as the N-vinyl-3-morpholinones; the N- vinyl-2-oxazolidinones; and certain of the N-vinyl-N- methyl-alkyl-sulfonarnides. Thus. the nitrile alloy may be comprised of the acrylonitrile polymer base that is prepared by graft or block copolymerization of acrylonitrile or an acrylonitrilecontaining monomer mixture upon a minor proportion of an already formed polymer derived from any of the indicated varieties of azotic monomers or their mixtures. Or, as mentioned, it may consist of a graft copolymer product of any of the indicated varieties of azotic monomers on an already formed and preferably already fabricated acrylonitrile polymer base. Advantageously, and frequently, with consummate suitability, the nitrile alloy fiber may be comprised of the acrylonitrile polymer base in which there is permanently incorporated by physical blending in minor proportion of any of the polymer products from the specified azotic 1 l monomers or mixtures thereof, primarily as dye-assisting adjuvants.

Such species of nitrile alloy fibers are capable of being accurately described as synergetic and anisotropic clathrates that are composed of a hydrophobic polymer in combination with a hydrophilic polymer. In such varities of the nitrile alloy fibers (as well as in other of the forms in which they may be obtained) there is a mutually enhancing cooperative union of a highly crystalline polymer which provides strength, durability, wrinkle recovery and high melting point in the fibers with an usually non-ionic polychelate that provides dye-receptivity as well as moisture regaining powers for the fiber and other aesthetic characteristics that lend to the wearing comfort of textile goods manufactured from the fiber. The nitrile alloy fibers have been described by G. W. Stanton in an article entitled Zefran appearing in the Textile Research Journal, volume XXVII, No. 9, for September 1957 at pgs. 703413. They have also been recognized as a distinct class of man-made synthetic textile fibers in Textil Organon, September 1956, at pages 129130.

As indicated, the adjuvant or beneficial constituent in the nitrile alloy fiber may be homopolymeric in nature or it may be a straight copolymer of any of the azotic monomers specified with other monoand polyfunctional monomers. Adjuvants of this variety are ordinarily physically blended with the essential acrylonitrile polymer base in order to secure the desired intimate incorporation of the beneficial constituent and the resulting alloying effect in the fiber. Likewise, there may be similarly utilized for physical blending purposes adjuvants or additaments that are graft copolymeric in nature and which consist of various monomers that are graft copolymerized on substrates consisting of polymers of any of the indicated azotic monomers, such as poly-N-vinyl-lactam substrates; poly-N-vinyl-Z-oxazolidinone substrates; and poly-N-vinyl-N-methylall ylsulfonamide substrates. Similarly, just as suitably, graft copolymeric additaments may be provided and employed when they consist of any of the specified or closely related azotic monomers (such as Nvinyl lactam monomers, N-vinyl-Z-oxazolodinone monomers and N-vinyl-N-methyl-alkyl-sulfonamide monomers) graft copolymerized on other functional polymer substrates.

It is usually beneficial for the polymer products of the azotic functional monomers to be present as the beneficial component in nitrile alloy fibers in an amount that is in the neighborhood or range of from about to percent by weight, based on the weight of the nitrile alloy composition. It is frequently quite desirable to employ a homopolymeric N-vinyl lactam polymer, such as poly-N-vinylpyrrolidone (which may also be identified as poly-N-vinyl-Z-pyrrolidone or, with varied terminology, poly-N-vinyl-2-pyrrolidinone), poly-N-vinyl caprolactam, or somewhat related thereto, a poly-N-vinyl- 3-morpholinone; or a homopolymeric N-vinyl-Z-oxazolidinone or poly-N-vinyl-S-methyl-2-oxazolidinone; or a homopolymeric N-vinyl-N-methylalkylsulfonamide polymer such as homopolymeric N-vinyl-N-methyl-methylsulfonamide; as the polymeric adjuvant that is blended with the essential acrylonitrile polymer base in the nitrile alloy composition. When physically blended nitrile alloy products are prepared that utilize, as the beneficial additament or constituent, copolymeric or graft copolymeric products of the indicated azotic monomers, it is usually beneficial for the polymeric adjuvants that are employed to be those which are comprised of at least about 50 percent or even as much as 80 or more percent by weight of the products of the indicated constituents derived from the azotic monomers.

