AU613404B2 - Spin fiber lubricant compositions - Google Patents

Description

217 c AU-Al-22566/88 WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau a PCr INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 01071 D06M 13/16, CIO M 1/08 C07C 69/24, 69/533, 69/58 Al (43)Jlrqjona blic ~'on 9nebruary 1989 (09.02.89) (21) International Application Number: PCT/US88/02498 (81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (Eropean patent), DE (Eu- (22) International Filing Date: 22 July 1988 (22.07.88) ropean patent), FR (European patent), GB (European patent), IT (European patent), JP, LU (European patent), NL (European patent), SE (European (31) Priority ApplicatioL Number: 082,769 patent).

(32) Priority Date: 6 August 1987 (06.08.87) Published (33) Priority Country: US With international search report Before the expiration of the tae limit for amending the claims and to be republished in the event of the receipt of (71) Applicant: THE LUBRIZOL CORPORATION [US/ amendments.

US]; 29400 Lakeland Boulevard, Wickliffe, OH 44092

(US).

(72) Inventors: YODICE, Richard 9115 Ambleside Drive, 20 APR 1989 Mentor, OH 44060 LENTZ, Gregory, A. 2237 Sherwin Drive, Twinsburg, OH 44087 (US).

(74) Agents: CORDEK, James, L. et al.; The Lubrizol Cor- AUSTRALIAN poration, 29400 Lakeland Boulevard, Wickliffe, OH 44092 1 Mf 1989 PATENT

OFFICE

(54) Title: SPIN FIBER LUBRICANT COMPOSITIONS 0

II;

R-CO CH 1 2

R

1 2R (57) Abstract A spin fiber lubricant composition is disclosed, The composition is essentially comprised of a liquid carrielt having therein an ester of general structural formula wherein RI, R 2

R

3 and R 4 are hydrocarbyl groups preferably in t e fortn of alkyl groups containing 1,6 carbon atoms, The composition may also include an emulsifying agent. The composition has been found to be useful A connection wvith providing materials with lubricating properties which are desirable for the spinning of fibers, r

I.

WO 89/01071 PCT/US88/02498 -1- Title: SPIN FIBER LUBRICANT COMPOSITIONS FIELD OF THE INVENTION This invention relates to the preparation of esters of neoalcohols and to the use of such esters as an additive in a spin fiber lubricant. More particularly, the invention relates to spin fiber luoricant compositions comprised of a liquid carrier and esterified neoalcohols of a particularly defined structural formula.

BACKGROUND OF THE INVENTION Spin finish, spinning finish, dressing, treating agent, spinning lubricant, coating fiber finish, processing agent, textile treating agent, textile treating composition, conditioning agent--all, of these terms are used to designate the same material: an antistatic lubricant applied to the surface of man-made fibers as soon as practical after the fiber has been formed. The properties of the applied material are dictated by several factors, among which are the fiber to which it is applied and the processing to which the fiber is to be subjected.

In general, once the fiber has been converted into yarn and then into fabric, the role of the finish is complete; it is usually removed prior to or during dyeing.

Natural fibers have their own finish. Cotton, for example, has a wax coating. The crude material extracted from raw cotton fiber by chlorAform, carbon tetrachloride, benzene, or other organic solvents is usually called wax.

Presumably most of the wax is located in the cuticle, WO 89/01071 PCT/US88/02498 -2which lies on the outside of the fiber. Most cotton which is spun contains its natural wax. Dewaxed cotton does not spin well. The wax undoubtedly has desirable lubricating properties for spinning.

In the production of synthetic continuous filament yarns, it is necessary to apply to the filaments during the spinning operation a lubricating composition to reduce friction developed as the yarns pass over the metal and ceramic machinery surfaces. Since they are applied during the spinning step, they are frequently referred to as spin finishes. Such finishes usually conta:Ln a lubricating ingredient to reduce friction, an antistatic agent to reduce the build-up of static electrical charges on the surfaces of the yarn as it passes over various machinery components, an antioxidant or thermal stabilizing agent to reduce the build-up of resin deposits on the machinery and the yarn itself, and an emulsifying agent in order that the total system may be applied to the yarn from an aqueous emulsion.

The primary function of a finish is to provide surface lubricity to the yarn such that smooth high-speed transfer over various metallic guides can take place with a minimum of fiber breakage.

Finishes also bring about fiber to fiber cohesiveness which is necessary to maintain uniform diameter and uniform twist configurations in the continuous multi-filament yarn system and winding.

Most synthetic fibers, due to their hydrophobic nature; are static prone--that is, they demonstrate a marked tendency to retain electrostatic charges. During the processing of the yarn, high-speed operations accelerate generation and retention of electrostatic charges. Without static protection of yarn, several problems may occur thereto such as'ballooning of yarn due to like charge repulsion between individual filaments, and tactile shock upon contact with processing equipment.

