US2566157A

US2566157A - Triple ether lubricant

Info

Publication number: US2566157A
Application number: US702102A
Authority: US
Inventors: George E Barker
Original assignee: Elgin National Watch Co
Current assignee: Elgin National Watch Co
Priority date: 1946-10-09
Filing date: 1946-10-09
Publication date: 1951-08-28
Anticipated expiration: 1968-08-28

Description

.oxygen ether linkages.

as acrylic resins of the stated molecular weight, solubility, and stability.

This composition has a viscosity of 14.2 centistokes at 100 degrees F., and 50.2 at 32 degrees F.; no cloud point and a pour point of minus 90 degrees F. This formulation of the composition provides compatibility with mineral oils and with mineral-type cleaning solvents, that is, aliphatic and alicyclic compounds; hence, it may be employed without preliminary removal of hydrocarbon lubricant oils, and may be introduced to bearing surfaces as a penetrating oil in admixture including a mineral-type cleaning solvent having a vapor tension at exposure temperature sufficiently high to promote the early escape thereof, e. g., a cleaning naphtha or benzine.

Example I Va A composition, with 100 parts by weight of beta, beta prime-diamyldithiodlethyl ether, 0.20 part of tertiary butyl catechol, 0.50 part of tri-nbutylamine rosinate, and 4.50 parts of an acrylic resin as above, has essentially the physical properties and compatibility of Example IV. In general, the dithiomonoxy ethers set out can be employed in the absence of an additive ester, as the triple ether is the dominant or basic lubricating agent in the formulations while the additive ester improves the solvent power and the evaporation resistance.

A major ingredient in each of these examples is a linear triple ether having two sulfur and one A general formula for such substances is. AS --BO-B'--S-A; in which A and A are saturated aliphatic groups of 2 to 18 carbon atoms; S represents the sulfur ether linkage; B and B are saturated aliphatic groups containing 2 to 18 carbon atoms; and represents the central oxygen ether linkage. The total number of carbon atoms in the four alkyl groups, A, A, B, B, should be at least 10, to avoid excess volatility; and less than about 32 when the material must have a pour point below minus 60 degrees F. The total number of carbon atoms is a dominant factor in determining the viscosity level-it is preferred to have an odd number of carbon atoms in the intermediate groups, as this is accompanied by a lower melting point than that of the homolog having the next-lower'but even number of carbon atoms. Mixtures of isomers are preferably employed, and such is the result from the preferred manner of preparation: in addition homologs can be usefully introduced: all with the result of preventing crystallizing or freezing, and hence permitting use down to the ultimate pour point limit. The specific examples above employ symmetrical triple ethers in which the intermediate linkages at either side of the central oxygen group, and the terminal groups, are respectively identical hydrocarbon groups: that is, A, A are each amyl terminal groups, and B, B are eachethyl intermediate groups.

Among the other dithiomonoxy ethers which can be employed are dikeryldithiodiethyl ether: keryl is the name herein given to a hydrocarbon group of the 12-14 carbon atom range derived from kerosene and without specific identification of the individual hydrocarbons or of the structural connection of the carbon atoms, and is to be regarded as a mixture of isomers and homologs with the stated carbon range. This compound of itself exhibits a viscosity of 16.6 centistokes at 100 degrees F., and 95.5 at 32 degrees F., and has 1 apour point of minus 80 degrees F. Thus, the viscosity is higher than that of the correspond- 4 ing triple ether of the specific examples above, but the compositions in which this is substituted for the triple ethers of the foregoing examples are useful where the demand for continued flow and lubricating efiect at the low temperature ranges of minus degrees and minus degrees F. are not present. Further, it may be employed without the bridging aryl ester, when a resin compatible with the keryl-alkyl tri-ether is employed, inclusive of alkyl-soluble acrylic resins. This compound may be regarded as coming under the above general formula, wherein A and A are aliphatic groups of 12 to 14 carbon atoms.

Correspondingly, the unsymmetrical ether having terminal amyl and keryl groups and intermediate ethyl groups, which may be denominated amylthioethyl-kerylthioethyl ether, has a viscosity of 9.1 centistokes at degrees F. and 38.7 at 32 degrees F. and a pour point of minus 100 degrees F. This material may likewise be substituted into any of the above formulations, in cases where employment down to the low pour points of minus 80 or minus 90 degrees F. is not demanded or can be employed without a bridging aryl-type ester when the resin is alkyl-compatible and soluble in the ether directly, and then is useful essentially down to its own low pour point. Suitable resins are set out above for mixture with keryl compounds.

