Патент USA US2407087код для вставки
2,407,087 Patented Sept. 3, 1946 UNITED STATES PATENT OFFICE 2,407,087 MINERAL OIL LUBRICATING COMPOSITION Eugene Lieber, Staten Island, N. Y., and Aloysius F. Cashman, Bayonne, N. J ., assignors to Stand ard Oil Development Company, a corporation of Delaware 'No Drawing. Application December 26, 1940, Serial No. 371,788 6 Claims. (Cl. 252-52) 2 1 This invention relates to a novel type of chemi cal condensation product and. to methods of pre paring such products and using themfor various purposes, more particularly as pour depressors in waxy lubricating oils. _ It has been known for some time that substances which reduce the A. S. T. M. pour point of waxy mineral lubricating oils can be made by various FeCla, ZnClz, BF3, etc. The Friedel-Crafts type of catalyst is preferred. Auto-condensation in the presence of catalysts of the above types re sults in the substantial removal of oxygen and the formation of a high molecular weight essen tially hydrocarbon product. wax with naphthalene. However, a new method has now been discovered for preparing condensa The amount of condensation agent to be used will, of course, vary with the particular type of ‘condensing agent used. Generally about .01 to ‘.10, preferably .02 to .05, mols of a Friedel-Crafts catalyst should be used per mol of ketone. .With activated clays or mineral acids, larger amounts of the condensing agent should be used. It is not tion products having pour-depressing properties necessary to use a solvent or diluent in carrying groups. sired to use a solvent, a re?ned kerosene or naph chemical condensation reactions involving organic compounds containing long aliphatic hydrocarbon chains, such as by reacting chlorinated para?in from a class of organic compounds containing 15 out the condensation, especially with the lower molecular weight ketones; however, if it isde low molecular weight aliphatic hydrocarbon tha, which has been pretreated with strong sul furic acid or A1013 to make it inert, will serve as tion of wax modifying agents by subjecting low molecular weight aliphatic ketones to auto-con 20 a suitable solvent. If a solvent or diluent is used, generally a slightly larger amount of catalyst is densation. Such ketones may be represented by required. the general formula R--CO-—R’, where R and The temperature for carrying out the conden R’ are aliphatic hydrocarbon groups having a combined total of less than 12 carbon atoms, , sation should be between the approximate limits of room temperature and about 300° F. It is pre preferably less than 8 carbon atoms. More ferred to add the catalyst to the ketone at low broadly the invention comprises the auto-condene temperatures and then heat the reaction mass to sation of ketones having the general formula the desired maximum temperature, usually be X—R—CO--R'-X', where X may be hydrogen, tween about 100° F. and 200° F. A reaction time hydroxyl, or halogen, and X and X’ may be the same or different, and where R and R’ are ali 30 of about 1/2 hour to 20 hours, preferably 1 to 5 hours, may be used. The temperature and time phatic hydrocarbon groups which maybe either should be adjusted for the desired combination saturated or may contain an ole?nic linkage and Broadly, ‘the invention comprises the produc R and R.’ may be the same or different. Ketones of yield and‘ potency of pour depressor. , After the reaction has been completed, which having the formula R-CO-R', where Rand R’ are alkyl radicals having each less than 6 carbon 35 may be judged by testing small samples of the product, the condensing agent is separated from atoms are preferred. the reaction mass according to known methods. Speci?c examples of these ketones include For instance if a Friedel-Crafts catalyst was used, acetone, methyl ethyl ketone, diethyl ketone, the reaction mixture is preferably cooled and methyl propyl ketone, dipropyl ketone, methyl butyl ketone, dibutyl ketone, methyl amyl ketone, diamyl ketone, ethyl propyl ketone, ethyl butyl ketone, ethyl amyl ketone, methyl isobutyl ketone, methyl tertiary butyl ketone, methyl isoamyl ketone, phorone (di-iso propylidene acetone), 40 diluted with an inert diluent, such as a re?ned kerosene and then neutralized by adding to it, or pouring it into, water, an aqueous solution of caustic soda, or an alcohol, or a mixture thereof such as a mixture of water and alcohol. The acetonyl acetone, and others. Mixtures of two 45 keroseneextract is then allowed to settle and the catalyst-sludge layer is drawn off. The kerosene extract is