In addition to products of N-vinyl-pyrrolidone or N- vinyl caprolactam, other of the N-vinyl (or l-vinyl) lactams which may be utilized includes any of those (or their mixtures) that have been described or which are involved in U.S. Patents Nos. 2,265,450; 2,355,454 and fit 12 2,371,804. Particular mention may also be made of N- vinyl-S-methyl-pyrrolidone; N-vinyl-3,3-dimethyl gamma valerolactam; and N-vinyl piperidone. Particular mention may also be made of somewhat related products derived in any of the ways described from N-vinyl-3-morpholinones of the structure:

wherein each substituent R unit is independently selected from the group consisting of hydrogen, 1 to about 4 carbon alkyl radicals, 6 to about 10 carbon aryl radicals and equivalents thereof.

Similarly, besides unsubstituted N-vinyl-Z-oxazolidinone, other N-vinyl (or 1-vinyl)-2-oxazolidinone products which may be used as polymeric adjuvants include those derived from monomers represented by the formula:

R1 t? Rg-C o=o TRIP-CH2 in which at least one of the substituent R R R or R groups, when it is not hydrogen, may be a 1 to about 4 carbon atom alkyl radical or a 6 to about 10 carbon atom aryl radicals or their equivalents. Typical of such monomers may be mentioned N-vinyl-5-methyl-2-oxazolidinone; N-vinyl-5-chloromethyl-2-oxazolidinone; N-vinyl- 4,5 dirnethyl 2 oxazolidinone, N vinyl 5 ethyl 2 oxazolidinone; N-vinyl-5-phenyl-2-oxazolidinone; and the like.

The N vinyl N methyl alkylsulfonamide monomers whose polymeric products may be advantageously utilized for the nitrile alloys include those represented by the formula:

wherein R is hydrogen, a 1 to about 4 carbon alkyl radical, a 6 to about 10 carbon aryl radical or some equivalent thereof.

Suitable nitrile alloy products may also be manufactured from other beneficial additaments or components that are more or less equivalent to those derived from the azotic monomers indicated in the foregoing. Thus, other varieties of N-heterocyclic monomers more or less similar or related to the specified N-2-propenyl types and analogous related azotic compounds may frequently be employed in combination with or to replace the several beneficial additaments or constituents that have been delineated.

What is claimed is:

1. An improvement in the textile art consisting of a destaticizing treatment which comprises applying between about 0.5 and 10 weight percent to a shaped nitrile alloy article an antistatic agent which is a hydrophilic derivative of a polyphcnolic polymer that is selected from the group consisting of those represented by the general formul e:

no 0R Ucit CH2 wherein n is a whole integer having an average value of from about 2 to 8 and each R is independently selected from the group consisting of hydrogen and polyoxyethylene groups containing from 2 to 20 moles of ethylene oxide with the limitation that at least onequarter and not less than 3 of the R substituents in each molecule are hydrogen;

on on R'z fion CR on ca wherein n is a number having an average value of from about 2 to 8; each R is independently selected from the group consisting of hydrogen and methyl with the limitation that not more than a single R is hydrogen in any given linkage; R is selected from the group consisting of oxyethylene and oxypropylene; and x is a number having an average value from 2 to 10;

y 07GB 2 i 2 U wherein n is a number having an average value of from about 3 to 8; each R is independently selected from the group consisting of oxyethylene and oxypropylene; x is a number having an average value of from 2 to 10; each R is independently selected from the group consisting of hydrogen and methyl with the limitation that not more than a single R is hydrogen in any given linkage; and y is a number having an average value of from 1 to 10;

