US3578594A

US3578594A - Fiber treating compositions

Info

Publication number: US3578594A
Application number: US685335A
Authority: US
Inventors: Bernard A Dombrow
Original assignee: Diamond Shamrock Corp
Current assignee: Diamond Shamrock Chemicals Co; Diamond Shamrock Corp
Priority date: 1967-11-24
Filing date: 1967-11-24
Publication date: 1971-05-11
Anticipated expiration: 1988-05-11

Abstract

FIBER TREATING COMPOSITIONS CONTAINING FROM ABOUT 10% BY WEIGHT TO ABOUT 75% BY WEIGHT OF AN ESTER OF AN ETHOXYLATED ARYLPHENOL AND FROM ABOUT 90% BY WEIGHT TO ABOUT 25% BY WEIGHT OF AN ESTER OF AN ETHOXYLATED ALIPHATIC ALCOHOL HAVE REDUCED HIGH TEMPERATURE VOLATILITIES AND ENHANCED HIGH TEMPERATURE STABILITY. A USEFUL FIBER TREATING COMPOSITION CONTAINS 25% BY WEIGHT OF AN ESTER OF AN ETHOXYLATED BENZYLPHENOL AND 75% BY WEIGHT OF AN ESTER OF AN ETHOXYLATED ALIPHATIC ALCOHOL HAVING FROM ABOUT 11 TO ABOUT 15 CARBON ATOMS. ALSO, FIBERS CAN BE TREATED WITH ESTERS OF LINEAR SECONDARY ALCOHOLS OR ESTERS OF ETHOXYLATED SECONDARY LINEAR ALCOHOLS HAVING LOW POUR POINTS. A TYPICAL EXAMPLE IS FIBER TREATED WITH THE ESTER OF AN ETHOXYLATED SECONDARY LINEAR ALCOHOL HAVING FROM ABOUT 11 TO ABOUT 15 CARBON ATOMS.

Description

United States Patent US. Cl. 252-83 8 Claims ABSTRACT OF THE DISCLOSURE Fiber treating compositions containing from about 10% by weight to about 75% by weight of an ester of an ethoxylated arylphenol and from about 90% by weight to about 25% by weight of an ester of an ethoxylated aliphatic alcohol have reduced high temperature volatilities and enhanced high temperature stability. A useful fiber treating composition contains 25 by weight of an ester of an ethoxylated benzylphenol and 75 by weight of an ester of an ethoxylated aliphatic alcohol having from about 11 to about 15 carbon atoms. Also, fibers can be treated with esters of linear secondary alcohols or esters of ethoxylated secondary linear alcohols having low pour points. A typical example is fiber treated with the ester of an ethoxylated secondary linear alcohol having from about 11 to about 15 carbon atoms.

This invention relates to fiber treating compositions and to processes for treating fibers. More particularly, this invention relates to fiber treating compositions containing an ester of an ethoxylated arylphenol and an ester of an ethoxylated aliphatic alcohol having reduced high temperature volatility and enhanced high temperature stability in processes using these compositions. This invention also relates to another process for treating fibers with esters of secondary linear alcohols or esters of ethoxylated secondary linear alcohols having low pour points. Secondary linear alcohol esters with or without ethylene oxide chains on the alcohol have been found to be low pour point esters which are useful in fiber treating processes.

Processing of synthetic fibers has created the need for fiber treating compositions having reduced high temperature volatility and enhanced high temperature stability. For example, the manufacture of stretch yarns by heat setting mechanical deformation requires heating of yarns at about 150 C. to about 250 C. Fiber treating compositions for use in the manufacture of stretch or textured yarns should have the following properties: they should not volatilize or decompose readily at the above temperatures; such compositions should produce little if any smoke or fumes at the above temperatures; these compositions on heating should not form objectionable residues which clog the heated tubes in the texturing equipment; and the compositions should not form baked on lacquers either on the fibers or texturing equipment. Fiber treating compositions used in false twisting nylon, polyester and acrylic fibers have similar requirements. Similar compositions are required in the tensilizing of nylon and polyester tire cords and in the heat setting process for crimpsetting of acrylic fibers. Further, there was a need for fiber treating compositions in liquid form having low pour points.

An object of this invention is to produce fiber treating compositions having reduced high temperature volatility and enhanced high temperature stability. A further object is to provide fiber treating processes employing these compositions. Another object is to provide treated fibers having as a coating thereon the treating compositions of this invention. A further object is to provide another process for treating fibers, i.e., with an ester of a secondary linear aliphatic alcohol. Still another object is to provide treated fibers produced by applying an ester of a secondary linear alcohol to the fibers. Other objects will become apparent from the detailed description given herein. It is intended, however, that the detailed description and the specific examples given herein do not limit this invention but merely indicate preferred embodiments thereof.

The above objects as well as other objects of this invention have been achieved in the following manner. I have prepared fiber treating compositions having reduced high temperature volatility and enhanced high temperature stability and have used these compositions in the treatment of fibers. These fiber treatment compositions contain from about 10% to by weight of at least one ester of an ethoxylated arylphenol and from about to 25% by weight of at least one ester of an ethoxylated aliphatic alcohol. Ethoxylated arylphenols include ethoxylated benzylphenols and the like. I have found that incorporation of about 10% to about 75% by weight of an ester of an ethoxylated arylphenol into a composition containing from 90% to 25% by weight of at least one ester of an ethoxylated aliphatic alcohol results in a substantial reduction in the volatility of the ester of the ethoxylated aliphatic alcohol. The ester of the ethoxylated arylphenol appears to inln'bit or reduce the high temperature volatility of the ester of the ethoxylated aliphatic alcohol. Further, the presence of the ester of ethoxylated arylphenol enhances the high temperature stability of the ester of the ethoxylated aliphatic alcohol. Although the action of the ester of the ethoxylated arylphenol is not completely understood, it is believed that the ester of the ethoxylated arylphenol inhibits or prevents thermal decomposition of the polyether chain in the ester of the ethoxylated aliphatic alcohol. From about 0.1% to about 6% by weight of these compositions based on the weight of the fiber are applied to fibers.

Further, I have found another process for treating fibers wherein an ester of a secondary linear alcohol having from about 8 to about 21 carbon atoms and having a low pour point is applied to the fiber. From about 0.1% to about 6% by weight of an ester of the secondary linear alcohol having from about 8 to about 21 carbon atoms is applied to the fiber. Fibers treated with these esters of secondary linear alcohols have enhanced properties because of the low pour points of the esters.

Although amine antioxidants such as symmetrical dibeta-naphthyl-paraphenylenediamine and phenothiazine inhibit decomposition of polyether chains in esters of ethoxylated aliphatic alcohols, they cause discoloration of the esters of ethoxylated aliphatic alcohols and therefore are not satisfactory as inhibitors for these esters in fiber treating compositions. Likewise, hindered phenols are unsatisfactory as inhibitors for these esters. Hindered phenols provide a low order of protection at elevated temperatures and therefore are unsatisfactory.

In view of the unsatisfactory results obtained with both amine and phenol inhibitors, it was completely unexpected that the esters of ethoxylated arylphenols would satisfactorily inhibit thermal decomposition of polyether chains in the esters of ethoxylated aliphatic alcohols. Further, the inhibitory action of the esters of ethoxylated arylphenols actually increased when compositions containing these esters were heated for extended periods of time, whereas the inhibitory action of amine and hindered phenol antioxidants decreased when compositions containing these antioxidants were heated for extended periods of time. This increase in inhibition with time was completely unexpected and could not be predicted on the basis of the results obtained with the known inhibitors described above.

I have found that fiber treating compositions having reduced high temperature volatility and enhanced high temperature stability are produced when the compositions contain 1) from about 10% to about 75% by weight of at least one ester of an ethoxylated arylphenol such as and (III) R). t 2 I lZ wherein X is hydrogen, chlorine, bromine or an alkyl radical having from about one to about fifteen carbon atoms; R is an aryl radical or a substituted aryl radical having from about six to about twenty four carbon atoms; R is hydrogen or an alkyl radical having from about one to about five carbon atoms; R is hydrogen or an alkyl radical having from about one to about five carbon atoms; R is an alkyl radical having from about one to about twenty-one carbon atoms; R is an alkylene radical having from about one to about twenty-one carbon atoms and includes radicals such as --CH OCH and n is an integer of from about one to about twenty and contains (2) from about 90% to about 25% by weight of at least one ester of an ethoxylated aliphatic alcohol such as wherein R is an alkyl radical having from about one to about twenty-one carbon atoms; R is an alkyl radical having from about one to about thirty carbon atoms; R is an alkylene radical having about one to about twentyone carbon atoms and includes radicals such as and m is an integer of from about one to about twenty.