WO 89/01071 PCT/US88/0492 3 The electrostatic charges occurring on synthetic fibers may sometimes be disturbing to such a degree that they strongly impede or render completely impossible the further processing of the fibers.

To minimize wear and tear, heat damage, accumulation of static charges, and other like processing headaches, it has been found advantageous to enhance interfilament friction characteristics and fiber bundle cohesion generally by the use of finishes.

In preparation of yarns suitable for textile manufacture it is necessary to apply a lubricant to the filaments to permit processing of the yarn with minimum difficulty. As is well known in the art, selection of a suitable lubricant composition is not readily made, since many diverse requirements are imposed on the lubricant composition by the nature of a yarn's use and the manner in which it is manufactured. Of particular concern in high-temperature processing is the formation of hard insoluble resins and the- fuming of the finish when contacting heated surfaces. Some earlier attempts at providing spin fiber lubricants are referred to below.

DESCRIPTION OF RELATED ART U.S. Patent 3,993,571 (Marshall, November 23, 1976) relates to yarn finishing for multifilament yarns used in food packaging. The preferred finishing composition comprises butyl stearate, sorbitan monoleate and polyoxyethylene (20) sorbitan monooleate.

U.S. Patent 3,827,114 (Crossfield, August 6, 1974) is directed to a synthetic fiber finish which provides improved processing performance, heat stability, and the like, and comprises a heat stable, hydrophilic antistat of ah alkoxylated polyhydric alcohol fatty acid ester or an ocylated alcohol ester; and a heat stable, hydrophilic emulsifier comprising alkylene oxide condensate of polyhydric alcohols and/or long chain fatty acid esters or alkylene oxide condensates of an alkaryl hydroxy terminated compound.

U.S. Patent 4,049,766 (Eskridge, September 20, 1977) relates to a continuous spindraw winding of nylon 6 to produce yarn filaments of mixed beta-alpha crystalline morphology. The improvement is wherein prior to drawing, a spin finish emulsion containing from about 0.1 to about 6% by weight of benzyl alcohol is applied to the filaments to enhance conversion of the beta uniformity of dye acceptance to the drawn filaments.

U.S. Patent 3,859,122 (Burks, Jr. et al, January 7, 1975) relates to improved feed yarn for draw-texturing that has a finish composed of about parts by weight of an ester oil lubricant, about 45 parts of a nonionic surface active emulsifier, and about 0.6 to 2 parts of poly(oxyethylene-oxy-1, 2-propylene) glycol having a viscosity of about 9,000 SUS. A preferred ester oil is di(tridecyl) adipate.

A preferred emulsifier is a tetraoleate-laurate of a condensaLe of sorbitol with ethylene oxide, plus a small amount of a condensate of nonylpheno 'ith ethylene oxide. Twist slippage and broken filaments are reduced to provide uniform textured yarn, and objectionable deposits on equipment are avoided.

SUMMARY OF THE INVENTION The ptesent invention is a spin fiber lubricant composition comprised of a liquid carrier and ester having the general formula: O R 2 II I R- CO-CH- C- R 3 R4 wherein R 1 is selected from the group consisting of C 10 -C2 alkyl, C 4 -C50 alkenyl,

R

2 R, and R 4 are independently straight chain hydrocarbyl groups, branched -4chain hydrocarbyl groups or mixtures thereof.

S.

S S

SOS.

S.

S S 5555 55 S S SOS S S5 S 0@ OS S 5@

S

SOS...

S

Se SO S 59 5 0 0 SO SO 5 0

S

S

55055S 0 4a I WO 89/01071 PCT/US88/02498 A primary object of the invention is to provide a novel group of spin fiber lubricant compositions which include a liquid carrier having particularly defined ester compounds therein.

A feature of the invention is that the esters as well as the spin fiber lubricant compositions can be easily and economically manufactured.

An advantage of the present invention is that the spin fiber lubricant composition provides lubricating properties which are desirable for spinning materials.

These and other objects, advantages and features of the present invention will become apparent to those skilled in the art upon reading the details of the structure, synthesis and usage as more fully set forth below. Reference being made to the accompanying general structural formula forming part hereof wherein like symbols refer to like molec fXar moieties throughout.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION Before the present spin fiber lubricant compositions and processes for making such are described, it is to be understood that this invention is not limited to the particular compositions, materials or processes described as such, compositions and processes may, of course, vary.

It is also to be understood that the terminology used herein is for the purpose of describing particular preferred embodiments only, it is not intended to be limiting since the scope of the present invention will be limited only by the appended claims.

In order to clarify the following description of the 'pin fiber lubricant compositions of the invention individual components of the composition will be described. Thereafter, examples of such components will be put forth followed by specific examples of the compositions including some and all of the individual components.

I

WO 89/01071 PCT/US88/02498 6 It must be noted that as used in this specification and the appended claims, the singular forms "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to "a composition" includes mixtures of such compositions, reference to "an ester" includes reference to mixtures of such esters, and reference to "an emulsifying agent" includes mixtures of emulsifying agents and so forth.