H oa' 6 B 'R o on wherein each A is independently selected from the group consisting of methylene, ethylene and propylene; each B is independently selected from the group consisting of isopr-opylidene, sulfone and sulfinyl; R and R are independently selected from the group consisting of hydrogen, oxyethylene units and polyoxyethylene units of up to moles of ethylene oxide per unit; it is a number that has an average value of from 2 to 8 when R is hydrogen and an average value of from 3 to 8 when R and R are identical with the limitations that at least three hydroxyl groups are adjacent to one another in each molecule and at least one R per molecule is a polyoxyethylene units containing an average of from about 2 to 10 moles of ethylene oxide;

we on GR" accu c-cnz c-cn I I a R R wherein R and R are independently selected from the group consisting of hydrogen and oxyethylene; R is selected from the group consisting of hydrogen and methyl; and n is a number having an average value of from about 2 to 8 with the limitation that at least 3 hydroxyl substituents are present in each molecule;

wherein x is a plural number having an average value up to about 20;

wherein n is a number having an average value of from wherein n is a number that has an average value from about 2 to 8; and each R is selected from the group consisting of para-hydroxyphenyl and polyoxyethylated oxyphenyl units containing up to 20 moles of ethylene oxide with the limitations that at least one R is a polyoxyethylene oxyphenyl unit and not less than two of them are para-hydroxyphenyls; and mixtures thereof, said nitrile alloy being selected from the class of synthetic polymer compositions consisting of (A) intimate polymer blends comprised essentially of (Al) at least about 8'0 weight percent, based on composition weight, of an acrylonitrile addition polymer with (A2) up to about 20 weight percent, based on composition weight, of an azotic polymeric dye-assisting adjuvant selected from the group consisting of addition polymers of at least about 50 weight percent, based on the weight of the azotic polymer of (A2a) N-vinyl lactam monomers; (A212) N- viny1-3-morpholinone monomers of the structure:

0 RCH HCR RdH =0 wherein each substituent R unit is independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and -6 to about 10 carbon atom aryl substituents; (A2c) N-vinyl-Z-ox-azolidione monomers of the structure:

HC=OH in which R R R and R are independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A2d) N-vinyl-N-methyl-alkylsulfonamide monomers of the structure:

position weight, of a pre-formed acrylonitrile addition polymer substrate with graft copolymerized substituents thereon of (B2) up to about weight percent, based on composition weight, of addition polymerized azotic monomer substituents of at least about Weight percent, based on the weight of graft copolymerized substituent, or (B2a) N-vinyl lactam monomers; (B212) said N-vinyl- 3 morpholinone monomers; (B20) said N -vinyl-2- oxazolidinone monomers (B2d) said N-vinyl-N-methylalkylsulfonamide monomers; and (B2e) mixtures thereof; and (C) graft copolymers comprised essentially of (C1) at least about 80 weight percent, based on composition Weight, of acrylonitrile graft copolymerized on (C2) up to about 20 weight percent, based on composition Weight, of a pre-formed, dye-assisting, azotic addition polymer substrate of at least about SOweight percent, based on the weight of said substrate, of (C2a) N-vinyl lactam monomers polymerized in the substrate; (C2b) said N-vinyl-3-morpholinone monomers polymerized in the substrate; (C20) said N-vinyl-2-oxazolidinone monomers polymerized in the substrate; (C2d) said N-vinyl- N-methyl-alkylsulfon-amide monomers polymerized in the substrate; and (C22) mixtures thereof.

2. The treatment of claim 1, wherein said nitrile alloy is comprised of an intimate composition of polyacrylonitrile and polymerized N-vinyl-2-pyrrolidone.

3. The treatment of claim 1, wherein the antistatic agent is a polyphenolic compound of the structure:

cHg l" OH J2 (VII) 4. The treatment of claim 1, wherein between about 1.0 and 2.0 percent by weight of said antistatic derivative of the polyphenolic polymer is applied to said nitrile alloy substrate.