I have found that these compositions have reduced high temperature volatility and enhanced high temperature stability at about 150 C. to about 250 C. and hence are superior to esters of ethoxylated aliphatic alcohols when used as fiber treating compositions at these temperatures. These compositions also have the further advantage in that they show less tendency to produce smoke or fumes at these temperatures than the esters of the ethoxylated aliphatic alcohols. Further, the compositions do not form objectionable residues on fiber or on the texturing equip- 4 ment at these temperatures. This is highly advantageous in that residues which clog the heated tubes of the equipment are not formed and baked on lacquers are not formed on the surface of the fibers or the equipment.

The esters of ethoxylated arylphenol are produced by esterifying an ethoxylated arylphenol with an aliphatic saturated monocarboxylic acid or dicarboxylic acid or their derivatives such as the corresponding acid chloride, acid anhydride or the like. Normally, the ethoxylated arylphenol is reacted with an equivalent or slight deficit of the desired acid or derivative. This reaction is usually carried out at temperatures up to about 150 C. and under a vacuum of about 25 mm. Hg until esterification is substantially completed. Likewise, a mole of an ethoxylated arylphenol can be reacted with about 1.05 moles of an acid anhydride at about C. and the reaction mixture vacuum stripped at about C. to remove any unreacted acid anhydride and by-products.

Aliphatic saturated monocarboxylic acids having from about two to about twenty two carbon atoms can be used in the esterification. Useful acids include acetic acid, proprionic acid, butyric acid, isobutyric acid, caproic acid, caprylic acid, capric acid, Z-ethylhexoic acid, lauric acid, myristic acid, plamitic, stearic acid, behenic acid, their isomers, their mixtures and the like.

Aliphatic saturated dicarboxylic acids having from about three to twenty three carbon atoms can be used. These acids include dicarboxylic acids having alkylene radicals from about one to about twenty-one carbon atoms and those having alkylene radicals such as CH OCH and the like. Useful aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, brassylic acid, roccellic acid, diglycollic acid and the like.

Ethoxylated arylphenols (ethoxylated benzylphenols) can be prepared by condensation of from about one to about twenty moles of ethylene oxide per phenolic hydroxyl present in the benzylphenol. A useful procedure for the condensation of ethylene oxide with benzylphenols is given in Example I of US. Pat. No. 3,333,983, Sellet, Aug. 1, 1967.

Arylphenols include substituted phenols of Formula VI R1 tat R2 X wherein X is hydrogen, chlorine, bromine or an alkyl radical having from about one to about fifteen carbon atoms; A is an aryl radical or a substituted aryl radical having from about six to about twenty four carbon atoms; R is hydrogen or an alkyl radical from about one to about five carbon atoms and R is hydrogen or an alkyl radical having from about one to about five carbon atoms. For example, X can be a straight or branched chain alkyl radical having from about one to about fifteen carbon atoms such as metyhl, ethyl, n-propyl, i-propyl, n-btuyl, i-butyl, s-amyl, t-octyl, nonyl, dodecyl, pentadecyl or the like. R can be an unsubstituted aryl radical or a substituted aryl radical having from about six to about twenty four carbon atoms such as phenyl, chloro-phenyl, octylphenyl, diphenyl, hydroxybenzyl, di-octyl-o-hydroxybenzyl, 2-hydroxy-3-(ohydroxylbenzyl)phenyl, naphthyl or the like. R can be a straight or branched chain alkyl radical having from about one to about five carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-amyl or the like. R can be a straight or branched chain alkyl radical having from about one to about five carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-amyl or the like. B is arylphenols such as those obtained by condensing two moles of the above arylphenols with one mole of formaldehyde can also be used. Preparation of a typical bis arylphenol is described in Example VIII. The above his arylphenols are well known in the art and have been the subject of numerous patents and publications. Preparation of an arylphenol, ie.g., a benzylphenol which is a methylbenzylphenol, that is, a mixture of a-methylbenzylp-phenol and a-methylbenzyl-o-phenol is described in Example 1 below.

As examples of esters of ethoxylated arylphenols and his arylphenols which can be used in the present invention there may be mentioned the acetate ester of the condensation product of five moles of ethylene oxide with one mole of benzylphenol; the lauric ester of the condensation product of twenty four moles of ethylene oxide and one mole of his benzylphenol; the stearate ester of the condensate of ten moles of ethylene oxide and one mole of a-methylbenzylphenol; and the butyrate ester of the condensation product of one mole of ethylene oxide with one mole of a-methyl-p-chlorobenzyl-phenol. Other esters of ethoxylated benzylphenols include the neutral adipate ester of the condensation product of two moles of ethylene oxide with one mole of a,oK-dimethylbenzylphenol; the dipelargonate ester of the condensation product of seventeen moles of ethylene oxide and one mole of his methylbenzylphenol; the neutral malonate ester of the condensation product of eight moles of ethylene oxide with one mole of ozphenyl-benzylphenol; the palmitate ester of the condensation product of three moles of ethylene oxide with one mole of ot-methylbenzylphenol and the like.

Aliphatic alcohols of the formula R OH, which can be used to prepare esters of ethoxylated aliphatic alcohols include aliphatic alcohols having from about one to about thirty carbon atoms as well as their mixtures. These alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol, the corresponding secondary alcohols, tertiary alcohols, their isomers, their mixtures and the like. Useful alcohols include those produced by hydrogenation of fatty acids or glycerides obtained from animal or vegetable oils and waxes such as coconut oil, castor oil, tall oil, tallow oil or the like. Other alcohols can be produced by the Oxo process. This process involves catalytic reaction of ot-olefins with carbon monoxide and hydrogen under pressure to obtain primary aliphatic alcohols having branched chains. Oxo alcohols include i-octyl alcohol, decyl alcohol, tridecyl alcohol, pentadecyl alcohol, their mixtures such as Neodol alcohols (Shell Chemical Co.) and the like. Other primary aliphatic alcohols include those produced by the polymerization of ethylene with Ziegler type catalyst and subsequent reaction of the metal alkyls formed in this polymerization to obtain mixtures of straight chain primary alcohols such as the Alfols (Continental Oil Company). These alcohols can be used as mixtures or as specific primary alcohols such as hexyl alcohol, octyl alcohol, decyl alcohols and may be mixtures of or individual primary alcohols having chain lengths of from about eight to about twenty eight carbon atoms. Secondary linear aliphatic alcohols such as those represented by the base materials used in the Tergitol ethoxylates (Union Carbide) may also be used.

The above aliphatic alcohols are condensed with from about one to about twenty moles of ethylene oxide per mole of aliphatic alcohol to obtain ethoxylated aliphatic alcohols of the formula R OCH CH OH wherein R is an alkyl radical having from about one to about thirty carbon atoms and m is an integer from about one to about twenty. These aliphatic alcohols can be condensed with ethylene oxide by the procedure described in Example I(B) below with the exception that a-methylbenzylphenol is replaced with the desired alcohol.

Methods for the ethoxylation of aliphatic alcohols are well known and have been the subject of many patents and publications. For example, ethoxylated aliphatic alcohols 6 can be prepared by condensation of from about one to about twenty moles of ethylene oxide per hydroxyl group present in the alcohol. A procedure for the condensation of ethylene oxide with aliphatic alcohols is given in US. Pat. 1,970,578, Schoeller et al., Aug. 21, 1934.

The esters of ethoxylated aliphatic alcohols are produced by esterifying an ethoxylated aliphatic alcohol with an aliphatic saturated monocarboxylic acid or dicarboxylic acid or a derivative such as the corresponding acid chloride, acid anhydride or the like. Normally, the ethoxylated aliphatic alcohol is reacted with an equivalent or slight deficit of the desired acid. The reaction is usually carried out at temperatures up to about 150 C. and under a vacuum of about 25 mm. Hg until esterification is substantially complete. Likewise, a mole of an ethoxylated aliphatic alcohol can be reacted with about 1.05 moles of an acid anhydride at about 100 C. and the reaction mixture vacuum stripped at about 150 C. to remove any unreacted acid anhydride and by-products.

Aliphatic saturated monocarboxylic acids having from about two to about twenty two carbon atoms can be used in the esterification. Useful acids include acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, caprylic acid, capric acid, Z-ethylhexoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, their isomers, their mixtures and the like.

