US3432343A - Fibers and fabrics coated with an alkyl phosphite-polyolefin wax adduct and process therefor - Google Patents

Description

United States Patent FIBERS AND FABRICS COATED WITH AN ALKYL PHOSPHITE-POLYOLEFIN WAX ADDUCT AND PROCESS THEREFOR Isaac J. Levine, East Brunswick, and Arthur K. Ingberman, Somerville, N.J., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Continuation-impart of applications Ser.

Nos. 469,840 and 469,890, July 6, 1965. This application June 28, 1966, Ser. No. 561,005

U.S. Cl. 117-1395 11 Claims Int. Cl. C08j 1/44 ABSTRACT OF THE DISCLOSURE Textile fibers and fabrics are coated with a finishing agent comprising an alkyl phosphite-polyolefin wax adduct. In the process, the coated fibers and fabrics are subjected to a post heating step.

This application is a continuation-in-part of copending applications Ser. No. 469,840, filed July 6, 1965 and Ser. No. 469,890, filed July 6, 1965.

This invention relates to the finishing of fiber and articles made from fibers such as textiles. More particularly, the invention relates to novel finishing agents for fibers and textiles.

Fibers useful herein can be classified as natural, semisynthetic, synthetic or glass fibers and include natural organic fibers comprising essentially cellulosic fibers (from vegetable sources) such as cotton, hemp, flax (linen), ramie, sisal, jute and the like; polymeric natural organic fibers e.g. proteinaceous fibers (from animal sources) such as silk (produced from the moth of the Bombyx species), wool and the like; polymeric semi-synthetic organic fibers comprising rayons or cellulose derivatives made from wood pulp or cotton linters such as regenerated cellulose rayons such as viscose rayon and cuprammonium rayon, cellulose esters such as acetate rayon and cellulose ethers such as ethyl cellulose; polymeric synthetic organic fibers e.g., nylons (polyamides), polyesters (reaction product of polybasic acids and glycols) polyethylene, polypropylene, vinyl chloride/vinyl acetate copolymer, vinyl chloride/acrylonitrile copolymer polyacrylonitrile, vinyl chloride/vinylidene chloride copolymer, polyurethanes and the like; and glass fibers such as Fiberglas.

Finishing herein refers to treatment of fibers either per se or as a textile or fabric to impart new characteristics and properties such as handle, appearance, drape, touch (surface lubricity, flexibility, compressibility and elastic recovery), softness, sheen, durability, shrink resistance, proofing against crushing, slip, water and moths.

Cationic salts of simple primary amines such as hexadecyl amine hydroacetate, salts of simple tertiary amines such as hexadecyl dimethyl amine hydroacetate, quaternary ammonium salts such as hexadecyl dimethyl benzyl ammonium chloride, salts of amino acids such as monostearoyl diethylene triamine dihydroacetate, quaternary ammonium salts of amino amides such as fi-diethyl aminoethylstearamide ethosulfate, salts of imidazolines such as ,u-heptadecyl, N-aminoethyl imidazoline dihydroacetate, quaternary derivatives of imidazolines, salts of amino esters such as B-dihydroxyethyl amine stearatehydroacetate and quaternary ammonium salts of amino esters have heretofore been used as finishing agents. Practically all materials that are in commercial use are derivated from stearic acid. Hydrocarbon chains of greater length have been sought but high cost and poor availability have barred their general use despite promising experimental results.

Heretofore, modified polyolefin waxes have been prepared by oxidation or by adducting polyolefin waxes with polar compounds such as maleic anhydride, thioglycolic acid, and the like. Oxidation, however, is a random reaction that produces a variety of products that are usually undesirably colored and have objectionable odors. Adduction with polar compounds also suffers from serious drawbacks. For example, the adduction with maleic anhydride is a very high temperature reaction that requires long heating times leading to some decomposition of the maleic anhydride. Moreover, during the reaction some of the molecules are made longer by copolymerization and oxidative cross-linking. After emulsification, there is a tendency toward instability and breaking of the emulsion or creaming. While many of the problems met with maleic anhydride are obviated through the use of thioglycolic acid, the high cost and unpleasant odor of this acid render its adducts with polyolefin waxes unsuitable for commercial use.

