MXPA98007263A - Ethylene / alpha-substantial-lineine polymers as viscosity index importers or agents gelify - Google Patents

Abstract

Substantially linear ethylene polymers, such as ethylene / octene copolymers and modified ethylene / propylene, diene polymers, when added in a viscosity modifying amount to an oleaginous material, such as a lubricating oil, provide the material A viscosity index that exceeds that of the material alone. The substantially linear ethylene polymers, prepared by catalysis of restricted geometry, can be grafted with one or more unsaturated organic compounds, such as maleic anhydride, containing ethylenic unsaturation. The grafted polymer can be functionalized by reactions with, for example, an alcohol compound or an amine. Substantially linear ethylene polymers, when subjected to a cutting action either before or after addition to an oleaginous material, improve the shear stability of the oleaginous material. Substantially linear ethylene polymers, whether grafted, grafted and further reacted or not, also work as a thickening agent for compositions such as those used in greases, cable fillers and cosmetics. In addition, substantially linear ethylene polymers provide effective results when mixed with other components of compositions containing conventional oleaginous materials.

Description

«Yes * POLYMERS OF ETHYLENE / ALPHA-OLEFINES SUSTA CTALLY LINEARS AS IMPROVERS OF THE VISCOSITY INDEX OR AGENTS GELIFICANTS DESCRIPTION OF THE INVENTION This invention relates generally to oleaginous compositions containing at least one ethylene / alpha-olefin interpolymer (α-olefin) as a Viscosity Index (VI) improver or as a gelling agent. This invention relates more particularly to those compositions in which the interpolymer is substantially linear, especially with a homogeneous distribution of branches and a narrow molecular weight distribution (MWD). The interpolymer can be modified by one or more reactions to further improve functionality. One such reaction of particular interest involves. grafting an olefinically unsaturated organic compound, such as maleic anhydride, in the polymer. The resulting grafted polymer can then be further reacted with one or more additional compounds such as an amine. I «F- 2T09 A VI promoter, when incorporated into an oleaginous composition, provides the composition with a desirable or improved viscosity at elevated temperatures. An improvement or increase of the viscosity at high temperature without other changes results in an improvement of the VI. A VI is an empirical number used as a measure of the viscosity and temperature stability of a lubricant. A high VI indicates resistance to thinning at high or high temperatures. A low VI indicates a tendency towards thinning at those temperatures. Indicators of LV improvement include thickening capacity, shear stability, and chemical and oxidative thermal stability, all of which are related to the polymer structure. The ability of a given VI improver to provide a desirable high temperature viscosimetric behavior depends on factors such as the molecular weight of the polymer, the concentration and structure in relation to the chemical structure of the oleaginous composition. The stability to the cut depends to a large extent on the molecular weight of the polymer and the MWD. A variety of oil soluble polymers such as improvers have been used. of the VI for lubricating oils. Exemplary polymers include hydrogenated styrene / diene polymers, hydrogenated polyisoprene, polymethylacrylates and ethylene / α-olefin copolymers such as ethylene / propylene copolymers and ethylene / propylene / diene terpolymers as well as various derivatives of those copolymers and terpolymers. These polymers allow the preparation of oils of multiple degrees (for example 10W-30), those that satisfy the viscosimetric requirements of the SAE (Society of Automotive Engineers) at high and low temperatures. At least some of the oil-soluble polymers are also useful as thickeners or gelling agents for other oleaginous materials such as mineral oils, paraffinic oils and naphthenic oils to prepare compositions suitable for use as fats or cosmetic materials. LV improvers have been described based on copolymers of ethylene and olefins prepared in the presence of metallocene catalysts, for example in USP 5,151,204 and USP 5,446,221.

Brief Description of the Invention One aspect of the invention is an oleaginous composition comprising an oil material and a > amount of a substantially linear ethylene polymer (SLEP); effective, to modify the viscosity, the SLEP is characterized by having: (i) a melt flow ratio, I? o / I2 = 5.63: (ii) an MD, Mw / Mn, defined by an equation where Mw / Mr, < (I10 / I2) - 4.63; and (iii) a critical cutting speed at the beginning of the surface melt fracture (OSMF) of at least 50 percent greater than the critical shear rate in the OSMF of a linear olefin polymer having the I2 and Mw / Mn similar. In a first related aspect, the amount of polymer is an effective thickener or gelling amount, whereby the composition becomes suitable for use in preparing fats or cosmetic materials. In a second related aspect, the oleaginous composition further comprises an amount of a pour point depressant (PPD) sufficient to improve the properties of the composition at a low temperature relative to a similar composition lacking PPD. In a third related aspect, at least a portion of the SLEP is replaced with a modified SLEP per cut, whereby the shear stability of the oil composition is increased. The cut-modified polymer is prepared in a suitable manner by subjecting a SLEP to one. enough cutting action to increase its melt index (I2). In a fourth related aspect, the oleaginous composition also comprises, in addition to the SLEP, at least one polymer selected from hydrogenated polyisoprene, styrene / butadiene block polymers, styrene / isoprene block polymers, styrene / butadiene hydrogenated block polymers, polymers of hydrogenated styrene / isoprene blocks, styrene / butadiene graft block polymers, styrene / isoprene graft block polymers, polymethacrylates, polyalkyl acrylates, ethylene polymers and acrylate / methacrylate copolymers. Each of the aspects and the related aspects have three additional related aspects (a) to (c). In aspect (a), the SLEP has an ethylene content within the range of 20 to 80 weight percent (% by weight), based on the weight of the polymer. In the aspect (b), the SLEP is grafted with at least 0.01% by weight, based on the weight of the grafted SLEP, of an unsaturated organic compound containing an i? jertable portion. In the aspect (c), the grafted SLEP, which contains a reactive portion, further reacts with a compound having a hydroxyl or amine functionality. Illustrative compounds include alcohols, especially saturated aliphatic monoalcohols, acids and amines, especially primary amines. The "block polymer" includes polymers of two blocks, polymers of three blocks, polymers of radial blocks or blocks in the form of a star and tapered interpolymers. "Ethylene polymers" means an ethylene / α-olefin copolymer or diene-modified ethylene / α-olefin copolymer. Exemplary polymers include ethylene / propylene copolymers. (EP), ethylene / octene (EO) copolymers and modified ethylene / propylene / diene interpolymers (EPDM). "Substantially linear" means that a polymer has a backbone substituted with 0.01 to 3 long chain branches per 1000 carbons in the backbone. '"Long chain branching" or "LCB" means a chain length of at least 6 carbon atoms. Above this length, nuclear magnetic resonance spectroscopy of carbon 13 (C-13 NMR) can not distinguish or determine a real number of carbon atoms in the chain. In some cases, the length of the chain can be long as the skeleton of the polymer to which it is attached. "Interpolymer" refers to a polymer having at least two monomers polymerized therein. This includes, for example, copolymers, terpolymers and tetrapolymers.