Aliphatic saturated dicarboxylic acids having from about three to twenty three carbon atoms can be used. These acids include dicarboxylic acids having alkylene radicals from about one to about twenty one carbon atoms and those having alkylene radicals such as and the like. Useful aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, brassylic acid, roccellic acid, diglycollic acid and the like.

As examples of esters of ethoxylated aliphatic alcohols which may be used in the present invention, there may be mentioned the acetate ester of the condensation product of ten moles of ethylene oxide with one mole of methyl alcohol; the lauric ester of the condensation product of twelve moles of ethylene oxide and one mole of isopropyl alcohol; the stearate ester of the condensation product of six moles of ethylene oxide and one mole of lauryl alcohol and the butyrate ester of the condensation product of one mole of ethylene oxide with one mole of stearyl alcohol. Other useful esters include the neutral adipate of the condensation product of ten moles of ethylene oxide and one mole of tridecyl alcohol (Oxo alcohol); the pelargonate ester of the condensation product of one mole of ethylene oxide and one mole of melissyl alcohol; the stearate ester of the condensation product of about twelve moles of ethylene oxide and about one mole of a mixture of secondary alcohols having chain lengths from about eleven to about fifteen carbon atoms, and the like.

The fiber treating compositions are prepared by mixing from about 10% to about by weight of at least one of the above esters of ethoxylated arylphenols with about to about 25% by weight of one of the above esters of ethoxylated aliphatic alcohols. If the two components are liquids, they can be mixed at room temperature. If one or both of the components are solids, the components can be heated to their melting points and the resulting liquid mixture then mixed at such elevated temperature until uniform and finally cooled to room temperature.

Volatilities of the fiber treating compositions are determined in the following manner:

Let

V =volatility of aryl compound (ethoxylated arylphenol component) at concentration (by weight) V =volatility of aliphatic compound (ethoxylated aliphatic alcohol component) at 100% concentration (by weight), and

V=volatility of composition of aryl compound and aliphatic compound at the indicated concentration (by weight) P concentration of aryl compound (decimal), and

P =cncentration of aliphatic compound (decimal).

The term (decimal) means that the concentration of the compound is less than 1.00. Thus, the apparent volatility activity of aliphatic compound can be determined by the formula:

Apparent percent by weight Volatility Activity of Aliphatic Compound VP V PZVZ (100) Values of V V and V are determined experimentally by placing 5 grams of a sample of (a) the aryl compound, (b) the aliphatic compound and (c) the combination of the aryl compound and the aliphatic compound respectively in separate aluminum dishes. These aluminum dishes have a diameter of 2% inch and a height of inch. The aluminum dish containing each sample is then placed in an air circulating oven at 200 C. for a period of one hour. At the end of this period, each aluminum dish is removed from the oven and placed in a calcium chloride desiccator where it is allowed to cool to room temperature. After cooling to room temperature the sample is removed from the dessiccator and weighed. The values of V V and V are determined by the following formula.

weight of sample at 20 C before placing in oven The sample is then placed in the air circulating over at 200 C. for an additional hour, removed from the oven, cooled in a desiccator and weighed. The values of V V and V are determined after the second hour of heating. Values of V V and V are then determined after the third, fourth and fifth hours of heating.

The smoke points of the aryl compounds, the aliphatic compounds and their compositions are determined in the following manner. The A.O.C.S. Official Method Ce 9a-48 for Smoke Points was modified, that is, the cabinet which enclosed the heated cup was not used.

Antistatic properties of treated fibers containing from about 0.1% to about 6% by weight of the compositions based on the weight of fibers are determined in the following manner. A Rothschild Static Voltmeter R-1019 (Haberline, Inc., Raleigh, NC.) is used in the charge generation test. Charge generation is a dynamic test where in a yarn specimen is passed over a friction surface to generate a static charge and the static charge generated with that surface is recorded. Antistatic half-life tests are also made on the treated fibers. The antistatic half-life test is a test whereby a given charge is placed on a yarn specimen and the time required for one half of the charge on the specimen to dissipate from the test specimen is measured and recorded as the antistatic half-life of the treated fiber.

The lubricating properties of these fiber treating compositions are determined in the following manner. The coefficient of friction of the composition is measured using a Rothschild F-Meter 1081 for Measuring Coefiicients of Friction (Haberline, Inc., Raleigh, N.C.) with two Rothschild Electronic Tensiometers (Haberline, Inc., Raleigh, N.C.). The composition is applied to about 0.1% to about 6% by weight based on the weight of fiber to the fiber and the treated fiber conditioned for 24 hours at 50% Relative Humidity and 72 F. The coefiicients of friction are then measured on the conditioned fiber using the apparatus described above. Lubricating properties of the esters of secondary linear alcohols are also measured by this procedure.

The fiber treating compositions can be applied directly to natural or synthetic fibers by any known method such as by means of a spray, by means of a bath, by means of an aqueous solution or dispersion or by means of a solvent such as a solution of the composition in a solvent such as chlorinated hydrocarbons, water or the like. The compositions have the advantage in that they can be easily applied to the fibers at the spinning cabinet Where the fibers are formed or at the conclusion of the spinning op eration. The compositions can be applied to natural fibers at the picking stage since they are soluble or dispersible in water and organic solvents. A convenient method of application is to apply the fiber treating composition in the form of a spray which is prepared by using the minimum amount of solvent or water that will dissolve or disperse the composition so that a drying or solvent removal step is not required. If desired, the compositions can be applied in solvent free form. After the composition has been applied to the fiber, the fiber is ready for processing into yarn, either through the filament yarn route or into spun yarns. It is during these processing and/or manufacturing steps that the compositions impart desirable properties such as improved softening to the fibers, lubricity of the fiber or fibers, and the like during processing and impart satisfactory handling characteristics. Further, the reduced volatility of the compositions as well as their improved heat stability greatly improve the fiber processing steps. Esters of secondary linear alcohols can be applied to fibers by the same procedures.

The fiber treating compositions of this invention can be used to treat textile fibers. Textile fibers include those derived from natural, man-made and synthetic fibers such as cotton, wool, silk, jute, sisal, hemp, fur, flax, kapok, rayon, cellulose acetate, cellulose triacetate, polyamides such as nylon, polyesters such as polyethylene terephthalate (Dacron), acrylics such as polyacrylonitrile, vinyl resins such as copolymers of polyvinyl chloride and polyvinyl acetate, copolymers of vinylidene chloride and vinyl chloride, copolymers of acrylonitrile and vinyl chloride, or the like, polystyrene, polyethylene, polypropylene, polyurethane, glass, ceramic, asbestos, protein fibers such as vicara and peanut protein blends of these or the like. Blends of these fibers can also be used. The term fiber includes textile materials in the form of fibers, continuous or spun yarns, filaments, rovings, slivers, tops and the like. Esters of secondary linear alcohols can also be used to treat these fibers.

Esters of secondary linear alcohols, which can be used in the treatment of fibers, include wherein R is an alkyl radical having from about 1 to about 20 carbon atoms; R is selected from the group consisting of an alkylene radical having from about 1 to about 21 carbon atoms and an alkylene radical of the formula CH -OCH R is alkyl radical having from about 8 to about 21 carbon atoms which is the residue of a secondary alcohol; 11 is an integer of from about 0 to about 20. These esters have low pour points. Useful esters include (1) the stearate of a mixture of C secondary alcohols; (2) the stearate of a mixture of C secondary alcohols; (3) the stearate of a mixture of C1144 secondary alcohols; (4) the stearate of a mixture of C secondary alcohols+3 E0; (5) the adipate of a mixture of C secondary alcohols-l-3 15.0.; (6) the pelargonate of a mixture of C1145 secondary alcohols-l-S BO; (7) the coconutate of a mixture of C1145 secondary alcohols+3 E0. and (8) the acetate of a mixture of C secondary alcohols+3 E0. The term E.O. means ethylene oxide and the number represents the number of moles of ethylene oxide reacted with one mole of the alcohol. These esters can be prepared using the abovementioned fatty acids and esterification procedures. Esters of secondary linear alcohols are applied to the material and synthetic fibers described below by the same procedure as those used in the application of the compositions. Fibers treated with esters of secondary linear alcohols have enhanced properties such as lubrication and the like. Further, their applications on fibers are more uniform and satisfactory because the esters are liquids rather than solids and have low pour points, that is, they remain in liquid form at lower temperatures than the esters of the corresponding primary alcohols.

For a fuller understanding of the nature and objects of this invention reference may be made to the following examples which are given merely to illustrate the invention and are not to be construed in a limiting sense. All weights, proportions and percentages are on a weight basis unless otherwise indicated. Likewise, all temperatures are C. unless otherwise indicated.