5. The treatment of claim 1, wherein the antistatic derivative of the polyphenolic polymer is applied from a liquid dispersion and including the step of drying the shaped nitrile alloy after application of said derivative.

6. The treatment of claim 1, wherein the shaped 11itrile alloy article substrate is in an aquagel condition and including the steps of applying the derivative of a polyphenolic polymer from a liquid dispersion by immersing the shaped nitrile alloy aquagel article therein CHQ t 6 and subsequently drying the shaped article after application of said derivative.

7. A treatment in accordance with the treatment set forth in claim 6, wherein said shaped article is an article in filamentary form.

8. The treatment of claim 1, wherein said antistatic derivative of the polyphenolic polymer is applied to said shaped nitrile alloy article while the latter is in an undyed condition.

9. The treatment of claim 1 and including the additional step of dyeing said shaped nitrile alloy article prior to said application of said antistatic derivative of the polyphenolic polymer.

10. A shaped article comprising a substrate of a synthetic nitrile alloy polymeric material characterized in being substantially free when dry from propensity to accumulate static electrical charges, said article having between about O.5 and 10 Weight percent of a derivative of a polyphenolic polymer applied thereto as an antistatic agent, said antistatic derivative of a polyphenolic polymer being selected from the group of those having the generic Formulae I, Ila, 1119, III, IV, Va, Vb, VI and mixtures thereof, said nitrile alloy being selected from the class of synthetic polymer compositions consisting of (A) intimate polymer blends comprised essentially of (A1) at least about weight percent, based on composition weight, of an acrylonitrile addition polymer with (A2) up to about 20 weight percent, based on composition weight, of an azotic polymeric dye-assisting adjuvant selected from the group consisting of addition polymers of at least about 50 weight percent, based on the Weight of the azotic polymer, of (A2a) N-Vinyl la-ctam monomers; (A2b) N-vinyl-3-morpholinone monomers of the structure:

in which R R R and R are independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A211!) N-vinyl-N-methyl-alkysulfonamide monomers of the structure:

wherein R is selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; and (A2e) mixtures thereof; (B) graft copolymers comprised essentially of (B1) at least about 80 weight percent, based on composition weight, of a pre-formed acrylonitrile addition polymer substrate with graft copolymerized substituents thereon of (B2) up to about 20 weight percent, based on composition weight, of addition polymerized azotic monomer substituents of at least about 50 Weight percent, based on the weight of graft copolymerized substituent, of (B2a) Nviny1lactam monomers; (B212) said N-vinyl-3-morpholinone monomers; (B20) said N-vinyl- 2-oxazolidinone monomers (B2d) said N-vinyl-N-methyl alkylsulfonarnide monomers; and (B20) mixtures thereof; and (C) graft copolymers comprised essentially of (Cl) at least about 80 weight percent, based on composition weight, of acrylonitrile graft copolymerized on (C2) up to about 20 weight percent, based on composition weight, of a pro-formed, dye-assisting, azotic addition polymer substrate of at least about 50 weight percent, based on the weight of said substrate, of (C2a) N-vinyl lactam monomers polymerized in the substrate; (C2b) said N-vinyl-3-morpholinone monomers polymerized in the substrate; (C20) said N-vinyl-Z-oxazolidinone monomers polymerized in the substrate; (C2d) said N- vinyl-N-methyl-alkylsulfonamide monomers polymerized in the substrate; and (C22) mixtures thereof.