It particularly includes a polymer prepared by the polymerization of ethylene with at least one comonomer, typically an α-olefin of 3 to 20 carbon atoms (C3-C20). Exemplary α-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and styrene. The α-olefin desirably has an α-olefin of C3-C??. Preferred copolymers include EP and an ethylene-octene. Exemplary terpolymers include an ethylene / propylene / octhane terpolymer as well as terpolymers of ethylene, a C3-C2o α-olefin and a diene such as dicyclopentadiene, 1-hexadiene, piperylene, 5-ethylidene-2-norbornene, 1 , 7-octadiene and vinyl norbornene. Substantially linear ethylene and α-olefin interpolymers ("SLEP" or "substantially linear ethylene polymers") can be prepared as described in U.S. Patent Nos. 5,272,236 and 5,278,272, relevant portions of both of which are incorporated herein by reference. reference. USP 5,272,236 (column 5, line 67 to column 6, line 28) describes the production of SLEP via a controlled polymerization process using at least one reactor, but allows the use of multiple reactors, at a temperature and polymerization pressure sufficient to produce a SLEP that has the desired properties. Polymerization preferably occurs via a solution polymerization process at a temperature of 20 ° C to 250 ° C, using the restricted geometry catalyst technology. Suitable restricted geometry catalysts are described in column 6, line 29 to column 13, line 50 of USP 5,272,236. These catalysts can be described as those comprising a mechanical coordination complex comprising a metal of groups 3-10 of the Lanthanide series of the Periodic Table of the Elements and a pi-linked, delocalized portion substituted with a portion that induces restrictions. The complex has a restricted geometry around the metal atom, so that the angle in the metal between the centroid of the pi-linked, substituted, delocalised portion, and the center of at least one remaining substituent is less than such an angle in a similar complex containing a pi-linked portion, similar, lacking such a substituent that induces restriction. If such complexes comprise more than one pi-substituted, delocalized, pi-linked portion, only one such portion for each metal atom of the complex is a pi-substituted, delocalized, cyclically linked portion. The catalyst further comprises an activation coctalizer such as tris (pentafluorophenyl) borane. The specific catalyst complexes are discussed in USP 5,272,236 in column 6, line 57 to column 8, line 58 and in USP 5,278,272 in column 7, line 48 through column 9, line 37. The teachings regarding the catalyst complexes in general and in those specific complexes are incorporated herein by reference. A SLEP is characterized by a narrow MWD, and if it is an interpolymer, by a narrow comonomer distribution. A SLEP is also characterized by a low residue content, specifically in terms of catalyst residues, unreacted comonomers and low molecular weight oligomers generated during polymerization. A SLEP is further characterized by a controlled molecular architecture that provides good processability even when the MWD is narrow in relation to conventional olefin polymers. A preferred SLEP has a number of different characteristics, one of which is a comonomer content that is between 20 and 80% by weight, more preferably between 30 and 70% by weight, ethylene, with the remainder comprising one or more comonomeros. The content of SLEP comonomers can be measured using infrared (IR) spectroscopy according to Method B of ASTM D-2238 or ASTM D-3900. The comonomer content can also be determined by Nuclear Nuclear Magnetic Resonance Spectroscopy 13. Additional distinct SLEP characteristics include I? and the melt flow ratio (MFR or I) 0 / I2). The interpolymers desirably have an I2 (ASTM _ D-1238, condition at 190 ° C / 2.16 kilograms (kg) (condition E mainly), 0.01-500 grams / 10 minutes (g / 10 min), more preferably from 0.05-50 g / 10 min.SLEP also has an MFR (ASTM D-1238) = 5.63, preferably from 6.5-15, preferably from 7 to 10. For a SLEP, the ratio I? / I2 serves as an indicator of the degree of LCB so that a greater ratio of I? / I2 'is equal to a greater degree of LCB in the polymer.An additional distinguishing characteristic of a SLEP is the MWD (M "/ Mn or" polydispersity index "), as a measure of gel permeation chromatography (GPC) .The Mw / Mn is defined by the equation: The MWD will desirably be > 0 and < 5, especially from 1.5 to 3.5, and preferably from 1.7 to 3.

