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  • Oil Soluble Ester PPD Additive For Lubricant

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    Shan Rana
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    Lubricant Additive composition

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    Oil Soluble Ester PPD Additive for Lubricant

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    Lubricant Additive composition

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    54 Ansichten4 Seiten

    Oil Soluble Ester PPD Additive For Lubricant

    Hochgeladen von

    Shan Rana
    Lubricant Additive composition

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    © All Rights Reserved
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    United States Patent 1 Rossi [4] OIL SOLUBLE ESTER POUR POINT DEPRESSANT ADDITIVE FOR LUBRICANTS [75] Inventor: Albert Rossi, Warren, NI 73] Assignee: Exxon Research and Engineering Co., Florham Park, NJ. [21] Appl No: 568,161 [22] Filed: Dec. 23, 1983 Related US. Application Data [63] Continuation of Ser. No. 269,754, Jun. 2, 1981, sban- ddoned, which is 2 continuation i-part of Ser. No, 98,626, Nov. 28,197, abandoned [sy] Inc c1oM 1/28 [2] usa. va, 252/86 D [58] Field of Search 252/36 D, 56 R [59] References Cited US. PATENT DOCUMENTS 2.655479 10/1953 Munday et 252/56 R 2666746 1/1954 Munday et 252/56 D 2.720877 10/1955. Popkin e 382/56 DX 3729296 4/1973. Miller 252/56 DX (1) Patent Number: 45] Date of Patent: 4,514,314 Apr. 30, 1985 3,965,849 10/1093 Thnyeky) et al, 251/56 DX 5151068 4/1979 Ross 252/56 DX FOREIGN PATENT DOCUMENTS 248879 9/1971 Primary Examiner-—Andrew Metz Attorney, Agent or Firm—Frank T. Jobmann i ABSTRACT ‘An oil soluble copolymer, useful asa poue point depres- sant for lubricating ols, is a Co2-Cio, preferably Cyp-Cag, branched alkyl ester based polymer. These alkyl esters of copolymers are essentially free of olefinic unsaturation and have a number average molecular weight of from 1,000 to 40,000, preferably 2,000 to 15,000, optimally 2,000 to 8,000, ‘These alkyl ester copolymers are usefully admixed with lubricants in an amount of from 0.01 to 2 wt. %e based on. the total weight of the admixture and are of the class ‘consisting of s Co9-Capbranched alkyl ester ofa copoly ‘mer of a Cz to Cx I-olefin and maleic anhydride and -Cag branched alkyl ester based copolymer derived from an ethylenically uncatarsted Sierbonylic aid material 2 Prior Att ‘A Wide variety of compositions comprising. poly- meric materials derived from the addition reaction of {olefins and ethylenically unsaturated carboxylic acid materials have been described in the Hterature ax add- tives for fuels and lubricants, For example: US. Pal No. 2,615,845 teaches that the copolymer of maleic aniydride and a straight chain L-lein having up to 20 carbon atoms which is subsequently estenfed with long, crsight chain saturated aleohols in order vo make it suitably oilzoluble ean be usefully added to.a mineral Iubriating ol for pour point depression; and U.S. Pa. No. 2688,479 points out that a factor of particularly reat effect on the pour depressant activity of sexyc ‘ster polymers is the length of the alkyl sige chains {pparently a fonction ofthe oil solubilizing effect ofthe alkyl side chain) except that polymers of single exters axe rarely pour point deprestnts; and US. Pat. No 2,809,203 teaches of a pour depressant for ube oils ibcing composed of a polymer ofa di~Cioto Ciealky)) fumarate Te is also known to use ester bated copolymers for various other applications relating to the processing ‘nd/oruilization of petroletm products, eg” U.S. Pa. No. 3,449,236 teaches asa dewaxing ai, a copolymer of Ceto Cx dolein with maleic anhydride which is thea caterfed of amidated with a Ci to Cy lcohol or mine; US, Pat No 151,069 teaches that olefin maleic anhydride copolymers esterified with Cig to Co linear alkyl side chains are filtration ads for dewaxing of waxy Iubricating oll, and copolymers of Copy olefins with maleic anhydride with Cx alcohols have been taught 4B Muiityimprovers in vatious types of liga hydro- carbons boiling