KR19990087593A - Substantially linear ethylene / alpha-olefin polymer as viscosity index enhancer or gelling agent - Google Patents

Abstract

Substantially linear ethylene polymers, such as ethylene / octene copolymers and ethylene / propylene / diene modified polymers, provide a material with a viscosity index greater than that of the material alone when added to oily materials such as lubricating oils in viscosity-adjusted amounts. do. Substantially linear ethylene polymers produced by forced geometry catalysis may be grafted with one or more unsaturated organic compounds, such as maleic anhydride, containing ethylenic unsaturations. The grafted polymer can be further functionalized, for example by reaction with alcohol or amine compounds. Substantially linear ethylene polymers improve the shear stability of the oily material if subjected to shearing before or after addition to the oily material. Substantially linear ethylene polymers act as thickeners in the composition, such as those used in greases, cable filling compounds and cosmetic materials, whether grafted, grafted and further reacted or not. In addition, substantially linear ethylene polymers provide effective results when blended with other components of conventional oily material compositions.

Description

Substantially linear ethylene / alpha-olefin polymer as viscosity index enhancer or gelling agent

This application claims the benefit of US Provisional Application No. 60 / 024,913, filed August 30, 1996, and US Provisional Application No. 60 / 013,052, filed March 8, 1996.

The present invention generally relates to oleaginous compositions containing at least one ethylene / alpha-olefin (α-olefin) interpolymer as a viscosity index (VI) enhancer or as a gelling agent. More particularly, the present invention relates to compositions in which the copolymer is substantially linear, in particular having a uniform branching distribution and narrow molecular weight distribution (MWD). Copolymers may be modified by one or more additional reactions to provide additional functionality. One particularly applicable reaction involves grafting olefinically unsaturated organic compounds, such as maleic anhydride, to the copolymer. Thereafter, the grafted polymer formed can be further reacted with one or more additional compounds, such as amines.

The VI enhancer provides a composition having a preferred or improved viscosity at high temperatures when incorporated into an oily composition. The improvement or increase in high temperature viscosity translates into VI enhancement without other changes.

VI is an experimental value used as a measure of lubricant viscosity and temperature stability. High VI shows dilution resistance at high temperatures. Low VIs tend to be diluted at such temperatures.

Indicators of VI viscosity performance under practical conditions of use include thickening, shear stability and chemical and thermal oxidation stability, all related to polymer structure. The ability of the VI enhancer to provide the desired high temperature viscous behavior depends on factors such as polymer molecular weight, concentration and chemical structure related to the chemical structure of the oily composition. Shear stability is highly dependent on polymer molecular weight and MWD.

Various oil soluble polymers have been used as VI enhancers for lubricating oils. Examples of polymers include hydrogenated styrene / diene polymers, hydrogenated polyisoprene, polyalkylmethacrylates, and ethylene / α-olefin copolymers such as ethylene / propylene copolymers and ethylene / propylene / diene terpolymers and their copolymers. And various derivatives of terpolymers. These polymers enable the production of multigrade oils (eg, 10 W-30) that meet high and low temperature Society of Automotive Engineers (SAE) viscosity method requirements.

At least some of the oil soluble polymers are also useful as thickeners or gelling agents for other oily materials such as mineral oils, paraffinic oils and naphthenic oils for preparing compositions suitable for use as grease or cosmetic materials.

VI enhancers based on ethylene olefin copolymers prepared in the presence of metallocene catalysts are also described, for example, in US Pat. Nos. 5,151,204 and 5,446,221.

Summary of the Invention

One aspect of the invention

(i) melt flow rate, I ₁₀ / I ₂ ≧ 5.63;

(ii) MWD, M _w / M _n defined by the following formula; And

M _w / M _n ≤ (I ₁₀ / I ₂ ) -4.63

(iii) substantially characterized by having a critical shear rate in OSMF that exceeds 50% or more of the critical shear rate at the onset of surface melt fracture (OSMF) of linear olefin polymers having similar I ₂ and M _w / M _n An oil-based composition comprising a linear ethylene polymer (SLEP) viscosity-adjusting effective amount and an oil-based substance.

In a first related aspect, the amount of polymer is a thickening or gelling effective amount so that its composition is suitable for use in preparing greases or cosmetic materials.