EXAMPLE I Preparation of the stearate ester of an ethoxylated benzylphenol (A) Preparation of a benzylphenol, an arylphenol.-95 lb. (1.005 mole) of molten phenol and a catalyst composed of 1.47 lb. (0.021 mole) of boron trifluoride and 0.15 lb. (0.0011 mole) of a 50% by weight aqueous solu tion hypophosphorous acid were added to a reaction kettle. The contents were heated to about 70 C.

To this heated mixture was slowly added with agitation, 52.5 lb. (0.505 mole) of styrene. After the styrene addition was completed, the reaction mixture was heated at 70 C. for another hour. The reaction product was then neutralized to a pH of 8.0 with 4.6 lb. (0.021 mole) of a 25% by weight sodium methylate in methanol solution followed by the addition of 0.75 lb. of a diatomace us earth as a filter aid. These steps were carried out while agitating the reaction product at about 70 C.

The liquid reaction product was then filtered and the clear filtrate was charged into a distillation kettle for the removal of methanol and excess phenol. Methanol and unreacted excess phenol were removed by vacuum distillation. Vacuum distillation was continued until a pot temperature of 175 C. and a vacuum of 55 mm. Hg were reached. About 48 1b. (0.51 mole) of unreacted phenol were removed by distillation. Last traces of unreacted phenol were removed by sparging with nitrogen, the residue remaining in the distillation kettle. After cooling down the residue in the kettle under nitrogen, the residue was found to be a liquid having a color range of off white to amber and having a refractive index of 1.5880i0.0020. This residue was the desired a-methylbenzylphenol and was composed of a mixture of a-methyl benzyl-para-phenol and a-methylbenzyl-ortho-phenol.

(B) Preparation of an ethoxylated benzylphenoL-Into a reaction kettle were charged 230 lb. (1.16 moles) of amethylbenzylphenol prepared by the process described in part (A) above and 0.35 lb. (0.006 mole) of potassium hydroxide flakes. The kettle was then heated to 150 C. and purged with nitrogen. 446 lb. (10.1 moles) of ethylene oxide were then added while allowing the exotherm of the reaction to maintain the temperature range of the reaction at about 150 C. to about 200 C. After addition of the ethylene oxide, the temperature of the reaction mixture was held at about 150 C. to about 200 C. for one hour and then cooled to room temperature. The resulting reaction product was the desired ethoxylated a-rnethylbenzylphenol, that is, the condensation product of about nine moles of ethylene oxide and about one mole of a-methylbenzylphenol. The reaction product was neutralized to a pH of about 7 with 85% by weight phosphoric acid and the molecular weight verified by determination of the hydroxyl number.

(C) Preparation of the stearate ester of an ethoxylated benzylpheno1.-Into a reaction kettle, 756 g. (1.35 mole) of the ethoxylated u-methylbenzylphenol obtained in part (B) above, 354 g. (1.29 mole) of commercial stearic 10 acid, 3.3 g. (0.025 mole) of a 70% by weight aqueous solution of methane sulfonic acid and 2.2 g. (0.016 mole) of a 50% by weight aqueous solution of hypophosphorous acid were charged. The reactants were sparged with nitrogen gas while lowering pressure on the kettle to mm. Hg and were then slowly heated to C. while removing the water of esterification being evolved during esterification. At the end of three hours, the pressure on the kettle was lowered to 20 mm. Hg and the esterification mixture heated at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/ g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. Water of neutralization and other volatile materials were stripped from the reaction product by heating the product to C. and 20 mm. Hg. The reaction product was then cooled, treated with 1% by weight of filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired ester of an ethoxylated wmethylbenzylphenol, that is, the stearate ester of the condensation product of about nine moles of ethylene oxide and about one mole of a-methylbenzylphenol. The final product was a light yellow liquid, having an acid value under 4, a viscosity at 25 C. of 196 cps. and a pour point of 65 F.

EXAMPLE II Preparation of the neutral adipate ester of an ethoxylated benzylphenol The procedure of Example I(C) above was repeated with the exception that 94.5 g. (0.645 mole) of adipic acid was substituted for 354 g. 1.29 mole) of stearic acid used in Example 1(0). The resulting product was the desired neutral adipate ester of an ethoxylated a-methylbenzylphenol, that is, the adipate ester of the condensation prodnot of about nine moles of ethylene oxide and one mole of ot-methylbenzylphenol. The product was a liquid having a Gardner color of less than 2, an acid value of less than 3, a viscosity at 25 C. of 975 cps. and a pour point of 5 F.

EXAMPLE III Preparation of the acetate ester of an ethoxylated benzylphenol 300 g. (0.5 mole) of the ethoxylated a-methylbenzylphenol which was the condensation product of nine moles of ethylene oxide and one mole of a-methylbenzylphenol obtained in Example I(B) above and 61.2 g. (0.6 mole) of acetic anhydride were refluxed for 3.5 hours at 150 C. under a nitrogen atmosphere. After 3.5 hours of reflux, pressure on the reaction kettle was slowly reduced to 100 mm. Hg and then to 10 mm. Hg stripping out the acetic acid of reaction and the excess unreacted acetic anhydride. The reaction product, which was the acetate ester of the condensation product of about nine moles of ethylene oxide and one mole of a-methylbenzylphenol, was a liquid having a Gardner color of less than 2.

EXAMPLE 1V Preparation of the stearate ester of an ethoxylated benzylphenol (A) Preparation of an ethoxylated benzylphenol.The procedure of Example I(B) was repeated with the exception that 4.2 moles of ethylene oxide was reacted with ot-methyl'benzylphenol instead of 9 moles of ethylene oxide. The resulting reaction product was the desired ethoxylated a-methylbenzylphenol, that is, the condensation product of about 4.2 moles of ethylene oxide and about one mole of a-methylbenzylphenol.

(B) Preparation of an ester of an ethoxylated benzylphenol.-The procedure of Example I(C) above was repeated with the exception that 79 g. (0.174 mole) of an ethoxylated u-methylbenzylphenol obtained in part (A) above which was the condensation product of'about 4.2 moles of ethylene oxide and one mole of a-methylbenzylphenol was substituted for the ethoxylated oc-methylbenzylphenol which was the condensation product of about 9 moles of ethylene oxide and about one mole of a-methylbenzylphenol was reacted with 47.4 g. (0.166 mole) of commercial stearic acid. The quantity of catalyst was reduced proportionately. The resulting product was the desired stearate ester of an ethoxylated a-methylbenzylphenol, that is, the stearate ester of the condensation product of about 4.2 moles of ethylene oxide and about one mole of a-methylbenzylphenol. The final product was a light, yellow liquid, having an acid value of less than 3.

EXAMPLE V Preparation of the neutral adipate of an ethoxylated benzylphenol The procedure of Example IV(B) above was repeated with the exception that 34 g. (0.233 mole) of adipic acid was substituted for 64.2 g. of stearic acid that would have been necessary based on the quantity of ethoxylated a-methylbenzylphenol used. The resulting product was the desired neutral adipate ester of the condensation prodnet of about 4.2 moles of ethylene oxide and about one mole of u-methylbenzylphenol. The product was a light yellow liquid, having an acid value of less than 3 and a pour point of F.

EXAMPLE VI Preparation of the acetate ester of an ethoxylated benzylphenol 109 g. (0.25 mole) of the ethoxylated a-methylbenzylphenol which was the condensation product of 4.2 moles of ethylene oxide and one mole of a-methylbenzylphenol obtained in Example IV(A) above and 30.6 g. (0.3 mole) of acetic anhydride were refluxed for 3.5 hours. at 150 C., under a nitrogen atmosphere. After 3.5 hours of reflux, pressure in the reaction kettle was slowly reduced to 100 mm. Hg and then to 10 mm. Hg to strip out the acetic acid formed by reaction as well as the unreacted acetic anhydride. The final reaction product which was the acetate ester of the condensation product of about 4.2 moles of ethylene oxide and one mole of tie-methylbenzylphenol was a liquid having a Gardner color of less than 2.

EXAMPLE VII Preparation of the stearate ester of an ethoxylated benzylphenol (A) Preparation of an ethoxylated benzylphenol.The procedure of Example I(B) was repeated with the exception that 1.2 moles of ethylene oxide was reacted with u-methylbenzylphenol instead of 9 moles of ethylene oxide. The resulting reaction product was the desired ethoxylated a-methylbenzylphenol, that is, the condensation product of about 1.2 moles of ethylene oxide and about one mole of a-methylbenzylphenol.

