US2399817A

US2399817A - Mineral oil

Info

Publication number: US2399817A
Application number: US505965A
Authority: US
Inventors: Ronald E Meyer
Original assignee: Socony Vacuum Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1943-10-12
Filing date: 1943-10-12
Publication date: 1946-05-07
Anticipated expiration: 1963-05-07

Description

' change and to impart substantial improvement ketones and aldehydes, in'the presence of this group, butadiene- ,Patented May 7', 1946 UNITED S ATES PATENT orrlcs,

uranium I g 3 Ronald E. Meyer, Socony-Vacuum No Drawing.

, 14 Claims.

This invention has to do withlubricating oils of improved viscosity characteristics and more specifically has to do with lubricating oils enhanced by the incorporation therein of small amounts of oil-soluble polymers.

As is well known to art, the viscosity of an oil fraction varies considerably' with temperature change. It is this characteristic that has limited the utility of certain oils to only those operations where temperature change is relatively small. The naphthenic oils are notable in this regard inasmuch as the viscosity change over a temperature range of 100 F., for example, is extreme. On the other hand, parafllnic oils suffer a substantially smaller change over the same temperature range. This characteristic has generally been expressed in the art as the viscosity index (V. 1.) which is the rate of change of viscosity of naphthenic and parailinic oil fractions with temperature is described in detail by Dean and Davis in the Chem. &Met. Eng. 36, 618 (1929).

Inasmuch as many of the hitherto useful lubricating oil fractions have been found to be un-' suitable for use in several present day operations which require 'oils having relatively high viscosity indexes, a demand has arisen for new lubricants. In general, the new lubricants which have been developed can be divided into two categories: synthetic lubricants, and lubricating oil fractions enhanced by small amounts of improving agents which have been termed viscosity-index improving agents. This invention is directed to lubricants of the latter category and, more particularly, is predicated upon the discovery of a new class of viscosity index improving agents.

those familiar with the Woodbm, N. 3., udgnor to company, corporation of New York, 1

Application October 12, 1943, Serial No. 505.965

Incorporated. a 1

formic acid is decarboxylated, the product is pre- While the foregoing dedominantly aldehydes. carboxylation products may be used in the pure state in the reaction with a dioleiin, crude dego tic,

about 150 C.

peroxide type are preferably employed in preparnish type resins, it is preierredthat the carboxylation products may also be used.

of the foregoing compounds, however, the unsaturated ketones are preferred, and of this group, dioleyl and unsaturated naphthenyl ketones are particularly preferred.

Co-polymers of unsaturated carbonyl compounds and dioleflns are oil-soluble and neutral, and possess different properties depending upon the method of polymerization resorted to for their preparation. For example, soft, plastral co-polymers are-preferably prepared by using from about to about moi per cent of the unsaturated carbonyl compound in the reaction, and temperatures in to about 300 C. Catalysts of the ing such resins. Illustrative of such catalysts are benzoyl peroxide and sodiumperborate. In order to prepare hard, brittle, transparent-varunsatushould be present in the amount of from about rated carbonyl compound the reaction mixture in V 50 to about mol per cent or moreand that The improving agents which we have found I in viscosity characteristics to lubricating oil fractions, are oil-soluble, neutral co-polymers obtained by reacting dioleflns with carbonyl compounds selected from the group consisting of unsaturated of various catalysts. v

While, in general. all dioleiins may be used in the production of the co-polymers defined above, conjugated dioleilns are preferred and, is particularlypreferred.

The carbonyl compounds used herein are, as aforesaid, unsaturated aliphatic ketones and aldehydes.- These compounds may 'also be defined as decarboxylation products of aliphatic, cycloaliphatic and aliphatic-cycloaliphatic acids. For

example, when oleic acid is decarboxylated, the P5- about temperatures of the order of -40 C. to about +25 0. should be used. The catalysts which are preferred for the preparationv of this latter type of co-polymer are of the metal halide type, for example, AlCla, BFs, SnCh, etc. In each of these illustrative methods of preparation, organic solvents such as ethylene dior tetrachloride may be present.