A homogenously branched SLEP surprisingly has an MFR that is essentially independent of its MWD. This contrasts markedly with homogeneously branched, linear and heterogeneously branched, linear, conventional ethylene copolymers, where the MWD must be increased to increase the MFR. A SLEP can be fully characterized as having a critical shear rate at a OSMF of at least 50% greater than the critical shear rate of the OSMF of a linear olefin polymer having an I2 and Mw / Mn, similar. SLEPs that meet the criteria mentioned above include, for example, polyslefin elastomers ENGAGEMR and other polymers produced via geometry-restricted catalysis by DuPont, Dow Elastomers L.L.C. An SLEP can be added to oleaginous compositions with or without modification as by grafting. If grafting is modified, the resultant grafted SLEP can also be added to the oil compositions with or without one or more additional reactions before the addition.The grafting can also be carried out after the SLEP is added to an oil composition. unsaturated containing at least one ethylenic unsaturation (at least one double bonds), and will be grafted to a SLEP which can be used to modify a SLEP Illustrative unsaturated compounds include vinyl ethers, vinyl substituted heterocyclic compounds, vinyl oxazolines , vinyl amines, vinyl epoxides, unsaturated epoxy compounds, unsaturated carboxylic acids and anhydrides, ethers, amines, succinimide amides or esters of such acids Representative compounds include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, a- crotonic and cinnamic methyl and its anhydrides, ester derivatives or ethers r, vinyl substituted alkylphenols and glycidyl methacrylates. Suitable unsaturated amines include those of organic aliphatic and heterocyclic nitrogen compounds containing at least one double bond and at least one amine group (at least one primary, secondary or tertiary amine). Representative examples include vinyl pyridine and vinyl pyrrolidone. Maleic anhydride is the preferred unsaturated organic compound. The unsaturated organic compound content of a grafted SLEP is > 0.01% by weight, and preferably = 0. 05% by weight, based on the combined weight of the polymer and the organic compound. The maximum unsaturated organo compound content may vary, but is typically = 10% by weight, preferably = 5% by weight, more preferably <. 2% by weight. An unsaturated organic compound can be grafted to a SLEP by any known technique, such as those taught in USP 3,236,917 and USP 5,194,509, the relevant teachings of which are incorporated and made part of this application as a reference. In USP 3,236,917, a polymer, such as an EP copolymer, was introduced into a two-roll mixer and mixed at a temperature of 60 ° C (° C). The unsaturated organic compound, such as maleic anhydride, is then added together with the free radical initiator, such as benzoyl peroxide, and the components are mixed at 30 ° C until the graft is complete. USP 5,194,509 describes a process similar to that of USP 3,236,917, but with a higher reaction temperature (210 ° C to 300 ° C, preferably 210 ° C to 280 ° C) and omitting or limiting the use of the initiator of free radicals. USP 5,194,509 specifically teaches that the peroxide-free grafting of unsaturated carboxylic acids, anhydrides and their derivatives can be carried out in a conventional twin-screw extruder, such as ZCSK 53 from Werner & Pfleiderer, or some other conventional apparatus such as the Brabender reactor. The ethylene polymer and, if required, the monomer to be grafted is melted at 140 ° C or more, mixed thoroughly and then reacted at elevated temperatures (210 ° C to 300 ° C, preferably 210 ° C to 280 ° C). C, and more preferably 210 ° C to 260 ° C). It is not important if the monomer to be grafted is introduced into the reactor before or after melting the ethylene polymer. The monomers to be grafted are used at a concentration of 0.01-0.5, preferably 0.05-0.25% by weight, based on the weight of the ethylene polymer. An alternative and preferred method of grafting is taught in USP 4,950,541, the relevant teachings of which are incorporated herein by reference. The alternative method employs a double screw devolatilizing extruder as a mixing apparatus. The SLEP and the unsaturated organic compound are mixed and reacted within the extruder at temperatures at which the reactants melt in the presence of a free radical initiator. The unsaturated organic compound is preferably injected into an area that is kept under pressure within the extruder. A second alternative and preferred method of grafting is grafting in solution as taught in USP 4,810,754, the relevant teachings of which are incorporated herein by reference. The method involves mixing an initiator, a monomer to be grafted and a polymer, such as an EP polymer, in a solvent, such as mineral oil, and then reacting at a temperature sufficient to initiate the grafting reaction. One such temperature is 190 ° C. A grafted modified SLEP can be subjected to an additional reaction with a modifying material to introduce one or more additional functionalities which in turn will lead to improved properties, such as improved dispersibility of the oxidative or combustion byproducts, improved viscosity to low temperature and improved oxidative / thermal stability, in an oily composition containing a grafted SLEP and subjected to an additional reaction. Exemplary modifying materials include alcohols, long-chain fatty acids (typically up to 36 carbon atoms), and amines. Examples of alcohols include aliphatic and aromatic alcohols that have >; two carbon atoms, preferably > 12, more preferably < 36 carbon atoms. Representative long chain fatty alcohols and fatty acids include decyl, lauryl and stearyl alcohols and acids. Examples of amines include those of aliphatic and heterocyclic nitrogen compounds containing > a primary amine and / or > a secondary, and optionally > a tertiary Certain amines, such as triethylene tetramine, tetraethylene pentamine, and polyethylene polyamine (such as Ethylene E-100, commercially available from The Dow Chemical Company) have aliphatic and heterocyclic portions. Commercial polyethylene polyamines are typically combinations or mixtures of linear, branched and heterocyclic amines. Representative examples include polyethylene amines (such as diethylene triamine) ,. 1- (3-aminoethyl imidazole), aminoethylpiperazines, 4- (3-aminopropyl) morpholine and polyoxyalkylene polyamines (such as the Jeffamines "" produced by Huntsman Chemical). Additional alcohols and amines are described in USP 5,401,427, particularly in column 45, line 40, to column 49, line 29, the relevant teachings of which are incorporated herein by reference. USP 5,401,427 teaches that other suitable alkylene polyamines include methylene amines, ethylene amines butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, the cyclic and higher homologs of such amines. such as piperazines, and piperazines substituted with aminoalkyl, etc. These amines include, for example, ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentaraine, trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl-3- ( 2-aminopropyl) i-idazoline, 4-methylimidazoline, 1,3-bis- (2-aminopropyl) imidazoline, pyrimidine, 1- (2-a-inopropy-piperazine, 1,4-bis (2-amyoethyl) piperazine, N, N ' -dimetiaminopropyl amine, N, N '-dioctylethyl amine, N-octyl-N'-methylethylene diamine, and 2-methyl-l- (2-aminobutyl) piperazine. Included within the scope of the term polyamines are hydroxyalkyl polyamines, particularly the hydroxyalkyl alkylene polyamines, having one or more hydroxyalkyl substituents on the nitrogen atoms Examples of such hydroxyalkyl substituted polyamines include N- (2-hydroxyethyl) ethylene diamine, N, N-bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) -piperazine, diethylene triamine substituted with monohydroxy-propyl, tetraethylene pentamine substituted with dihydroxypropyl, and N- (3-hydroxybutyl) tetramethylene diamine. The alcohols or polyols described in USP 5,401,427 include aliphatic polyhydric alcohols containing = 100 carbon atoms and from 2 to 10 hydroxyl groups. These alcohols can be substituted or unsubstituted, hindered or unimpeded, or branched chain or straight chain, as desired. Typical alcohols are alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, and polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributyl glycol and other alkylene glycol. glycols and ~ olyalkylene glycols in which the alkylene radical contains from 2 to 8 carbon atoms. A preferred class of aliphatic alcohols containing < 20 carbon atoms include glycerol, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol, 1, 2, 3-hexantriol, 1, 2, 4 -hexantriol, 1,2,5-hexantriol, 2, 3, -hexantriol, 1,2,3-butanediol, 1,2,4-butanediol, 2, 2, 6, 6-tetracis (hydroxymethyl) -cyclohexanol, and 1, 10-decanediol. A SLEP, SLEP modified by grafting and / or subjected to an additional reaction, SLEP modified by grafting, when added to a variety of oils or basic oleaginous materials improve at least one of the measurements of the VI, 'measurements of dispersity, stability measurements and measurements of gelling or thickening of such oleaginous materials in relation to oleaginous materials which are lacking of such SLEP or SLEP modified by grafting, or such SLEP modified by grafting and subjected to an additional reaction. Oleaginous materials or base oils suitable for use in lubricating oil formulations can comprise unrefined, refined and redefined (recovered) oils from both natural and synthetic sources. Illustrative oleaginous materials include any of a variety of hydrocarbon oils, lubricating oils based on alkylene oxide polymers and their derivatives, oils that are esters of dicarboxylic acids, or silicon-based oils, to form the compositions herein invention. Such oils can be natural or synthetic and include lubricating oils and fuel oils. Examples of suitable oils include liquid petroleum oils, mixed paraffinic, naphthenic, and paraffinic naphthenic types, coal oil oils or oil shale oils, poly (α-olefin) oils, vegetable oils, animal oils, polyoxyalkylene polymers or copolymers prepared from one or more of ethylene oxides, propylene oxides or oxides and 'Butylene, tetrahydrofuran, polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils, and silicate oils. Mixtures of such oils can also be used.

