US3565926A - Amine salts of perhalogenated monobasic carboxylic acids - Google Patents

Abstract

A COMPOSITION OF MATTER COMPRISING AN AMINE SALT OF AN UNSUBSTITUTED ALIPHATIC MONOAMINE AND A PERHALOGENATED MONOBASIC CARBOXYLIC ACID. THE ACID IS ONE HAVING THE GENERAL FORMULA: C1(CF2CFC1)NCF2COOH, HERE N IS AN INTEGER FROM 1 TO 4, OR ONE HAVING THE GENERAL FORMULA: F(CF2)MCOOH, WHERE M IS AN INTEGER FROM 3 TO 9. THE SALT IS SOLUBLE IN LUBRICATING OIL AND FUEL COMPOSITIONS, AND SERVES TO REDUCE WEAR, PARTICULARLY SCUFFING WEAR, DURING NORMAL USE OF THE LUBRICANT OR FUEL.

Description

United States Patent Oflice 3,565,926 Patented Feb. 23, 1971 3,565,926 AMINE SALTS OF PERHALOGENATED MONO- BASI'C CARBOXYLIC ACIDS Michael J. Furey, Latham, N.Y., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 305,805, Aug. 30, 1963, which is a continuation-in-part of abandoned application Ser. No. 853,471, Nov. 17, 1959. This application May 4, 1966, Ser. No. 547,416

Int. Cl. C09f 7/00 US. Cl. 260-404 7 Claims ABSTRACT OF THE DISCLOSURE A composition of matter comprising an amine salt of an unsubstituted aliphatic monoamine and a perhalogenated monobasic carboxylic acid. The acid is one having the general formula: Cl(CF CFCl) CF COOH, where n is an integer from 1 to 4, or one having the general formula: -F(CF COOH, where m is an integer from 3 to 9. The salt is soluble in lubricating oil and fuel compositions, and serves to reduce wear, particularly scuffing wear, during normal use of the lubricant or fuel.

This application is' a continuation-in-part of application Ser. No. 305,805, filed Aug. 30, 1963 now US. Pat. 3,269,- 948, which in turn was a continuation-impart of application Ser. No. 853,471, filed Nov. 17, 1959, said latter application having subsequently been abandoned.

DESCRIPTION OF THE INVENTION This invention relates to salts of aliphatic amines and monobasic perhalogenated carboxylic acids. More particularly, the invention relates to amine salts formed by reacting primary, secondary, or tertiary C to C aliphatic monoamines with monobasic halogen-containing carboxylic acids known as perhalogenated acids, wherein the number of halogen atoms exceeds the number of carbon atoms. Said salts are useful in lubricating oil and fuel compositions to reduce wear (particularly scufling) during normal use of the lubricant or fuel.

It is well known in the prior art that halogen-containing organic compounds may be used as additives in mineral lubricating oils to improve such properties as load carrying ability. However, many of such halogenated compounds have been found to be corrosive toward metals. It has now been found that by reacting perhalogenated monobasic carboxylic acids with unsubstituted aliphatic monoamines, compounds are formed which are not only non-corrosive but which have particular utility as additives for lubricants and fuels and related liquid compositions in that they reduce wear and metal-to-metal contact. The perhalogenated monobasic carboxylic acids used in this invention have the following general formulae:

Cl (CF CFCl) DCF2COOH (l) F(CF COOH (2) and The amines useful in forming the salts of this invention include primary, secondary or tertiary C to C unsubstituted aliphatic and cycloaliphatic monoamines. Specific examples of amines which may be used include the Primenes (C to C made by Rohm and Haas, the Armeens made by Armour, (e.g., technical dodecylamine and technical octadecylamine), propylamine, amylamine, diamylamine, triamylamine, hexylamine, octylamine, oleylamine, linoleylamine and cyclohexylamine. The higher molecular weight amines in the range of C to C are particularly useful since their salts are more oil-soluble than those of the lower molecular weight aliphatic amines. The tertiary alkyl amines are also preferred because the higher degree of branching within the aliphatic chain imparts greater solubility to the salts formed therefrom.