then ?ltered, if necessary, to remove cial products consisting essentially of. one or more any insoluble material and then distilled to re ketones of theclass described, together with minor move the solvent and low boiling products, this amounts of substances which are either inert or do notinterfere with the desired auto-condensa 50 distillation being preferably carried out under or more ketones may be used, as well as commer tion of the ketones. " To effect the auto-condensation-it is preferred to use a condensation agent or catalyst, such as vacuum or with ?re and steam, in the latter case carrying the temperature up to about 600° F. The ketone auto-condensation product of this activated clay, alumina, silica gel, and various - invention generally has a colorand ‘texture-rang catalysts of the Friedel-Crafts type, c.‘ g., A1012, 55 ing from a green viscous oil to a brown,‘britt1e 2,407,037 3 . 1 .1 .. A‘ ‘v 4 resin. It is soluble in hydrocarbon oils. It has a fairly high molecular weight and is substantially non-volatile at temperatures below about 600° F. Although the chemical structure of these auto— kerosene extract containing the desired product tainty, itvis believed that they are composed green cast was obtained as product. The pour was washed further with water and then distilled with ?re and steam to 600° F. to remove solvent and low boiling products. A bottoms residue com condensation products is not known with cer- 5 prising 14 grams of a very viscous oil of dark essentially of very highly branched linear chains depressing potency of this condensation product and are composed essentially of hydrocarbons, especially when made from unsubstituted ketones. was determined by dissolving 2% of it in a waxy mineral lubricating oil base stock having a pour The product of this invention has the property 10 of modifying the crystal structure of waxes such as para?in wax present when added to compositions containing the same. For instance, when about .05-l0.0%, preferably .2-5.0%, of this wax point of +30° F. and then testing the resultant blend for pour point according to the standard A. S. T. M. method. A number of other 'condensations were carried out in the same manner, except that di?erent ' modi?er is added to a waxy lubricating oil such 15 amounts and types of catalyst were used to effect as a Pennsylvania type lubricating oil having a the condensation and various ketones and reac relatively high pour point, the resultant blend tion conditions were used. The proportions of will have a substantially lower pour point; in . materials used as well as the operating conditions, other words, this wax modi?er is an effective pour yield of product and pour-depressing potency of depressor for waxy oil. A small amount of this 20 the product are summarized in the following wax modi?er is also useful as a dewaxing aid for table. ' Table Raw materials Reaction Product Test Ketone Catalyst _ N . o Solvent Name Amt. Name Phorone _________ __ d .d Mtethyl ethyl keon . . - Acetoiie _________ _. 100gm_. HsP041-_._ . P t, T2??? Thlfgf’" Yield ° §Pgfplglleliid Gm _ Acetonylacetone. V01. (2- conc') 3 3 2 5 l 14 40 65 66 88 ~30 —l5 —l5 +10 Dark green visc. oil. Brown resin. Brown brittle resin. Brown resin. Black resin. 3 14 —25 Brown resin. - "288 4 ~35 +10 Do. 8 _________ ._do ___________ __ l00gm.. NaOHL" 2288 11 —20 Do. 9 ____ __ Mtethyl ethyl ke- 100E111" resou...~ 2288 2a —20 Do. 011 . l0 ........ “d2 ___________ .. 100 5111.. HaPOUM- 288 5 —35 1l___._ Methyl isobutyl 840 8 —5 ketonc. 300gm_. H2S044..._ Do. Red resin. 1 85% strength. I Followed by re?ux at ISO-200° F. for 1 hour. a Dry pellets. ‘ 96.5% strength. removing wax from mineral lubricating oils of 45 This table shows that the auto-condensation undesirably high wax content. In similarly small products of the low molecular weight ketones, amounts, this wax modi?er may also be incor lowered, i. e., depressed, the +30° F. pour point porated into paraffin wax or compositions con of a waxy mineral lubricating oil by at least 20° taining the same to be used for various purposes F. and in some cases by as much as 65° F. (i. e. such as for coating or impregnating paper, etc., 50 down to _—35°F.) , thus indicating that the prod or for making various molded products. ucts of this invention are potent pour depressors. If desired, the yield of potent pour depressor obtained in these auto-condensation reactions can be increased by subjecting some of the in One liter of acetone was placed in a suitable 55 termediate condensation products which have reactor equipped with a mechanical stirrer, ther- . been recovered overhead when subjecting the mometer and re?ux condenser open to the atmos condensation products to the ?re and steam dis phere. The reactor was cooled by an external tillation up to 600° F., to a further condensation bath of cold running water. 100 grams of an with an additional quantity of aluminum chloride hydrous aluminum chloride was now slowly added 60 or othercatalyst, and then subjecting the result while agitating the acetone and maintaining the ant condensation product to a catalyst-removal temperature at 65° F. 30 minutes were required treatment and ?nal ?re and steam distillation, for the addition of the A1C13. After the addition the same as described above. of the A1C13 the reaction temperature was raised The condensation products of the low molec-' to re?ux and maintained thereat for 3 hours. As 65 ular weight aliphatic ketones not only are pour the condensation of the acetone by the AlCla pro- e ‘I depressors but also impart other valuable prop gressed, the temperature of the reaction mixture erties to mineral lubricating oil when added gradually increased until at the end of 3 hours a thereto, such as resistance to oxidation, decreased reaction temperature of 140° F. was attained. sludge formation and enhanced oiliness. ' The reaction mixture was then diluted with 500 70 It is not intended that this invention be lim cc. of kerosene and cooled below 80° F. The cata— » ited to any of the speci?c examples which we're lyst was then decomposed by slowly adding 1000 given merely for the sake of "illustration nor to cc. of water to the reactor while stirring. After any theory as to the mechanism- of the oper For the sake of illustration, but without limit ing the invention to the particular materials used, the following experimental data are given: settling, the aqueouslayer containing the alumi: nous sludge was drawn off and discarded. The ation of the invention but only by the appended claims ‘in which itvis intended‘ to claim all nov 2,407,087 5 6 elty inherent in the invention as broadly as the prior art permits. 6 carbon atoms, said wax modifier being substan tially non-volatile under ?re and steam distilla tion conditions at temperatures below 600° F. We claim: _ 1. A composition comprising as a base a hydro carbon product containing hydrocarbon wax and a small amount of an auto-condensation prod uct of an aliphatic ketone having less than 12 carbon atoms, said condensation product being substantially non-volatile under ?re and steam distillation conditions at temperatures below 10 4. A lubricating oil composition comprising a waxy mineral lubricating oil base containing dis solved therein a pour-depressing amount of an oil-soluble high molecular ‘Weight auto-condensa tion product of acetone substantially non-vola tile at temperatures up to about 600° F. 5. A lubricating oil composition comprising a waxy mineral lubricating oil base containing dis 600° F. solved therein a pour-depressing amount of an 2. A composition comprising a hydrocarbon auto-condensation product of methyl ethyl ke product containing a hydrocarbon wax and asso tone. ciated therewith a high molecular weight auto 6. A composition according to claim 3 in which condensation product of a ketone having less 15 than 12 carbon atoms and having the general formula X—R—CO—R'—-X', where X and X’ the auto-condensation product has been derived by subjecting the ketone to auto-condensation in the presence of .01—l.0 mols of aluminum chlo are either hydrogen, hydroxyl or halogen, X and ride as a catalyst per mol of ketone, at a tem X’ are the same or different, R and R’ are ali phatic hydrocarbon groups and R and R’ ‘are 20 perature between the approximate limits of room temperature and 300° F., for about Me hour to either the same or different, said auto-condensa tion product being substantially non-volatile under ?re and steam distillation conditions at temperatures below 600° F. 3. A composition comprising a waxy mineral lubricating oil base and a small amount of a wax modi?er consisting essentially of ,an auto-con densation product of a ketone having the general formula R--CO—R’, where R and R’ are the same or different alkyl groups having less than 30 20 hours, hydrolyzing and removing the catalyst, and distilling the condensation product in the presence of an inert volatile hydrocarbon solvent with ?re and. steam to about 600° F. to obtain the desired high molecular weight product as dis tillation residue. EUGENE LIEBER. ALOYSIUS F. CASHMAN.