It has also been proposed to produce a modified polyethylene wax by thermally degrading a high molecular weight linear polyethylene at a temperature of from to 400 C. in the presence of an organic phosphite to form an addition product having an average molecular weight of from 200 to 4000. However, there are several drawbacks to this approach and the products produced thereby. For example, the thermal degradation of high molecular weight linear polyethylene in the presence of an organic phosphite requires impractically long reaction times and causes the organic phosphite, which is markedly unstable at polyethylene thermal degradation temperatures, to decompose to phosphine and related by-products, which are malodorous and toxic. Kosolapoff, Organophosphorus Compounds, John Wiley & Sons, Inc., New York, (1950), p. 182. Moreover, the product produced is undesirably colored and while emulsifiable yields a poorly colored emulsion.

It is an object, therefore, of the present invention to provide finishing agents of relatively very great molecular weight for improving the tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance of fibers. It is another object to provide textile and fabrics having improved handle. It is another object to increase the water repellency of textiles and fabrics, especially of proteinaceous and cellulosic fiber textiles.

A fiber finishing agent has not been discovered comprising an alkyl phosphite modified polyolefin wax. Textiles and fabrics having improved tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance are obtained by treating the textile with an alkyl phosphite modified polyolefin wax. It has also been found that these modified waxes also overcome the problems heretofore associated with modified polyolefin waxes.

The term polyolefin is used herein to denote normally solid homopolymers of alpha monoolefinically un-- saturated hydrocarbons as well as normally solids copolymers thereof. Suitable polyolefins include polyethylene, polypropylene, polyethylene-polypropylene copolymers and the like. Polyolefin waxes useful in this invention have an average of at least one-half, and preferably one, olefinic double bond per polymer molecule and a molecular weight of from about 1000 to about 5000. Polyolefin waxes typically contain at least one type of olefinic double bond and sometimes a combination of two or three different types of double bonds. A polyolefin wax molecule containing an olefinic double bond can be represented by the formula RRflhCHR wherein R is an alkyl group and R and R each are hydrogen or an alkyl group. Where R and R are both 0 hydrogen, the bond is termed a terminal vinyl type of double bond. Where R is hydrogen and R is an alkyl group, the bond is termed a vinylidene type of double bond and wherein R is hydrogen and R is an alkyl group, the bond is termed an internal type of double bond. All of these types of olefinic double bonds are capable of entering into an addition reaction with organic compounds of the class described herein.

Polyolefin waxes can be prepared by the pyrolysis or thermal degradation of higher molecular weight polyolefin polymers or by the direct polymerization of an olefin monomer or monomers to a wax of desired molecular weight. Pyrolysis, for example, can be carried out in a heated pyrolysis tube at about 450 to 600 C. Linear, high density polyethylene waxes having a density of 0.94 and above are preferred. Polyethylene waxes having lower densities, as well as other polyolefin waxes can also be employed.

Polyolefin wax adducts useful in this invention are prepared by adducting at least about 25 percent, preferably about 50 percent, of the olefinic double bonds in the polyolefin wax with an alkyl phosphite having at least one hydrogen atom capable of entering into an addition reaction with an olefinic double bond.

Suitable alkyl phosphites that can be reacted with polyolefin waxes to form an adduct thereof can be represented by the formula II H-P-O Rs wherein X represents an oxygen of a sulfur atom, R is an alkyl group having from 1 to 16 carbon atoms and A is hydrogen or -OR wherein R is an alkyl group having from 1 to 16 carbon atoms. Thus as used herein, the term phosphite refers to both phosphites and thiophosphites. It should be understood that when A is -OR R and R, can be the same or different alkyl groups. Suitable alkyl phosphites include methyl dihydrogen phosphite, ethyl dihydrogen phosphite, nbutyl dihydrogen phosphite, n-heptyl dihydrogen phosphite, n-hexadecyl dihydrogen phosphite, dirnethyl hydrogen phosphite, diethyl hydrogen phosphite, dipropyl hydrogen phosphite, di-n-butyl hydrogen phosphite, din-octyl hydrogen phosphite, di-n-pentadecyl hydrogen phosphite, methyl ethyl hydrogen phosphite, ethyl-ndecyl hydrogen phosphite, methyl dihydrogen thiophosphite, ethyl dihydrogen thiophosphite, n-undecyl dihydrogen thiophosphite, dimethyl hydrogen thiophosphite, diethyl hydrogen thiophosphite, di-n-butyl hydrogen thiophosphite, di-n-heptyl hydrogen thiophosphite, di-nhexadecyl hydrogen thiophosphite and the like. Inasmuch as the alkyl thiophosphites produce a modified polyolefin wax having a typical mercaptan odor, and the alkyl dihydrogen phosphites can under certain condition lead to crosslinking, the dialkyl hydrogen phosphites are preferred for purposes of this invention. These preferred phosphites have the formula wherein R and R are as defined above. It should be noted that trialkyl phosphites are not suitable reactants in this invention because they do not have a hydrogen atom available to enter into a free radical addition reaction with the olefinic double bond present in polyolefin waxes. For a detailed discussion of the mechanism of the free radical addition reaction between alkyl phosphites of the class described herein and the olefinic double bond, reference is made to Stacey et al., Organic Reactions, 13, 218-225, John Wiley and Sons, Inc., New York (1963).