Before describing the individual components of the invention, it should also be noted that the spin fiber lubricant composition is essentially comprised of the liquid carrier and the ester as defined further below.

However, other embodiments of the invention include the liquid carrier, ester and an emulsifying agent. Further, the invention also includes material having thereon the fiber lubricant comprised of the liquid carrier and the ester as well as materials having thereon the fiber lubricant comp sed of the liquid carrier, ester and emulsifying agent. Methods of utilizing the spin fiber lubricant compositions and the esters described herein are also disclosed.

Liquid Carrier The purpose of the liquid carrier is to solubilize the ester of a neoalcohol. The preferred liquid carrier is water; however, if the ester is not water soluble, a liquid carrier consisting of oil may be used. The oil may be a mineral oil, vegetable oil or tynthetic oil.

Further, any carrier may be used with a solubilizer which increases the solubility of the ester in the carrier.

Neoalcohol Ester The neoalcohol esters which are used in the composition in accordance with the present invention are compounds characterized by the structural formula (1) L _LII~ 1_ O R2 Rf- CO CHyC-

R

3 (I) 4 wherein R 1 is selected from the group consisting of C10-C22 alkyl, C4-C50 alkenyl, aryl, alkaryl, aralkyl or mixtures thereof, R2, R 3 and R 4 are independently straight chain hydrocarbyl groups, branched chain hydrocarbyl groups or mixtures thereof.

The neoalcohol ester is made by the reaction of a neoalcohol with a carboxylic acid or anhydride or by transesterification of an ester with a neoalcohol. For example S

R

2 0 R 2 I II I l l. R COOH R 3 C CH2OH->R1 C

O

C- C R3

R

4

R

4 0 R 2 0 R SRCO" R 3 C- CH2OH-RjCOCi- 2 C-R 3

"OH

R4.

R

4 The neoalcohol ester is prepared by reacting equal equivalents of neoalcohol with 'equal equivalents of acid. However, in order to force the neutralization reaction to completion, an excess of the neoalcohol is employed.

Normally, the neoalcohol is present in a 100% excess on an equivalent basis.

Preferably, the neoalcohol is present in a 50% excess. The unreacted neoalcohol may be removed by distillation after the neutralization reaction is complete and ,used for further neutralization renctions.

4 y Normally, the neoalcohoi and acid are added to a reaction vessel at r 7 I room temperature. Stirring is begun and an acid catalyst is added to promote the reaction. The catalyst of choice is para-toluene sulfonic acid. Upon completion of the neutralization, the catalyst itself is neutralized with an appropriate base, such as aqueous sodium hydroxide.

7a WO 89/01071 PCT/US88/02498 8 The neoalcohol ester is normally formed at about 110 C: although it is preferred to conduct the reaction up to 150 0 C. The reaction further may be followed by monitoring the amount of water obtained.

As used in this specification and appended claims, the terms "hydrocarbyl" or "hydrocarbon-based" denote a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention. Such groups include the following: Hydrocarbon groups; that is, aliphatic alkyl or alkenyl) aluyclic cycloalkyl or cycloalkenyl), aromatic, aliphatic- and alicyclicsubstituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group). Such groups are known to those skilled in the art. Examples include methyl, ethyl, octyl deyl l, octadecyl, cyclohexyl, phenyl, etc.

Substituted hydrocarbon groups, that is, groups containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the group. Those skilled in the art will be aware of suitable substituents. Examples include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc.

Hetero groups; that is, groups which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms.

Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or 3 hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group, W6 89/01071 W~ 8901071PCT/US88/02498 9- Terms such as "alkyl-based group", "aryl-based group" and the like have meaning analogous to the above with respect to alkyl and aryl groups and the like.

The hydrocarbyl groups R 2

R

3 and I naPy be alkyl groups containing from 1 to about 16 oarbon atoms, preferably 1 to about 10 carbon atoms, and most preferably 1 to about 6 carbon atoms. Specific examples of alkyl groups of R 2 R 3 and R4includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and t-butyl.

Non-limiting examples of neoalcohols that may be employed in the practice of this invention are: 2,2-dimnethyl-1pripanol, 2,2-dimethyl-l-butanol, 2, 2-dimethyl-1-pentanol, 2,2-dimethyl-l-hexanol, 2,2-dimnethyl-1-heptanol, 2t2-dimethyl-l-octenol, 2 -methyl- 2-ethyl-l1-butanol 2-mnethyl-2ethyl- 1-pentanol, 2-rethyl-2-ethyl-l-hexanol, 2-methyl-2ethyl-l-heptanol, 2-methyl-2-ethyl-l-octanole 2, 2-diethyl- 1-butanol, 2, 2-diethyl-l-pentanol, 2r2-diethyl-1-hexanol, 2,2-diethyl-1-heptanol, 2,2-diethyl-1-octanol, 2,2,3-tmethyl-l butanol, 2,2,3-trixnethyl-I-peZntanol, 2,2, 3-tnimethyl-l-hexanol, 202t3-trimethyl-1-heptanolt 2,2,3-tnimethyl-l-ooctanol, 2, 3-dimethyl-2-ethyl-1-butanolt 2,2,4trimethyl-l-pentanol, 2,2,4-trimethyl-1-hexano., 2,2,4tnimethyl-l-heptanol and 20,2, 4-trimethyl-d-octanol.