USP 5,446,221 describes, in column 8, line 47 to column 10, line 34, additional information about various oleaginous materials that can be incorporated herein by reference. When a SLEP is used, whether ungrafted, grafted or grafted and subjected to further reactions, a VI modifier is used in an oil composition, the composition may also contain several different types of additives that increase the characteristics required in a formulation. containing such compositions. These additives, which may include a conventional VI improver, generally include dispersants, detergents, antioxidants, antiwear and pressure agents, friction modifiers, PPD. corrosion inhibitors, ashless dispersants, (such as polyisobutenyl succinimides and their boron derivatives) and defoamers. These additives are generally present in amounts of 0.001-20% by weight, based on the weight of the oil. Conventional VI improvers include high molecular weight hydrocarbon polymers, polyalkyl methacrylates and polyesters containing copolymerized units of C3 to C8 mono and dicarboxylic acids. The additives can be introduced as concentrated solutions or dispersions in oil or without dilution. In the preparation of lubricating oil formulations, additives are commonly introduced as an active ingredient concentrate of 5 to 80% by weight oil. The use of concentrates makes the handling of different materials less difficult and facilitates the solution or dispersion of the additives in the formulation. The PPD decrease the temperature at which the lubricating oil will flow and can be poured. Such PPDs are well known. Typically those additives that can be used to decrease the fluidity of the lubricating oil with temperature are the copolymers of dialkyl fumarate and vinyl acetate, polymethacrylates (USP 2,091,627 and 2,100,993) and naphthalene waxes (USP 2,174,246). When a SLEP is added, either ungrafted, grafted or grafted and subjected to further reactions to an oleaginous composition as a thickener or gelling agent in the preparation of fats, materials for end-use applications for wires and cables or thixotropic gelling agents, they can - combined with any of all the additives specified as useful for the oil compositions used as lubricating agents. End-use applications in illustrative wires and cables include conventional uses such as fill compounds, water barriers and insulation materials. Those applications are particularly important for fiber optic cables. When such polymers are added to the oleaginous compositions as thickening or gelling agents for cosmetic applications, ointments or external medicinal applications, they can be combined with other additives such as fragrances, dyes, dyes, stabilizers, surfactants, emollients and oils (such as oil). coconut).

