Method for Treating Polymeric Fibers

To a glass reactor equipped with a stirrer, thermometer and water trap were charged 1030 grams (0.9 equivalent ratio) of dimer acid (Empol 1018 containing 83% C.sub.36 dibasic acid), 37.6 grams (0.1 equivalent ratio) azelaic acid and 1600 grams (2.0 equivalents) polyethylene glycol having an average molecular weight of 400. The reaction mixture was heated with stirring to about 200.degree.C and held for approximately 4 hours during which time 51 mls of water were removed. A vacuum of about 1 torr was pulled on the system to remove additional water of reaction. After one hour the reaction mixture was sampled and had an acid value of about 15.5. Heating was continued under vacuum for four more hours before the reaction mixture was cooled and poured up. The resulting lubricant ester composition had a final acid value of 6.7, hydroxyl value of 93.1, viscosities (ASTM D 445-65) at 100.degree.F and 210.degree.F of 548 cs and 70.4 cs, respectively, and flash and fire points (ASTM D 92-66) of 555.degree.F and 605.degree.F, respectively.

A portion (20 mls) of the ester composition was poured into 100 mls of cold tap water while stirring with a glass rod. An emulsion was immediately obtained. This emulsion was stable and showed no signs of phase separation after standing 48 hours at room temperature. Even after a week's time the emulsion appeared homogeneous. A sample prepared identically but with the azelaic acid excluded from the mixture was only difficulty emulsifiable. To obtain an emulsion required vigorous agitation with a mechanical stirrer. When this emulsion was allowed to stand at room temperature there was appreciable phase separation after only 24 hours with significant amounts of the oil settling to the bottom of the beaker.

To demonstrate the effectiveness of the ester compositions of this invention as lubricants they were evaluated with a Falex machine. This machine provides a convenient and reliable means to determine the film strength or load-carrying properties of materials as extreme pressures are applied. Falex testing is recognized throughout the industry as a means of masuring the relative effectiveness of various lubricants. The Falex wear test (ASTM D 2670-67) employs a 60 gram sample when the straight ester is being evaluated. A 600 gram sample is used when aqueous emulsions or solutions of the ester are to be tested. The loading device is attached and the cup containing the sample being evaluated positioned so that the steel pin and blocks are completely immersed in the sample. The load is then increased to 350 lbs and run for 5 minutes. After this time the load is further increased to 1000 lbs and maintained for 30 minutes when testing straight oils or one hour when evaluating lubricant emulsions or solutions. Readings are taken at the beginning of the hour, after thirty minutes, and at the end of the hour and the difference in the readings indicates the amount of wear.

Three samples of the lubricant ester composition of this example were evaluated in accordance with the described test procedure. The straight oil was evaluated and also 10% and 5% aqueous emulsions were tested. Test resuls obtained are as follows: SAMPLE UNITS WEAR ______________________________________ Straight ester: after 30 minutes 18 after 60 minutes 30 10% aqueous emulsion: after 30 minutes 154 5% aqueous emulsion: after 30 minutes 174 ______________________________________

When the above experiment was repeated employing a polyethylene glycol having an average molecular weight of about 800 similar results were obtained. The ester compositions were readily emulsifiable and the emulsions had excellent stability. A 4% aqueous emulsion of this ester exhibited superior lubricating properties in the Falex test and performed acceptably as a cutting oil with cold steel.

Employing identical reactants and a similar procedure to that described in Example I, 715 grams (0.5 equivalent ratio) dimer acid, 235 grams (0.5 equivalent ratio) azelaic acid and 2000 grams (2.0 equivalents ratio) polyethylene glycol were heated at 200.degree.C for 6 hours during which time 55 mls of water were removed. An additional 10 mls of water was taken off after pulling a vacuum on the system for one hour. The ester reaction mixture at this stage had an acid value of 19.8 and readily formed an emulsion with water. Additional heating of the reaction mixture for 2 hours under vacuum reduced the acid value to 12.1. The ester (containing about 8 weight percent azelaic acid) had a hydroxyl value of 105; viscosity at 100.degree.F of 316 cs, viscosity at 200.degree.F of 36.6 cs, and flash and fire points of 530.degree. and 585.degree.F, respectively. The ester readily dissolved in water in all propertions. No cloudiness was observed -- the resulting solutions were clear and homogeneous.