(B) Preparation of the stearate ester of an ethoxylated benzylphenol.The procedure of Example I(C) above was repeated with the exception that 63 g. (0.236 mole) of the ethoxylated a-methylbenzylphenol obtained in part (A) above which was the condensation product of about 1.2 moles of ethylene oxide and one mole of tat-methylbenzylphenol was substituted for the ethoxylated a-methylbenzylphenol which was the condensation product of about 9 moles of ethylene oxide and about one mole of a-rnethylbenzylphenol and was reacted with 62 g. (0.226 mole) of commercial stearic acid. The quantity of catalyst was reduced proportionately. The resulting product was the desired stearate ester of an ethoxylated a-methylbenzylphenol, that is, the stearate ester of the condensation product of about 1.2 moles of ethylene oxide and about one mole of a-methylbenzylphenol. The product was a light yellow liquid having an acid value of under 3.

12 EXAMPLE VIII Preparation of the dipelargonate ester of an ethoxylated bis benzylphenol (A) Preparation of a bis benzy1phenol.198 g. (1.0 mole) of a-methylbenzylphenol produced by the process described in Example I(A) above and 21 g. (0.7 mole) of paraformaldehyde were charged into a reaction kettle and heated to about 65 C. The paraformaldehyde dissolved in the phenol on heating to 65 C. 2 g. (0.02 mole) of 37% by weight aqueous hydrochloric acid was then added as a catalyst. An exothermic reaction occurred; the reaction temperature rose to C. from the exotherm and then slowly dropped to 70 C. The reaction mixture was then held at about 70 C. for four hours to form his u-methylbenzylphenol. The mineral acidity of the his u-methylbenzylphenol was neutralized with 50% aqueous caustic potash. The bis a-methylbenzylphenol was then vacuum stripped of volatile materials by heating to 150 C. under 10 mm. Hg. The bis a-methylbenzylphenol formed a hard amber glass on cooling to room temperature.

(B) Preparation of an ethoxylated bis benzylphenol. Into a reaction kettle were charged 102 g. (0.25 mole) of bis ot-methylbenzylphenol prepared by the procedure described in part (A) above and 0.2 g. (0.0035 mole) of potassium hydroxide flakes. The kettle was then heated to about 150 C. and purged with nitrogen. 193 g. (4.4 mole) of ethylene oxide were then added while allowing the exotherm of the reaction to maintain the reaction temperature at about 150 C. to about 200 C. After the ethylene oxide addition was completed, the temperature of the reaction mixture was held at about 150 C. to about 200 C. for one hour and then cooled to room temperature. The resulting reaction product was the desired ethoxylated bis a-methylbenzylphenol, that is, the condensation product of about seventeen moles of ethylene oxide and about one mole of bis a-methylbenzylphenol.

(C) Preparation of the dipelargonate ester of an ethoxylated bis benzylphenol.-Into a reaction kettle 150 g. (0.127 mole) of the ethoxylated bis a-methylbenzylphenol obtained in part (B) above, 3 8 g. (0.24 mole) of pelargonic acid, 0.6 g. (0.0043 mole) of a 70% by weight aqueous solution of methane sulfonic acid and 0.4 g. (0.003 mole) of a 50% by weight aqueous solution of hypophosphorous acid were charged. The reactants were sparged by nitrogen gas, while pressure on the kettle was lowered to mm. Hg. They were slowly heated to C. removing the water of esterification being evolved during the esterification. At the end of three hours, the pressure on the kettle was lowered to 20 mm. Hg and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/ g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was stripped by distillation of the water of neutralization and other volatile materials by heating the product to C. under 20 mm. Hg. The reaction was then cooled, treated with 1% by weight of :filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired dipelargonate ester of an ethoxylated bis a-methylbenzylphenol, that is, the dipelargonate ester of the condensation product of about seventeen moles of ethylene oxide and about one mole of his a-methylbenzylphenol. The product was a light yellow liquid, having an acid value under 4.

EXAMPLE IX Preparation of the stearate ester of an ethoxylated alcohol Into a reaction kettle, 415 g. (0.525 mole) of an ethoxylated alcohol which was the condensation product of twelve moles of ethylene oxide and one mole of a mixture of secondary linear alcohols, 138 g. (0.5 mole) of stearic acid, 1.5 g. (0.011 mole) of a 70% by weight aqueous solution of methane sulfonic acid and 1.0 g. (0.0076 mole) of a 50% by weight aqueous solution of hypophosphorous acid were charged. The ethoxylated alcohol was a commercial surfactant. Tergitol 15S12 (Union Carbide). The reactants were sparged by nitrogen gas, while the pressure on the kettle was lowered to 100 mm. Hg. They were heated slowly to 140 C., removing the water of esterification being evolved during the esterification. At the end of three hours, the pressure of the kettle was lowered to 20 mm. and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than (mgm. potassium hydroxide/ g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was stripped by distillation of the water of neutralization and other volatile materials by heating the product to 150 C. under 20 mm. Hg. Then the reaction product was cooled, treated with 1% by weight of filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired stearate ester of an ethoxylated secondary alcohol, that is, the stearate ester of the condensation product of about twelve moles of ethylene oxide and about one mole of a secondary alcohol. The product had a pour point of 69 F. and an acid value under 3.

EXAMPLE X Preparation of the stearate ester of an ethoxylated alcohol The procedure in Example IX was repeated to produce a second sample of the stearate ester of the condensation product of about twelve moles of ethylene oxide and one mole of a mixture of C1145 secondary linear alcohols. The ethoxylated alcohol was Tergitol 15-S-12. The final product had a pour point of 69 F. and an acid value under 3.

EXAMPLE XI Preparation of the neutral adipate ester of an ethoxylated alcohol Into a reaction kettle, 508 g. (0.78 mole) of an ethoxylated alcohol which was the condensation product of nine moles of ethylene oxide and one mole of a mixture of C secondary linear alcohols, 54.4 g. (0.37 mole) of adipic acid, 1.7 g. (0.012 mole) of a 70% by weight aqueous solution of methane sulfonic acid and 1.1 g. (0.0085 mole) of a 50% weight aqueous solution of hypophosphorous acid were charged. The ethoxylated alcohol was a commercial surfactant, Tergitol 15-S9 (Union Carbide). The reactants were sparged by nitrogen gas, while the pressure on the kettle was lowered to 100 mm. Hg. They were heated slowly to 140 C., removing the water of esterification being evolved during esterification. At the end of three hours at 140 C., the pressure on the kettle was lowered to 20 mm. Hg and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/ g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was stripped by distillation of the water of neutralization and other volatile materials by heating the product to 150 C. under 20 mm. Hg. Then the reaction product was cooled to 30 0., treated with 1% by weight of filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired neutral adipate ester of an ethoxylated alcohol, that is, the neutral adipate ester of the condensation product of about nine moles of ethylene oxide and about one mole of an alcohol. The product was a liquid having an acid value under 2, a viscosity at 25 C. of 150 cps. and a pour point of 27 F.

14 EXAMPLE XII Preparation of an ester of an ethoxylated alcohol Into a reaction kettle were charged 399 g. (0.63 mole) of an ethoxylated alcohol which is the condensation product of nine moles of ethylene oxide with one mole of a mixture of C alcohols, 128 g. (0.6 mole) of commercial coconut fatty acids, 1.5 g. (0.011 mole) of a 70% by weight aqueous solution of methane sulfonic acid and 1.0 g. (0.00076 mole) of a 50% by weight aqueous solution of hypophosphorous acid. The ethoxylated alcohol was a commercial product available under the name of Neodol 25-9 (Shell Chemical Co.) and was produced from Neodol 25, a mixture of primary alcohols of chain lengths of eleven to fifteen carbon atoms. The reactants were sparged by nitrogen gas while the pressure of the kettle was reduced to mm. Hg. They were then heated slowly to C. removing the water of esterification being evolved during esterification. At the end of three hours at 140 C., the pressure on the kettle was lowered to 20 mm. Hg and the reaction mixture held at 140 C. and 20 mm. until a total acid value of less than 5 (mgm. potassium hydroxide/g. of sample) was obtained. The reaction product was cooled to 50 C. and its mineral acidity neutralized. The neutralized reaction product was vacuum stripped to remove the water of neutralization and other volatile materials by heating at C. under 20 mm. Hg. The reaction product was cooled to 50 C., mixed with 1% by weight of filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired coconut fatty acid ester of an ethoxylated alcohol which was the coconutate ester of the condensation product of about nine moles of ethylene oxide with about one mole of a mixture of C1145 alcohols. The final reaction product was a liquid, having an acid value under 3, a viscosity at 25 C. or 52 cps. and a pour point of 62 F.