In a second related aspect, the oleaginous composition further contains an amount of PPD sufficient to improve the low temperature properties of the composition as compared to similar compositions lacking a pour point depressant (PPD).

In a third related aspect, the shear stability of the oily composition is increased by replacing at least a portion of the SLEP with a shear modified SLEP. Shear modified polymers are suitably made by allowing SLEP to undergo sufficient shearing action to increase its melt index (I ₂ ).

In a fourth related aspect, the oily composition may comprise, in addition to SLEP, hydrogenated polyisoprene, styrene / butadiene block polymer, styrene / isoprene block polymer, hydrogenated styrene / butadiene block polymer, hydrogenated styrene / isoprene block polymer, grafted styrene / butadiene block polymer, grafted It further contains one or more polymers selected from styrene / isoprene block polymers, polyalkylmethacrylates, polyalkylacrylates, ethylene polymers, and acrylate / methacrylate copolymers.

Each face and associated face further have three related faces (a) to (c). In one aspect (a), the SLEP has an ethylene content of 20 to 80 weight percent (wt%) based on the polymer weight. In another aspect (b), the SLEP is grafted to at least 0.01 wt% (based on the grafted SLEP) of an unsaturated organic compound containing graftable residues. In another aspect (c), the grafted SLEP containing the reactive moiety is further reacted with a compound having hydroxyl or amine functionality. Examples of such compounds include alcohols, in particular aliphatic saturated monoalcohols, acids and amines, in particular primary amines.

"Block polymers" include diblock polymers, triblock polymers, spin block or star block polymers and tapered copolymers.

"Ethylene polymer" means an ethylene / α-olefin copolymer or a diene modified ethylene / α-olefin copolymer. Examples of polymers include ethylene / propylene (EP) copolymers, ethylene / octene (EO) copolymers and ethylene / propylene / diene modified (EPDM) copolymers.

"Substantially linear" means that the polymer has a backbone substituted with from 0.01 to 3 long chain branches per 1000 carbons in the backbone.

"Long chain branch" or "LCB" means a chain length of at least 6 carbon atoms. Above this length, carbon-13 nuclear magnetic resonance (C-13 NMR) spectroscopy cannot distinguish or identify the actual number of carbon atoms in the chain. In some instances, the chain length can be as long as the polymer backbone to which it is attached.

"Interpolymer" means a polymer having two or more monomers polymerized therein. Examples thereof include copolymers, terpolymers and quaternary copolymers. Specific examples include polymers prepared by polymerizing ethylene with one or more comonomers, typically α-olefins having 3 to 20 carbon atoms (C ₃ -C ₂₀ ). Examples of the α-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and styrene. As the α-olefin, C ₃ -C ₁₀ α-olefin is preferable. Examples of preferred copolymers include EP and ethylene-octene. Examples of terpolymers are ethylene / propylene / octene terpolymers and ethylene, C ₃ -C ₂₀ α-olefins and dienes such as dicyclopentadiene, 1,4-hexadiene, piperylene or 5-ethylidene The terpolymer of 2-norbornene is mentioned.

Substantially linear ethylene α-olefin copolymers (“SLEP” or “substantially linear ethylene polymers”) are prepared as described in US Pat. Nos. 5,272,236 and 5,278,272, the disclosures of which are incorporated herein by reference. Can be. U.S. Patent 5,272,236 (columns 5, 67 to columns 6, 28) discloses continuous controlled polymerization using one or more reactors (multiple reactors are also acceptable) at a polymerization temperature and pressure sufficient to produce a SLEP with the desired properties. It describes the production of SLEP through the process. The polymerization preferably takes place via a solution polymerization process at a temperature of 20 to 250 ° C. using a forced geometry catalyst technique.

Suitable forced geometry catalysts are described in US Pat. No. 5,272,236, column 6, line 29 to column 13, line 50. Such catalysts may be described as containing metal coordination complexes consisting of lanthanide and Group 3-10 metals of the Periodic Table of the Elements and an unlocalized pi-bonded component substituted with a forced induction component. The complex is the angle of the analog complex in which the angle in the metal between the uncentered, center of gravity of the substituted pi-bonded component and the center of the one or more residual substituents contains similar pi-bonded components lacking such forced induced substitution Has a forced geometry around the metal atom to be less. When such a complex consists of more than one unlocalized, substituted pi-bonded component, the only component for each metal atom of the complex is a cyclic, unlocalized, substituted pi-bonded component. The catalyst further contains an activating promoter such as tris (pentafluorophenyl) borane. Certain catalyst complexes are described in US Pat. No. 5,272,236, columns 6, 57 to column 8, 58 and US Pat. No. 5,278,272, column 7, 48 to column 9, 37. General catalyst complexes and techniques relating to these specific complexes are incorporated by reference.