11. A shaped article comprising a substrate of a synthetic nitrile alloy polymeric material, said nitrile a1- loy being selected from the class of synthetic polymer compositions consisting of (A) intimate polymer blends comprised essentially of (A1) at least about 80 weight percent, based on composition weight, of an acrylonitrile addition polymer with (A2) up to about 20 weight percent, based on composition weight, of an azotic polymeric dye-assisting adjuvant selected from the group consisting of addition polymers of at least about 50 weight percent, based on the weight of the azotic polymer, of (A2a) N- vinyl lactam monomers; (A2b) N-vinyl-3-morpholinone monomers of the structure:

wherein each substituent R unit is independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A20) N-viny1-2-oxazo1idinone monomers of the structure:

in which R R R and R are independently selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; (A2d) N-vinyl-N-methyl-alkysulfonamide monomers of the structure:

wherein R is selected from the group consisting of hydrogen, 1 to about 4 carbon atom alkyl substituents and 6 to about 10 carbon atom aryl substituents; and (A28) mixtures thereof; (B) graft copolymers comprised essen tially of (B1) at least about weight percent, based on composition weight, of a pre-formed acrylonitrile addition polymer substrate with graft copolymerized substituents thereon of (B2) up to about 20 weight percent, based on composition weight, of addition polymerized azotic monomer substituents of at least about 50 weight percent, based on the weight of graft copolymerized substituent, of (B211) N-vinyl lactam monomers; (B2b) said N-vinyl-3-morpholinone monomers; (B20) said N-vinyl- 2-oxazo lidinone monomers (B2d) said N-vinyl-N-methylalkylsulfonamide monomers; and (B2e) mixtures thereof; and (C) graft copolymers comprised essentially of (C1) at least about 80 weight percent, based on composition weight, of acrylonitrile graft copolymerized on (C2) up to about 20 weight percent, based on composition weight, of a pre-formed, dye-assisting, azotic addition polymer substrate of at least about 50 weight percent, based on the weight of said substrate, of (C212) N-vinyl lactam monomers polymerized in the substrate; (C2b) said Nvinyl-3-morpholinone monomers polymerized in the substrate; (C20) said N-vinyl-2-oxazolidinone monomers polymerized in the substrate; (C2d) said N- vinyl-N-methyl-alkylsulfonamide monomers polymerized in the substrate; and (C2e) mixtures thereof; said shaped nitrile alloy article substrate characterized in being substantially free when dry from propensity to accumulate static electrical charges, said article having between about 0.5 and 10 weight percent of a derivative of a polyphenolie polymer applied thereto as an antistatic agent, said antistatic derivative of a polyphenolic polymer being selected from the group consisting of those having the generic Formulae: I, Ila, IIb, III, IV, Va, Vb, VI and mixtures thereof.

12. The article of claim 11, wherein the derivative of the polyphenolic polymer has the structure of Formula VII.

13. The article of claim 11, wherein between about 1:0 and 2.0 percent by weight of the antistatic derivative of the polyphenolic polymer is applied thereto, based on the dry weight of the shaped nitrile alloy article.

14. A nitrile alloy fiber article in accordance with the article of claim 11, wherein said nitrile alloy is comprised of an intimate composition of polyacrylonitrile and polymerized N-vinyl-2-pyrrolidone.

15. An article in accordance with the article set forth in claim 14, characterized in being undyed and resistant to staining by dyestuffs and coloring agents.

16. An article in accordance with the article set forth in claim 14, characterized in consisting of a dyed acrylonitrile polymer substrate over which said antistatic derivative of the polyphenolic polymer is applied.

References Cited in the file of this patent UNITED STATES PATENTS 2,454,541 Beck et al Nov. 23, 1948 2,519,013 Banigan Aug. 15, 1950 2,558,734 Cresswell July 3, 1951 2,676,896 Cohen et al. Apr. 27, 1954

Claims

1. AN IMPROVEMENT IN THE TEXTILE ART CONSISTING OF A DESTATICZING TREATMENT WHICH COMPRISES APPLYING BETWEEN ABOUT 0.5 AND 10 WEIGHT PERCENT TO A SHAPED "NITRILE ALLOY" ARTICLE AN ANTISTATIC AGENT WHICH IS A HYDROPHILIC DERIVATIVE OF A POLYPHENOLIC POLYMER THAT IS SELECTED FROM THE GROUP CONSISTING OF THOSE REPRESENTED BY THE GENERAL FORMULA: