Graft polymers and lubricant compositions thereof
United States Patent [1 1 Waldbillig CRAFT POLYMERS AND LUBRICANT COMPOSITIONS THEREOF [75] inventor: James O. Waldbillig, Wappingers Falls NY.  
 [73] Assignee: Texaco lnc., New York. NY.  
 [22] Filed: Apr. 18, 1973 [21] Appl. No.: 351,914  
 [52] U.S. Cl. 252/515 A: 252/56 R; 260/878 R [51] Int. Cl ..C10m 1/32 [58] Field of Search 252/515 A, 56 R; 260/878 R [56] References Cited UNITED STATES PATENTS 8/1959 Bancs ct al. 252/50 X 8/1972 Abbot 252/56 R X [451 Apr. 22, 1975 [57] ABSTRACT A graft polymer and lubricating oil compositions thereof, said polymer functioning as a multipurpose lube oil additive having viscosity index improving properties pour depressing properties and detergentdispersant properties. said graft polymer comprising an oil soluble substantially linear hydrocarbon terpolymer backbone having grafted thereon polymethacrylate polymers, said terpolymer backbone composed of ethylene. terminally unsaturated straight chain alkene of 3 to 12 carbons and terminally unsaturated non conjugated diolefin of 5 to 8 carbons. said polymethacrylate graft being composed of monomer member(s) selected from the group consisting of l N.N- dialkylaminoalkyl methacrylate, (2). a mixture of C C, alkyl methacrylate and C -C alkyl methacrylate and (3). a mixture of l and 2.  
 5 Claims, No Drawings GRAlFT POLYMERS AND LUBRICANT COMPOSITIONS THEREOF BACKGROUND OF INVENTION Lubricating oils of present day internal combustion engines contain a multitude of additives functioning as detergent-dispersants, viscosity index (V1) improvers. oxidation inhibitors. pour depressors. oiliness agents. etc. in order to meet the demands placed thereon. A widely used class of additives are the polymers of one or more alkyl methacrylates and/or a dialkylaminoalkyl methacrylate finding principal use as combination viscosity index improvers and pour depressants. Another class of additives widely used in lubricating oils are the type described in US. Pat. No. 3.691.078. namely. the linear interpolymers of ethylene and a comonomer selected from the group consisting of monoolefins of 3 to 10 carbons. omega-phenyl-l-alkenes of 5 to carbons. 2-norborene. terminally unsaturated. non conjugated diolefins of 5 to 8 carbons. dicyclopentadiene. 5-methylene2-norborene and mixtures thereof. They have been found useful as viscosity index improvers. However, the advent of high speed automotive engines coupled with increased engine operating temperatures and increased complexity of anti-pollution devices associated with automotive engines has resulted in a substantial increase in additive quantities in automotive lubricating oils to meet todays and tomorrows requirements. The quantities of employed additives are now fast reaching a point of being so large as to negatively effect the primary mission of the lubricating oil, that is. to lubricate. One answer to this problem is to develop lube oil additives having multi-properties. i.e.. to develop a single additive which can satisfy many or all the requirements of the petroleum engine oil. With such an additive, the quantity of overall additive employed in the lubricating oil base stock can be substantially reduced since a single unit quantity will fulfill multiple requirements rather than multiple unit quantities fulfilling said multiple requirements.  
 DESCRIPTION OF THE INVENTION 1 have discovered and this constitutes my invention a novel graft polymer which when incorporated in a mineral lubricating oil in amounts of between about 0.1 and 10 wt. 7: functions as a triproperty additive, namely. as a viscosity index improver. a pour point depressor and detergent-dispersant. The novel graft polymer comprises an oil soluble substantially linear hydrocarbon terpolymer backbone composed of between about and 75 wt. ethylene, between about and 85 wt. 7: terminally unsaturated straight chain alkene of 3 to 12 carbons and between about 0.10 and 15 wt. 7( terminally unsaturated non conjugated diolefins of 5 to 8 carbons. said backbone having an average chain length of between about 700 and 7,000 carbons having recurringly grafted on said backbone polymerized monomer member selected from the group consisting of (l). a 10:1 to 1:10 weight ratio mixture of C10&#39;C15 alkyl methacrylate and Clo-C2 alkyl methacrylate, (2). dialkylaminoalkyl methacrylate of the formula:  
 where R and R are alkyl of l to 2 carbons and A is a divalent alkylene radical (alkadiyl) of from 2 to 4 carbons and (3). mixtures thereof. said graft polymer having an inherent viscosity of between about 0.6 and 1.9 as a 0.10 wt. 7r solution in tetrachloroethylene at 30C. and having a weight ratio of backbone component to said graft component of between about l.000:l and 1:10.  
