US3464922A

US3464922A - Trimethylolalkane esters and method of treating textile filaments therewith

Info

Publication number: US3464922A
Application number: US513070A
Authority: US
Inventors: William F Bernholz; Thomas C Cox
Original assignee: Drew Chemical Corp
Current assignee: Drew Chemical Corp
Priority date: 1965-12-10
Filing date: 1965-12-10
Publication date: 1969-09-02
Anticipated expiration: 1986-09-02

Description

United States Patent Office 3,464,922 Patented Sept. 2, 1969 3,464,922 TRIMETHYLOLALKANE ESTERS AND METH- OD OF TREATING TEXTILE FILAMENTS THEREWITH William F. Bernholz, Wayne, and Thomas C. Cox, Boonton, N.J., assignors to Drew Chemical Corporation, New York, N.Y., a corporation of Delaware N Drawing. Filed Dec. 10, 1965, Ser. No. 513,070 Int. Cl. D06m 13/20 U.S. Cl. 2528.6 20 Claims ABSTRACT OF THE DISCLOSURE This disclosure is directed to trimethylolalkane esters, to textile finishes therefrom, and to the method of applying these finishes to synthetic linear organic polymer filaments. For example, the trimethylolalkane mixed triester of capric, lauric, myristic, and palmitic acids in an aqueous emulsion may be used as a finish for polyamide yarns.

The present invention relates to finishes for filaments of synthetic linear organic polymers. The present invention further relates to a method of applying these finishes to synthetic linear organic polymer filaments.

Synthetic linear organic polymers, for example, polyamides such as nylon are commonly formed into filaments by the process of melt-spinning, and the resultant filaments are drawn in the solid state in order to develop a high degree of tenacity so that they become suitable for textile purposes. To facilitate the drawing of the filaments and other textiles processing to which they may be submitted, it is necessary to apply a finish to the newly melt-spun material, in order to reduce friction during passage of the filaments over surfaces in textile machinery. Such reduction in coefficient of friction between the fiberto-metal surfaces prevents filament abrasion. The finishes must be capable of lubricating the filaments so that they do not break during drawing. In the case of multi-filament yarn it is furthermore necessary that the finish provide some degree of balanced cohesion between the constituent filaments of the yarn. This cohesion is particularly important in flat warp knitting. It is also very desirable that the finish have a high degree of oxidation resistance, including resistance of both discoloration and formation of insoluble resinous or polymeric compounds. It is further desirable that the finish exhibit high temperature stability and resistance to smoke generation at temperatures encountered during the processing of the synthetic linear organic polymer filaments. These latter characteristics are particularly applicable to the hot stretching operation used during the production of synthetic linear organic polymers.

It is an object of the present invention to provide finishes for filaments of synthetic linear organic polymers.

Another object of the present invention is to'provide finishes for filaments of synthetic linear organic polymers to reduce the coefficient of friction between fiber-to-metal surfaces.

A further object of the present invention is to provide finishes for filaments of synthetic linear organic polymers to provide balanced cohesion between the fiber-tofiber surfaces.

A still further object of the present invention is to provide finishes for filaments of synthetic linear organic polymers that are resistant to oxidation, discoloration, and the formation of insoluble resinous or extraneous polymeric materials.

A still further object of the present invention is to provide finishes for filaments of synthetic linear organic polymers that exhibit thermal stability and resistance to smoke generation, particularly during hot-stretch processing to orient the polymer in order to obtain maximum uniformity of tensile strength, such as in nylon tire cord production.

A still further object of the present invention is to provide a method of applying finishes to filaments of synthetic linear organic polymers.

A further object is to provide an improvement in the manufacture of filaments and yarns of synthetic linear organic polymers by treating such filaments or yarns with a finishing composition having lubricity and resistance to oxidation and discoloration at elevated temperatures.

Accordingly, the present invention consists of finishes for filaments of synthetic linear organic polymers which are trimethylolalkane esters represented by the general formula:

wherein R is an alkyl group containing from 1 to 4 carbon atoms and R, R, and R' are saturated and/or unsaturated acyl radicals containing from 2 to 24 carbon atoms. Both simple trimethylolalkane esters, i.e. those where R, R", and R are the same acyl radical and mixed trimethylolalkane esters are contemplated in the present invention. Preferably the trimethylolalkane ester should contain at least two different acyl radicals wherein at least one radical contains from 2 to 12 saturated carbon atoms and at least one radical contains from 14 to 24 saturated and/ or unsaturated carbon atoms. While it is preferred that the acyl radical be derived from saturated and unsaturated straight chain acids, acyl groups derived from branched chain acids such as the neo-acids, for example .neoheptanoic acid, neononanoic acid, etc., or isoacids such as isostearic acid, are contemplated.

The methods of preparation of the trimethylolalkane esters are known in the art of esterification. In general, three moles of the acid or acid mixture is reacted, generally with refluxing, with one mol of the trimethylolalkane in the presence of toluene or other suitable diluent. The uncatalyzed reaction occurs at temperatures ranging from C. to 265 C. and over a period of time ranging from 4 to 12 hours until the theoretical amount of Water of reaction is released and collected. The reaction may also be catalyzed with, for instance, an aromatic sulfonic acid such as para toluene sulfonic acid, which will substantially reduce the reaction time. The resultant substantially completely esterified trimethylolalkane ester is then recovered, illustratively by stripping under vacuum, to obtain the ester product having a low free fatty acid value.

Suitable illustrative esters coming within the scope of this invention are trimethylolethane monoacetate dioleate, trimethylolethane monooleate diacetate, trimethylolpropane triisopentanoate, trimethylolethane triheptanoate, trimethylolpropane heptanoate, trimethylolethane tripelargonate, trimethylolpropane monocaprylate dicaprate, trimethylolethane dicaprylate monocaprate, trimethylolpropane dicaprylate monocaprate, trimethylolethane neoheptanoate, trimethylolethane neononanoate, and the trimethylolpropane mixed ester of lauric and myristic acids. Further examples are the trimethylolethane and trimethylolpropane triesters, monoacetate diesters, diacetate monoesters, diisopentanoate monoesters, monoisopentanoate diesters and monooleate diesters of the following mixed acids in the stated proportions: about 0-10% capric, about 45-75% lauric, about 5-35% myristic and about 020'% palmitic, or desirably, about 0.34% capric, about 50-70% lauric, about 1025% myristic and about 2-16% palmitic. An advantageous mixture of acids comprises about 15% capric, about 53-68% lauric, about 1525% myristic and about 3- palmitic.

The finishes may be applied neat to the filaments of the synthetic linear organic polymers or dissolved in a solvent or as an aqueous emulsion. In general, the method of application is governed by the percentage of lubricant, type of polymer, type of process, and the type of equipment available. The mode of application of the finish to the yarn filaments will depend upon the system which is most suited to the method of synthetic linear polymer processing. Generally, from 0.5 to finish by weight of the organic polymer is applied thereto. The finish may be further applied by internal addition to the organic polymer prior to melt spinning of it with subsequent bleeding to the surface.

In preparing an aqueous emulsion containing the finish, any singular surfactant or combination of surfactants compatible with the finish and capable of forming a stable emulsion may be utilized. A sample aqueous emulsion is prepared, using conventional procedures, with the following proportional ingredients:

15 parts Other suitable surfactants are sulfated trioleate ethoxylated tridecyl alcohol, polyglycerol esters such as decaglycerol tetraoleate, triethanolamine oleate, ethoxylated nonyl phenol, etc. Generally the aqueous emulsion con tains from 1 to 25% nonaqueous solids which in turn consists of from 50 to 80 parts of the finish and 50 to parts of the emulsifier.

Suitable solvents for use in applying the finishes include the lower molecular weight alkanols, such as ethanol or propanol; ketones such as acetone; and hydrocarbons such as toluene or petroleum ether. The solvent selected should be compatible with the polymer to which is is applied.

Other ingredients such as antistatic agents, emulsification aids, lubricant aids to impart cohesion properties, etc. may be used in conjunction with the finishes of the present invention provided they do not seriously affect or alter the characteristics of said finishes.

The invention includes the application of the finishes to the filaments and the filaments which have been so treated. The term filaments is to be understood as including monofilamentous and multifiamentous yarn whether twisted or not.