The liquid compositions to which the salts of this invention may be added include mineral lubricating oils, synthetic lubricating oils and distillate fuels boiling in the range from about 50 F. to 750 F. The lubricating oil may be a mineral lubricating oil, a synthetic hydrocarbon oil or other synthetic lubricating oil such as diethylhexyl sebacate, carbonate esters, glycol esters such as C 0x0 acid diesters of tetraethylene glycol, other diesters, silicone polymers, complex esters as for example the complex ester formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethyl hexanoic acid, etc. The lubricating oil will have a viscosity at 210 F. in the range of 30 to 200 SSU, preferably 35 to 100 SSU at 210 F.

Because of the excellent lubricating qualities of the salts of this invention they may also be used in hydrocarbon compositions designed for extremely low temperature lubrication. For instance, the aerospace industry has developed a need for fluids which may be used at temperatures to 250 F. for a variety of purposes. Hydraulic, heat transfer, shock-absorber and power transmission fluids will be required for use in vehicles traveling on the surface of the moon, for example, where the temperature ranges from 250 F. at midnight to +250 F. at midday. Isoparaflinic hydrocarbons such as isopentane, isohexane and the like, are, in general, suitable base stocks for this use. They have a wide liquid range, and good stability, but they are not good lubricants by themselves. Additives are required, and solubility at temperatures below 65 F. limits the choice. However, the Primene salts of the fiuoro-acids of this invention are soluble and are unique in their solubilities at temperatures below -100 F. These salts will remain dissolved in isopentane down to the freezing point of -255 F. at 0.25% by weight. Their lubricant qualities are such that the wear of hydraulic pumps, etc. will be effectively controlled.

Other isoparaffinic solvents that may be used to prepare lubricants of this general type comprise highly refined synthetic hydrocarbons obtained, for example, from alkylation and fractionation processes, e.g. from an alkylation reaction involving isobutane and a C to C olefin, or by hydrogenation of branched chain olefins. Such isoparaffinic solvents contain preferably at least volume percent, and more preferably at volume percent of isoparaffinic hydrocarbons.

Representative isoparaffins include tetramethyl hexanes, tetramethyl heptanes and tetramethyl octanes, such as 2,2,4,4-tetramethyl hexane, 2,3,3,5-tetramethyl heptane and 2,2,4,6-tetramethyl octane. The preferred isoparaflinic hydrocarbon compositions are those wherein the contents of unsaturated hydrocarbons, such as aromatics and olefins are less than about 1%, and more preferably less than 0.1% by weight and the contents of cycle and normal parafiins are less than 10%, and preferably less than about 5% by weight, and those wherein the total concentrations of non-hydrocarbon impurities such as peroxides, acids, carbonyls, alcohols or other oxygenated compounds are below about 0.01% by weight.

The distillate fuels utilizing the salts of the instant invention include aviation turbo-jet fuels, rocket fuel (MIL-R-25576B), gasolines, kerosenes, diesel fuels and heating oils. Aviation turbo-jet fuels in which the amine salts of the present invention may be used normally boil between about 50 F. and about 550 F. and are used in both military and civilian aircraft. Such fuels are more fully defined by US. Military Specifications MILF 5624F, MIL-F-25656A, MIL-F-25554A, MIL-F- 25558B, and amendments thereto, and in ASTM D- 1655-62T. Kerosenes and heating oils will normally have boiling ranges between about 300 and about 750 F. and are more fully described in ASTM Specification D-396 4ST and supplements thereto, where they are referred to as No. 1 and No. 2 fuel oils. Diesel fuels in which the amine salts may be employed are described in detail in ASTM Specification D-975-35T and later versions of the same specification; Gasolines which may be benefited include both motor gasolines and aviation gasolines such as those defined by ASTM Specifications D-910-56 and D-439-56T.