Symmetrical diamyldithiodi-isopropyl ether has a boiling range (one composition of isomers and probably homologs) of -154 degrees C. at 1 mm.; a viscosity of 4.3 centistokes at 100 degrees F. and 13.7 at 32 degrees F.; a pour point below minus 90; no corrosion on brass or steel; and a surface tension of about 31.8 dynes/cm. This can be substituted in the above examples and employed in cases where the higher maximum temperature viscosity relationship is not objectionable.

It is, however, preferred to avoid hydrocarbon linkages including larger side groups or highlybranched chains, that is, the preferred compounds have the main chain methylene groups dominant, for the reason that the viscosity temperature factor of compounds with large or multiple side groups is higher than with'straightchain linkages; and hence preference is given to essentially straight-chain groups, wherewith the.

A and A groups may be methyl, ethyl, propyl, butyl, amyl, and up to stearyl; andthe B, B groups have similar carbon numbers in straight chain, and including isomers having few side selected which have boiling points above that of I the triple ethers, and which have desirably low melting points, so that they serve to reduce the vapor pressure of the mixture, to a point below the vapor pressure of the dithiomonoxy etherof itself. 7 Thus, diamyldithiodiethyl ether itself (mixture of isomers) has a boiling range of -465 degrees C. at 1 mm. pressure; a viscosity of 4.4 centistokes at 100 degrees F. and 12.9 at 32 degrees F., a pour point of minus 90 degrees and is free-from corrosion on brass or steel and 51" has a surface tension of 33.7 dynes/cm. Correspondingly, the butyl phenylundecanoate (an isomeric mixture) has a boiling range of 170-180 degrees C. at 1 mm.; a viscosity of 10.0 centistokes at 100 degrees F. and 51.0 centistokes at 32 degrees F.; a pour point of minus 85 degrees F. no corrosion on brass or steel; and a surface tension of about 34.9 dynes/cm. Amyl phenylundecanoate (mixture of isomers) has a boiling range of 175-185 degrees C. at 1 mm. 10.8 centistokes at 100 degrees F. and 55.1 at 32 degrees F.; a pour point of minus 75 degrees F.; no corrosion on brass or steel; and a surface tension of about. 34.5-

dynes/cm.

The aralkyl ester of the examples thus serves to assure maintenance of the polystyrene resin in S01ution when a very low range of temperature must be met. Presumptively, the molecular similarities of the styrene resins and of the aryl group in the ester, on the one hand; and presence of the long alkyl groups in the ester and in the triple ether, on the other hand, are efiective to maintain inter-solution. Thus, in Example III above, a cloud point appears at minus 20 degrees F. in the absence of such an ester: but the material continues useful as a lubricant although it should not be employed at lower temperature over a great length of time. The ester is capable of maintaining such resins in solution at the low temperatures, and correspondingly it will be noted that the compositions of Examples I and II exhibit no cloud point down to the pouring limit. On the other hand, the ester itself exhibits an excessively high viscosity and the pour point was too high, as witness the pour points ofminus 80 and minus 90 degrees F. for the above examples compared with a pour point of minus 65 degrees F. for a composition such as 100 parts by weight of n-amyl phenylundecanoate, 0.200 part of dodecylpiperidine stearate, 0.100 part of tertiary butyl catechol, and 0.500 part of polystyrene. This composition has a viscosity of 13.9 centistokes at 100 degrees F and 74.0 centistokes at 32 degrees F.; a pour point of minus 65 degrees F.; no corrosion on brass or steel; a surface tension of about 34.4 dynes/cm.; and an evaporation residue of 90 per cent,

The n-butyl phenylundecanoate and the namyl phenylundecanoate are illustrations of organic esters which include a long-chain alkyl group and an aryl group which in the two examples are provided by the phenylundecanoic acid. Other acid groups can be employed, for example with the number of carbon atoms in the alkyl structures, from to 24, e. g. from octyl phenylacetate to amyl phenylstearate, representing a total of 16 to 30 carbon atoms inclusive of the nucleus. The acids of low alkyl-carbon number tend toward excessive volatility, and are preferably to be employed as the esters of long-chain alcohols: so that the total number of carbon atoms in the alkyl chain of the acid and in the alkyl chain of the alcohol and including the aryl group, will be from 16 to 30. Furthermore, it is not necessary that the aryl group should be in an acid portion: since for example phenylamyl alcohol ester of decanoic or undecanoic acid may be used.