The polyolefin wax adducts described herein can be prepared by blending the polyolefin wax and alkyl phosphite, in the liquid phase, for example in the melt or in solution, and reacting them in the presence of an addition reaction initiator with agitation at a temperature of from about C. to about 200 0, preferably from about C. to about C. Blending and agitation can be carried out in any manner which insures intimate admixing of the reactants and good heat transfer throughout the reaction mass during the reaction time.

If the addition reaction is conducted in solution, the reaction medium should be a liquid organic solvent inert with respect to the reactants under the reaction conditions and which is a solvent for the polyolefin wax and alkyl phosphate. Suitable solvents include benzene, toluene, xylene, cyclohexane, methylcyclohexane, isooctane, and the like, and halogenated hydrocarbon sol vents such as chlorobenzene, orthodichlorobenzene, 1,1,2-trichloroethane, bromobenzene, a-chloronaphthalene and the like. It is preferred to use only as much solvent as will completely dissolve the polyolefin wax and alkyl phosphite.

It is preferred to conduct the addition reaction in the melt by heating the polyolefin wax to its melting point and above and blending in the alkyl phosphite.

Generally an excess over the amount of alkyl phosphite theoretically necessary to react with the olefinic double bonds present in the polyolefin wax molecules should be used in order to achieve good rates of reaction and to insure complete reaction. A high reaction rate is not necessarily the sole factor in determining the optimum amount of alkyl phosphite to be used. For example, it is only required that about 25 percent, preferably 50 percent, or above of the olefinic double bonds be adducted to provide an ultimately emulsifiable product. Thus, the use of more alkyl phosphite than is required is unnecessary except to reduce the time needed to conduct the addition reaction.

The addition reaction between the polyolefin wax and the alkyl phosphite can be initiated by organic peroxides, organic azo compounds, ultraviolet radiation, and X-radiation. Stacey et al., supra, p. 219. Suitable organic peroxide initiators or catalysts include di-t-butyl peroxide, 2,5 dimethyl 2,5-di(t-butyl peroxy) hexyne-S, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, and the like. Suitable organic azo compounds include azonitriles such as azo-bis-butyronitrile and the like. In using ultraviolet radiation as the initiator, a photosensitizer such as benzophenone should be present.

The addition reaction between an olefinic double bond and an alkyl phosphite, and the adduct formed can be shown as follows:

wherein A, R and X are as defined previously. As indicated above the reactive olefinic double bond in the polyolefin wax molecule can be a terminal, vinylidene, or internal type of double bond. The addition product is termed a phosphonate ester of a polyolefin wax which as indicated above, includes thiophosphonate esters.

Polyolefin wax-alkyl phosphite adducts while emulsi fiable under certain circumstances, can be rendered readily emulsifiable in one of two ways: (1) by converting at least about 25 percent, and preferably about 50 percent of the oxyalkyl groups attached to phosphorus atoms in the adduct to hydroxyl groups, for example 1'; l l Z wherein A, R, and X are as defined previously, or (2) by reacting the phosphonate ester groups of the polyolefin wax-alkyl phosphite adduct with an amine having at least one reaction amino hydrogen atom.

The conversion of the oxyalkyl groups in the polyolefin wax-alkyl phosphite adduct to hydroxyl groups can be accomplished by acid hydrolysis, base hydrolysis or pyrolysis, and the converted product can be termed a modified polyolefin wax-alkyl phosphite adduct.