The liquid lubricating oil compositions utilizing the products of this invention will comprise a major proportion of the lubricating oil and 0.01 to weight percent, or more, usually 0.1 to 3 weight percent, based upon the total weight of the composition, of the amine salts of the halogen-containing acids. The liquid fuel compositions will likewise comprise a major proportion of the liquid fuel and about 0.001 to 5 weight percent, based on the total weight of the composition, of the amine salts of the halogen-containing acids, and more usually 0.01 to 0.20 weight percent.

Other additives which may be used in the liquid compositions include viscosity index improvers, pour point depressants, corrosion inhibitors, thickeners, sludge dispersants, rust inhibitors, anti-emulsifying agents, antioxidants, dyes, dye stabilizers and the like.

The amine salts of this invention are prepared by simple addition of the halogen-containing monobasic carboxylic acid to about an equal molar proportion of the C to C aliphatic amine. The reaction is exothermic and will normally proceed at temperatures between 70 and 200 F. Care should be taken to prevent the temperature from exceeding 200 F. since water may be driven off and an insoluble amide might be formed in place of the amine salt reaction product of this invention.

The following examples which include a preferred embodiment, are submitted as illustrating the practice of this invention, but are in no way intended to limit the invention.

EXAMPLE 1 To illustrate the preparation of the amine salts of this invention and their use in lubricating oil compositions, an amine salt of Cl(CF CFCl) CF COOH Kel-F acid 8114) was prepared by adding one mole (480 grams) of the acid to one mole of Primene JM-T (315 grams based on neutralization equivalent) at room temperature with constant stirring. Primene JM-T is a mixture of tertiary alkyl primary amines (C18H37NH2 to C H NH The reaction occurred immediately and the temperature rapidly climbed to 100 F. The product when cooled to room temperature was a clear amber viscous fluid. The percent chlorine in this product was 17.2% which compares well with the theoretical value of 17.8%. This salt was then added in several concentrations to a mineral lubricating oil of Mid-Continent origin having a viscosity at 210 F. of 40.8 SSU. The salt was also blended in 1 weight percent concentration in two separate SAE W-30 lubricating oils containing detergent inhibitors. Each of the resultant lubricating oil compositions was then tested for valve train wear, which is a problem of increasing importance in automotive lubrication. The tests were carried out in a laboratory multicylinder engine equipped witth radioactive steel valve lifters. These tests were run for three hours at 1000 r.p.m., no load, with normal valve spring tension, and the jacket outlet temperature controlled to F. The valve lifter wear is calculated from the total amount of radioactive wear debris contained in the oil recovered from the three-hour test. The engine is flushed with fresh oil before and after each test run. Under thse conditions, the radioactive Wear test gives good correlation with field tests using the same oils, engines, and valve train metallurgy. This test is more fully described in the July, 1958 issue of Lubrication Engineering, a journal of the American Society of Lubrication Engineers, pages 302 to 309.

The results obtained with each base oil and each blend are given in Table I, which follows.

TABLE I.-INFLUENOE OF PRIMENE .TM-T SALT OF Cl (CFzCFCDs CFzCOOH ON VALVE TRAIN WEAR Relative valve lifter wear 1 10W-30 SAE mineral lubricating oil base.

2 Mixture of 37.5% calcium sullonate and 62.5% P28 treated barium iso-nonyl phenol sulfide. (Additive concentrate containing approximately 58 Wt. percent mineral oil.)

3 Mixture of barium iso-nonyl phenol sulfide, P285 treated polyisobutylene of 1100 molecular weight and a barium alkyl benzene sullonate. Contains 1.28 wt. percent phosphorus, 8.59 wt. percent barium and 4.18 Wt. percent sulfur. (Additive concentrate containing approximately 50 wt. percent mineral oil.)

The data in Table I show that the salt of this invention was eifective not only in a simple blend in mineral lubricating oil but was also extremely effective in reducing valve train wear when used in lubricating oils which also contained conventional detergent inhibitors.