from about 75° Fto about 1,000" F, including distiates, crudes and residual eis, in Dutch ‘Application No. 69/13277 SUMMARY OF THE INVENTION In contrast tothe teachings of the various prior art references described above it has been discovered that branched alkyl, pendant chains having from 22 10 40, preferably 32-36, carbons when derived from the exter. fication ofan escrbase copolymer obtained from ey - cncally unsaturated dicarboxslic acid material provides Nighly useful pour point depressant activity in hbrica ing oll, said copolymer having a number average mo- Teeular weight Mp) of from 1,00 to 40,000 preferably 2,000 to 15,000, optimally 2,000 to 8000 ‘These oilsoluble exter bate copolymers are useful as pour point depressants when compounded in lubricat 5 2» 2 “0 4s 0 38 © 2 ing ils in a least a pour point depressing amount pref erably to 0.01 to 1.0 wt %, optimally 005 00.3 wt. % based on the total composition, and are preferably pro- duced by the polymerization of: (a) I-olefin of from 2 to 20, optimally 14 to 18, carbons and maleic anhydride Followed by the reaction of said copolymer with from, 1.2020 moles ofa Cz2to Cap e.g. C2410 Ca, optimally Cr2 0 Cas, branched alcohol per mole of maleic anhy’ ride moiety in said copolymer or (b) « di-(Cp2t0 Can eg. Cag to Cap preferably Csz t0 C3g branched alkyl) fumarate and vinyl acetate. DESCRIPTION OF THE PREFERRED EMBODIMENTS ‘The ester base copolymer found 10 be the highly advantageous pour point depressants for lubricating oils, fare characterized by polymers having long chain branched alkyl pendant groups positioned along the ‘backbone of the polymer. These ester base copolymers are of the class consisting of (8) Cxz to Cap branched alky] esters of the copolymer of a C3 to Cap I-olefin and an ethylenically unsaturated dicarboxylic acid material and (b) d(C t0 Ceo branched alky))fumarate-vinyl C)-Cs ester, preferably vinyl acetate ‘The ethylenically unsaturated dicarboxylic acid ma- terial is intended to include the acid, anhydride and Tower alkyl, ie, C)-cx esters. Preferably these copoly. mers are derived from the ethylenically unsaturated dicarboxylic anhydride such as maleic and itaconie, eg an addition polymer of a Cys Iolefin and maleic anhy- ride The addition reaction between the dicarboxylic ac, anhydride or ester and olefin having from 1 to 20 carbons can conveniently be carried out by mixing the Trolefin with an equimolar amount of anhydride or Gerivative and heating the mixture to a temperature of from about 50° C. to about 155° C, preferably from 80° C.to 120° C. A free radical polymerization promoter such as t-butyl hydroperoxide, azoisobutyl nitrile, ben- zoyl peroxide, -butylperbenzoate or di-t-butyl peroxide is normally used. ‘The resulting addition polymeric product has 2 number average molecular weight (My) ff about 1,000 to 30,000, more usually 1,500 to 20,000 and suitabiy about 2,000 to 10,000. ‘The addition product thus prepared is reacted with about 2 moles per mole of dicarboxylic acid material of a branched alcohol containing from 22 to 40, preferably 24 to 36, optimally 32 to 36, carbon atoms per molecule. Reaction is readily carried out by heating at from 50° to 150° C. until all of the water of esterification is re moved. A catalyst may be used to accelerate the esterifi- cation. Suiable catalysts are methane sulfonic acid and p-toluene sulfone acid ‘The dialkyl fumarate-viny] ester addition copolymer is readily produced by esterification of fuarie acid or fumaryl chloride with the C22 to Cap branched, prefera- bly 2-Coa to Cu, allanols to yield a diester Which is thereafter polymerized with a vinyl Cy-Cy ester, prefer- ably vinyl acetate by techniques well-known in the art and are usually made by free radical initiation, eg. a peroxide, in a solvent. 