SLEP is characterized by a narrow comonomer distribution in the case of narrow MWDs and copolymers. SLEP is also characterized by low residual content, especially in terms of catalyst residues, unreacted comonomers and low molecular weight oligomers generated during the polymerization. SLEP is further characterized by a controlled molecular configuration that provides a good processability although MWD is narrower than conventional olefin polymers.

Preferred SLEPs have a number of distinct properties, one of which is the comonomer content, where the balance consists of one or more comonomers, 20 to 80% by weight, more preferably 30 to 70% by weight ethylene. SLEP comonomer content can be measured using infrared (IR) spectroscopy according to ASTM D-2238 Method B or ASTM D-3900. Comonomer content may be confirmed by C-13 NMR spectroscopy.

Other clear SLEP properties include I ₂ and melt flow ratio (MFR or I ₁₀ / I ₂ ). The comonomer is preferably 0.01-500 grams / 10 minutes (g / 10 minutes), more preferably 0.05-50 grams / 10 minutes of I ₂ (ASTM D-1238, conditions 190 ° C./2.16 kilograms (kg) ( Originally has condition E. SLEP also has an MFR (ASTM D-1238) of ≧ 5.63, preferably 6.5-15, more preferably 7 to 10. For SLEP, the I ₁₀ / I ₂ ratio is It is provided as an indication of the degree of LCB such that a larger I ₁₀ / I ₂ ratio is equal to the high LCB in the polymer.

Another distinct property of SLEP is MWD (M _w / M _n or "polydispersity index") measured by gel permeation chromatography (GPC). M _w / M _n is defined by the following equation.

<Equation 1>

M _w / M _n ≤ (I ₁₀ / I ₂ ) -4.63

The MWD is preferably greater than 0 and less than 5, in particular 1.5 to 3.5, more preferably 1.7 to 3.

Uniformly branched SLEP surprisingly has an MFR that is essentially independent of its MWD. This is in sharp contrast to conventional linear uniformly branched ethylene copolymers and linear heterogeneously branched ethylene copolymers in which MWD should be increased to increase MFR.

SLEP can also be characterized as having a critical shear rate in OSMF that is at least 50% greater than the critical shear rate in OSMF of linear olefin polymers having similar I ₂ and M _w / M _n .

SLEPs meeting this criterion include, for example, ENGAGE® polyolefin elastomers and other polymers produced through forced geometry catalysis by DuPont Dow Elastomers L.L.C.

SLEP can be added to oily compositions with or without modifications such as grafting. When modified by grafting, the grafted SLEP formed may also be added to the oleaginous composition in the presence or absence of one or more additional reactions prior to addition. Grafting may also be done after SLEP is added to the oleaginous composition.

Any unsaturated organic compound containing one or more ethylenic unsaturations (one or more double bonds) and to be grafted to the SLEP can be used to modify the SLEP. Examples of unsaturated compounds include vinyl ethers, vinyl substituted heterocyclic compounds, vinyl oxazolines, vinyl amines, vinyl epoxy, unsaturated epoxy compounds, unsaturated carboxylic acids, and anhydrides, ethers, amines, or esters of such acids. . Representative compounds include maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, α-methyl crotonic acid and cinnamic acid and its anhydrides, ester or ether derivatives, vinyl substituted alkylphenols and glycidyl methacrylates. Included. Suitable unsaturated amines include those of aliphatic and heterocyclic organic nitrogen compounds containing one or more double bonds and one or more amine groups (one or more primary, secondary or tertiary amines). Representative examples include vinyl pyridine and vinyl pyrrolidone. Maleic anhydride is a preferred unsaturated organic compound.

The unsaturated organic compound content of the grafted SLEP is ≧ 0.01% by weight, preferably ≧ 0.05% by weight, based on the total weight of polymer and organic compound. The maximum unsaturated organic compound content can vary, but is typically <10% by weight, preferably <5% by weight, more preferably <2% by weight.