Hydrolysis can be carried out in a solvent for the polyolefin wax-alkyl phosphite adduct or in the heated wax adduct itself. Acid hydrolysis can be accomplished using monovalent acids such as hydrochloric acid, chloroacetic acid, and the like. Polyvalent acids such as sulfuric acid, phosphoric acid, and the like can be used to hydrolyze but the salt by-products must be washed out before emulsification. Basic hydrolysis can be accomplished using bases such as alkyl metal hydroxide such as potassium hydroxide, sodium hydroxide, and the like and aqueous ammonia and the like. It should be understood that basic hydrolysis produces a salt which itself is readily emulsifiable, Thus as used herein the phrase hydroxyl groups is intended to include the salts thereof as well.

A preferred method for converting the oxyalkyl groups to hydroxy groups is by pyrolysis. Pyrolysis is carried out either in batch or continuously in suitable apparatus at a temperature of from about 280 C. to about 475 C. for a period of time sufficient to accomplish the aforementioned degree of conversion. It has been found that a methyl phosphite modified polyolefin wax will not undergo pyrolysis and this wax adduct must be hydrolyzed to convert the oxymethyl groups to hydroxyl groups. The pyrolysis method of conversion is preferred because it provides for a high conversion rate, uses low cost equipment, does not require a catalyst, and does not require an additional reagents as in hydrolysis thus eliminating blending problems. The by-product of the pyrolysis reaction is the alkene corresponding to the R or R alkyl group.

The reaction product of a polyolefin wax-alkyl phosphite adduct and an amine can be termed an amine modified polyolefin wax-alkyl phosphite adduct. Suitable amines can be represented by the formula wherein R represents a monovalent organic radical having from 1 to 12 carbon atoms, R represents hydrogen or a monovalent organic radical having from 1 to 12 carbon atoms, and R and R when interconnected, represent a heterocyclic ring. The phrase monovalent organic radica refers to unsubstituted radicals as Well as to sub stituted radicals. Exemplary of such monovalent radicals are the following: alkyl radicals, such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, 2-ethyl-n-hexyl, n-octyl, n-dodecyl, and the like; cycloalkyl radicals, such as cyclohexyl and the like; unsaturated aliphatic and cycloaliphatic radicals, such as allyl, cyclopentenyl, and the like; halogenated alkyl and cycloalkyl radicals, such as chloroethyl, bromoethyl, fluoroethyl, 2-chloro-n-propyl, 2-bromo-n-propyl, 2-chloro-n-butyl, 3-chlor0-n-amyl, 3-bromon-amyl, 2 chloro-n hexyl, Z-chlorocyclohexyl, and the like; alkoxy and aryloxy substituted alkyl and cycloalkyl radicals, such as methoxymethyl, ethoxyethyl, 3-ethoxyn propyl, 4-ethoxy-n-butyl, 3-ethoxy 2 ethyl-n-hexyl 2 methoxycyclohexyl, phenoxymethyl, 2 phenoxyethyl, 3-phenoxy-n-propyl, 2 phenoxycyclohexyl, and the like; hydroxy substituted alkyl and cycloalkyl radicals; tertiary amino substituted alkyl and cycloalkyl radicals; aralkyl radicals, such as benzyl, 2-phenylethyl, B-phenyl-n-propyl, l-phenyl-n-butyl, l-phenyl-n-dodecyl, and the like; aryl radicals, such as phenyl, naphthyl, and the like; halogenated aryl radicals, such as p-chlorophenyl, pbromophenyl, p-fluorophenyl, p-iodophenyl, 2-chloronaphthyl, 2-bromonaphthyl, and the like; alkoxy and aryloxy substituted aryl radicals, such as p-methoxyphenyl, p-ethoxyphenyl, p-n-propoxyphenyl, and the like; hydroxy substituted aryl radicals; tertiary amino substituted aryl radicals; alkaryl radicals, such as o-methylphenyl, p-ethylphenyl, p-n-dodecylphenyl, p-( 2 ethyl n hexyl)phenyl, and the like; nitro substituted aryl radicals such as p-nitrophenyl, Z-nitronaphthyl, and the like.