2aalkylalkanols useful in preparing the above types of polymers include those having 10 to 18 carbons in the alkyl portion and 12 to 22 carbons in the alkanol por- tion. Such alcohols include 2-decy! dodecanol, 2-decyl tetradecanol, 2-dodecyl dodecanol, 2-dodecyl tetradec- 4,514,314 3 anol, 2-etradecyl hexadecanol, 2-etradecyl octadeca- nol, 2-hexadecyl octadecanol and mixtures thereof. Particularly preferred are 2-alkyl alkanols wherein the alkyl portion contains 10 to 18 carbons and the alkanol portion contains 12 10 22 carbons, which in- clude those of the formula: i eons k where R is a straight chain alkyl group of 10 to 18 carbons and R’ isa straight chain alkyl group of 12 1020 carbons, preferably R is 14 to 16 carbons and R’ is 16 t0 18 carbons, Alcohols of this formula are commercially available from Henkel, Inc. where R’ is 2 carbons greater than R, under tradenames Standamul GT-2428 Where R is 10 and 12, while R'is 12 and 14; and Stan- damsel GT-3236 where R is 14 and 16 while R'is 16 and 18. ‘The oil-soluble ester based copolymeric additives can be incorporated in lubricating oil compositions, e-. automotive crankease lubricating oils in concentrations within the range of about 0.01 to 2.0 wt. %, preferably 0.01 to 1.0, optimally 005 to 03 wt. 9%, of the total ‘composition. The lubricants to which the ester base ‘copolymeric products of this invention can be added include not only hydrocarbon oils derived from petro- eum, tar sand ot shale but also include synthetic oils of the hydrocarbon polyester variety and mixtures thereof. ‘The additive may be conveniently dispensed as a concentrate comprising 20-98 parts by weight, pre ferred about 50 parts by weight of the additive dis- solved in from 2 to 80 parts by weight of a mineral Iubricating oil with or without other additives being present The invention can be more fully understood by refer cence to the following examples: EXAMPLE 1 Copolymer of Cig t-olefin and maleic anhydride The laboratory preparation of this maleic anhydride- I-olefin copolymer was as follows: To a 2000 mi. 4necked flask having a stirrer, ther mometer, and charging funnel were added: 200 ml. of| toluene, 670 ml. ofa Cig l-olefin and 10.5 ml. of -buty perbenzoate. The solution was heated to about 120° C. ‘and at this temperature a solution of 172 grams of maleic anhydride in 500 ml. of toluene was added over a period ‘of 4 hours and held for a further 2 hours. The reaction mixture was cooled to ambient temperature and the ‘copolymer isolated by removal of volatile components. ‘The copolymer yield was about 89%. EXAMPLE 2 Copolymer of di.(Crz to C34 2-alky!)fumarate and vinyl ‘A500 ml. flask was used for preparing the di-(Cra to Cag alkyi)fumarate wherein 3.2 (0.034 mol) fumeroyl chloride dissolved in 25 ml. of toluene was added over ‘23 hour period to a mixture of 21 g (0.04 mol) of Star: damul GT3236 [a mixture of 2alkyl alkanols (Cr2, Css, C4) Branch-Chain Alcohols wherein said alkyl’ por. tions are linear and contain 14 and 16 carbon atoms and the alkanol portions are also linear and contain 18 and 20 carbon atoms, sold by Henkel, Inc. Hoboken, NJ. 45 5s 65 4 (07020), 30 ml. of triethylamine and 300 ml. of toluene. After the addition was completed, the reactants were heated to 65" C. and held for 16 hours. The system was then cooled to room temperature and the ester precipi tated by adding, 1500 ml. of methanol and 83 ml. of HCI. ‘The crude product was recrystallized in methanol and analyzed for 79.8 wt. % C, 12.8 wt. % H, had a (M,) of, 939 as measured by Vapor Phase Osmometry (VPO) and gave a yield of 63% of theoretical 500 gr. (0.003 mol) of the C32-Cag branched dialkyl fumarate prepared ss above was reacted with 0.4 ml (0.0004 mol) of vinyl acetate in the presence of 40 mg. (of Lucidol 70, a 70% active benzoyl peroxide aqueous solution sold by Wallace and Tiernan of Buffalo, N.Y., in 8 ml. of hexane at about 70° C. for 16 hours. The copolymer was isolated by dialysis with a yield of 22.5%. EXAMPLE 3 Copolymer of di-(Cas 10 Cas 2alkyDfumarate and vinyl acetate ‘The procedure of Example 2 was followed except that Standamul GT3236 was replaced with Standamul, 2428 [a mixture of 2alkyl alkanols (C4, Cas, Cos) Branch-Chain Alcohols wherein sai alkyl portions are linear and contain 10 and 12 carbon atoms and said alkanol portions are linear and contain 14 and 16 carbon. atoms, sold by Henkel, Ine] The yield of di-{C2s to Cag2-

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