The hydrocarbyl group Ri of formula is linked to an acid or anhydride selected from the group consisting of maleic acid, nialeic anhydnide, phthalic anhydride, aryi, dicarboxylic acids, flOOC(C!-1 2 )n wherein n is from, eabout 2G; dimenizei acids of unsaturated mahocarboxylic acids that contain at least 12 carbon atz:as, ~I COOH, Pn CuCOOn

R

CH

2 COOH- and n o WO 89/01071 W089/1071PCT/US88/02498 10 The hydrocarbjyl group R 1 may also be an aliphatic or aromatic group selected from the group consisting of I .Slky., alkenyl, aryl, alkaryl and aralkyl and mixtures thereof. The rrc b7 J~.~a~eyL grounq- nnntainina from 4 to aboth z~n~ .~os preferably/ f rom 4 to about 22 carbon, atoms, and most preferably from 10 to about 22 carbon atoms. Preferably Ris an alkyl group containing from 14 to 18 carbon atoms. Specific examples of alkenyl groups containing from 14 to 18 carbon atoms include the various tetradecenes, the various hexadecenes and the various octadecenes. The most preferred octadecene is 1-oleyl.

When RIis an aryl group the preferred hydrocarbyl groups are phenyl, alpha-naphthyl and beta-naphthyl.

1s When R1is an araJ2kyl group the preferred hydrocarbyl groups are alkyl-substituted phenyl, alkyl-substituted alpha-naphthyI, and alkyl-substituted beta-naphthyl wherein the alkyl group is from 4 to 22 carbon atoms, and most .preferably from 6 to 18 carbon atoms.

Non-limiting -jxamples of carboxcylic acids or anhydrides that may b r reacted W.t neoalcohols are: formic acid, acetic,; acid, propionic acid, butyric acid, valeric ac, d, carroic acid, caprylic acid, capric actdf lauric acid, rnyristic acid, palmitic acid, stearic acide oJ.eic acid, linoleic acid, 1linolenic acid, phenylacetic acid, benzoic acid o-toluic acid, m-toluic acid,p-toJluil acid, oxalic acid, malonic acid, succini~c acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azeLaic acid, sebacic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic anhydride, maleic anhydride and phthalic anhydride.

The carboxylic acid or anhydride is reacted with a neoalcohoJ. in the presence of a catalyst such as para-toluene sulfonic acid. The course of the reaction is followed by monitoring the amount of water of neutralization obtainzd. The netralization is conducted Lip to a temnperatur~e of 1506C. The C-atalyst is neutralized hil WO 89/01071 PCT/US88/02498 11 with a base, and the reaction mass is filtered to yield the product.

Emulsifying Agent The emulsifier of this invention is an alkylene oxide adduct of an organic compound having an active hydrogen atom. Useful emulsifiers also function as lubricants.

Compounds suitable for use in preparing such adducts are fatty acids and fatty alcohols, preferably unsaturated, having 12 to 20 carbon atoms in their chains, polyhydric aliphatic alcoho-s and partial esters thereof, and alkyl phenols. Another class of suitable nonionic emulsifiers includes the partial fatty acid esters of polyols or their ethylene oxide adducts. As is known, othylone oxide adducts have hydrophilic properties due to the ethylene oxide moiety, and when the other portion of the adduct is primarily hydrocarbon so as to provide a hydrophobic moiety, the compound can be expected to exhibit surface active properties. In general, ethylene oxide adducts containing a chain of at leaJt at about 10 ,carbon atoms and at least three ethylene oxide units are useful in the practice of this invention. Preferably, the surface active adducts will contain at least about 10 ethylene oxide units in their molecules, since such compounds provide a composition with a high propensity for resisting the accumulation of electrostatic charges in addition to improving the manner in which the composition can were the filaments. Preferred surface active agents are the 1, adducts of ethylene oxide with a partial ester of fatty acids having at least 12 carbon atoms with polyols containing 3 to 6 hydroxyl groups, and the products obtained by esterifying an adduct of ethylene oxide and a polyol having 3 to 6 hydroxyl groups with a fatty acid having 12 to 22 carbon atoms. These products may be partial or complete esters and will preferably contain to 50 ethylene oxide units in their molecules. A particularly preferred member cQ this class of surfactants WO 89/01071 PCT/US88/02498 12is the material prepared by reacting one mole of sorbitol with about 30 moles of ethylene oxide and esterifying the product with about 5 moles of a 4:1 mixture of oleic and lauric acids, it is preferred to use a miture of this surfactant with an alkylphenoxy polyoxyethylene e thanol which, preferably, is the product of about 5 or 6 moles of ethylene oxide with one mole of nonylphenol. The combination of small quantities of about 2 to (percentages of finish ingredients herein are weight percentages based on the weight of non-aqueous finish ingredients), of this emulsifier with the sorbitol derivative surfactant performs excellently. It is essential that the emulsifiers fully emulsify the ester component of the finish in water. The emulsifier should be stable under conditions of use, it should have little tendency to smoke and form insoluble deposits when the yarn carrying the finish contacts hot surfaces.