In order to more fully illustrate the co-polymers contemplated herein-as mineral oil lmproving agents, the preparations. of several preferred polymers are described below:

50 (Jo-polymer of unsaturated naphthenyl ketone RUBBER-LIKE (IO-POLYMERS Exams: 1 a

and butadiene (a). Preparation of unsaturated naphthenyl ke- 1 tone: I a i a A naphthenic acid, having a boiling range from rubber-like (elastomeric), oil-soluble, neuthe range of from C. to about 300 C., was passed over calcium oxide which was contained in a heated mume furnace, at a rate ot'about 25 to about 40 grams per hour and at a temperature of about 300 to 475 C. The product obtained by this treatment is an unsaturated naphthenyl ketone boiling from about 100 C. to-about 350 C.

(b) Preparation of co-polymer of butadiene and (a):

One hundred and iiity grams of the unsaturated naphthenyl ketone prepared as described in (a), 174 grams of butadiene and grams of benzoyl peroxide were charged to a 500 cc. steel shaker bomb. The temperature of the bomb was held at about 190 C. to about 260 'C. for nine hours during which time the polymerization occurred. The reaction product was then diluted with benzol, filtered, washed with water and dis- I Co-(polumer of oleul ketone and butadiene A one-liter, three necked flask equipped with a motor stirrer, a thermometer and a 500cc.

dropping tunnel was cooled to 40 C. Then 46 grams of oleyl ketone and 92 grams oi butadiene were added to the flask. A quantity of 4 grams of anhydrous aluminum chloride which had previously'been dissolved in 200 cc. of. ethylene dichloride was placed in the dropping tunnel and added tothe mixture in the flask, drop by drop, over a 1% hour period. when the additionhad been completed, the temperature was allowed to rise to about 25 C. and stirring was continued for 16 hours. The reaction product was then filtered through super Filtrol clay and the filtrate was distilled to a maximum temperature of 230 C. at 760 mm. The co-polymer thus obtained, co-polymer II, was a soft, plastic, transparent, rubberlike, oil-soluble, neutral resin.

RESINOUS CO-POLYMERS Co-polumers of unsaturated na'phthenyi ketone and butadiene A one-liter, three-necked flask, equipped with a motor stirrer, a thermometer and a long glass tube extending to the bottom of the flask, was cooled to about. -20 C.. Eighty-live grams of unsaturated naphthenyl ketone prepared as described in (a), 28 grams of butadiene and 200 cc. oi ethylene dichloride were then added to the dash. The lowest temperature at which the unsaturated naphthenyl ketone remained insolution with the ethylene dichloride and butad'ilene was about --20 0. Boron triiiuoride was en very slowly bubbled into the reaction mixture and the temperature was maintained at about 5" C.

for about fifteen minutes. There was then a vig-. .orous reaction with the temperature rapidly rising to about +5 C. The temperature was allowed to rise-to 18" C. where it was held constant tor-one hour. The reaction product was diluted with benzol, flitered through grams of Super Filtrol clay and distilled to a maximum temperature of 230 C. at 5 mm. The co-polymer obtained was a very hard, brittle. transparent, neutral resin oi the varnish typeioil soluble) having amolecularweigh't oi 1092, and is identified herein as co-polymer III. A

,0! adiolefln and a carbonyl compound selected Exams: 4

(Jo-polymer of oleill ketone and butadiene A one-liter, three necked flask equipped as described in Example 3 was cooled to -35 C. and grams of oleyl ketone, 30 grams of butadiene and 200m. of ethylene diechloride were then added to the flask. Alter cooling the reaction mixture to -35 0., boron trifluoride was'bubbled slowly into the mixture. The temperature remained at -35 C. for fifteen minutes and then began to rise very slowly to 25 C. where it was held constant for 1 hours with constant stirring. "The reaction product was filtered through Super Filtrol clay. In this way a soft, plastic, transparent, oil-soluble, neutral resin having a molecular weight of 838 was obtained. This product is referred to herein as co-polymer IV.

The effectiveness of the co-polymers of the type contemplated herein in improving the viscosity index of lubricating oils is demonstrated herein by viscosity data obtained on a lubricating oil and on oil blends of the same oil containing small amounts or co-polymer I. The oil used was a viscous mineral oil oi. the lubricant type and the data wasobtained inwthe conventional manner from the kinematic voscosities of the oil and of the oil blends at 100 Fyand at 210 F. The results are shown below in the table.

Table kinematic viscosity Improving agent 1 about 0.25% to about 2.0%.