Falex wear tests gave the following results:

A water-soluble ester lubricant containing about 8% by weight adipic acid was obtained from the reaction of 0.4 equivalent dimer acid (83% C.sub.36 dibasic acid), 0.6 equivalent adipic acid and 2.0 equivalents polyethylene glycol having a molecular weight of 400. The reaction was continued until an acid value of 10.3 as achieved. The resulting ester composition had a viscosity of 163 cs at 100.degree.F. The ester lubricant mixed with water in all proportions to give clear solutions. Water solutions containing 10% and 5% of the so-prepared ester were evaluated in the Falex test machine and showed only 132 and 156 units of wear, respectively, after 30 minutes testing at 1000 psi.

Repeating the above example using 0.5 equivalent dimer acid and 0.5 equivalent adipic acid and running the reaction to an acid value of 12.9 gave useful ester lubricants. These compositions when mixed with water did not give clear solutions but did form stable emulsions without the use of external emulsifying aids. The emulsions had excellent shelf lives and were effective lubricants.

When Example I was repeated using 0.7 equivalent dimer acid, 0.3 equivalent azelaic acid and 2.0 equivalents polyethylene glycol, a useful ester lubricant composition having an acid value of 9.1 was obtained. The ester had a viscosity of 425 cs at 100.degree.F and was readily emulsifiable in cold tap water with minimal stirring and without addition of external emulsifying aids. The emulsion so-produced had excellent shelf life and was an efficient lubricant. A 5% aqueous emulsion of this ester gave less than 150 units wear in the Falex machine after 30 minutes at 1,000 psi.

Ester lubricant compositions were also prepared which incorporated up to 0.2 equivalent of an amine corrosion inhibitor such as diethanolamine or dimethylaminepropylamine. The presence of these amines significantly improved the corrosion properties of the lubricant composition without adversely affecting the emulsion and lubrication characteristics. In some instances the amines enhance the emulsion properties of the ester composition even at reduced polyethylene glycol levels.

Example I was repeated using 0.8 equivalent dimer acid, 0.2 equivalent azelaic acid and 2 equivalents polyethylene glycol. The lubricant ester (acid value 15.5) was easily emulsified. Stable emulsions were obtained which were useful cutting oils when used with a tungsten carbide bit.

To demonstrate the ability of the present esters to function as fiber/metal lubricants and improve the resistance of the so-lubricated fibers to static charge buildup several of the ester products were applied as finishes to polyester yarn and compared against a commercially available product used by the industry as a component for textile finishes. Three samples (A-C) were prepared and applied at 0.5% o.w.f. on 150 denier polyester yarn which had been solvent-stripped to remove any finish applied by the producer. Samples A and B contained the esters of Examples I and II, respectively, while Sample C was prepared with Emerest 2650 a product of Emery Industries, Inc., identified as polyethylene glycol 400 monolaurate. The finishes were all applied from aqueous systems with an Atlab Finish Applicator and the treated fibers then conditioned for 24 hours at 70.degree.F and 65% relative humidity prior to testing. Frictional properties were measured with a Rothschild F-Meter with the initial tension held constant at 10 grams, a yarn speed of 100 M/minute and yarn/metal contact angle of 180.degree.. Test results are reported below. Antistatic properties were also determined by insulating one of the pulleys on the F-meter and connecting it to a voltmeter and measuring the static charge produced on the pulley after an 8-second interval. The voltage "buildup" is reported in the table below. A static measurement for antistatic properties was made by placing a 100 volt charge on a strand of the yarn connected to a ground and determining the time required for the charge to dissipate to 50 volts. This data is reported in the table below under the columm headed "Bleed-off."

The above data demonstrates the ability of the esters of this invention to reduce fiber/metal friction and to impart antistatic properties to polyester yarns treated therewith. The antistatic properties obtained were superior in both the static and dynamic testing to properties obtaind with the commercial product. Reduction of friction compared favorably with the commercial product.

Single strand nylon (Dupont 15847) was immersed in 0.5% water emulsion/solution of the following:

The fibers were then conditioned at 68.degree.F and 40% relative humidity and tested using the static bleed-off test. Results were as follows:

A fiber which was not treated with either of the above solutions showed no dissipation of charge even after 10 minutes.