  The graft polymers of the invention are prepared by the metallation techniques set forth by Tate. et al.. Metallation of Unsaturated Polymers and Formation of Graft Copolymers. Journal of Polymer Science. Vol. 9. pages 139-145. More specifically. the method is a two stage procedure:  
  The first stage comprises contacting an oil soluble substantially linear terpolymer consisting of between about 15 and wt. 7r ethylene. between about 25 and wt. terminally unsaturated straight chain alkene of 3 to 12 carbons and between about 0.10 and 15 wt. 9? terminally unsaturated non conjugated alkadiene of 5 to 8 carbons. said linear terpolymer reactant having an average carbon chain length of between about 700 and 7.000 and an inherent viscosity of between about 0.6 and 1.9 at 0.10 wt. 7! solution in tetrachloroethylene at 30C. with an alkyl lithium of from 3 to 10 carbons in the presence of a liquid alkane as solvent of from 5 to 10 carbons and N.N.N&#39;.N&#39;-tetralkylalkylene diamine promoter wherein said alkyl and alkylene moieties in said diamine are from 1 to 4 carbons to form a lithiated terpolymer intermediate. that is. a terpolymer having lithium atoms attached along the linear chain. The first stage contacting is conducted under anhydrous conditions (less than 0.0] wt. water) and in an inert atmosphere, e.g.. nitrogen and at a temperature between about 20 and C. normally for a period of between l and 25 hours. The first stage contacting is further conducted employing between about 1.0 and 200 mmoles alkyl lithium/100 g. of linear terpolymer and a mole ratio of alkyl lithium to diamine promoter of between about 0.40 and 2.0.  
  In the second stage the lithiated linear hydrocarbon terpolymer intermediate is then contacted with a methacrylate monomer member selected from the group consisting of 1 a mixture of C, -C, alkyl methacrylate and C -C alkyl methacrylate in a weight ratio of between about 1:10 and 10:1, (2). dialkylaminoalkyl methacrylate of the formula:  
  0 R1 &#34;I CH2=C-C-0A-N I CH3 where R and R are alkyl of l to 2 carbons and A is alkadiyl of from 2 to 4 carbons. and (3). mixtures of( l and (2). at a temperature between about 100 and l00C. under anhydrous conditions and in an inert atmosphere utilizing a weight ratio of lithiated intermediate to total methacrylate reactant of between about 0.221 and 1.000;]. The reaction period in the second stage is normally between about 0.5 and 24 hours.  
  The graft polymer product is recovered from the final reaction mixture by standard means: adding a lower alkanol from 1 to 4 carbons. e.g., in quantities of between about 0.1 and wt. 91 of the reaction mixture to destroy the alkyl lithium and diamine promoter followed by washing the solution with dilute aqueous mineral acid. (e.g.. 5-l0 wt. aq. HCl) and then with water followed. if desired. by further standard purification techniques such as precipitation.  
  In the first stage of the reaction. lithium moieties are randomly placed along the terpolymer chain. the lithiated locations being where the polymethacrylate graft component attaches via replacement of the lithium moieties.  
  Examples of the alkene component in the terpolymer reactant include propylene. l-butene. lpentene. lhexene. l-heptene. l-octene, l-nonene. l-decene. and l-dodecene. Suitable alkadiene components in said terpolymer reactant include 1.4-pentadiene. l,4- hexadiene. l.5-hexadiene. 2-methyl-l.5-hexadiene. 1.6-heptadiene and 1.7-octadiene. Preferably. the terpolymer is derived from about 40 to 55 wt. 7! ethylene. about 40 to 60 wt. 71 propylene and about 1 to 5 wt. l.4-hexadiene and ofa carbon chain length of between about 800 and 5000. Most preferably. the terpolymer reactant contains 50.5 wt. ethylene, 46 wt. propylene and 3.5 wt. 7r 1.4-hexadiene and ofa carbon chain length of between about 900 and 2600.  