Oil compositions exhibiting improved properties at low temperature comprise an oil material, a PPD, and an effective amount of a SLEP to modify the viscosity. When the SLEP is essentially amorphous (it may contain = 6% crystallinity, preferably <3 and more preferably = 1, but = 0,% crystallinity), any conventional PPD can be used as long as the appearance of crystallization (Ts) for the waxes contained in the oleaginous material is not within the Tc range of the waxes contained in the SLEP. When the SLEP is semi-crystalline (a crystallinity of 6 to 25%, preferably 6 to 20%, and more preferably 6 to 16%), satisfactory properties are achieved at low temperature with certain preferred PPD's are copolymers of di-n-alkyl fumarates and vinyl acetate. The copolymers used as PPD are prepared in a suitable manner as described in USP 4, 839,074, the teachings of which are incorporated herein by reference. USP 4,839,074 teaches, in part, that the dicarboxylic acids, such as fumaric acid, are first esterified and then reacted or copolymerized with a copolymerizable monomeric compound, such as a vinyl ester, using the techniques of free radical polymerization conventional to obtain random polymers. The polymerization occurs suitably in an inert hydrocarbon solvent, such as Hexane or heptane, in an oxygen-free environment, such as a nitrogen atmosphere, at a temperature of 65 ° C to 150 ° C. Although the complete esterification of all the carboxyl groups of the dicarboxylic monomer is preferred, partial esterification, of = 70 mol% of the available esterifiable carboxylic groups, may be sufficient. The esterification is typically conducted with mixtures of alcohols. The alcohols may be slightly branched, but preferably straight chain aliphatic alcohols of Ci to C2o are more preferably aliphatic alcohols of. C6 to C2o. It is believed that a semicrystalline SLEP that works well with a di-n-alkyl vinyl acetate fumarate copolymer has a peak crystallization temperature (as determined by differential scanning calorimetry (DSC)) which differs from that of the waxes contained in the oleaginous material, so that the SLEP and the waxes contained in the oleaginous material desirably do not co-crystallize. Since the peak crystallization temperatures of the oleaginous materials vary considerably due to factors such as the wax content, each combination of the oleaginous material, semicrystalline SLEP and di-n-alkyl vinyl acetate fumarate copolymer should be evaluated to determine the properties at low temperature. The compositions of the present invention are formed by adding a SLEP, with or without modification such as a graft, and, if grafted, with or without additional reactions, to an oil or oleo-composition by the conventional mixing techniques. The polymers can be added crude or as oil concentrates. In general, the amount of added polymer will be in the range of 0.1 to 20% by weight as dry polymer, based on the weight of the oil to be modified, preferably 0.2 to 5% by weight of dry polymer for modification of the viscosity and from 5 to 15% by weight of the dry polymer for thickening or gelling applications. In the preparation of lubricating oil formulations, the additives are commonly introduced as concentrates of active ingredient in a hydrocarbon oil, such as a mineral lubricating oil, or some other suitable solvent. The concentrates typically have an active ingredient content of 5 to 80% by weight, based on the weight of the concentrate. In the formation of finished lubricants, such as engine crankcase oils, concentrates are usually diluted with 3 to 100, sometimes 5 to 40 parts by weight (pp) of lubricating oil per pp of a package of additives. The concentrate makes use of the handling of several less difficult and cumbersome additives and can facilitate the solution or dispersion of additives in a finished lubricant. By way of example, a typical VI improver could be employed as a concentrate of 5 to 20% by weight in a lubricating oil fraction. This invention relates in part to oleaginous or oily compositions exhibiting improved VI, especially with oily compositions comprising lubricating oil and, as an improved VI, a SLEP. Oily compositions containing such a VI improver exhibit improved viscosity at elevated temperatures compared to oil compositions that do not contain such an VI improver. LV improvers can also be derivatives to impart other properties or functions, such as the addition of dispersing properties to the fuel and lubricating oil compositions. Derived polymers include grafted SLEPs such as SLEP grafted with maleic anhydride (prepared as described above in column 3), line 67 to column 4, line 24 'of USP 5,346,963) which can be further reacted with an "alcohol, or an amine as shown in USP 3,702,300 (column 4, line 56 to column 5, line 60 , which relates to the esterification of a carboxy-containing interpolymer, such as an interpolymer containing maleic anhydride, with mixed alcohols and then neutralizing the remaining carboxy radicals with a polya ina); USP 4,089,794 (column 3, line 37 to column 4, line 59, which relates to the solution graft of an ethylenically unsaturated carboxylic acid material, such as maleic anhydride, on an ethylene / α-olefin polymer, such as an EP copolymer, and then reacting a polyamine with the grafted polymer); USP 4,160,739 (column 6, lines 35-52, which relate to the production of carboxyl groups provided by grafts of maleic acid or anhydride with a non-polymerizable polyamine); or USP '4, 137, 185 (column 7, lines 4-17, which relate to the reaction, in solution, of a grafted carboxylic acid material, such as the ethylene / α-olefin polymer grafted with maleic anhydride with a poly (primary amine)); or a SLEP grafted with nitrogen compounds as shown in USP 4,068,056 (column 4, line 47 to column 5, line 23, which relates to the reaction of a catalyzed hydrocarbon polymer with Ziegle.r-Natta catalyst. , in the presence of an oxygen-containing gas, with an amine compound while mixing the polymer and the amine compound from 130 ° C to 300 ° C); USP 4,146,489 (column 2, line 49 to column 3, line 15, which relates to the polymerization of the free-radical graft of a C-vinylpyridine or N-vinyl pyrrolidone on an EP rubber or an EPDM rubber); and USP 4,149,984 (column 4, lines 3-20, which relate to the grafting of a polymerizable heterocyclic compound, such as vinyl pyridine or vinyl pyrrolidone, onto a polymer formed by the polymerization of a methacrylic acid ester of an alcohol of C8-C? 8 in a solution of a polyolefin polymer). The relevant teachings of those patents are incorporated herein by reference. The following examples illustrate but do not, either explicitly or by implication, limit the present invention. Unless otherwise stated, all parts and percentages are by weight, based on total weight.

Examples Eleven primary polymers, eight representing the present invention, were used in the examples. The polymers B, E and I do not represent the invention. The polymers were: A. An ethylene / octene copolymer (61.7% by weight ethylene content) commercially available from DuPont Dow Elastomers L.L.C. as EG 8200. B. An ethylene / butene copolymer commercially available from Exxon Chemical Company as EXACTMR 4024.

C. An ethylene / octene copolymer (68.2% by weight ethylene content) commercially available from DuPont Dow Elastomers L.L.C. as EG 8100. D. A developmental ethylene / propylene / ethylidene-5 norbornene terpolymer (57% by weight ethylene content) made by DuPont Dow Elastomers L.L.C. E. An EP copolymer commercially available from Mitsui Petrochemical as TAFMERMR P-0480. F. An ethylene / octene copolymer (ethylene content of 64.7% by weight) commercially available from DuPont Dow Elastomers L.L.C. as EG 8150. G. An ethylene / octene copolymer (61.0% by weight ethylene content) commercially available from DuPont Dow Elastomers L.L.C. as DEG 8180. 15 H. A developmental EP copolymer (53.1% by weight ethylene content) made by DuPont Dow Elastomers L.L.C. I, An EP copolymer commercially available from Mitsui Fetroche icai co or TAFMER? * P-0480. J. A developmental EP copolymer (content of 34.2% by weight, emitted by DuPont Dow Elasroers LLCK A developmental ethylene / styrene copolymer (60% by weight ethylene content) made by The Dow Chemical Company. Tables IA and IB contain information on the physical properties of the AK primary polymers.