The Primene salt was also tested in the SOD Bearing Corrosion Test at 340 F. This is a test for oxidation stability and corrosion resistance and involves determination of bearing weight loss and oil viscosity increase when a copper-lead bearing is immersed in the test oil at 340 F. for 20 and 24 hours. Results are shown in Table II.

TABLE II.EFFECT OF PRIMENE JM-T SALT OF XlP(g4IO g%FCD3CFzCOOH ON SOD BEARING CORROSION Wt. percent Primene JM-T/Cl (CFzCFCDaCFzCOOH salt in Tables I and II illustrate the fact that salts of this invention serve as wear reducing additives without adversely affecting corrosion When used in internal combustion engines.

The extreme pressure properties of the primene salt in mineral lubricating oils were tested by means of the standard 4-ball EP test. This test uses an apparatus having three lower balls fixed in a pot which also h0lds the test lubricant. The fourth ball, held in a chuck, is pressed against the three lower balls with a known force and is rotated at a selected speed. The machine is usually 0perated with the lubricant at ambient temperature, with the upper ball rotating at 1800 r.p.m. A series of short duration tests are run at gradually increasing load increments until initial seizure occurs. Table III illustrates the maximum load which could be carried in the 4-ball EP test for one minute without film failure or scufiing.

TABLE 111 Effect of primene JM-T salt of Cl(CF CFCl) CF COOH on extreme pressure properties of oil Wt. percent additive in mineral oil 40.8 SSU viscosity metallic contact occurs in a given period of time. Friction between the ball and cylinder is recorded simultaneously with contact. This is noted as coeflicient of friction, which is the ratio of friction force to the load. It has been found that there is, in general, a good correlation at 2l0 F.: 5 between metallic contact measured in this manner and Maximum load earned 1n 4-ball E.P. Test 1 111 kgthe amount of surface damage which occurs.

None 4 The evaluations of the compositions were obtained un- 0.1 0 der the following conditions: 1.0 70 AISI 52100 steel 10 1 I) b 11 1 Steel-on-steel at 1800 r.p.m. /2 dlama on fil hiaaimum loadffithat can be carried for 1 minute without Syst m; 1%" diam, cylinder m 111111901 Speed (r.p.m.) 240 EXAMPLE 2 Running time (min.) 32 This example illustrates the reduction in valve train 15 011 temperature 0 77 wear obtained in a Volkswagen engine Where small quan- Load (grams) 1000: 4000 tities of an amine salt of this invention are added to the Calculated meal} Hertz lubricating oil. The Volkswagen cyclic test is a valve train Pressure P 88,000; 141,000 Wear and intake valve deposit test. It is designed to The results of the tests are summarized in Table V and evaluate the protection against valve train Wear in the show that the addition of only 0.1% by weight of the Volkswagen engine which an oil affords and to evaluate Kel-E ac1d salts of various amines markedly reduces the tendency of an oil to give deposits on the undersides metallic contact. of int k alve TABLE V.METALLIC CONTACT TESTS I t t 11' t t- Test operatmg cond1t1ons Addifiyein base mineral men me a cycle: 011 (wt. percent) 240 g. 1, 000 g. 4, 000 g. 5 min. at 600 :25 r.p.m. No load 8125/10? 92.0 97.9 98.2 nmene e ac sa t 42.8 80.6 94.3 10 f at 1200:25 -P- N0 load 0.1% ro lamine Kel-i acid salt 0.3 0.7 99.1 1 min. at shutdown 1% amylamiue/Kel-F acid salt.-. 1. 1 2.0 2. 3 3O 0. 1% dramylamine/Kel-F acid salt- 11. 8 24. 8 86. 7 Test duratlon and the test results are reported in Table y amu1e/Ke1Fac1d salt.-- 10.2 12.4 62.6 IV 0.1% octylam1ne/Kel-F acid salt 59.5 77.9 80.6

TABLE IV.VOLKSWAGEN VALVE TRAIN WEAR Intake Tappet wear in Cam wear in Total wear in 0.0001 Tappet valve de- 0.0001 in. 0.0001 in. in. failures posit wts. Additive, wt. percent in Tlme 0.001 in gms base oil 1 (hrs.) Average Range Average Range Average Range wear) (average) 33. 4 (767) 50.1 (17-108) 48 (-54) 98 (68-160) s 0. 93 0.5 (0-1) 1.1 (0-3) pg 1-3 1.5 (04 3 (1-5) Test stopped at 79 hrs. because of electronic control difilenlties. Extrapolated.