  In regard to the acrylate reactants contemplated herein. examples of the CHI-C alkyl methacrylates are decyl methacrylate. undecyl methacrylate. dodecyl methacrylate. penetadecyl methacrylate and mixtures of the alkyl methacrylates in the defined 10 to l5 carbon alkyl carbon atom range. Mixtures are formed in the alkyl methacrylate monomer manufacture when commercial alcohols are employed since the commercial alcohols themselves are mixtures of adjacent and closely adjacent homologs with normally one chain length predominating.  
  Specific examples of the C -C alkyl methacrylates contemplated herein are hexadecyl methacrylate. heptadecyl methacrylate. octadecyl methacrylate. nonadecyl methacrylate. eicosyl methacrylate and mixtures of the alkyl methacrylates in the defined 16 to 20 alkyl carbon range.  
  In regard to the dialkylaminoalkyl methacrylates, ex amples are the N,N-dimethylaminoethyl methacrylate. N.N-diethylaminoethyl methacrylate, N.N- dimethylaminopropyl methacrylate and N,N- diethylaminopropyl methacrylate.  
  Examples of alkyl lithium are butyl lithium. hexyl lithium. octyl lithium and decyl lithium.  
  Examples of N.N.N&#39;,N&#39;-tetralkylalkylene diamine are N.N.N&#39;.N-tetramethylethylene diamine. N.N.N,- N-tetramethylpropylene diamine, N,N.N&#39;.N-tetramethylbutylene diamine, and N,N.N&#39;.N- tetrabutylmethylene diamine.  
  Examples of suitable inert reaction solvents are hexane. cyclohexane and heptane.  
  In the lubricating oil compositions contemplated herein. the graft polymer normally constitutes between about 0.l and 10 wt. 71 of the composition, preferably between about 0.5 and 5 wt. /r. Also contemplated are the concentrates thereof wherein the graft polymer product content is between about l0 and 50 wt. /z. Concentrates are formulated for ease of handling. storage and transportation. The finished lubricating oil compositions are prepared from the concentrates via dilution with additional base oil.  
  The hydrocarbon base oils employed in major amounts in the finished lubricating oil compositions are derived from a wide variety of hydrocarbon base oil materials such as naphthenic base, paraffinic base and mixed base mineral oils or other hydrocarbon products such as synthetic hydrocarbon oils, e.g., polyalkylenes such as polypropylene, polyisobutylene of a molecular weight of about 250 and 2,500. Advantageously, the base oils employed in the finished lubricating compositions have an SUS viscosity at l00F. of between about 50 and 2,000. preferably between about and 375.  
  Surprisingly, the graft polymer products of the invention have been found .to be effective detergentdispersants in addition to pour depressors and V] improvers when incorporated in the contemplated lubricant compositions. It is surprising because terpolymer component functions only as V] improver. Further, the graft component. namely, the polymethacrylate functions only as Vl improver and pour depressor. Neither the terpolymer backbone nor polymethacrylate alone of in physical admixture evidence detergent-dispersant properties. Therefore, it is unexpected that when these two components are chemically bound in the graft polymer of the invention as defined a new property surfaces, namely. detergent-dispersancy.  
  In the finished lubricating oil compositions of the invention. additional additives such as supplementary detergent-dispersants, oxidation inhibitors. corrosion inhibitors. anti-foamants, etc. may be employed in addition to the graft polymer.  
  Examples of the supplementary detergentdispersants contemplated herein are the ethylene oxide derivatives of inorganic phosphorus acid free. steam hydrolyzed polyisobutene (700-5000 m.w. )-P- ,S reaction product; and overbased calcium alkyl aromatic sulfonate having a total base number at least about 300; and sulfurized normal calcium alkylphenolate. These supplementary detergent-dispersants are disclosed in US. Pat. Nos. 3,087,956. US. 3,549,534 and US. 3,537,966.  
  Examples of suitable antioxidants contemplated herein are zinc and calcium dialkyl dithiophosphates and diaryl dithiophosphates. the alkylated diphenyl amines, sulfurized alkylated diphenylamines, unsulfurized and sulfurized alkylphenols, phenolates and hindered phenols.  
  Examples of suitable corrosion inhibitors are zinc dialkyl dithiophosphate, zinc diaryl dithiophosphate, basic calcium. barium and magnesium sulfonates; calcium, barium and magnesium phenolates.  