Table IA Table IB - Description of the Polymer Polymer / Property H K I2 (g / 10 min) 0.50 0.47 0.3 0.64 2.0 Density (g / cmJ) 0.863 0.860 0.870 0.855 0.974 Ratio of I? O / I2 7.30 8.85 6.10 10.5 9.5 Mw / Mn 2.00 1.91 1.95 2.62 3.1 OSMF 101 134 58 90 critical cut speed (sec _1) * Not available Examples 1-8 Seven SLEPs were tested as VI improvers in Base A Oil (FN1365 100N available from Exxon Chemical Con.). Concentrates of each SLEP (at a polymer concentration of 6% by weight) were prepared by dissolving the polymer in hot base oil (110-120 ° C). The concentrates were then added to the base oil and tested. Kinematic viscosities (KV) were determined in centistokes. (cSt) on Base Oil A and on each combination of Oil, Base A and 0.9% by weight of a SLEP. The KV values were determined at 40 ° C and 100 ° C according to ASTM D-445. Those values of KV and the contribution of the polymer to the KV at 100 ° are shown in Table II.

Table II Table II (continued) * It is not an example of the invention ** It was not measured.

The KV values shown in Table II indicate that SLEPs can function as an oily additive and, when added to an oil composition, produce an improved viscosity at temperatures as high as 100 ° C. These KV values also indicate the thickening power of the polymeric additive and can also be used to calculate the amounts to be added to fully formulated oils such as a 5W-30 motor oil.

Examples 9-13 Five SLEPs were tested as VI enhancers in ^ a 5W-30 oil formulation. The concentrates (at 6% by weight) of the SLEPs were prepared as Examples 2-8. Table III shows the compositions of oily formulations. Two different base oils, Base A Oil and Base B Oil (FN1243 150N oil, Exxon Chemical Company) were used to prepare these formulations. The dispersant inhibitor (DI-1) additive (DI) was 8482-A1 (Ethyl Corp). The PPD additive (PPD-1) was a developmental polyalkyl ethacrylate polymer designated XPD-194 (Rphm &Haas). The oil formulations containing a SLEP as an improver "of the VI were subjected to three tests: KV (at 100 ° C), according to what was determined in Examples 1-7; Cold Crankshaft Simulator (CCS), according to determined at -25 ° C for the SAE J300 appendix, and Hot High Temperature Cutting (HTHS), as determined at 150 ° C according to ASTM D-4741 and ASTM D-4683. Table III also shows the results of those tests.

Table III Table III (continued) The data in Table III show that the formulations of Examples 9-13, all of which contain a SLEP according to the present invention, satisfy the SAE SH classification criteria for a 5W-30 lubricating oil formulation. The criteria are a KV of 9.1 to 12.5 cSt, a CCS < 3500 cP and an HTHS > 2.9 cP.

Examples 14-21 The polymers G (ethylene / octene copolymer) and D (ethylene / propylene / ethylidene norbornene terpolymer) were evaluated in oil formulations 5W-30 (Examples 14, 15, 18 and 19) and 10W-30 (Examples 16, 17 , 20 and 21) prepared from neutral solvent (SN) and base oils subjected to catalytic thermofraction (HC). SN base oils were Base A and B Oils. HC base oils were available from Chevron USA Products Company as 100R RLOP oil (Base C oil) and 240R RLOP oil (Base D oil). The DI (DI-2) was Paramins ™ PDN2977 and the PPD was PPD-1. The polymers G and D were added as concentrates at 6% by weight as in Examples 2-8. Table IV shows the amounts of the components and the test results using the same tests as in Examples 9-13. The SAE SH classification criteria for the 10W-30 lubricating oil formulation are the same as those for the 5W-30 formulation except that the CCD was determined at -20 ° C.

Table IV The data in Table IV show that both polymers work well with the Base Oils A, B, C and D in terms of the SAE SH classification criteria for the 10W-30 lubricating oil compositions. In Base Oil A, Polymer G satisfies all SAE SH classification criteria for 5W-30 lubricating oil compositions while Base B Oil, Polymer G, satisfies all criteria except HTHS. In Base Oils A and B, Polymer D satisfies only the KV criterion of 5W-30. It is believed that one skilled in the art could easily use the formulation for Examples 15, 18 and 19 to satisfy the SAE SH criterion for the 5W-30 formulations.

Examples 22-25 Examples 14-21 were duplicated except for the use of Base Oils and D only, changing the DI to either Hitec ™ 1117 (DI-3) (Examples 22 and 24), obtained from Ethyl Corp., or OLOA 9250R XA1736 (DI-4) (Examples 23 and 24), obtained from the Oronite Company, and by changing the PPD (PPD-3) to dialkyl fumarate commercially available as Paramins Paraflov / "1 392 from Exxon Chemical Company. The results of the test are shown in Table V.

Table V The data shown in Table V show that the substantially linear ethylene polymers of the present invention can satisfy both classification criteria SAE SH 5W-30 and 10W-30 and function as VI improvers for a lubricating oil.

Examples 26-28 The procedure of Examples 1-7 was doubled except for the use of Polymer G in admixture with one of three other polymers in amounts as shown in the Table.

VII. The other three polymers were Polymer D (Example 26), an EP copolymer commercially available from Exxon Chemical such as Paratone ™ 8452 (Example 27) and a styrene block polymer commercially available from Shell Chemical as ShellVisR 250 (Example 28). The KV values, determined at 40 ° C and 100 ° C and the contribution of the polymer to the KV at 100 ° C, all determined as in Examples 1-7, are also shown in Table VI together with the results of Example 1.

Table VII It is not an example of the invention The data presented in Table VI demonstrate that a SLEP, particularly a SLEP EPDM, can be mixed with other polymers and still function as an effective oil additive imparting better viscosity at elevated temperatures.