Unsaturated organic compounds may be grafted to SLEP by known techniques such as those disclosed in US Pat. Nos. 3,236,917 and 5,194,509, the art of which is incorporated herein by reference and is a part of this application. In US Pat. No. 3,236,917, polymers, such as EP copolymers, are introduced into a variant roll mixer and mixed at a temperature of 60 degrees Celsius (° C.). Thereafter, an unsaturated organic compound such as maleic anhydride is added with a free radical initiator such as benzoyl peroxide and the components are mixed at 30 ° C. until grafting is complete.

US Pat. No. 5,194,509 sets forth a procedure similar to that of US Pat. No. 3,236,917, except that higher reaction temperatures (210 ° C to 300 ° C, preferably 210 ° C to 280 ° C) and the use of free radical initiators are omitted or limited. It was. U.S. Pat.No. 5,194,509 specifically describes peroxide free grafting of unsaturated carboxylic acids, anhydrides and derivatives thereof such as conventional twin screw extruders, such as WERNER & Pfleiderer's ZDSK 53, or Brabender. It has been suggested that it can be carried out in other conventional apparatus such as reactors. The ethylene polymer and, if necessary, the monomer to be grafted are melted at 140 ° C. or higher, thoroughly mixed, and then high temperature (210 ° C. to 300 ° C., preferably 210 ° C. to 280 ° C., more preferably 210 ° C. to 260 ° C.) Reaction at It does not matter whether the monomer to be grafted is introduced into the reactor before or after the ethylene polymer is melted. The monomer to be grafted was used at a concentration of 0.01 to 0.5% by weight, preferably 0.05 to 0.25% by weight, based on the weight of the ethylene polymer.

Other preferred grafting methods are described in US Pat. No. 4,950,541, which is incorporated herein by reference. The alternative uses a twin screw devolatilizing extruder as mixing device. SLEP and unsaturated organic compounds are mixed and reacted in the extruder in the presence of free radical initiators at the temperature at which the reactants are melted. The unsaturated organic compound is preferably injected in a zone maintained under pressure in the extruder.

A second preferred grafting method is solution grafting as set forth in US Pat. No. 4,810,754, which is 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.

Graft-modified SLEP is an oil-containing grafted and more reacted SLEP to introduce one or more additional functional groups that lead to improved properties such as improved dispersibility of oxidation or combustion byproducts, improved low temperature viscosity and improved oxidation / thermal stability. It may further react with the modifying material in the composition. Examples of modifying materials include alcohols, long chain (typically up to 36 carbon atoms) fatty acids, and amines. Examples of alcohols include aliphatic and aromatic alcohols having ≧ 2, preferably> 12, more preferably <36 carbon atoms. Representative alcohols and long chain fatty acids include decyl, lauryl and stearyl alcohols and acids. Examples of amines include those of aliphatic and heterocyclic nitrogen compounds containing at least one primary amine and / or at least one secondary amine, and optionally at least one tertiary amine. Any amines such as triethylene tetramine, tetraethylene pentamine, and polyethylene polyamines (e.g., ethyleneamine E-100, available from The Dow Chemical Company) may contain aliphatic and heterocyclic moieties. Have it all. Commercially available polyethylene polyamines are typically blends or mixtures of linear branched and heterocyclic amines. Representative examples include polyethylene amines (eg, diethylene triamine), 1- (3-aminoethyl imidazole), aminoethyl piperazine, 4- (3-aminopropyl) morpholine, and polyoxyalkylene polyamines (eg For example, Jeffamines (registered trademark) produced by Huntsman Chemical may be mentioned. Other alcohols and amines are described in US Pat. No. 5,401,427, column 45, line 40 to column 49, 29, the disclosure of which is hereby incorporated by reference.