1 10W-30 SAE mineral oil (commercial lubricant containing 4 vol. percent. of the detergent-inhibitor of Footnote 3 of Table I).

2 Primene JIM-T salt of Cl (CF2CFC3) CFzCOOH.

It is seen from Table IV that the amine salt of the invention was very effective in reducing valve train wear.

EXAMPLE 3 In order to demonstrate further the scope of the present invention, amine salts of Cl(CF CFCl) CF COOH (KelF 8114) were prepared by adding 1 gram mole (480 grams) of the acid to 1 gram mole of each of the following amines: Primene JM-T, propylamine, amylamine, diamylamine, triamylamine and octylamine. The resulting salts were added to separate portions of a mineral lubricating oil of Mid-Continent origin having a viscosity at 210 F. of 40.8 SSU.

The respective oil compositions were tested for wear and scuffing in a rotating cylinder apparatus designed to measure metallic contact and friction between sliding, lubricated surfaces. The test is more fully described in the paper Metallic Contact and Friction Between Sliding Surfaces, by M. J. Furey, ASLE Transactions, vol. 4, pages 1-11, 1961. The paper is by reference herewith incorporated in its entirety in this application. The apparatus consists basically of a fixed metal ball loaded against a rotating steel cylinder. The extent of metallic contact is determined by measuring both the instantaneous and average electrical resistance between the two surfaces. It is expressed as the percent of the time that EXAMPLE 4 It has further been found that amine salts of perfluoro acids having the general formula F(CF COOH, where m may range from 3 to 10, are extremely effective in reducing wear and metallic contact. In order to demonstrate this, a Primene JMT salt of decapentylfluoro octanoic acid was prepared in the following manner and then subjected to a series of tests.

Separate solutions were made of 0.1 mole (30.3 g.) of Primene JM-T in g. of tetrahydrofuran and 0.1 mole (41.4 g.) of decapentylfiuoro octanoic acid in 200 g. of tetrahydrofuran. The acid solution was slowly added at room temperature to the amine solution with stirring. The temperature rose from 25 C. to 35 C. The tetrahydrofuran was then evaporated by passing nitrogen over the solution overnight followed by heating to 75 C. for 5 minutes. The yield was 72.2 grams, indicating that only 0.5 gram of tetrahydrofuran remained. The :final product was an amber, viscous fluid, soluble in hydrocarbons. Thereafter, 0.1% by weight of the above amine salt was dissolved in a straight mineral oil, namely a solvent-extracted distillate having a viscosity of 35 cs. at 77 F. and a V.I. of 110, and the resulting test sample 7 subjected to the Ball-on-Cylinder test of Example 3. The

results obtained appear in Table VI.

TABLE VI.-EFFEOT OF PRIMENE/ CTFIECOOH SALT ON METALLIC CON- TAC'I IN BALL ON CYLINDER TESTS Percent metallic contact As shown by Table VI, the Primene-C F COOH salt is extremely effective in reducing metallic contact over a wide range of loads.

Further evidence of the effect of the above amine salt on wear was obtained in the Four-Ball Wear Test. The test was conducted as follows: Test solutions were placed in the cup of the machine and heated to 100 C. The test cup contained 3 steel balls which were fixed in position by a screw cap. A fourth steel ball, held in a chuck, was pressed against the 3 lower balls with a force of 40 kilograms and rotated at 1200 r.p.m. for a period of 1 hour. At the end of the test, the amount of wear was determined by measuring the diameter of the wear scar on each of the balls and averaging the results. As can be seen from the data in Table VII, the addition of 0.1% by weight of Primene-C F COOH salt to the base oil reduced wear by over 60%.