Illustrative of suitable amines where R is a monovalent radical and R is hydrogen or a monovalent radical are methylamine, ethylamine, n-butylamine, n-octylamine, dimethylamine, diethylamine, ethyl-n-propylamine, di n butylamine, allylamine, cyclohexylamine, cyclopentylamine, ethoxyethylamine, Z-bromo-n-propylarnine, 3-ethoxy-2-ethyl n hexylamine, 2-hydroxyethylamine, Z-hydroxypropylamine, Z-arnino-l-butanol, 3-(N,N-di-nbutylamino)propylamine, Z-phenylethylarnine, l-phenyl-nbutylamine, aniline, m-toluidine, 2,3-xylidine, mesidine, l-naphthylamine, N-methylaniline, 4-(N,N-diethylamino) aniline, 4 chloroaniline, 2 chloro 1 naphthylamine, 4 methoxyaniline, 4 ethoxyaniline, 4 hydroxyaniline, 4-nitroaniline, N-propylallylamine, N-phenylbenzylamine, N cyclohexylheptylamine, 3 (aminomethyl)pyridine, 1-naphthalenemethylamine, 2-pyrenamine, and the like. Illustrative of suitable amines where R and R together form a heterocyclic ring are pyrrole, Z-methylpyrrole, 3-ethylpyrrole, and the like.

Polyolefin wax-alkyl phosphite adducts can be reacted with an amine either in solution or in the melt at temperatures of from about 150 to about 300 C. for a period of time to react at least 25%, preferably 50%, of the wax phosphonate ester groups with the amine. Generally about a stoichiometric amount of amine is employed but readily emulsifiable products can be obtained using less than stoichiometric amounts. In calculating the stoichiometry, one phosphonate ester group is presumed to react with one amino hydrogen atom. It is preferred to conduct the reaction in the absence of oxygen to secure a white product.

From the foregoing it should be evident that polyolefin wax adducts useful in this invention fall into the following groups: (1) adducts of polyolefin waxes and an alkyl phosphite; (2) polyolefin wax-alkyl phosphite adducts having at least about 25 percent of the oxyalkyl groups attached to phosphorus atoms converted to hydroxyl groups and (3) amine modified polyolefin wax-alkyl phosphite adducts. Groups (2) and (3) are preferred because of their case of emulsifiability as compared to group (1).

The application of the phosphite modified wax to fibers or textiles can be readily accomplished by use of a hot melt or solution of the wax and roller coating, dip coating, spray coating or otherwise.

Alternatively, and advantageously, the limitations of hot melt or solution application or incorporation can be avoided by use of an anionic, cationic or non-ionic emulsion of the phosphite modified wax as the coating mixture. Typically water emulsions are prepared by melting together the alkyl phosphite modified polyolefin wax and a fatty acid such as, for example, propionic, butyric, valeric, caproic, enanthylic, caprylic, capric, lauric, tridecoic, myristic, pentadecanoic, palmitic, megaric, stearic, nondecylic, arachidic, behenic, carnaubic, hyenic, carborceric, cerotic, laccroic, melissic, montanic, psyllic, acrylic, crotonic, iso-crotonic, vinylacetic, methylacrylic, tiglic, angelic, senecioic, hexenic, oleic, elaidic, erucic, brassidic, propiolic, propynoic, terolic, 2-butynoic, pentinoic, 2-pentinoic, amylpropiolic, palrnitotic, stearolic, behenolic, sorbic, linoleic and linolinic acids. These acids have the general formula wherein n is an integer from 0 to 32 and x is an odd number from 5 to +1 with the proviso that when n=0, x=+l. An amine soap is then added such as monoand triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, morpholine, N,N-dimethylethanolamine and N,N-diethylethanolamine. The mixture is stirred until thoroughly mixed or until it becomes clear. Other emulsifying aids such as polymeric glycols and ethoxylated soybean oils can also be used depending on whether an anionic, cationic or non-ionic emulsion system is desired. Water which has been heated to about C. is added and the mass stirred under pressure. The mixture is then vigorously agitated in a suitable device, e.g., a bladed mixer, colloid mill or other shear producing apparatus to form the emulsion. An alkyl phosphite modified polyolefin wax solids content of from 0.1 to 25 percent is preferred in emulsions to be used as finishing agents.

The water emulsion of the modified wax is easily coated onto the fiber substrate by any of the conventional techniques including brushing, dipping, spraying, roller coating and the like. The water of the emulsion is evaporated either by allowing the coated-on emulsion to stand at room temperature or preferably by force drying as by air movement around and/or application of heat to the emulsion coating. Upon drying there remains a nontacky and non-blocking coating which imparts improved handle, lubricity and abrasion resistance to fibers.