The synthetic linear organic polymers include polyamides such as polyhexamethylene sebacamide, poly- Kappa-aminoundecanoic acid, poly-epsilon-caprolactam, etc.; acrylic polymers made largely from acrylonitrile; polyolefins such as polymethylene, polyethylene, polypropylene, etc.; polyesters such as polyethylene terephthalate, and other polyesters formed by reaction of a dihydric alcohol and a diacid, etc.; and polyureas such as polyhexamethylene urea, etc.

The following examples further describe the invention.

Example 1 A trimethylolethane mixed triester (TME) made from a mixture of acids comprising 4% capric, 57% lauric, 32% myristic, and 7% palmitic was tested for its resistance to oxidation; discoloration, and the formation of insoluble resinous or extraneous polymerized material in comparison to a commercial rearranged vegetable oil textile fiber finish. Both the mixed esters of the present invention and the control finish were subjected to strong oxidizing conditions, namely, constant heat for 24 hours at a temperature of about 180 C. with continuous air sweep of 2 liters per minute (1 liter per kilogram of material). These conditions were regarded as simulating in situ plant processing conditions. Changes in saponification value (A.O.C.S. method Cd 3-25) and viscosity at F. (Saybolt Universal Seconds) are indicative of the formation of resinous or polymerized material. Hydroxyl value (A.O.C.S. method Cd 440) and free fatty acid (A.O.C.S. method Ca 5a-40) are indicative of hydrolytic thermal stability. The color measurements are made using the Lovibond color scale.

B More ox idatiou After oxidation TME ME Finish CRVO 1 ester CRVO 1 ester Test results:

FFA (free fatty acids) H 0. 01 0.035 5. 8 4. 5 Hydroxyl No 0 1.0 33. 4 26. 5 Saponification value 257. l 242. 8 283. 4 289. 2 Viscosity e 350 285 Color 6.0/1.0 2. 0/0. 2 16. O/4. 0 8. 0/1. 5

1 CRVO stands for Commercial Rearranged Vegetable Oil.

The foregoing results clearly illustrate the high thermal stability, greater resistance to discoloration and low amount of resinous or polymerized materials exhibited by the trimethylolethane mixed triester as compared to the commercial rearranged vegetable oil finish.

Example 2 The fiber-to-fiber friction characteristics of 840/ 140 denier polyamide yarn were tested by the solvent application of 1% trimethylolalkane ester by weight of the yarn in comparison to a control yarn from which the finish had been scoured. Conditions of test were a temperature of 72 F. and a relative humidity of 25%. The attenuation was as follows:

Turn of yarn 1 /2 (540) times. Pendent weight 20 gms.

Chart speed 2.5 mm./sec. Speed of yarn 1.07 mm./sec.

' Both the coefiicient of friction expressed in gms. and millimeters between slipstick were evaluated as follows:

Cocil'. of Mm. between Finish friction slip-stick Control (scoured) 85 O l Trimethylolethane triester 65 2. 5 Trimethylolethane oleate este 65 2. 5

l Trirnethylolethane mixed triester of the following acids in the Stated proportions: 2% eapric, 65% lauric, 25% myristic, and 8% palmitic.

2 50 parts of the above triester rearranged with 50 parts of trimethylolethane triolate.

Example 3 The fiber-to-rnetal friction characteristics of a 840/140 denier polyamide yarn which had been treated with a 1% solvent application of the trimethylolalkane ester, versus such characteristics of a scoured (without finish) yarn. Conditions of the test were as follows:

Temperature F 72 Relative humidity percent 25 Speed of yarn m./min 100 Total weight of pulley gms 100 Radians 5 The differential friction in grams, which is indicative of greater friction as it increases, is expressed in grams:

Finish: Differential friction None (scoured control) 200 Trimethylolethane triester of Example I 110 The foregoing results indicate the superior fiber-tO-metal lubricity of the trimethylolalkane ester.

Example 4 The smoke, fire, and flash characteristics (A.O.C.S. method Cc-9a-48) of the trimethylolethane mixed triester of Example I was compared to those of a commercial rearranged vegetable oil filament finish. The results which are as follows illustrates the minimized tendency of trimethylolethane ester to cause smoke formation.

Smoke, Flash, Fire,

Finish F. F F.