, The dodecylpiperidine stearate is illustrative of long-chain alkylpiperidine soaps which may be employed; each of which has the piperidine group connected on the one hand to a saturated alkyl chain or branched chain of 10 to 18 carbon atoms, and on the other hand to an acid group ill 6. having a saturated alkylchain or branched chain of 10to 18 carbon atoms.

The tertiary butyl catechol is illustrative of an antioxidant which is soluble in the mixture.

Other catechols and soluble commercial antioxidants may be substituted.

The polystyrene or acrylic'resin is added as a viscosity improver. That is, it operates to modify the viscosity at higher temperatures without greatly changing the behavior at lower temperatures. The polystyrene resins .are employed in compositions having an aryl component, such as the phenylundecanoic esters of Examples I and II and where admixtures with mineral oils will not occur; while aliphatic resins such as methyl to butyl acrylates and methacrylates are employed in the absence of such aryl compounds (Example IV-a) or where the lubricant may become mixed with mineral oils and exposed to low temperatures.

While it is presently preferred to employ an ester having an alkyl chain of at least 8 carbon atoms and an aryl group such as phenyl or naphthyl, it is also permissible to employ complex aliphatic alcohol-aliphatic acid esters, such for example as 5-ethy1nonyl-2 undecanoate. In general, such a full substitution is feasible when aliphatic-type resins are used such as the acrylics.

Mixtures of isomers and'homologs are to be preferred, both in the ether and the ester, as they operate to depress the freezing point without a major increase of the viscosity and of vapor tension at the higher temperatures of operation.

The triple others may be prepared invarious ways, as for example:

I. PREPARATION OF DIAMYLDITHIODI- ETHYL ETHER 2184 grams of a mixture of isomeric amyl mercaptans and 1430 grams of dichlorodiethyl ether were dissolved in 4000 cc. of methyl alcohol. This solution was agitated by means of a mechanical stirrer and was heated over a steam bath until refluxing commenced. Steam heating was then discontinued while there was slowly added a solution composed of 1700 grams of 50 per cent aqueous sodium hydroxide diluted with 850 grams of methyl alcohol. This addition was made with constant stirring and was made at a rate just sufficient to allow the heat of reaction to keep the mixture vigorously refluxing. After completion of the addition, steam heating was resumed, and the reaction mixture was stirred and refluxed for six hours. The material was then permitted to cool, and the precipitated sodium chloride was separated by filtration. The methyl alcohol was removed by distillation over a steam bath, and the residual liquid was permitted to separate into two layers. The lower aqueous layer was drawn oiT and discarded. The oil layer was then washed once with dilute (5%) hydrochloric acid and rewashed several times with fresh water until the washings were found to be neutral. When the washed oil was distilled at a pressure of 1 millimeter of mercury, there were obtained 2152 grams of diamyldithiodiethyl ether with a boiling range of -165 C.

II. PREPARATION OF DIKERYLDI'IHIO- DIETHYL ETHER I 34.6 grams of metallic sodium were dissolved in 1 liter of ethanol, and to the resulting solution of sodium ethylate were added 325 grams-of mixed keryl mercaptans (C1: to C14 range). This mixture was stirred and refluxed over a steam bath for two hours, after which steam heating was discontinued and 107 grams of dichlorodiethyl ether were added at a rate just sufficient to permit the heat of reaction to keep the mixture refluxing. After completion of the addition steam heating was resumed and the material was refluxed for an additional two hours. The mixture was then cooled, the precipitated salt was separated by filtration, and the alcohol was removed from the filtrate by evaporation over a steam bath. The residual oil was washed with dilute hydrochloric acid and rewashed with successive portions of fresh water until the wash waters were found to be neutral. When the oil was distilled at a pressure of 1 millimeter of mercury, there were obtained 120 grams of prodduct with a boiling range of 235 to 250 C.