The poly(oxyethylene-oxy-l,-2-propylene) diol of the present invention can be prepared as shown in U.S. Patent No. 2,425,845. Of the polyoxyalkylenes useful for this invention, the weight ratio of ethylene oxide groups, the groups (CH2-CH 2 to propylene oxide groups, the groups CH -0

CH

3 is between about 3:1 and 1:1 in order that the material 4 remain fluid and water soluble. It is important that the viscosity of the polyoxyalkylene diol be between 5,000 and 50,000 2US at 100 preferably, its viscosity is about 9,000 SUS at 100 0 F. If the viscosity is too low, broken filaments of the yarn carrying the finish result; whereas, if the viscosity is too high, unwanted twist slippage in the draw texturing process occurs. It is also important that the finish contain not more than 5 percent, and preferably not more than 2 percent, of the diol component.

SW 89/01071 PCT/US88/02498 13 If the finish contains more than aLbut 5 percent, unwanted twist slippage occurs in the draw texturing process.

Generally, if the viscosity of the diol is high, less is needed and vice versa.

The following examples illustrate the preparation of the ester of neoalcohols represented by formula Unless otherwise indicated in the examples and elsewhere in this specification and claim. all parts and percentages are by weight, and all temperatures are in degrees Centigrade.

EXAMPLE A Add a mixture. consisting of 100 grams (0.82 equivalents) brassylic acid (tridecanedioic acid) and 159.8 grams (1.23 equivalents) of 2,2,4-trimethyl-lpentanol to a reaction vessel. Stir and heat while passing nitrogen through the system at 0.5 cubic feet per hour. Add one gram of para-toluene sulfonic acid and heat the contents to 105 0 C. Collect about 10 milliliters of water in a Dean Stark Trap. Heat the contents to 150°C.

Obtain the neutralization number (acidic) and add aqueous sodium hydroxide to neutralize. Filter the contents and obtain the filtrate which should have a neutralization nuiber (acidic) of about EXAMPLE B Following essentially the same procedure of Example A, 160 grams (0.47 mcles) erucic acid (cis

CH

3

(CH

2 CH=CH(CH2 11COOH and 92 grams (0.71 moles) 2,2,4-trimethyl-l-pentanol are mixed and reacted. The neoalcohol ester obtained has a nil neutralization number (acidic).

EXAMPLE C Following essentially the same procedure of Example A, 190 grams (0.61 moles) behenic acid and 119 grams (0.91 WO) 89/01071 PCT/US88/02498 14 moles) of 2,2,4-trimethyl-l-pentanol are mixed and reacted, The neoalcohol ester 13 obtained in 84% yield.

EXAMPLE D Following essentially the same procedure of example A, 100 grams (1.14 equivalents) azelaic acid and 222 grams (1.70 equivalents) 2,2,4-trimethyl-l-pentanol are mixed and reacted. The neoalcohol ester obtained has a 3.1 neutralization number (acidic).

EXAMPLE E Five thousand, seven hundred seventy-five parts (25.33 moles) of a commercially available C 15 18 alphaolefin fraction (having a carbon number distribution of 1%

C

14 29% C 15 28% C 1 6 27% C 17 14% C 18 and 1% C 19 are passed through, a 12-inch column packed with activated alumina into a 12-liter flask containing 2485 parts (25.35 moles) maleic anhydride. The mixture is heated to 214°C and maintained at that temperature for 7 hours with a nitrogen sparge (0.2 standard cubic feet per hour) and cooled to room temperature. The mixture is heated to 214 0 C and maintained at that temperature for 7 hours with a nitrogen sparge (0.2 standard cubic feet per hour) and cooled to room temperature. The mixture is then heated to 209 0 -21"C and maintained at that temperature for 7 hours, then cooled to room temperature. 1500 parts of textile spirits are added and the mixture is stirred for one hour.