Examples 29-32 Examples 22-25 were duplicated except for the substitution of the Polymer G blends and an additional polymer by the Polymer G. The additional polymers were a polyethacrylate polymer, commercially available from Rohm & amp;; Haas as Acryloid: 'R 954 (Example 29), an ethylene / propylene / hexadiene terpolymer commercially available from DuPont Dow Elastomers L.L.C. as Nordel® 4523 (Examples 30 and 32), and an ethylene / propylene / hexadiene terpolymer, commercially available from DuPont Dow Elastomers L.L.C. as Nordel "5 4549 (Example 31)." Acryloid® 954 was prepared and added as a 40% concentrate in hot oil.The Nordel® 4523 and Nordel'9 4549 were, like Polymer G, prepared and added as 6% concentrate in hot oil The amounts of the components and the test results are shown respectively in Tables VIIA and VI IB Table VIIA Table VIIB The data presented in Table VII (A and B) demonstrate that polymer samples incorporating a SLEP can function as IV modifiers in lubricating oil compositions that meet SAE classification criteria SH 5W-30 and 10W-30.

Examples 33-36 Examples 22-25 were duplicated using DI-3, any of PPD-3 (Examples 34 and 36) or PPD-1 (Examples 33 and 35) and concentrates of either Polymer G (Examples 33 and 34) or Polymer J ( Examples 35 and 36). In addition, the physical properties tests included a Brookfield (SB) temperature scan, determined at 30,000 centipoises (cP) according to ASTM D-5133. The SAE SH criteria for the 5W-30 formulation include a SB temperature of -30 ° C. The amounts of the components and the test results are shown in Tables VIIIA and VIIIB.

Table VIHA Table VIIIB The data in Table VIII show that the improved viscosities at low temperature are obtained with PPD incorporating a dialkyl fumarate (Examples 34 and 36) although the effect is more pronounced with an ethylene and octene copolymer (Example 34) than with a EP polymer (Example 36) for which any PPD produced satisfactory results. As all other criteria for the SAE SH 5W-30 classification are satisfied by the formulation of Example 33, one skilled in the art would be able to modify the formulation of Example 33 to satisfy the SB criterion as well.

Example 37 and 38 It was doubled to the procedure of Examples 1-7 using Polymer H, either cut (Example 38) and uncut (Example 37), and Base Oil A. Polymer H had an I2 of 1.72 g / 10 minutes (min) before cutting and 4.20 g / 10 min. after the cut. The polymer was cut in a twin rotor, high speed mixer (Haake) at 200 revolutions per minute (rpm) for 20 minutes at 250 ° C. Other known mechanical devices, such as an extruder, could have been used instead of the high-speed mixer. For each example, a Cut Stability Index (SSI) was also determined. The SSI was determined according to a formula where SSI = 100 x (V0 - Va) (V "- Vb), where V is the KV of the solution before being tested at 100 ° C, V .., is the KV of the solution after being tested at 100 ° C and V- is the KV of the base oil. A low SSI value was considered as an indication that a polymer-oil solution is more stable to cutting than a polymer-oil solution with a higher SSI value. The base oil had a KB before being tested at 4,009 (Example 1). Example 37 had a V, - of 6.55 cSt, a V., of 5.81 cSt and an SSI of 29.1. Example 38 had a V0 of 5.94 cSt, a V3 of 5.64 cSt and an SSI of 15.5.

In the data presented in Examples 37 and 38 they demonstrate that cutting a SLEP before adding it to an oil and subjecting the resulting polymer-oil solution to a cut stability test improves the cut stability (lower SSI). ) of the solution. Results similar to those shown in Examples 1-38 are expected when the polymer has been cut after the formation of the polymer-oil solution as well as with other SLEP and oleaginous materials, all of which have been described above.

Example 39 Polymer G was grafted with maleic anhydride using the procedure described in USP 5,346,963. In particular, Polymer G was fed into a Werner-Pfleiderer ZSK70 double co-rotating screw extruder at a rate of 340 Kilograms (750 pounds) of polymer per hour. The extruder was operated at a screw speed of 260 rpm and with the following barrel zone temperatures: Zone 1 = cooling with water; Zone 2 = 370 ° C (188 ° F); Zone 3 = 380 ° F (193 ° C); Zone 4 = 430 ° F (221 ° C); Zone = 410 ° F (210 ° C); Zone 6 = 410 ° F (210 ° C); Zone 7 = 410 ° F (210 ° C); Zone 8 = 430 ° F (221 ° C); Zone 9 = 410 ° F (210 ° C); Zone 10 = 345 ° F (174 ° C); Zone 11 = 345 ° F (174 ° C); and Matrix = 360 ° F (128 ° C) to provide a polymer melting temperature of 446 ° F (230 ° C). The maleic anhydride (MAH) was fed to the end of Zone 1 of the extruder through an injection nozzle by means of a metering pump at a rate of 6.57 kilograms per hour (14.5 pounds per hour). Peroxide, IPERSOL; 130, (2,5-di (t-butylperoxy) hexin-3 manufactured and sold by Atochem), was fed at the end of Zone 4 of the extruder through an injection nozzle by means of a metering pump at a rate of 0.68 kilograms per hour (1.5 pounds per hour). The extruder was maintained at a vacuum level of > of 66 centimeters (26 inches) of mercury to facilitate the devolatilization of the solvent, unreacted MAH and other contaminants. The percent incorporation of MAH in polymer G was 1.2%. The extrusion output is granulated via granulation in water at a temperature of 60 ° F (16 ° C). The SLEP grafted with MAH was then mixed and reacted with a monofutional developmental amine terminated in a polybutylene oxide compound having an M "of 1500 and prepared by The Dow Chemical Company. Mixing and reaction occurred in a Werner-Pfleiderer ZSK-30 double screw extruder operated at a screw speed of 150 rpm, tracking at 9 kg / hr (20 lb / hr) and an extrusion temperature of 190 ° C. The amine compound was added to the graft polymer at a ratio of amine compound to polymer of 0.15 to 1. The resulting polymer, grafted was reacted, tested as an LV improver using the same base oil and with the procedures of Examples 1-8. The KV values were as follows: 60.45 cSt at 40 ° C and 9,706 cSt at 100 ° C. The polymer contribution to the KV at 100 ° C was 6,611 cSt. Example 39 shows that a SLEP, when grafted with an unsaturated organic compound, such as maleic anhydride, and further reacted with a functionalizing compound, such as an amine-terminated compound, provides satisfactory results when used as an enhancer. VI or an oil composition. From examples 2-39 also show that the addition of a SLEP improves the VI of the oleaginous composition. Other properties of the oleaginous composition can be optimized by making variations to the formulation. Similar results are expected with other SLEPs, unsaturated organic compounds and functionalizing compounds, all of which were described above. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates.