TABLE VII Effect of Primene/C F COOH salt on wear in the 4-bal1 wear test 1 Additive in mineral Avg. scar diam. in lubricating oil: 4-ball test mm.) None 1.65 0.1% Primene/C F COOH salt 0.59

-Steel-on-steel, 40 kg. load, 1 hr., 100 0., 1200 1'.p.m.

EXAMPLE 5 The utility of the amine salts of the present invention Was further evaluated by adding Primene salts of decapentylfluoro octanoic acid and Kel-F 8114 acid to various liquid compositions. The resulting test compositions were tested in Ryder Gear Apparatus (E.A. Ryder, ASTM Bulletin 184. 41 (1952)). The results of those tests appear in Table VIII.

TABLE VIII Effect on load-carrying capacity in the Ryder gear test Ryder rating Test composition: (lbs/inch) Synthetic lubricant A (1) 1650 A+0.2% Primene-C F COOH salt 2250 Synthetic lubricant B (2) 2500 B|-0.2% Primene-C F COOH salt 2760 B+0.25% Primene-Kel-F (8114) acid salt 3010 Jet fuel (3) 400 Jet fuel+0.0l% Primene-Kel-F (8114) acid salt 980 Jet fuel+0 1% Primene-Kel-F (8114) acid salt 2290 1 A blend of 69% of (ii-2 ethyl hexyl scbacate with 17.3% C8 azelate and 13.7% C10 adipate. The oil also contained tricresyl phosphate for load-carrying capacity.

2 A blend of 55% trimethylol-propane triester of pelargonic acid and 45% complex ester of neopentyl glycol, trimethyl pentanol and sebacic acid.

A highly isoparafiinic fuel of 375-500 F. boiling range, liiglti tthermal stability, low freezing point and low sulfur con en The above data further demonstrate the effectiveness of the amine salts of the present invention in improving the antiwear and anti-scufliing properties of both hydrocarbon liquids and synthetic ester lubricants.

Silicone fluids have certain properties which make them of interest as lubricants. For example, they have uniquely 8 low temperature coeflicients of viscosity. However, silicones also have a serious drawback: they are very poor lubricants under conditions of boundary lubrication and particularly when the rubbing surfaces are steel. Under such conditions, the use of silicones as lubricants leads to high friction and wear, galling and seizing.

EXAMPLE 6 The benefit of employing the amine salts of the present invention in silicone fluid lubricants is shown by the data in Table IX. A blend was prepared bysimple mixing of 1 wt. percent of the Primene JM-T salt of decapentafluoro octanoic acid, prepared as described in Example 4, and 99 wt. percent of Dow Corning methyl silicone fluid DC-200. This blend was compared with the methyl silicone fluid alone in tests run with the ball-on-cylinder described in Example 3. Coefficient of friction and average wear were measured at various loads as shown in Table TABLE IX.EFFEOT OF PRIMENE .IM-T SALT OF C1F15COOH ON FRICTION AND WEAR IN SILICONES Additive in methyl silicone fluid 1 Load Coeff. of Avg. wear 1 DC200-10 (10 cs. vicosity at 77 F.) made by Dow-Corning. 2 Ball-on-cy1inder tests with AISI 52100 steel, 240 r.p.m. 32 min. 3 Discontinued at 1 min. due to excessive chattering.

It can be seen that the silicone by itself gave extremely high friction. In fact, the vibration was so excessive that the metallic contact data were of no value. At the highest load (240 g.), the test had to be stopped right away because of the high friction and excessive chattering. On the other hand, the silicone containing the additive ran smoothly at all loads and gave less than one-tenth the friction. In addition, wear at the lower loads was cut in half. The extent of metallic contact with the additive fluid ranged from 48 to 61% depending upon the load. This compares very favorably with that observed with Bayol 55, a white oil of the same viscosity, which gave from 47 to 86% metallic contact.