Commercial rearranged vegetable oil 400 570 610 Trimethyiolethane triester of Example 1 450 575 635 om-on' n- -oni-on" Hr-OR' wherein R is an alkyl group containing from 1 to 4 carbon atoms and R, R, and R are selected from the class consisting of saturated and unsaturated acyl radicals containing from 2 to about 24 carbon atoms per radical, and mixtures thereof wherein at least one of the chemical moieties R, R", and R consist of an acyl radical containing 2 to 12 saturated carbon atoms and at least another of the said chemical moieties consist of at least one acyl radical containing 14 to 24 saturated or unsaturated carbon atoms.

2. The trimethylolalkane ester of claim 1 comprising predominantly trimethylolethane monoacetate dioleate.

3. The trimethylolalkane ester of claim 1 comprising predominantly trimethylolethane monooleate diacetate.

4. The trimethylolalkane esters of claim 1 comprising predominantly trimethylolalkane mixed triester of mixed acids, said mixed acids comprising about 10% capric, about 45-75% lauric, about 35% myristic, and about 020% palmitic.

5. The trimethylolalkane esters of claim 1 consisting essentially of the trimethylolethane monooleate diester of mixed acids, said mixed acids comprising about 0-10% capric, 45-75% lauric, 5-35% myristic and 015% palmitic.

6. The trimethylolalkane esters of claim 1 comprising predominantly trimethylolalkane mixed triester of mixed acids, said mixed acids comprising about 0.3-7% capric, about 50-70% lauric, about -25% myristic and about 2-16% palmitic.

7. The trimethylolalkane esters of claim 1 comprising predominantly trimethylolalkane mixed triester of mixed acids, said mixed acids comprising about 15% capric, about 53-68% lauric, about -25% myristic and about 310% palmitic.

8. A textile finish comprising an aqueous emulsion of the trimethylolalkane esters of claim 1.

9. A textile finish composition comprising the trimethylolalkane esters of claim 1 and a solvent for said esters.

10. The method of finishing synthetic organic polymers which comprises adding the esters of claim 1 in a solvent to synthetic organic polymers, wherein the amount of said esters used is in the range of from 0.5-

5 15% based on the Weight of synthetic organic polymers.

11. The method of finishing filaments which comprises adding the esters of claim 1 to synthetic organic polymers and forming filaments therefrom wherein the amount of said esters used is in the range from 05-15% based on the weight of said filaments.

12. The trimethylolalkane esters of claim 4 comprising predominantly the trimethylolethane monoacetate diester of said mixed acids.

13. A textile finish comprising an aqueous emulsion of the trimethylolalkane esters of claim 4.

14. A method of treating filaments of synthetic linear organic polymers comprising adding to said filaments a finish comprising at least one trimethylolalkane ester represented by the general formula:

wherein R is an alkyl group containing from 1 to 4 carbon atoms and R, R, and R' are selected from the class consisting of saturated and unsaturated acyl radicals containing from 2 to about 24 carbon atoms per radical, 3 and mixtures thereof, wherein at least one of the chemical moieties R, R and R consists of an acyl radical containing 14-24 saturated or unsaturated carbon atoms, wherein the amount of said one or more esters used is in the range of from about 0.515% based on the weight of said filaments.

15. A method according to claim 14 wherein said finish consists essentially of trimethylolethane triheptanoate.

16. A method according to claim 14 wherein said finish consists essentially of trimethylolethane monoacetate dioleate.

17. A method according to claim 14 wherein said finish consists essentially of trimethylolethane mixed triester of mixed acids, said mixed acids comprising about 0.3- 10% capric, about 45-75% lauric, about 5-35% myristic and about 115% palmitic.

18. A method according to claim 14 wherein said finish comprises trimethylolethane monoacetate diester of the following acids in the stated proportions: 010% C capric, 4575% C lauric, 5-35% C myristic, 0- 15 C palmitic.

19. A method according to claim 14 wherein said finish comprises trimethylolethane monooleate diester of the following acids in the stated proportions: 0-10% capric, 4575% lauric, 535% myristic, 0-15 palmitic.

20. The method of claim 14 wherein said one or more esters are added in the form of an aqueous emulsion.

References Cited UNITED STATES PATENTS 2,917,410 12/1959 Vitalis 1l7--138.8 2,991,297 7/1961 Cooley et al 260410.6 3,000,917 9/1961 Babayan 260-4106 X 3,160,511 12/1964 Skeen et a1. 1l7-139.5X 3,282,971 11/1966 Metro et a1. 260410.6

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner 0 7 U.S. Cl. X.R.