US Pat. No. 5,401,427 discloses methylene amine, ethylene amine, butylene amine, propylene amine, pentylene amine, hexylene amine, heptylene amine, octylene amine, other polymethylene amines, and other cyclic polyamines in other suitable alkylene polyamines. And higher homologues such as piperazine, amino-alkyl substituted piperazine, and the like. These amines include, for example, ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di (Trimethylene) triamine, 2-heptyl-3- (2-aminopropyl) imidazoline, 4-methylimidazoline, 1,3-bis- (2-aminopropyl) imidazoline, pyrimidine, 1 -(2-aminopropyl) piperazine, 1,4-bis (2-aminoethyl) piperazine, N, N'-dimethylaminopropyl amine, N, N'-dioctylethyl amine, N-octyl-N ' -Methylethylene diamine, and 2-methyl-1- (2-aminobutyl) piperazine. The range of polyamines includes hydroxyalkyl polyamines, especially hydroxyalkyl alkylene polyamines, having one or more hydroxyalkyl substituents on the nitrogen atom. Examples of such hydroxyalkyl substituted polyamines include N- (2-hydroxyethyl) ethylene diamine, N, N-bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) -piperazine, Monohydroxy-propyl substituted diethylene triamine, dihydroxypropyl substituted tetraethylene pentamine, and N- (3-hydroxybutyl) tetramethylene diamine.

Alcohols or polyols described in US Pat. No. 5,401,427 include aliphatic polyhydric alcohols containing ≦ 100 carbon atoms and 2 to 10 hydroxyl groups. These alcohols may be substituted or unsubstituted, blocked or unblocked, branched or straight chain as desired. Typical alcohols include 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, tributylene glycol, and other alkylene glycols and polyalkylene glycols in which the alkylene radical contains 2 to 8 carbon atoms. Preferred classes of aliphatic alcohols containing ≦ 20 carbon atoms include glycerol, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptane Diol, 2,4-heptane diol, 1,2,3-hexanetriol, 1,2,4-heptane triol, 1,2,5-hexanetriol, 2,3,4-hexanetriol, 1 , 2,3-butanetriol, 1,2,4-butanetriol, 2,2,6,6-tetrakis (hydroxymethyl) -cyclohexanol, and 1,10-decanediol.

SLEP, graft modified SLEP and / or more reacted and graft modified SLEP, when added to various crude oils or oleaginous materials, compared to oil materials lacking such SLEP or graft modified SLEP or more reacted and graft modified SLEP Enhance one or more of the VI measurements, dispersibility measurements, stability measurements, and gelation or thickening measurements of such oily material.

Oily materials or crude oils suitable for use in lubricating oil formulations may consist of unrefined, refined and reclaimed (reclaimed) oil utilizing both natural and synthetic raw materials. Examples of oily substances include any of various hydrocarbon oils, lubricating oils based on alkylene oxide polymers and derivatives thereof, oils which are esters of dicarboxylic acids, or silicon based oils, which form the compositions of the present invention. Such oils can be natural or synthetic and include lubricants and fuel oils. Examples of suitable oils include liquefied petroleum, paraffinic, naphthenic and mixed paraffinic-naphthenic types of lubricating oils, oils derived from coal or shale, poly (α-olefin) oils, vegetable oils, animal oils, one or more oxidations. Polyoxyalkylene polymers or copolymers prepared from ethylene, propylene oxide or butylene oxide, tetrahydrofuran, polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils, and silicate oils. . Blends of such oils may be used. U. S. Patent No. 5,446, 221, column 8, line 47 to column 10, line 34 discloses additional information regarding the various oily materials cited herein by reference.

When used as a VI enhancer in an oily composition, whether grafted, grafted or grafted and further reacted, the composition may contain several different types of additives to enhance the properties required for the formulation containing such composition. It may be. These additives, which may include conventional VI enhancers, generally include dispersants, cleaners, antioxidants, abrasion and pressure resistant agents, friction modifiers, PPDs, corrosion inhibitors, ashless dispersants (e.g., polyisobutenyl succinimide and Borate derivatives thereof) and antifoaming agents. These additives are generally present in amounts of 0.001 to 20% by weight, based on the weight of the oil. Common VI enhancers include high molecular weight hydrocarbon polymers, polyalkylmethacrylates, and polyesters containing copolymerized units of unsaturated C ₃ to C ₈ mono and dicarboxylic acids. These additives may be introduced as oils or as undiluted concentrated solutions or dispersions.

When preparing the lubricating oil blend, the additive is usually introduced as a 5 to 80% by weight active ingredient concentrate in oil. The use of concentrates makes the handling of the various materials less difficult and facilitates the dissolution or dispersion of the additives in the formulation.