  A widely used antifoamant can be included in the finished compositions of the invention. namely, the dimethyl silicone polymers normally employed in amounts of between about 1 and 1.000 ppm.  
  The following examples further illustrate the invention but are not to be construed as limitations thereof.  
 EXAMPLE I There was dissolved in 750 mls. of dry cyclohexane 50 grams of a terpolymer of ethylene. propylene and 1.4-hexadiene. The weight ratio of ethylene:- propylenezhexadiene in the terpolymer was 50:46: 8. Further, the terpolymer reactant had an intrinsic viscosity of l.l as 0.10 wt. 7? in tetrachloroethylene at 30C., approximately one mole of unsaturation per 2.000 grams of terpolymer. and a carbon chain length of about 1.500.  
  The polymer solution was added to a flame dried 1- liter resin flask equipped with a high speed stirrer. Dry nitrogen was bubbled through the solution during the entire reaction. To the nitrogen bubbled solution there was charged 16.3 mls. (0.03 mole) of a wt. solution of butyl lithium in cyclohexane. During the addition. the temperature was maintained at C. and introduction of the butyl lithium was accomplished via a hypodermic syringe. There was then added to the resultant solution 5.3 mls. (0.035 mole) of N.N.N&#39;.N&#39;- tetramethylethylene diamine and the resultant solution was then heated and maintained at 50C. with continued nitrogen bubbling for a period of 4 hours. The reaction mixture was then cooled to 25C. and a mixture of 9.6 grams (0.038 mole) ofa mixture of alkyl methacrylate derived from a synthetic alkanol having a carbon distribution ranging principally from C to C in a weight ratio of C,- :C,;,:C :C, of 8:7:7:5. in addition there was added 5.5 grams (0.013 mole) of an alkyl methacrylate derived from a synthetic alkanol mixture of principally C to C alcohols in a weight ratio of C zC zC of about :6:22. The addition of the methacrylates was accomplished with a hypodermic syringe. The temperature was then raised to C. over a period of one hour and maintained at 50C. for an additional hour. At the end of the hour reaction period 10 mls. of isopropyl alcohol was added to destroy the tetramethylethylene diamine promoter. A 50 mls. sample of the reaction solution was washed twice with 150 mls. of 10 wt. 7r aqueous hydrochloric acid and twice with 200 mls. portions of water. The graft polymer product solution was then precipitated in boiling isopropyl acetate and redissolved in a small amount of toluene. then filtered and precipitated a second time in boiling isopropyl acetate. The recovered solid polymer was then washed in boiling isopropyl alcohol. Infrared examination of the polymer products showed it to be a graft polymer composed of an ethylene-propylenehexadiene backbone having copolymer grafts thereon of C. -C alkylmethacrylate and C -C alkylmethacrylate.  
  The remaining polymer reaction solution was precipitated in 2.000 mls. of boiling methanol, redissolved in about 600 mls. of toluene then precipitated in 200 mls. of boiling acetone. The solid polymer was treated with boiling acetone and dried at 100C. (0.05 mm Hg) and 45.3 grams of graft polymer were recovered.  
 EXAMPLE II This example illustrates the preparation of a second species of the graft polymer.  
  The procedure of Example I was repeated with the exception that 2.67 grams of N.N dimethylaminoethyl methacrylate was substituted for the alkyl methacrylate mixture reactants of Example 1. There was recovered 21.7 grams of graft polymer product identified as a polymer consisting of an ethylene-propylene-l.4- hexadiene terpolymer backbone having grafts thereon 5 of poly-N.N-dimethylaminoethyl methacrylate. said graft polymer having a nitrogen content of 0.039 wt. (7(.  
 EXAMPLE [11 This example illustrates the lubricating oil composilU tions of the invention. the effectiveness of the graft polymer as a multiple purpose additive. namely. as a V1 improver. pour depressor and detergent-dispersant. and further demonstrates the unexpectedness of the detergent-dispersant property thereof.  
  The base oil employed in all the representative and comparative lubricating oil formulations was a paraffinic lubricating oil having an SUS viscosity at 100F of about 128. at 210F. of about 41.5, a maximum pour point of 0F. and a minimum viscosity index of 95.  