It is thus seen that the addition of a minor amount of the Primene JM-T salt of C F COOH to dimethyl silicone markedly reduces friction, wear and surface damage in a steel-on-steel system. This is of great interest because most of the conventional antiscuff and antiwear additives developed for use in hydrocarbons are not soluble in silicone fluids, and most of those that do dissolve in silicones do not give the expected benefit.

Silicone blends containing the Primene salt are perfectly clear and show no signs of haze or settling even after two months storage.

The amine salts of this invention are also useful for forming antiwear films under situations where the carrier liquid may not remain in place to do the lubricating. One application of this technique is to employ the amine salt as an additive or pretreatment to use in rocket fuel so that fuel pumps pumping kerosene will not 'wear out in a few minutes. Another application is one in which a complex device cannot be continuously lubricated but must be lubricated or treated so that the bearings etc. can travel a. fair distance before being lubricated again. An example is a plastic extruder or biaxial stretching machine such as that described in US. Pat. 3,150,433 of E. Kampf. Such a machine contains thousands of bearings and other con tacting sliders and must go through a high temperature oven for an appreciable distance and length of time. Ordinary lubricants and even high temperature greases ap parently do not work satisfactorily under such conditions. Here the best approach is to use a material capable of forming very durable films, films which will protect the surfaces from wear and which will last for quite a while until replenishing lubricant can reach those surfaces. A blend consisting of 1 wt. percent of the Primene JMT salt of KelF acid 8114, prepared as described in Example 1, in 99 wt. percent of a solvent neutral mineral lubricating oil (100 SSU viscosity at 100 F.) successfully lubricated, with no difliculty whatever, the hardened stainless steel slipper bearings and hardened steel guideways of a stretching machine of the type described in U.S. Pat. 3,150,433 which 'was being used for stretching a thermoplastic web at 350 F. In contrast, when these parts were lubricated with a conventional oxidation-inhibited lubricating oil, undesirable deposits built up on the slipper bearings and guideways, and galling of the surfaces was encountered.

There is no intention that the scope of this invention be limited to the specific embodiments herein described. The invention is defined by the appended claims.

What is claimed is:

1. As a composition of matter, an amine salt of an unsubstituted alkyl, alkenyl, or cyclohexyl monoamine having from about 12 to 24 carbon atoms per molecule and of a halogen-containing acid selected from the group consisting of perhalogenated monobasic carboxylic acids have the general formula:

where n is an integer from 1 to 4, and perhalogenated monobasic carboxylic acids having the general formula:

where m is an integer from 3 to 9.

2. A composition according to claim 1 wherein said amine is a tertiary-alkyl primary amine.

3. A composition according to claim 1 wherein said halogen-containing acid is: Cl(CF CFCl) CF- COOH.

4. A composition according to claim 1 wherein said halogen-containing acid is F(CF COOH.

5. A composition according to claim 1 wherein said amine is a mixture of tertiary C to C alkyl primary amines.

6. A composition according to claim 1 wherein said amine is a mixture of tertiary C to C alkyl primary amines and said halogen-containing acid is decapentafluoro octanoic acid.

7. A composition according to claim 1 wherein said amine is a mixture of tertiary C to C alkyl primary amines and said halogen-containing acid is References Cited UNITED STATES PATENTS 2,353,169 7/1944 Lincoln et a1 25254.6X 2,567,011 9/1951 Diesslin et al 260465.7 2,812,307 11/1957 Sai-ves 25254.6UX 2,875,072 2/1959 Dielman et a1. 106-14 2,877,182 3/1959 May 25254.6UX 3,232,970 2/ 1966 Hauptschein et a1. 260408 2,824,884 2/1958 Barnhart et a1. 260404 3,269,948 8/1966 Furey 260-501.16 3,444,170 5/ 1969 Norman et al. 260404 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.