Generally from about 0.01 to about 25% by weight of modified wax based on the fabric weight is coated onto the fabric. Preferred amounts are between 0.1 and 10% by weight on the same basis.

After application of the alkyl phosphite modified polyolefin wax to the fiber substrate, it is preferred to subject the coated substrate to a post-heating step, particularly by heating to a temperature above the melting point of the wax provided the fiber is not degraded thereby. This enables a greater degree of flow of the wax into the interstices of the fabric and facilitates reaction of the reactive groups of the wax with 'hydroxyl groups or acetate groups on cellulosic fibers such as cotton or rayon.

As mentioned above, the finishing of textile fibers improves the water repellency characteristics. Other aids can be simultaneously employed including N-octadecyl-N- ethylene urea, alkyl isocyanates, thiocyanates, organosilicon compounds, aluminum oxides and soaps, copper soaps, chromium soaps, zirconium soaps and oxide, organo-halosilanes, rare earth metal soaps, petroleum and vegetable waxes, methylol stearamide, pyridium chlorides. Flameproofing agents can also be combined with phosphite modified polyolefin wax prior to application to the textile fibers such as boric acid/borax mixtures, ferric hydroxide, antimony oxychloride, stannic oxide hydrated, titanic hydroxide, bismuth trioxide hydrated, zinc stannate, aluminum borate, lead peroxide, cerium lhydroxide, aluminum hydroxide, chromic hydroxide, silica hydrated, aluminum silicate, magnesium silicate and magnesium ammonium phosphate and with these pentachlorodiphenyl, neoprene, chlorinated parafiin, vinyl chloride resins and aniline hydrochloride.

Other flameproofing agents include volatile phosphates and sulfamates. Mothproofing agents and mildewcides too can be applied with the finishing agent such as inorganic fluorides, dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide, dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodium salt of pentachlorodihydroxy triphenylmethanesulfonic acid. Also rotproofing agents such as copper salts of rosin and tall oil, terpinol hydrate as well as alkalies, formaldehyde, dyes, pigments, sequestrants, dispersants, starch, dextrin, glue, gums, china clay, Epsom salts, glycerol, soaps, soluble oil, antichlors, antifoaming and antistatic agents, batching oils, enzymes, lubricants, rust preventatives, spotting and weighting aids.

The present invention is illustrated by the following examples. All parts and percentages are by weight unless otherwise stated.

PREPARATION OF ALKYL PHOSPHITE MODIFIED POLYOLEFIN WAXES EXAMPLES 1-5 Example 1 Into a 500 ml. flask equipped with a stirrer, thermometer, condenser and dropping funnel is placed 200 grams of polyethylene wax prepared by pyrolyzing at 480 C. polyethylene having a density of 0.96 and a melt index (ASTM D-l238-57T) of 5. The wax has a number average molecular weight of 2000 and contains an average of one olefinic double bond per polymer molecule, over percent of which are terminal vinyl groups. 200 ml. of chlorobenzene and 40 grams of diethyl hydrogen phosphite are added to the wax in the flask and the reaction mass is heated to reflux at 169 C. A solution of 1 gram of 2,5-dimethyl-2,5-di-(t-butoxy)-hexyne-3 initiator is added over about three minutes and the reaction mass is refluxed for four hours. Thereafter chlorobenzene and excess diethyl hydrogen phosphite are removed by vacuum distillation. The polyethylene wax-phosphite adduct is allowed to cool. The amount of reaction is determined by measuring the change in the vinyl double bond absorption of 11.02;. in the infrared and is found to be percent. The product is a hard, white wax with absorptions in the infrared at 8.00114, 8.59 9.44 and 9.67;.4 characteristic of an alkyl phosphonate ester.

Example 2 In an Erlenmeyer flask, g. of the phosphite adduct described in Example 1 is dissolved in 250 ml. of refluxing chlorobenzene and a solution of 7 g. of KOH in methanol is added. The mixture is boiled for 10 minutes and then poured into a large volume of cold methanol. The infrared spectrum of the precipitated product shows the 800a band to have shifted to 835 and the doublet at 9.44; and 9.67,u to have shifted to 930p and 9.39 indicating that hydrolysis has occurred.