  The polymers employed in the representative and comparative lubricating oil compositions are as follows:  
  1. Representative Polymer A is the graft copolymer of Example l.  
  2. Representative Polymer B is the graft copolymer prepared in Example 11.  
  3. Comparative Polymer C is the ethylene-propylene 1.4-hexadiene terpolymer reactant employed in Examples I and I1.  
  4. Comparative Polymer D is the copolymer prepared by the polymerization of the C to C alkyl methacrylate and the C to C alkyl methacrylate monomers in a /25 wt. 7: ratio.  
  The representative and comparative lubricant compositions were formulated by standard means. specifically mixing the test polymers in the base oil at a temperature of about 65C.  
  in addition to measuring the viscosity. pour point and viscosity index of the various formulations. the lubricant compositions were also tested for their detergentdispersancy utilizing a Bench Sludge Test as described as follows:  
  The Bench Sludge Test measuring the detergent properties of the additive comprises introducing into a 20 cc. bottle portions of the test oil composition. titanium oxide (6 wt. 7:) in oil, aqueous and hydrocarbon engine blow-by. The bottles are agitated at an elevated temperature for a period of time and a portion thereof is then centrifuged and visual observations are made of the sediment depth. The depth of the sediment is measured in mm. and the higher the measurement in mm. the poorer the dispersancy characteristics of the test oil composition. The following table describes the various representative and comparative lubricating oil compositions and test measurements thereof:  
 TABLE I Composition ingredients Wt. AA BB CC DD EE FF GG Polymer A 1.5 Polymer B 1 5 Polymer C 1.5 L5 Polymer D 0.17 0.17 1.5 0.17 Base Oil 98.5 98.33 98.33 98.5 98.5 99.83  
 TABLE l-Continued Composition Ingredients Wt. AA BB CC DD EE FF 06 Test Visc. 210F. SUS 68.4 72.8 67.6 67.6 50.3 42.2 41.5 Visc. 100F. SUS 377 415 385 362 201 131.7 128 Viscosity Index 163 167 156 166 148 105 96 Pour Point, F. &#39;-30 -35 45 40 -40 0 Bench Sludge, mm. 0.4 0.4 1.9 2.0 2.0 2.2 1.8  
  As can be seen from the above representative Polymers A and B impart a substantial improvement in V1. pour point and detergent dispersancy. whereas comparative Polymers C and D alone or in admixture although imparting improved V1 and/or pour point have essentially no or negative detergent-dispersant properties. lt is to be noted that Polymer C is the backbone component of Polymers A and B and Polymer D is essentially the graft component of Polymer A.  
 1 claim:  
  1. A lubricating oil composition comprising a major amount of mineral lubricating oil and between about 0.1 and 50 wt. of a graft polymer consisting of a linear terpolymer backbone component of between about 15 and 75 wt. 71 ethylene, between about 25 and 85 wt. 7! terminally unsaturated alkene of 3 to carbons and between about 0.10 and wt. 7: terminally unsaturated non conjugated alkadiene of from 5 to 8 carbons having grafts thereon of a polymethacrylate composed of monomer selected from the group consisting of 1 a mixture of a first alkyl-methacrylate of 14 to 19 carbons and a second alkyl methacrylate of to 24 carbons in a respective weight ratio of between about 10:1  
 terized by the formula:  
  2 CH R where R and R- are alkyl of from 1 to 2 carbons and A is alkadiyl of from 1 to 5 carbons, and (3). a mixture of 1) and (2). said backbone component to said graft component being present in a weight ratio in said graft polymer of between about l,000:1 and 1:10, said linear terpolymer backbone component having a carbon chain length of between about 700 and 7,000 carbons.  
  2. A lubricating oil composition in accordance with claim 1 wherein said graft polymer is present in an amount of between about 0.1 and 10 wt. 7(.  
  3. A lubricating oil composition in accordance with claim 1 wherein said alkene is propylene. said alkadiene is 1.4-hexadiene and said polymethacrylate is a copolymer of a first alkyl methacrylate of from 16 to 19 carbons and a second alkyl acrylate of from 20 to 22 carbons.  
  4. A lubricating oil composition in accordance with claim 1 wherein said alkene is propylene. said alkadiene is 1.4-hexadiene and said monomer is N.N- dimethylaminoethyl methacrylate.  
  5. A lubricating oil composition in accordance with claim 1 wherein said polymethacrylate is a mixture of first alkyl methacrylate of 14 to 19 carbons and a second alkyl methacrylate of 20 to 24 carbons in a respective weight ratio of between about 10:1 and 1:10.