Having described the invention as above, property is claimed as contained in the following:

Claims (4)

1. An oleaginous composition, characterized in that oleaginous material and an effective amount of a polymer to modify the viscosity, which is a substantially linear ethylene polymer or a substantially linear ethylene polymer grafted with at least 0.01% by weight based on the weight of the polymer grafted, of an unsaturated organic compound that. contains a grafting portion, the grafting portion contains at least one double bond, the substantially linear ethylene polymer has a backbone substituted with 0.01 to 3 long chain branches per 1000 coals in the backbone, each long chain branch has a length chain of at least 6 carbon atoms, the polymer - is characterized because it has: a) a flow relation in the molten state, I? O / I2 > 5.63; b) a molecular weight distribution, Mw / Mn, defined by the equation Mw / M- < (I ^ / I?) - 4.63; and c) a critical shear rate at the beginning of the melt fracture of the surface of at least 50 percent greater than the critical shear rate at the beginning of the melt fracture of the surface of a linear olefin polymer having 1? and M "/ Mn similar. The composition according to claim 1, characterized in that the polymer is a substantially linear grafted ethylene polymer and the unsaturated organic compound is selected from vinyl ethers, vinyl oxazolines, vinyl amines, vinyl epoxides, unsaturated epoxy compounds, carboxylic acids unsaturated and anhydrides, ethers, amines, amides, succinimides, or esters of such acids. 3. The composition according to claim 1 or claim 2, characterized in that the polymer is a copolymer of ethylene with a C3-Cn α-olefin and has an ethylene content in the range of 20 to 80 weight percent. , based on the weight of the polymer. 4. The composition according to claim 1 or claim 2, characterized in that the polymer is an interpolymer comprising copolymerized units of ethylene, α-olefins of C.-C2 (1 and at least one diene monomer selected from dicyclopentadiene, 1,4-hexadiene, piperylene, and 5-ethylidene-2-norbornene, 1,7-octadiene and vinyl norbornene.

5. The composition according to claim 1 or claim 2, characterized in that the molecular weight distribution is less than 5 and the melt flow ratio is 6.5 to 15. The composition according to claim 2, characterized in that the unsaturated organic compound is maleic anhydride or a carboxylic acid selected from maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, a-methyl crotonic acid and cinnamic acid. The composition according to claim 2 or claim 6, characterized in that the unsaturated organic compound is further reacted with a reagent which is an acid, an amine selected from organic nitrogen compounds. aliphatic containing at least one primary amine group and / or at least one secondary and, optionally, at least one tertiary amine group and which will react with the substantially linear, grafted ethylene polymer, or an alcohol which is an aliphatic polyhydric alcohol which It contains up to 100 carbon atoms and 2 to 10 hydroxyl groups. 9. The composition according to claim 8, characterized in that the amine is selected from polyethylene polyamines, alkylene polyamines, higher homologs of alkylene polyamines, polyoxyalkylene compounds terminated by amine and hydroxyalkyl polyamines. The composition according to claim 8, characterized in that the alcohol is an alkylene glycol, a polyglycol, or an aliphatic alcohol containing up to 20 carbon atoms. 11. The composition according to claim 2, characterized in that the unsaturated organic compound is vinylpyridine or n-vinyl-2-pyrrolidone. 12. The composition according to claim 1 or claim 2, characterized in that the oleaginous material is selected from hydrocarbon oils, lubricating oils based on alkylene oxide polymers and their derivatives, oils which are esters of dicarboxylic acids and oils based on silicon. 13. The composition according to claim 12, characterized in that the oleaginous material is selected from liquid petroleum oils, lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types, oils derived from coal or oil from shale, oils of poly (α-olefin), vegetable oils, animal oils, polyoxyalkylene polymers prepared from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils, and silicate oils. The composition according to claim 1 or claim 2, characterized in that the amount of polymer is a gelling or thickening amount. 15. The composition according to claim 1 or claim 2, characterized in that it further comprises an amount of a pour point depressant sufficient to improve the low temperature properties of the composition in relation to a similar composition lacking a depressant of the composition. pour point. 16. The oleaginous composition according to claim 1 or claim 2, characterized in that it further comprises at least one polymer selected from hydrogenated polyisoprene, styrene / butadiene hydrogenated block polymers, styrene / isoprene hydrogenated block polymers, grafted polymers of styrene / butadiene, grafted block polymers of styrene / isoprene, polymethacrylates, polyalkyl acrylates, ethylene polymers and acrylate / methacrylate coppers. 17. The oleaginous composition according to claim 1, characterized in that the polymer is a substantially linear ethylene polymer, modified by cutting.

18. An oily additive concentrate composition, characterized in that it comprises a mineral oil diluent and from 5 to 60 weight percent of the polymer according to claim 1 or claim

2. SUMMARY OF THE INVENTION Substantially linear ethylene polymers, such as ethylene / octene copolymers and modified ethylene / propylene-diene polymers, when added in a modified amount. viscosity to a ma! Oleaginous material, such as a lubricating oil, gives the material a viscosity index that exceeds that of the material alone. The substantially linear ethylene polymers, prepared by catalysis of restricted geometry, can be grafted with one or more unsaturated organic compounds, such as maleic anhydride, containing ethylenic unsaturation. The grafted polymer can be functionalized by reactions with, for example, an alcohol compound or an amine. Substantially linear ethylene polymers, when subjected to a cutting action either before or after addition to an oleaginous material, improve the shear stability of the oleaginous material. Substantially linear ethylene polymers, whether grafted, grafted and further reacted or not, also work as a thickening agent for compositions such as those used in greases, cable fillers and cosmetics. In addition, substantially linear ethylene polymers provide effective results when mixed with other components of compositions containing conventional oleaginous materials.