. an unsaturated aliphatic As will be apparent irom the foregoing data, substantial improvement in the viscosity characteristics oi lubricating oils is imparted by small amounts oi. the co-polymers contemplated herein. In general amounts oi! from about 0.1% to about 5% may be used. although appreciable improvement is obtained with amounts from It is to be understood that this invention is not limited to the foregoing illustrative reactants. reaction conditions and co-polymers but is to be construed in accordance with the broad disclosure setforth hereinabove. The invention, therefore, is to beinterpreted as coming within the spirit of the appended claims.

I claim: V

1. An improved mineral oil composition com-, prising a mineral oil fraction havingin therewith a minor proportion; suflicient to improve the viscosity characteristics' of said oil fraction, of an oil-soluble, neutral co-polymer from the group consisting 01' an unsaturated aliphatlc ketone and an aliphatic aldehyde.

2. An improved mineral oil comppsltion comprising a mineral oil fraction having in admixture therewith a minor proportion, from about 0.1 per cent to about 5.0 per cent, of an oil-soluble, neutral co-Dolymer of a dioleiln and a carbonyl compound selected from the group consisting of ketone and an aliphatic aldehyde. 7

3. An improved mineral oil composition comprising a mineral oil fraction having in admixture therewith a minor proportion, suflicient to imadmixture 4 prove the viscosity characteristics of said oil fraction, of an oil-soluble, neutral co-polymer of a diolefin and an unsaturated aliphatic ketone.

4. An improved mineral oil composition comprising a mineral oil traction having in admixture therewith a minor proportion, "sufllcient to improve the viscosity characteristics oi said oil fraction, of an oil-soluble, neutralco-polymer of a conjugated diolefin and an unsaturated aliphatic ketone.

5. An improved mineral oil'composition comprising a mineral oil fraction having in admixture therewith a minor proportion, sufflcient to improve the viscosity characteristics or said oil fraction, of an oi'i-so1uble,. neutral co-polymer of butadiene and an unsaturated aliphatic ketone.

6. An improved mineral oil composition comprising a mineral oil traction having in admixture therewith a minor proportion, sufllcient to improve the viscosity characteristics 0! said oil fraction, of an oil-soluble, neutral co-polymer of dioleyl ketone and butadiene.

'7. An improved mineral oil composition comprisinga mineral oil traction having in admixture therewith a minor proportion, suflicient to improve the viscosity characteristics, of said oil fraction, of an oil-soluble, neutral co-polymer 'of an unsaturated naphthenic ketone and butadiene.

8. An improved mineral oilcomposition comprising a mineral oil traction having in admixture therewith a minor proportion, suillclent to improve the viscosity characteristics of said oil fraction, of an oil-soluble, elastomeric, neutral co-poiymer obtained .by the reaction or an unsaturated aliphatic ketone and a dioieiin.

9. An improved mineral oil composition comprising a mineral oil traction having in admixture therewith a minor proportion. sufllcient to improve the viscosity characteristics of said oil traction, of an oil-soluble, resinous, neutral co-polymer obtained by the reaction of an unsatu.

rated aliphatic ketone and a diolefln. 10. An improved mineral oil composition comprising a mineral oil fraction having in admixture therewith a minor proportion, sufflcient to im-- prove the viscosity characteristics of said 011 fraction, of an oil-soluble, elastomeric, neutral co-polymer obtained by reaction of an unsaturated naphthenic ketone and butadiene.

' 11. An improved mineral oil composition comprising a mineral oil traction having in admixture therewith a minor proportion, sufficient to improve the viscosity characteristics of said oil fraction, 01 an oil-soluble, resinous, neutral copolym'er obtained by reaction of an unsaturated naphthenic ketone and butadiene.

12. An improved mineral oil composition comprising a mineral oil fraction having in admixture therewith a minor proportion, sufllcient to improve the viscosity characteristics of said oil traction, of an oil-soluble, resinous, neutral copolymer obtained by reaction of dioleyl ketone and butadiene. 1

13. An improved'mineral oil compositioncom prising. a mineral oil traction having in admixture therewith a minor proportion, sufficient to improve the viscosity characteristics or said 011 fraction, or an oil-soluble, neutral co-polymer of a dioleiin and an aliphatic aldehyde.

14. An improved mineral oil composition comprising a mineral oil traction having in admixture therewith a minor proportion, suiiicient to improve the viscosity characteristics of said oil fraction, of an oil-soluble, neutral co-polymer of a diolefln and a decarboxylation product or an acid selected from the group consisting ot'ali-' phatic, cycloaliphatic and aliphatic-cycloaliphatic acids.

.. RONALD E. MEYER.