The mixture is' filtered with diatomaceous earth. The mixture is stripped under a vacuum of 0.7 mm Hg. at 168 0

C

then cooled to room temperature. The mixture is filtered with diatomaceous earth at room temperature. The filtrate is the desired product. 316 grams (2 equivalents) of the C15-1 8 substituted succinic anhydride and 602 grams equivalents) of 2,3,3-trimethyl-l-octanol are mixed and reacted according to the procedure of Example A.

WO: 89/01071 PCT/US88/02498 15 EXAMPLE F Charged to a reaction vessel are 198 parts (2.02 moles) of maleic anhydride and 500 parts (1.36 moles) of a commercial mixture of C 18 24 olefins available from Ethyl Corporation wherein these olefinr are typically 10% C 18

C

2 0 25% C22 and 15% C24 and are comprise! predominantly of substantially straight chain alpha, 1, 1-di-substituted and 1, 2-disubstituted olefins. This reaction mixture is heated to 200 0 C and held at 200-220 0

C

for 10 hours. Unreacted starting materials are removed by vacuum distillation to 5mm Hg. at 2000C. The reaction mixture is filtered to yield the desired C 18 24 substituted succinic anhydride having an acid number of 290. 452 grams (2 equivalents) of the C 18 24 substituted succinic anhydride and 700 grams (3.25 equivalents) of 2, 2-dimethyl-l-pentanol are mixed and reacted according to the procedure of Example A.

EXAMPLE G Charged to a reactor are 463 parts (4.72 equivalents) of maleic anhydride and 1000 parts (5.95 equivalents) of polypropylene tetramer. This reaction mixture is heated to 182°C and held at this temperature for 9 hours.

Unreacted starting materials are removed by vacuum distillation at 190°C and 10 mm Hg. The reaction mixture is filtered to yield the desired polypropylene tetramersubstituted succinic anhydride having an acid number to phenolphthalein of 428. 296 grams (2.0 equivalents) of the polypropylene tetramer substituted succinic anhydride and 700 grams (3.25 equivalents) of 2-methyl-2-ethyl-lbutanol are mixed and reacted according to the procedure of Example A.

In one embodiment, the spin finish composition of the present invention comprises a concentrate of a two-component system of about 20-50% of the ester of a neoalcohol and 50-80% of a liquid carrier. Preferably, i i i' WO 89/01071 PCT/US88/02498 16 the ester is present at a level of 25-45% and the carrier at 55-75%, and most preferably, the ester is present at 30-40% and the carrier at 60-70%.

In another embodiment, the spin finish composition of the present invention comprises a concentrate of a three-component system of carrier, ester and emulsifying agent containing about 30-55% of the carrier, 30-50% of the neoalcohol ester and 13-25% of the emulsifying agent.

Preferably, the carrier is present at 35-50%, the ester at 35-45% and the emulsifying agent at 15-25%. Most preferably, the carrier is present at 40%, the ester at and the emulsifying agent at 20%, with all components at In one embodiment, the spin finish composition of the present invention comprises about 35-45 weight percent of a neoalcohol ester, 15-25 weight percent of an emulsifying agent and 35-50 weight percent of a carrier preferably in the form of coconut oil.

In applying the finishing composition of this invention to the filaments, nylon, conventional methods may be employed. In general, good results are obtained in both hot and cold drawing operations when the finishing composition is applied in amounts ranging from about 0.2 to 1.5 percent and more preferably 0.8 to percent by weight, based on the weight of the yarn. The finishing composition is desirably applied as an aqueous emulsion containing about 12 to 25 percent of the finishing composition. The finishing composition is applied to the yarn prior to drawing by conventional techniques which comprise, for example, bringing the yarn in contact with the composition while it moves during the course of production. The composition may be applied to the yarn by various methods and devices which may include use of lubricating roll, wick, or having the yarn pass through a bath containing the finishing composition.

The following table shows examples. of the spin fiber lubricant composition. These examples are provided so as i W6 89/01071 PCT/US88/02498 17 to provide those of ordinary skill in the art with a complete disclosure and description of how to make the spin fiber lubricant compositions of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers used relative amounts, temperature, etc.) but some experimental errors and deviation should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in degrees centigrade, and pressure is at or near atmospheric. The table demonstrates the use of the spin finish of the present invention.

A polycaprolactam yarn (200 denier-32 filament) is prepared by conventional spin-draw techniques.

Immediately after spinning the spin finish, in a three-component system, consisting of an ester of a neoalcohol, glycerol trioleate or an ethoxylated sorbitol ester of a mixture of oleic acid and la iric acid, and coconut oil is applied to the yarn at the rate of 0.1-2 weight percent based on the weight of the yarn and preferably 0.5 to 1 percent by weight of the yarn as weight percent emulsion in water by means of a conventional kiss roll application.

In a two-component system where the spin finish consists of coconut oil and an ester of a neoalcohol, the spin finish is applied to the yarn at the rate of 0.2-2.5 weight percent based on the weight of the yarn and preferably 0.8 to 1.5 percent by weight of the yarn.