PPD lowers the temperature at which lubricant can flow or be poured. Such PPDs are well known. Typical additives that can be used for the low temperature flow of lubricating oil are dialkylfumarate vinyl acetate copolymers, polymethacrylates (US Pat. Nos. 2,091,627 and 2,100,993) and wax naphthalenes (US Pat. No. 2,174,246).

Whether SLEP is grafted, grafted or grafted and further reacted when added to an oily composition as a thickener or gelling agent in the preparation of a material or thixotropy gelling agent for grease, wire and cable end use, it is used as a lubricant. It can be combined with any or all additives specified to be useful in the oily composition. Examples of wire and cable end uses are conventional applications such as ceramic manufacturing compounds, water barriers and insulating materials. These applications are particularly important for fiber optic cables.

When such polymers are added to oily compositions as thickeners or gelling agents for cosmetic use, ointment or topical use, they are fragrances, colorants, dyes, stabilizers, surfactants, thickeners, and oils (e.g. coconut oil). It can be combined with other additives such as

Oily compositions exhibiting improved low temperature properties consist of oily material, PPD and a viscosity modulating effective amount of SLEP. If SLEP is essentially amorphous (it may comprise ≦ 6% crystallinity, preferably ≦ 3, more preferably ≦ 1 but ≧ 0% crystallinity), the crystallization initiation point for the wax contained in the oily material ( Any conventional PPD can be used provided that T _c ) is not within the T _c range of the wax contained in SLEP. When SLEP is semicrystalline (6-25%, preferably 6-20%, more preferably 6-16%), satisfactory low temperature properties are copolymers of di-n-alkyl fumarate and vinyl acetate. Obtained with any desired PPD. Copolymers used as PPDs are suitably prepared as described in US Pat. No. 4,839,074, which is incorporated herein by reference.

U.S. Patent No. 4,839,074 discloses reacting or copolymerizing with a polymerizable monomer compound such as vinyl ester using conventional free radical polymerization techniques that first esterify a dicarboxylic acid such as fumaric acid and then form a random polymer. It is starting. The polymerization suitably takes place in an inert hydrocarbon solvent such as hexane or heptane at a temperature of 65 to 150 ° C. in an oxygen free environment such as a nitrogen atmosphere. While complete esterification of all carboxyl groups of the dicarboxylic acid monomer is preferred, partial esterification of available esterifiable carboxyl groups ≧ 70 mol% may be sufficient. The esterification is typically done with alcohol mixtures. The alcohol may be slightly branched, but is preferably a straight chain C ₁ to C ₂₀ aliphatic alcohol, more preferably C ₆ to C ₂₀ aliphatic alcohol.

Semicrystalline SLEPs that work well with di-n-alkyl fumarate / vinyl acetate copolymers have different peak crystallization temperatures (differential scans) than those of waxes contained in an oily substance such that the SLEP and wax contained in the oily substance preferably do not co-crystallize. It is believed to have a calorimeter (measured by DSC). When the peak crystallization temperature of the oily material varies considerably due to factors such as wax content, each combination of oily material, semicrystalline SLEP and di-n-alkyl fumarate / vinyl acetate copolymer should be evaluated for low temperature properties.

The composition of the present invention is formed by adding SLEP to the oil or oily composition by conventional blending techniques, either ungrafted or unmodified, by graft and, if grafted, by further or no reaction. The polymer may be added neat or as an oil concentrate. Generally, the amount of polymer added is 0.1 to 20% by weight, preferably 0.2 to 5% by weight dry polymer for viscosity adjustment and 5 to dry polymer for thickening or gelling applications, based on the weight of the oil to be modified. Will be 15% by weight.

In the preparation of lubricating oil formulations, additives are usually introduced as active ingredient concentrates in hydrocarbon oils, such as inorganic lubricating oils, or other suitable solvents. Concentrates typically have an active ingredient content of 5 to 80% by weight, based on the weight of the concentrate. When forming a finish lubricant, such as crankcase motor oil, the concentrate is generally diluted with 3 to 100, sometimes 5 to 40 pbw, lubricant per weight of additive package (pbw). The use of concentrates makes the handling of the various additives less difficult and facilitates the dissolution or dispersion of the additives in the finish lubricant. For the purposes of the examples, a typical VI enhancer will be used as a 5-20 wt% concentrate in the lubricating oil fraction.