III. PREPARATION OF AMYLTHIOETHYL- KERYLTHIOETHYL ETI-IER a Preparation of amylthioethyl-chloroethyl ether 200 grams of sodium hydroxide were dissolved in 1000 cc. of water and to this solution were added 520 grams of a mixture of isomers of amyl mercaptan. The mixture was agitated by means of a mechanical stirrer, and was heated over a steam bath. After stirring and refluxing had been maintained for one hour, steam heat: ing was discontinued and 685 grams of dichlorethyl ether was added at a rate just suificient to permit the heat of reaction to keep the mixture refluxing. When the addition had been completed, steam heating was resumed, and the material was continuously agitated and refluxed for fifteen hours. Then the mixture was cooled, the aqueous layer was separated and discarded, and the oil layer was washed once with dilute hydrochloric acid and several times with successive portions of fresh water until the washings were found to be neutral. The washed oil was distilled at a pressure of 10 millimeters of mercury, and there were obtained 732 grams of amylthioethyl-chloroethyl ether with a boiling range of 120 to 130 C.

5. Preparation amylthioethyl-kerylthioethyl ether 69' grams of metallic sodium were dissolved in one liter of ethanol, and to this solution of sodium ethylate were added 648 grams of mixed keryl mercaptans (C12 to 014 range). This mixture was refluxed over a steam bath and stirred continuously for one hour, after which time steam heating was discontinued and '74 grams of amylthio ethyl-chloroethyl ether were added at a rate just suflicient to maintain continuous refluxing. After the addition of the ether had been completed, steam heating was resumed, and the mixture was stirred and refluxed for an additional 2 hours. Then the material was cooled, the precipitated salt was removed by filtration, and the ethanol was driven off by evaporation over a steam bath. The residual oil was washed once with dilute hydrochloric acid and several times with successive portions of fresh water until the washings were found to be neutral. Then the washed oil was distilled at a pressure of 1 millimeter of mercury. There were obtained 641 grams of amylthioothyl-kerylthioethyl ether.

8 CORROSION TESTS In the above examples, the corrosion test was performed by submerging a carefully cleaned and bright instrument brass block 2.5 x 1 x 1 centimeters in size and having an area of 12 square centimeters, in about 10 cubic centimeters of the oil in a glass vessel: the temperature was maintained at 100 degrees C. for 100 hours while passing oxygen gas saturated with water vapor at 3 bubbles per second (0.2 cubic feet per hour): at the end of test, the lubricant was examined for change of viscosity and appearance, and the surface of the brass block was examined for pitting or other evidence of corrosion and weighed after removing the oil. The viscosity change was not over 5 per cent, and the weight loss of the brass block was not over 1 milligram for the products accepted as non-corrosive: surface staining without essential change of weight occurred in some instances. A second test, for corrosion on steel, is made by half-immersing a high-grade cleaned steel bearing ball in a 20 cc. beaker containing the lubricant, the beaker being then kept in a sealed vessel containing water to maintain a saturated atmosphere, at room temperature, for a period of several months: satisfactory lubricants resist this test for 5 or 6 months. A third test, for corrosion on steel, is conducted by immersing such a steel ball in the lubricant at degrees C. for one hour; then adding distilled water to displace the main body of oil and leave the ball immersed in the water; and then holding the ball so immersed until more than 10 per cent of the surface is covered with rust: a satisfactory" lubricant must resist for at least 2 days. (By comparison, most uninhibited mineral oils of highly refined types fail in a few hours under this test: some develop rust spots in a few minutes.)

The evaporation residue is calculated as the percentage of a 1.0000 gram sample of lubricant remaining after passing nitrogen gas at the rate of one-half cubic foot per hour through the oil for a period of 100 hours, the oil sample being contained in a special cell designed to promote saturation of the nitrogen with oil vapor, and the entire apparatus being maintained at C.

The lubricant use of ethers with triple linkages of sulfur or selenium is set out and claimed'in the copending Barker and Alter application, Serial No. 552,814, filed September 5, 1944, now Patent No. 2,592,510, patented May 15, 1951. The employment of alkyl piperidine salts is set out and claimed in my copending application, Serial No. 547,979, filed August 3, 1944, now Patent No. 2,412,956, patented December 24, 1946.

It is preferred to include small percentages (not exceeding substantially l per cent in all) of modifying agent to improve the oiliness and reduce the coefficient of friction to inhibit oxidation of the lubricant and of contacted surfaces, to improve temperature/viscosity relationships, etc.; but care must be taken to avoid the presence during the service of the lubricant of such an amount of mineral oil lubricant as to modify the behavior of the mixture or in itself to perform lubricating service unless specific precaution has been taken as in Example IV: this content for Examples I to III, for example, must never exceed 5 per cent because at this proportion there precipitates a dense white cloud at low temperatures. It should be kept as low as possible, and hence thesecompositions can be described as essentially free of mineral oil.