EXAMPLE XIII Preparation of an ester of an ethoxylated alcohol Into a reaction kettle were charged 376 g. (0.63 mole) of an ethoxylated alcohol which was the condensation product of 12.5 moles of ethylene oxide and one mole of methyl alcohol, 164 g. (0.6 mole) of commercial stearic acid, 1.5 g. (0.011 mole) of a 70% by weight aqueous solution of methane sulphonic acid and 1.0 g. (0.008 mole) of a 50% by weight aqueous solution of hypophosphorous acid. The ethoxylated alcohol was a commercial product, Carbowax Methoxy Polyethylene Glycol 550 (Union Carbide). The reactants were sparged by nitrogen gas while the pressure on the kettle was lowered to 100 mm. Hg. They were heated slowly to 140 C. while removing the water of esterification being evolved during the esterification. At the end of three hours, the pressure on the kettle was lowered to 20 mm. and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was vacuum stripped by distillation of the water of neutralization and other volatile materials by heating the product to 150 C. and under 20 mm. Hg. Then the product was cooled, treated with 1% by weight of filter aid and 1% by weight of filter clays and filtered. The filtrate was the desired stearate ester of an ethoxylated alcohol, that is, the stearate ester of the condensation product of about 12.5 moles of ethylene oxide and about one mole of methyl alcohol. The product was a white solid having an acid value under 3 and a drop point of 31 C.

EXAMPLE XIV Determination of Actual Percent by weight Volatility Loss of esters of ethoxylated aliphatic alcohols, esters of 1 ethoxylated benzylphenol compounds and their compositions and the Apparent Percent by weight Volatility Activity of their compositions.

The Actual Percent by weight Volatility Loss was determined for each of the esters of ethoxylated aliphatic alcohols shown in Table I as Aliphatic Compounds of Examples IX, X, XI and XII. Likewise, the Actual Percent by weight Volatility loss of the esters of ethoxylated benzylphenol compounds shown in Table II as the Aryl Compounds of Examples H through VIII were determined. The Actual Percent by weight Volatility Loss, V, was determined experimentally by placing 5 g. of a sample of the Aliphatic Compound (ethoxylated aliphatic alcohol component) or the Aryl Compound (ethoxylated arylphenol component) of the indicated example in an aluminum dish. The aluminum dish had a diameter of 2% inch and a height of inch. The aluminum dish containing this sample was then placed in an air circulating oven at 200 C. for one hour. At the end of one hour, the dish was removed from the oven and placed in a calcium chloride desiccator and allowed to cool to room temperature. After cooling to room temperature, the sample was removed from the desiccator and weighed. The value of the Actual Percent by weight Volatility Loss, V, was then determined by the following formula:

Weight of sample at 20 C. before placing in oven The sample was then placed in the oven at 200 C. for an additional hour, heated, removed from the oven, cooled in the desiccator and weighed. The value of V was determined after the second hour. Values of V were then determined after the third, fourth and fifth hour of heating at 200 C., in the oven. The results of these tests with Aliphatic Compounds are shown in Table I and the Aryl Compounds in Table II.

The Actual Percent by weight Volatility Loss of Compositions Containing 50% by weight specific Aryl Compounds and 50% by weight specific Aliphatic Compounds are determined by the procedure above. The Compositions shown in Table III were prepared by mixing equal parts by weight of the indicated Aryl Compounds and indicated Aliphatic Compounds. The Actual Percent by weight Volatility Loss of each of the Compositions, V, was then determined experimentally by this procedure. Results of these determinations are shown in Table III.

The Apparent Percent by weight Volatility Activity of Compositions Containing 50% by weight of the Aryl Compounds and 50% by weight of the Aliphatic Compounds shown in Table IV were calculated by the formula:

Apparent percent by weight Volatility Activity of Aliphatic Compound PZVZ (100) wherein V is the volatility of the Aryl Compound at 100% concentration (by weight), V is the volatility of the Aliphatic Compound at 100% concentration (by weight), V is the volatility of the composition of the Aryl Compound and the Aliphatic Compound at the indicated concentrations (by weight) and P is the concentration of the Aryl Compound (decimal) and P is the concentration of the Aliphatic Compound (decimal). Results of these calculations are shown in Table IV.

Table IV shows to what extent the volatility of the Aliphatic Compound in the composition with the aromatic compound was reduced by the presence of the aromatic compound. For example, in the composition in Table IV containing the Aryl Compound of Example V and the Aliphatic Compound of Example XI after three hours at 200 C., the Apparent Percent by weight Volatility of the Aliphatic Compound was 33% of what the Volatility would have been if the Aliphatic Compound had been present alone. That is, the Aliphatic Compound acted as 16 if it were present at 16.5% by weight instead of 50% by weight in the composition.

EXAMPLE XV Determination of Actual Percent by weight Volatility Loss of Compositions containing varying proportions of an ester of an ethoxylated aliphatic alcohol and an ester of an ethoxylated benzylphenol compound and the Apparent Percent by weight Volatility Activity of these compositions.

Compositions were prepared containing various percentages of the Aryl Compound of Example I and the Aliphatic Compound of Example XIII. The Aryl Compound of Example I was the stearate ester of the condensation product of about nine moles of ethylene oxide and about one mole of a-methylbenzylphenol. The Aliphatic Compound of Example XIII was the stearate ester of the condensation product of about 12.5 moles of ethylene oxide and about one mole of methyl alcohol. The compositions contained 0, 5, 10, 25, 50, 75 and by weight of the Aryl Compound of Example I and 100, 95, 90, 75, 50, 25 and 0% 'by weight of the Aliphatic Compound of Example XIII respectively.

Actual Percent by weight Volatility Loss of each of these compositions was determined by the procedure given in Example XIV. Results of these deterrrripations are shown in Table V. Likewise, the Apparent Percent by weight Volatility Activity of each of these compositions was determined using the formula given in Example XIV. Results of these determinations are shown in Table VI.

EXAMPLE XVI Determination of Actual Percent by weight Volatility Loss of Compositions containing varying proportions of an ester of ethoxylated aliphatic alcohols and an ester of an ethoxylated benzylphenol compound and the Apparent Percent by weight Volatility Activity of these compositions.

Compositions were prepared containing various percentages of the Aryl Compound of Example I and the Aliphatic Compound of Example XVI. The Aryl Compound of Example I was the stearate ester of the condensation product of about nine moles of ethylene oxide and about one mole of a-methylbenzylphenol. The Aliphatic Compound of Example XVI was the stearate ester of Tergitol 15-8-3 (Union Carbide). The stearate ester was prepared using the procedure described in Example IX with the exception that the commercial surfactant used was the condensation product of about three moles of ethylene oxide and one mole of a mixture of secondary linear alcohols having chain lengths of from about eleven to about fifteen carbon atoms. The compositions contained 0, 10, 25, 50, 75 and 100% by weight of the Aryl Compound of Example I and 100, 90, 75, 50, 25 and 0% by weight of the Aliphatic Compound of Example XVI respectively.

Actual percent by weight Volatility Loss of each of these compositions was determined by the procedure given in Example XIV. Results of these determinations are shown in Table VII. Likewise, the apparent percent by weight Volatility Activity of each of these compositions was determined using the formula given in Example XIV. Results of these determinations are shown in Table VIII.

The Smoke Points of these fiber treating compositions were determined by using a modification of the A.O.C.S. Ofiicial Method Ce 9a-48 for Smoke Points. The modification consisted of not using the cabinet which enclosed the heated cup. Gardner colors of the compositions were determined before and after the Smoke Points were measured. Results of these determinations are shown in Table IX-Smoke Points of Compositions of the Aryl Compound of Example I and the Aliphatic Compound of Example XVI. The data in Table IX show that the Smoke Points of the compositions were improved when the compositions contained 10% by weight of more of the Aryl Compound. Further, data in the table show that the Gardner colors of the compositions were unchanged by heating during the Smoke Point determinations.

EXAMPLE XVII Evaluation of lubricating and antistatic properties of an ester of an ethoxylated aliphatic alcohol, an ester of an ethoxylated benzylphenol and their compositions.

The Aryl Compound of Example I, which was the stearate ester of the condensation product of about 9 moles of ethylene oxide and about 1 mole of vt-methyl- *benzylphenol as described in part (C) of Example I, was used in these studies. The Aliphatic Compound of Example XVI which was the stearate ester of Tergitol 15-S-3 (Union Carbide) was also used. Compositions containing 100, 75, 50, 25, 10 and by weight of the Aryl Compound and O, 25, 50, 75, 90 and 100% by weight of the Aliphatic Compound of Example XVI respectively were prepared and used in these studies.