Example 3 One hundred grams of phosphite adduct prepared in Example 1 is pyrolyzed by heating under a nitrogen stream to 340 C. Gas evolution begins at about 280 C. and becomes more vigorous as the temperature increases. The wax is cooled rapidly. The infrared spectrum shows the original 8.00; phosphoryl absorption band to have shifted to 8.5a.

Example 4 A mixture of g. of the phosphonate ester was prepared in Example 1 and 30 ml. of N,N-di-n-butyl-1,3- propane diamine are heated with stirring under nitrogen for 1 hour in a 500 ml. flask equipped with a stirrer, thermometer, condenser and gas inlet tube. The molten wax is poured into a large volume of acetone and the precipitated product filtered, washed with acetone, and dried. The infrared spectrum of the product shows all of the original phosphonate ester bands shifted. For example, the phosphoryl absorption at 8.00 1. is shifted to 8.45 A chemical analysis indicates that two moles of amine are reacted.

Example 5 Example 4 is duplicated using 20 g. of aniline. The infrared spectrum of the product indicates complete reaction.

Example 6 One hundred grams of the modified wax of Example 2 is mixed with 20 grams of morpholine, 20 grams of oleic acid and 800 grams of water. The mixture is charged to a pressure reaction vessel and heated to 150 C. with agitation and immediately cooled. There is obtained a white emulsion having a solids content of 14.7%.

The above emulsion is diluted to 10 percent by weight polyethylene wax. A piece of rayon triacetate fabric is immersed in the emulsion. One section of the fabric is air dried and then heated for one minute at 350 F. A second section is only air dried. Both sections are well coated with an adherent covering of the modified wax. The heat-treated fabric is smoother and had better handle. Puncture of the post-treated fabric with a needle does not break the threads. Both sections of fabric are waterproof.

Example 7 Several emulsions of the modified wax of Example 4 are prepared as in Example 1 and diluted to solids contents of 2.5, 5, and 10%. Squares of cotton fabric are immersed in each of these emulsions. One-half of each square is air dried for two hours at room temperature. The other half of each square is oven dried at 130 C. for 45 minutes. The post-treated fabric is water resistant, with applied water balling up.

While not necessary, post-heat treatment of coated fabric at 60-137 C. for 1 to 60 minutes provides a superior product in terms of tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance. Heat-treated fabrics retain these properties, including water-proofness, after laundering.

Examples 8-9 Flex abrasion Example Solids on fabric resistance (cycles to failure) 8 0. 3 1, 550 9 0. 3 2, 527 Control I. 656 Control II. 0. 3 864 C ontrol III 0 395 Control IV 0. 3 763 Example Strips of fiber glass cloth (No. 181 weave, type 2967 finish), 4" x 8", are immersed in emulsions of the modifield polyethylene wax of Example 5. Emulsion solids content and immersion conditions are adjusted such that the cloth picks up 0.5, 1.0, 2.5, 5.0 and 10.0 wt. percent solids. The cloth samples are squeezed partly dry, then air dried at room temperature. The samples of dried cloth are heat treated at 140 C. for 10 minutes in an air oven to fuse the polyethylene wax coating.

After treatment the samples are examined visually and by feel to qualitatively rate the softness. The fabric stilfness is quantitatively rated also by the blending length test for fabrics (ASTM-1488-55T).

The fiber glass cloth sample treated with 0.5 wt. percent solids from a cationic or anionic emulsion is significantly improved in softness, hand, or drape properties.

The modified polyethylene wax coating functions as a lubricant and permits slippage at fiber interfaces. The results show that the 0.5% emulsion solids level gives the softest fabric, and the fabric becomes stiffer at higher levels.

As indicated above not only are cellulosic fibers such as cotton and rayon improved in the present invention but proteinaceous substrates such as wool are also improved. As an illustration, the application of a 2% by weight emulsion of the modified wax of Example 2 onto a woolen cloth imparts needle burn resistance and improved handle.

Synthetic fibers can also be improved particularly in handle by application of the modified wax in accordance with the present invention. Thus, polypropylene, nylon, and polyester fabrics can be improved in edgewear resistance',"needle burn resistance and durability by the ap plication of modified wax coatings.