It is obvious that the invention is not limited to the forms of practice described, but that the same Iclaimz.

1. A lubricant having as the dominant and major ingredient thereof mixed partially isomeric triple ethers of the general formula A-SB-OB'S-A where A, B, A and B are saturated aliphatic groups each containing 2 to 18 carbon atoms, S represents a sulfur ether linkage, and. represents an oxygen ether linkage; the total number of carbon atoms being from to about 32, a resin selected from the group consisting of polystyrene and acrylic resins having a molecular weight of 20,000 to 100,000; and, also, including an aralkyl ester ingredient intersoluble with said ether and a solvent of said resin, said ester ingredient being a mixture of isomers each having alkyl structures of 10 to 24 carbon atoms, the amount of said ester ingredient being less than the amount of ether ingredient and characterized in having a pour point not higher than minus 80 degrees F. and a cloud point not higher than degrees F., the amount of resin being 1 to 4% parts per 100 parts of the ether and ester ingredients combined.

2. A lubricant having as the dominant and major ingredient thereof mixed partially isomeric triple ethers of the general formula A-S-B--OB'-SA where A, B, A and B are saturated aliphatic groups each containing 2 to 18 carbon atoms, S represents a sulfur ether linkage, and 0 represents an oxygen ether linkage; the total number of carbon atom being from 10 to about 32, a resin selected from the group consisting of polystyrene and acrylic resins having a molecular weight of 20,000 to 100,000; and, also, including an aralkyl ester ingredient intersoluble with said ether and a solvent of said resin, said ester ingredient being a mixture of isomers each having an acid portion formed of an alkyl group of 10 to 24 carbon atoms and an aryl group and each having an alkyl alcohol portion of 4 to about 11 carbon atoms, the amount of the ester ingredient being less than the amount of the ether ingredient; and characterized in having a cloud point not higher than minus 20 degrees F., the amount of resin being 1 /2 to 4 parts per 100 parts of the ether and ester ingredients combined.

1 3. A lubricant consisting of 60 parts by weight of beta, beta prime-diamyldithiodiethyl ether, 40 parts of the phenylundecanoic ester of an alkyl alcohol of 4 to 6 carbon atoms, about 0.2

part of an alkylpiperidine soap having alkyl and acid group chains each of from 10 to 18 carbon atoms, 0.10 part of tertiary butyl catechol, and about 1.5 parts of a resin selected from the group consisting of polystyrene and acrylic resins having molecular weights rangin from 20,000 to 100,000.

4. A lubricant consisting of 60 parts by weight of beta, beta prime-diamyldithiodiethyl ether, 40 parts of n-butyl phenylundecanoate, about 0.20 part of an alkylpiperidine soap having alkyl and acid group chains each of from 10 to 18 carbon atoms, 0.10 part of tertiary butyl oateohol, and about 1.5 parts of a resin selected from the group consisting of polystyrene and acrylic resins having molecular weights ranging between 20,000 and 100,000.

5. A lubricant consisting of 60 parts by weight of beta, beta prime diamyldithiodi isopropyl ether, 40 parts of the phenylundecanoic ester of an alkyl alcohol of 4 to 6 carbon atoms, about 0.20 part of an alkylpiperidine soap having alkyl and acid group chains each of from 10 to 18 carbon atoms, 0.10 part of tertiary butyl catechol, and about 1.5 parts of a resin selected from the group consisting of polystyrene and acrylic resins having molecular weights ranging between 20,000 and 100,000.

6. A lubricant having as the dominant and major ingredient thereof about 60 parts mixed partially isomeric triple ethers of the general fromula A-SBOB'S-A' where A, B, A and B are saturated aliphatic groups each containing 2 to 18 carbon atoms, S represents a sulfur ether linkage, and 0 represents an oxygen ether linkage; the total number of carbon atoms being from 10 to about 32; with about 40 parts of an aralkyl ester ingredient intersoluble with said ether, said ester ingredient being a mixture of isomers each having alkyl structures of 10 to 24 carbon atoms and having a boiling point above that of the said ether ingredient and being a solvent for polystyrene in the molecular weight range below about 100,000; and about 1 /2 parts per hundred parts of the ether and ester ingredients combined of soluble polystyrene resin of a molecular weight between 50,000 and 100,000.