Isopropanol mixtures of the compositions were applied to 70/34 nylon filament yarn. Each sample of yarn was dried to remove the alcohol and was then conditioned for 24 hours at 50% Relative Humidity and 72 F. The conditioned, treated yarn, which contained 1% by weight of the composition based on the weight of the fiber, was evaluated to determine Fiber to Metal Coeflicients of Friction under both hot and cold conditions. Coefiicients of Friction were measured using a Rothschild F-Meter 1081 for Measuring Coefficients of Friction with two Rothschild Electronic Tensiometers. The incoming tension on the yarn was 0.5 g./Denier. Both the Hot and Cold Pins were Chrome Pin No. 2. Three loops were used on the Hot Pin and two loops on the Cold Pin. The Hot Pin was heated to 200 F. and the yarn speed was 40 yds./ minute. The Cold Pin was at room temperature and yarn speeds were 40 yds./minute and 300 yds./minute respectively. Results of these tests are shown in Table X below.

Further, Antistatic Properties of the conditioned, treated yarn were also determined. The Antistatic Half Life and the Charge Generation on the yarn were measured. Antistatic Half Life tests were made on the conditioned, treated fibers. A given charge was placed on the yarn and the time required for one half of the charge to dissipate from the yarn was measured and recorded in Table X below. A Rothschild Static Voltmeter R-1019 was used in the Charge Generation test. The yarn was passed over a friction surface to generate a static charge and the static charge generated on the surface was measured. The Charge Generation in Volts at various yarn speeds in Yards/ Minute are shown in Table X below. As indicated in Table X, there is the possibility of control of friction. Control of friction is important in fiber processing.

EXAMPLE XVIII Preparation of esters of alcohols action mixture was heated slowly to 140 C. to remove the water of esterification being evolved during the esterification. At the end of three hours, the pressure on the flask was reduced to 20 mm. Hg and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was stripped by volatilization of water of neutralization and other volatile materials by heating the product at 150 C. under 20 mm. Hg. The reaction product was then cooled, treated with 1% by weight of filter aid and 1% by weight of filter clay and filtered. The filtrate was the desired ester of the alcohol. These filtrates were treated further with steam under vacuum at mm. Hg and 150 C. to remove any impurities present in the original alcohol. The above procedure was used to prepare stearate esters of the following alcohols: (1) a mixture of C1145 secondary linear alcohols, (2) a mixture of C1143 secondary linear alcohols, (3) a mixture of C1445 secondary linear alcohols and (4) a mixture of C1145 primary linear alcohols. Typical analyses of the secondary linear alcohols described in (1), (2) and (3) are as follows:

Unsaturatesless than 1% Waterless than 0.5% Ketones-l .5

Sap. valueless than or equal to l Acidity0.001 mill. eq./gm. Color-5-3O Pt The representative molecular weights were The pour points and viscosities at 25 C. were determined for these stearates and are shown in Table XI below. The pour points were determined by the ASTM D-97-66 Method and the viscosities were determined using a Brookfield viscometer. When esters were solids, their drop points instead of pour points were determined. The drop points were determined by the ASTM-D-566-64 Meth- 0d.

The data in Table XI show that esters of mixtures of secondary linear alcohols were liquids having pour points whereas esters of mixtures of primary linear alcohols were solids which require the use of drop point characterization rather than pour point characterization.

EXAMPLE XIX Preparation of esters of ethoxylated alcohols 0.525 mole of each of the alcohols listed below, 0.5 mole of a monocarboxylic organic acid or 0.25 mole of a dicarboxylic acid, 0.011 mole of a 70% by weight aqueous solution of methane sulfonic acid and 0.0075 mole of a 50% by weight aqueous solution of hypophosphorous acid were charged into a glass flask. The reactants were sparged with nitrogen gas, while the pressure on the flask was lowered to 100 mm. Hg. The reaction mixture was slowly heated to C. under 100 mm. Hg to remove the water of esterification being evolved during esterification. At the end of three hours, the pressure on the flask was reduced to 20 mm. Hg and the esterification mixture held at 140 C. and 20 mm. Hg until a total acid value of less than 5 (mgm. potassium hydroxide/ g. of sample) was obtained. The esterification reaction product was then cooled to 50 C. and the mineral acidity was neutralized. The reaction product was stripped by volatilization of water of neutralization and other volatile materials by heating the product at C. under 20 mm. Hg. Then the reaction product was cooled, treated with l% by weight filter aid and 1% by weight filter clay and filtered. The filtrate was the desired ester of the ethoxylated alcohol.

The above procedure was used to prepare the esters of the following ethoxylated alochols: (1) The stearate of a mixture of C1145 secondary linear alcohols+3 E0. (3 moles of ethylene oxide), (2) the adipate of a mixture of C secondary linear alcohols+3 E.O., (3) the polargonate of a mixture of C secondary linear alcohols+3 E.O., (4) the coconutate of a mixture of C1145 secondary linear alcohols+3 E.O., (5) the acetate of a mixture of C1145 secondary linear alcohols+3 E.O., (6) the coconutate of a mixture of C primary linear alcohols-l-Z E.O., (7) the coconutate of a mixture of C primary linear alcohols-[-39 E.O., (8) the coconutate of a mixture of C1042 primary linear a1coho1s+6 .3 E.O., (9) the coconutate of a mixture of C1245 primary linear alcohols-H E.O., and (10) the stearate of a mixture of 19 C1245 primary linear alcohols-l-B E0. The term E.O. means ethylene oxide and the number represents the moles of ethylene oxide reacted with one mole of alcohol.

The pour points of these esters were determined and are shown in Table XII below. The pour points were determined by the ASTM D-97-66 Method.

The data in Table XII show that esters of ethoxylates of mixtures of secondary linear alcohols have lower pour points than esters of ethoxylates of mixtures of primary linear alcohols. It may be noted that the coconut oil fatty acids used in making of various esters of the ethoxylated primary alcohols are unfractionated and hence, contain some unsaturated fatty acids. Thus, liquids are obtained with ethoxylated primary alcohols. However, by comparison with (4) secondary alcohol ethoxylated esters, the pour points of the primary alcohol group are much higher.

Further, the Brookfield viscosities at 100 F. of (1) and respectively were 22 cps. and 33 cps. These results further show the advantages of the secondary alcohols as well as their ethoxylates over the primary alcohols and their ethoxylates.

EXAMPLE XX Evaluation of lubricating properties of esters of secondary linear alcohols The following esters were evaluated as fiber lubricants: 1) the stearate of a mixture of C secondary linear alcohols, (2) the sterate of a mixture of C1143 secondary linear alcohols and (3) the stearate of a mixture of C1445 secondary linear alcohols were evaluated as fiber lubricants.

Isopropanol mixtures of the esters were applied to 200/34 4 Z type 180 Du Pont nylon filament yarn. The yarns were dried to remove the alcohol and were conditioned for 24 hours at 50% relative Humidity and 72 F. The conditioned treated yarn which contained 1% by weight of one of the above esters based on the weight of the fiber, was evaluated to determine fiber to Metal Coefficients of Friction using both AlSiMag Pins and Chrome Pins. Coefficients of Friction were measured at room temperature using a Rothschild F-Meter 1081 for Measuring Coefficients of Friction with two Rothschild Electronic Tensiometers. Coeflicients on the AlSiMag Pins were measured using (1) two loops at a yarn speed of 22 yards per minute and (2) one loop at a yarn speed of 300 yards per minute. Coefficients on the Chrome Pins were measured using (3) three loops at a yarn speed of 22 yards per minute and (4) two loops at a yarn speed of 300 yards per minute. Results of these tests are shown in Table XIII below. These results show that the esters were eifeetive fiber lubricants. The AlSiMag Pins were from American Lava Corp. (Chattanooga, Tenn).