The composition of this invention may also be used with other agents such as anti-static agents, product stability agents, corrosion resistance agents, etc.

r WO 89/01071 PCT/US88/02498 18 Finish Compositions Components Composition in Weight Percent I II III IV V VI V VI VIII IX X XI 40 Composition of Example A

B

C

D

40 38 42 Glyceroltrioleate EtO/sorbitol acid/lauric acid (4/1)m] Coconut oil 15 18 20 20 22 20 20 15 17 17 45 45 42 42 45 38 40 38 47 45 The instant invention is shown and described -herein and was considered to be the most practical, and preferred embodiments. It is recognized, however, that departures may be made therefrom which are within the scope of the invention and that obvious modifications will occur to one skilled in the art upon reading this disclosure.

Claims (20)

1. A spin fiber lubricant composition coniprising a liquid carrier and at least one ester having the general formula O R II I R- CO CH 2 C- R 3 R 4 wherein R 1 is selected from the group consisting of C 10 -C2 alkyl, C 4 -C50 alkenyl, 10 aryl, alkaryl and aralkyl or mixtures thereof, R 2 R 3 and R 4 are straight chain 0 hydrocarbyl groups, branched chain hydrocarbyl groups or mixtures thereof.

2. The composition according to claim 1 wherein R 2 R 3 and R 4 are alkyl groups containing from 1 to 16 carbon atoms.

3. The composition according to claim 2 wherein R 2 and R 4 are methyl groups and R 3 is an isobutyl group. of 0

4. The composition according to any one of claims 1 to 3 wherein R 1 is an alkenyl group containing from 4 to 50 carbon atoms. S* 5. The composition according to claim 4 wherein the alkenyl group S containn 17 carbon atoms.

6. The composition according to any one of claims 1 to 3 wherein R 1 is an aryl group selected from the group consisting of phenyl, alpha-naphthyl and beta- naphthyl.

7. The composition according to any one of claims 1 to 6 wherein the .t liquid carrier is selected ftom the group consisting of oil and water. j 19

8. A spin fiber concentrate comprising from 50-80% of a liquid carrier and from 20-50% of the ester of claim 1.

9. A fibrous material having thereon a spin fiber concentrate of the composition according to claim 8 wherein the spin fiber concentrate is present on the material in an amount in the range of 0.1-2 percent by weight based upon the weight of the fibrous material. A spin fiber lubricant composition comprising a liquid carrier; at least one ester having the general formula OSOS *0 .1e SS *c S S 00 0 SO S. S S S. 0 R 2 II I R 1 CO CH 2 C- R 3 I S.. S OS 0 0* 0 S *5 0* :5 wherein R 1 is selected from the group consisting of Co 1 -C2 alkyl, C 4 -C50 alkenyl, S aryl, alkaryl and aralkyl or mixture? thereof, R 2 R 3 and R 4 are straight chain hydrocarbyl groups, branched chain hydrocarbyl groups or mixtures thereof; and an effective amount of an emulsifying agent. S 11. The composition according to claim 10 wherein the emulsifying agent is selected from the group consisting of an ethoxylated fatty alcohol; an ethoxylated fatty acid; an ethoxylated polyhydric alcohol; and an ethoxylated alkyl phenol.

12. A spin fiber concentrate composition according to claim 10 or 11 comprising from 30-55% of a liquid carrier, 30-50% of the ester and 15-25% of the emulsifying agent. Y i e r r~IF- QJ 'ru~~ i-

13. A fibrous material having thereon a spin fiber corcentrate of the composition according to any one of claims 10 to 12 wherein the spin fiber concentrate is present on the material in an amount in the range of 0.2-2.5 percent by weight based upon the weight of the fibrous material,

14. A process for preparing a spin fiber lubricant additive which comprises reacting a neoalcohol having the structure a. 0 0 06 ar C, 0r a. 0r R2 I R3-- C CH2OH 39 R4 wherein R 2 R 3 and R 4 are independently straight chain hydrocarbyl groups, branched chain hydrocarbyl groups or mixtures thereof, with an acid, RICOOH :5 wherein R 1 3s a hydrocarbyl group selected from the group consisting of C10-C2 alkyl, C 4 -C 50 alkenyl, aryl, alkaryl and aralkyl or mixtures therein. The process according to claim 14 wherein R 2 R 3 and R 4 are alkyl S groups containing from 1 to 16 carbon atoms, *00

16. The process according to claim 15 wherein R 2 and R 4 are methyl groups and R 3 is an isobutyl group.

17. The process according to any one of claims 14 to 16 wherein R 1 is an alkenyl group containing from 4 to 50 carbon atoms.

18. The process according to claim 17 wherein the alkenyl group contains 17 carbon atoms. S21- OS 0S..* 0 A 4S

19. The process according to any one of claims 14 to 16 wherein R 1 is an aryl group selected from the group consisting of phenyl, alpha-naphthyl and beta- naphthyl. The process according to any one of claims 14 to 19 wherein the equivalent ratio of neoalcohol to acid or anhydride is at least from 1:1 to 2:1.