'7. A lubricant consisting of about 60 parts of mixed isomeric triple ethers of the general formula A-SB-O-BS-A, where A and A are saturated aliphatic groups, and Where B and B are saturated aliphatic groups containing 2 to 3 carbon atoms, the total number of carbon atoms forming the molecular chain with intervening sulfur and oxygen atoms being from 10 to 32, and where S represents a sulfur ether linkage and 0 represents an oxygen ether linkage; about 40 parts of an aralkyl ester ingredient intersoluble with said ether and having a higher boiling point than the said ether, said ester ingredient being a mixture of isomer each having alkyl structures of 10 to 24 carbon atoms; together with 0.20 part of an alkylpiperidine soap having alkyl and acid chains each of from 10 to 18 carbon atoms, 0.10 part of tertiary butyl catechol and 1.5 to 4.5 parts of a resin selected from the group consisting of polystyrene and acrylic resins having molecular Weights ranging between 20,000 and 100,000.

8. A lubricant as in claim 3, and having dissolved therein 2 parts of a rust inhibitor selected from the group consisting of salts and esters of oxidized-petroleum acids, tri-n-butylamine rosinate, di-n-butylamine rosinate, and amylthiopropylipiperidine rosinate.

9. A lubricant having as the dominant and major ingredient thereof mixed partially isomeric triple ethers of the general formula AS-B-OB--SA where A, B, A and B are saturated aliphatic groups each containing 2 to 18 carbon atoms, S represents a sulfur ether linkage, and 0 represents an oxygen ether linkage; the total number of carbon atoms being from 10 to about 32; and also including about 0.50 part of tertiary butyl catechol; and characterized in having a cloud point not higher than minus 20 degrees F.

10. A lubricant as in claim 9, in which at least one of the saturated aliphatic groups is provided by the keryl hydrocarbon group having 12 to 14 carbon atoms and the said ethers are present as a mixture of isomers and homologs each responding to said general formula; and characterized by a pour point of not higher than minus F. and a cloud point not higher than minus 20 F.

'11 11. A lubricant having as the dominant and major ingredient thereof a mixture of diamylthiodi-isopropyl ether isomers; and characterized by a pour point ofa-not higher than minus 80 F. and a cloud point 'not higher than minus 5 20 F.

GEORGE E. BARKER.

REFERENCES CITED The following references are of record in the file of this patent:

Number 12 UNITED STATES PATENTS Name Date Moran Nov. 12, 1940 Moran Aug. 10, 1943 Barker Aug. 15, 1944 Morgan Mar. 5, 1946 Fenske et a1 Sept. 17, 1946 Evans Nov. 9, 1946

Claims

1. A LUBRICANT HAVING AS THE DOMINANT AND MAJOR INGREDIENT THEREOF MIXED PARTIALLY ISOMERIC TRIPLE ETHERS OF THE GENERAL FORMULA A-S-B-O-B''-S-A'' WHERE A, B, A'' AND B'' ARE SATURATED ALIPHATIC GROUPS EACH CONTAINING 2 TO 18 CARBON ATOMS, S REPRESENTS A SULFUR ETHER LINKAGE, AND O REPRESENTS A SULFUR ETHER LINKAGE; THE TOTAL NUMBER OF CARBON ATOMS BEING FROM 10 TO ABOUT 32, A RESIN SELECTED FROM THE GROUP CONSISTING OF POLYSTYRENE AND ACRYLIC RESINS HAVING A MOLECULAR WEIGHT OF 20,000 TO 100,000; AND, ALSO, INCLUDING AN ARALKYL ESTER INGREDIENT INTERSOLUBLE WITH SAID ETHER AND A SOLVENT OF SAID RESIN, SAID ESTER INGREDIENT BEING A MIXTURE OF ISOMERS EACH HAVING ALKYL STRUCTURES OF 10 TO 24 CARBON ATOMS, THE AMOUNT OF SAID ESTER INGREDIENT BEING LESS THAN THE AMOUNT OF ETHER INGREDIENT AND CHARACTERIZED IN HAVING A POUR POINT NOT HIGHER THAN MINUS 80 DEGREES F. AND A CLOUD POINT NOT HIGHER THAN 20 DEGREES F., THE AMOUNT OF RESIN BEING 1 1/2 TO 4 1/2 PARTS PER 100 PARTS OF THE ETHER AND ESTER INGREDIENTS COMBINED.