What is claimed is:

1. Textile fiber having a coating thereon of from 0.01 to about 25 percent by weight, based on the weight of said fiber, of a finishing agent comprising an adduct selected from the group consisting of (1) an adduct of an alpha mono-olefinically unsaturated hydrocarbon homopolymer or copolymer wax having an average of at least about one-half of an olefinic double band per polymer molecule and a molecular-weight of about 1000 to about 5000 and an alkyl phosphite having from 1 to 32 carbon atoms inclusive and at least one hydrogen atom capable of entering into an addition reaction with an olefinic double bond, at least about 25 percent of said double bonds being adducted with said alkyl phosphite, (2) an adduct of said wax and said alkyl phosphite wherein at least about 25 percent of the oxyalkyl groups containing from 1 to 32 carbon atoms inclusive attached to phosphorus atoms are converted to hydroxyl groups, and (3) an adduct of said wax and said alkyl phosphite containing phosphonate ester groups wherein at least about 25 percent of said phosphonate ester groups are reacted with an amine having at least one reactive amino hydrogen atom.

2. Fiber of claim 1 wherein the wax is a polyethylene wax.

3. Fiber claimed in claim 2 wherein said alkyl phosphite has the formula wherein X represents an atom selected from the group consisting of oxygen and sulfur, R is an alkyl group having from 1 to 16 carbon atoms inclusive, and A is selected from the group of hydrogen and OR.; wherein R is an alkyl group having from 1 to 16 carbon atoms.

4. Fiber of claim 3 wherein said fiber is organic.

5. Fiber of claim 3 wherein said fiber is glass.

6. Fabric comprising textile fibers having a coating thereon of from about 0.01 to about 25 percent by weight, based on the weight of said fabric, of a finishing agent comprising an adduct selected from the group consisting of (1) an adduct of an alpha mono-olefinically unsaturated hydrocarbon homopolymer or copolymer wax having an average of at least about one-half of an olefinic double bond per polymer molecule and .a molecular weight of about 1000 to about 5000 and an alkyl phosphite having from 1 to 32 carbon atoms inclusive and at least one hydrogen atom capable of entering into an addition reaction with an olefinic double bond, at least about 25 percent of said double bonds being adducted with said alkyl phosphite (2) an adduct of said wax and said alkyl phosphite wherein at least about 25 percent of the oxyalkyl groups containing from 1 to 32 carbon atoms inclusive attached to phosphorus atoms are converted to hydroxyl groups, and (3) an adduct of said wax and said alkyl phosphite containing phosphonate ester groups wherein at least about 25 percent of said phosphonate ester groups are reacted with an amine having at least one reactive amino hydrogen atom.

7. Fabric of claim 6 wherein said fabric comprises organic fibers.

8. Fabric of claim 6 wherein said fabric comprises glass fibers.

9. Fabric claimed in claim 6 wherein said alkyl phosphite has the formula wherein X represents an atom of the group of oxygen and sulfur, R is an alkyl group having from 1 to 16 carbon atoms inclusive, and A is selected from the group of hydrogen and -OR wherein R is an alkyl group having from 1 to 16 carbon atoms.

10. Method for treating textile fibers comprising applying to such fibers an adduct selected from the group consisting of (1) an adduct of an alpha mono-olefinically unsaturated hydrocarbon homopolymer or copolymer wax having an average of at least about one-half of an olefinic double bond per polymer molecule and a molecular weight of about 1000 to about 5000 and an alkyl phosphite having from 1 to 32 carbon atoms inclusive and at least one hydrogen atom capable of entering into an addition reaction with an olefinic double bond, at least about 25 percent of said double bonds being adducted with said alkyl phosphite (2) an adduct of said wax and said alkyl phosphite wherein at least about 25 percent of the oxyalkyl groups containing from 1 to 32 carbon atoms inclusive attached to phosphorus atoms are converted to hydroxyl groups, and (3) an adduct of said wax and said alkyl phosphite containing phosphonate ester groups wherein at least about 25 percent of said phosphonate ester groups are reacted with an amine having at least one References Cited UNITED STATES PATENTS 1,715,855 6/1929 McBerty 117-1395 1,803,936 5/1931 Frielaender 117-1395 1,819,241 8/1931 Hirschberger 117--139.5

WILLIAM D. MARTIN, Primary Examiner.

THEODORE G. DAVIS, Assistant Examiner.

U.S.Cl.X.R.