21. The process according to any one of claims 14 to 20 wherein the reaction of neoalcohol to acid or anhydride is conducted at a temperature from ambient up to 150 C.

22. The process according to any one of claims 14 to 21 wherein the reaction of a neoalcohol with an acid is conducted in the presence of an acid catalyst.

23. The composition according to claim 1 or 10 substantially as hereindescribed with reference to any one of the Examples.

24. The process according to claim 14, substantially as hereindescribed with 15. reference to any one of the Examples. DATED this 13 day of May 1991. e. THE LUBRIZOL CORPORATION By Their Patent Attorneys: CALLINAN LAWRIE r i-22- A- INTERNATIONAL SEARCH REPORT International Application NO PCT/US 88Z/ 2 498 1. CLASSIFICATION~ OF SUBJECT MATTER (it several classification aymnbois apply, Indicate all) According to Interniational Patent Classification (IPC) or to both National Classification and IPC IC4 D 06 M 13/16; C 10 M 1/08; C 07 C 69/24; C 07 C 69/533; IC C 07 C 69/58 1i. FIELDS SEARCHED Minimum Documentation SearchedI Classification System Classification Symbol$ 4 IPC D06 M; C 10M; C07C 69/00 Documentation Searched other than Minimum Documentation to the Extent that such Documents are included In the Fields SearchedI Ill. DOCUMEN4TS CONSIDERED TO ME RELEVANT'0 Category Cltat'l'n of Document, I' with Indication, where appropriate, of the relevant passages 12 Reievant to Claim No, 11 X GB, A, 1492052 (PVC INTERNATIONAL) 1-11,15-21 16 November 1977 see the whole document X US, A, 3464922 (BERNHOLZ, COX) 1-11,15-21 2 September 1969 see column 2, lines 13-24 A FR, A, 1336631 (BRITISH NYLON SPINNERS) 1-6,8-11, 22 July 1963 15-21 see example 2 A US, A, 4103068 (MARSHALL) 1-6,8-11 July 1978 see column 2, lines 33-68 A i US, A, 3177143 (MAUL-DIN) 11,5? 6 April. 1965 see example 1; claims A US, A, 3575856 (ANTON)1 April 1971 see claim 1 Special .ategovies of cited documents: Is later document published atter the International flig date document defining the general state of the art which in not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the Principle or theory undedlying the "Ellearierdocmen bu pulised a oraftr te iteratinal invention ingarle docet bupulseonrafthlnerntu document of particular relevance; the claimdd Invention filin datecannot be considered novel or cannot be considered to document which masy throw doubts on prority claim(s) or Involve en Inventive step which Is cited to establish the Publication date of another "Y document of particular relevance;' the claimed Invention citation or other apecial reason (as specified) cannot be considered to Involve an inveriliy step when the doc 1- rt refering to an oral disclosure, use, exhibition or document Is combined with one or More oth%:f quch docu. othe eiIs manta. such combination being obvious to a peison skilled 011,1 documoe", pubiished prior to the International fifing date but Ill the art. later thani the priority date claimed document member of the samoi patent family Date of the Actual Completion of the International Slearch Date of Mailing of this international Search Report 19th Decemiber? 1988 j7. 01. International Searchinoi Authority Slns .Are, o) EtROPEXI PATENT OFFICE Form PCT113A.'.1 (soond sheet) (Jantuary IMS) -1 I -2- Demand* International* N, PCT/US 88/02498, (SUITE DES RENP91IGNIZENTS INDIQUtS SUR LA Ill. DOCUMENTS CONSIDW~S COMME PERTINENTS DEUXIIEMIE FEFIALLE) Catlgarle .alio documewnts cite.. evec indicat~l, S4 A~m $hir*, w evo elicattons Ia~ol des p0s8a9. PeqtineE'Is FR, A, 1442882 (FARBWERKE HOECHST) 9 May 1966 ze~e page 1, right-hand coluvin, line 22,30-32,

36-38 FermuluI'm 'S;ISA21 ifeuile additonnalle) Warmlaw 103) I ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8802498 SA 23744 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 11/01/89 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document cited in search report Publication date Patent family member(s) Publication date GB-A- 1492052 16-11-77 None US-A- 3464922 02-09-69 None FR-A- 1336631 None US-A- 4103068 25-07-78 US-A- 4105568 08-08-78 JP-A- 52096236 12-08-77 US-A- 3177143 None US-A- 3575856 20-04-71 None FR-A- 1442882 NL-A- 6510136 07-02-66 BE-A- 667958 DE-A- 1257111 GB-A- 1092401 0For mr ail bou t nn Oicil ura t Eu Pa Ofi 0 For more details about this annex see Official Journal of the European Patent Office, No. 12/82