TABLE Ill-ACTUAL PERCENT BY WEIGHT VOLATILITY LOSS OF ALIPHATIC COMPOUNDS Actual percent by weight volatility loss after heating at 200 C. for (hours)- TABLE IL-ACTUAL PERCENT BY WEIGHT VOLA IL Y LOSS OF .ARYL COMPOUNDS T IT Actual percent by weight volatility loss after heating at 200 C. for (hours)- 100% of aryl compound of example:

TABLE III [Actual percent by weight Volatility Loss of Compositions Containing 50% by weight of the Aryl Compound oi the Indicated Example and 50% by weight of the Aliphatic Compound of the Indicated Examplel 5 Actual percent by weight volatility loss after heating at Aliphatic 200 C. for (hours) compound of Example 1 2 3 4 5 TABLE IV [Apparent percent by Weight Volatility Activity of Compositions Containing 50% by Weight of the Aryl Compound of the Indicated Example and 50% by Weight of the Aliphatic Compound oi the Indicated Example] Apparent percent by weight volatility activity of aliphatic compound after heating at Aliphatic 200 C. for (hours)- compound of Example 1 2 3 4 5 Aryl compound of example:

VIII X TABLE V [Actual percent by weight volatility loss of compositions of aryl compound of Example I and aliphatic compound of Example XIII] Percent by Actual percent by weight weight of volatility loss after heating aliphatic at 200 C. for (hours)- compound of Example XIII 1 2 3 4 5 5 Percent by weight of aryl co npound of Example I:

TABLE VI [Apparent percent by weight volatility activity of compositions of the aryl compound of Example I and the aliphatic compound of Example XIII] Apparent percent by weight volatility activity of Percent aliphatic compound after aliphatic heating at 200 C. for compound (hours) of Example XIII 1 2 3 4 5 Percent aryl compound of Example I:

TABLE VII [Actual percent by weight volatility loss of compositions of aryl compound of Example I and aliphatic compound of Example XVI] Percent by Weight of Actual percent by weight aliphatic volatility loss after compound heating at 200 C. for

(hours)- of Example XVI 1 2 3 4 5 Percent by weight of aryl compound of Example I:

TABLE VIII [Apparent percent by Weight volatility activity of compositions of the arylfiompound of Example I and the aliphatic compound of Example XV Apparent percent by weight Percent volatility activity of alialiphatic phatic compound after heatcompound ing at 200 C. for (hours) of Example XVI 1 2 3 4 5 Percent aryl compound of Example I:

1 The residue after the fifth hour cooled to form a slurry whereas the other residues cooled to form clear liquids. Initially, all of the compounds and their mixtures before heating Were liquids at room temperature.

TABLE IX [Smoke points of compositions of the aryl compound of Example I and TABLE XI.PHYSICAL PROPERTIES OF STEARATE ESTERS OF VARIOUS ALCOHOLS Pour Viscosity point, at 25 0.

F. (cps.) Drop point Stearate of:

1 a mixture of Orr-1s secondary alcohols 33 19. 5 2 a mixture of Oil-i3 secondary alcohols 37 19. 5 3 a mixture of 014-15 secondary alcohols 35 22.0 4 a mixture of 011-15 p mary alcohols 40 0. (104 F) TABLE XIL-PHYSICAL PROPERTIES OF ESTERS OF VARIOUS ETHOXYLATED ALCOHOLS Pour Esters point, F.

1 the stearate of a mixture of 011-15 secondary alcohols plus 3 E.O 49

2 the adipate of a mixture of 011-15 secondary 210011018 plus 3 E.O 0

3 the pelargonate of a mixture of 011-15 secondary alcohols plus 3 E.O 0

4 the coconutate of a mixture of 011-15 secondary alcohols plus 3 EG 0 5 the acetate of a mixture of 011-15 secondary alcohols us 3 E.0 0

6 the coconutate of a mixture of Clo-l2 primary alcohols plus 2 E.O 46

7 the coconutate of a mixture of Clo-12 primary alcohols us 3.9 E.O 31

8 the coconutate of a mixture of 010-12 primary alcohols plus 6.3 E.O 46

9 the cocouutate of a mixture of 012-15 Primary alcohols plus 3 E.O 65

10 the stearate of a mixture of 012-15 primary alcohols plus 3 15.0 1 73 1 Semisolid at room temperature.

TABLE XIII.-COEFFICIENTS OF FRICTION OF ESTERS OF SECONDARY LINEAR ALCOHOLS 1 Two loops at a yarn speed of 22 yards per minute. 2 One loop at a yarn speed of 300 yards per minute. 3 Three loops at a yarn speed of 22 yards per minute. 4 Two loops at a yarn speed of 300 yards per minute.

[Coefficients of friction and antistatic properties of the aryl compound of Example I and the aliphatic compound of Example XIV Composition Anti-static properties Percent Goeflicient of fiber aliphatic to metal friction Charge generation compound of Example Hot pin Cold Half Volts, Yards/ XVI at 200 F. pin life plus minute Percent aryl compound of Example I:

1 Conditions: Incoming tension: 0.05 gram/denier, hot pin and cold pin were chrome 23 What is claimed is: 1. A fiber treating composition, consisting essentially of (A) about to about 75% by weight of at least one ester of an ethoxylated arylphenolselected from the group consisting of ((IDCH2CH2) zr-O- R3 R1 (II-R i and wherein X is selected from the group consisting of hydrogen, chlorine and an alkyl radical having from about one to about fifteen carbon atoms;

R is selected from the group consisting of an aryl radical and a substituted aryl radical having from about six to about twenty four carbon atoms;

R is selected from the group consisting of hydrogen and an alkyl radical having from about one to about five carbon atoms;

R is an alkyl radical having from about one to about twenty one carbon atoms;

R is selected from the group consisting of an alkylene radical having from about one to about twenty one carbon atoms and a radical of the formula CH -O-CH and n is an integer of from about one to about twenty,

and

(B) about 90% to about 25% by weight of at least one ester of an ethoxylated aliphatic alcohol selected from the group consisting of and wherein R is an alkyl radical having from about one to about twenty one carbon atoms;

R is an alkyl radical having from about one to about thirty carbon atoms;

R is selected from the group consisting of an alkylene radical having from about one to about twenty one carbon atoms and a radical of the formula CH --O-CH and m is an integer of from about one to about twenty.

2. The composition of claim 1 wherein said composition consists essentially of (A) an ester of the ethoxylated arylphenol which is the stearate of the condensation product of about nine moles of ethylene oxide with about one mole of a-methylbenzylphenol, and

(B) an ester of the ethoxylated aliphatic alcohol which is the stearate of the condensation product of about twelve moles of ethylene oxide with about one mole of a secondary alcohol having from about twelve to fifteen carbon atoms.

3. The composition of claim 1 wherein said composition consists essentially of (A) about 50% by weight of said ester of the ethoxylated arylphenol, and

(B) about 50% by weight of said ester of the ethoxylated aliphatic alcohol.

4. The composition of claim 1 wherein said ethoxylated aliphatic alcohol is the condensation product of from about one to about twelve moles of ethylene oxide with about one mole of a mixture of primary alcohols having chain lengths of from about eight to about twenty eight carbon atoms.

5. The composition of claim 1 wherein said ethoxylated aliphatic alcohol is the condensation product of about seven moles to about twenty moles of ethylene oxide with one mole of methanol.

6. A textile fiber having applied thereto from about 0.1% by weight to about 6% by weight of the composition of claim 1.

7. Nylon fiber having applied thereto from about 0.1% by weight to about 6% by weight of the composition of claim 1.

8. Polyester fiber having applied thereto from about 0.1% by weight to about 6% by weight of the composition of claim 1.

References Cited UNITED STATES PATENTS 22 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 578,59 Dated May 1 l l97l IIWEn fl Bernard A. Dombrow It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, l ine 20, that portion of the formula reading (z-R should read (z-R R 2 Column 3, line 75, change "fiber" to --fibers-. Column l, line H change "completed" to -complete--; column l, line 2, change "plamitic" to palmitic-; column line 53, change "A" to --R--; column i, line 61, change "metyhl" to methyl--; column l, line 6i, change "btuyl" to -butyl-; column i, line 7 change "B is" to --Bis--. Column 7, line 65, change "to" to --at-. Column 8, l ine 52, insert "(2)" before 6 R column 8, l ine 58, after "is" insert -an--. Column l0, line 16, change "and" to under-; column l0, line l9, change "ester" to -esters--. Column 13, l ine 5i, after "5070 insert --by-. Column i l, line 36, change or" to -of-; column l i, line 63, after l50C. delete "and". Column l7, line 30, change 0.5 to -0.05--. Column l8, line 47, change "l iOC." to --l'+0C.--; column l8, line 62, change "alochols" to --alcohols--. Column 19, line 28, change "sterate" to --stearate--. Column 21 Table VI l I l ine 26, under heading Percent aliphatic compound of Example XVI" insert "(l)" as a superscript lOO"; column 2l third I ine from bottom, after "pin number" insert -2-.

Signed and sealed this 29th day of February 1972.

(SFM) ACT/03C;

FEW Pi NJ LETCHIJP JR. ROBERT GOTTSCHALK attestin Officer Commissioner of Patents