The present invention relates in part to an oily or oil composition which exhibits an improved VI, in particular for oil compositions consisting of lubricating oils and SLEP as VI enhancers. Oil compositions containing such VI enhancers exhibit improved viscosity at high temperatures compared to oil compositions that do not contain such VI enhancers. VI enhancers may also be derivatized to impart other properties or functions, such as adding dispersant properties to fuel and lubricating oil compositions. The derivatized polymers are esterified with U.S. Patent Nos. 3,702,300 (columns 4, 56 to columns 5, 60, carboxy containing copolymers such as maleic anhydride containing copolymers with mixed alcohols, and then the remaining carboxy radicals with polyamines. Description of neutralizing); U.S. Pat. No. 4,089,794 (columns 3, 37 to columns 4, 59, ethylenically unsaturated carboxylic acid materials such as maleic anhydride are solution grafted to ethylene / a-olefin polymers, such as EP copolymers, and then grafted. Of reacting a polymer with a polyamine); US Pat. No. 4,160,739 (columns 6, lines 35-52, description of the post-reaction of carboxyl groups provided by maleic acid or anhydride grafts with unpolymerizable polyamines); Or US Pat. No. 4,137,185 (columns 7, 4-17, description of reacting grafted carboxylic acid material such as maleic anhydride grafted ethylene / a-olefin polymer with poly (primary amine) in solution). Maleic anhydride grafted SLEP which can be further reacted with amines or alcohols as shown (prepared as described above and in column 3, line 67 to column 4, line 24 of US Pat. No. 5,346,963); Or US Pat. No. 4,068,056 (column 4, line 47 to column 5, line 23, Ziegler-Natta catalyzed hydrocarbon polymer and amine compound in the presence of an oxygen containing gas at 130 ° C to 300 ° C Description of reacting); US Pat. No. 4,146,489 (columns 2, 49 to columns 3, 15, description of free group graft polymerization of C-vinylpyridine or N-vinyl pyrrolidone to EP rubber or EPDM rubber); And US Pat. No. 4,149,984 (columns 4, lines 3-20, polymerizable heterocyclic compounds, such as vinyl pyridine or vinyl pyrrolidone, by polymerizing methacrylic acid esters of C ₈ -C ₁₈ alcohols in a solution of polyolefin polymers). Grafted SLEP, such as SLEP grafted with a nitrogen compound, as described in Grafting to a Formed Polymer). The related art of this patent is incorporated herein by reference.

The following examples illustrate the invention but do not explicitly or implicitly limit the invention. Unless otherwise indicated, all parts and percentages relate to weight based on total weight.

Eleven primary polymers were used in the examples, eight representing the present invention. Polymers B, E and I do not represent the present invention. The polymer is as follows:

A. Ethylene / octene copolymer (ethylene content 61.7 wt.%) Available from DuPont Dow Elastomers L.L.C. as EG 8200.

B. Ethylene / butene copolymer commercially available from Exxon Chemical Company as EXACT® 4024.

C. Ethylene / octene copolymer (ethylene content 68.2% by weight) commercially available from DuPont Dow Elastomers L.C. as EG 8100.

D. Developed ethylene / propylene / ethylidene / norbornene terpolymers produced by DuPont Dow Elastomers L.C. (ethylene content 57% by weight).

E. EP copolymer commercially available from Mitsui Petrochemical as TAFMER® P-0480.

F. Ethylene / octene copolymer (ethylene content 64.7 wt.%) Commercially available from DuPont Dow Elastomers L.C. as EG 8150.

G. Ethylene / octene copolymer (ethylene content 61.0 wt.%) Commercially available from DuPont Dow Elastomers L.C. as DEG 8180.

Developed EP copolymer (53.1 wt% ethylene content) prepared by H. DuPont Dow Elastomers L.C.

I. EP copolymer commercially available from Mitsui Petrochemical as TAFMER® P-0480.

Developed EP copolymer (ethylene content 34.7 wt.%) Prepared by J. DuPont Dow Elastomers L.C.

Developed ethylene / styrene copolymer (ethylene content 60% by weight) prepared by K. Dow Chemical Company.

Tables IA and IB provide physical property information for primary polymers A-K.

Polymer / Characteristics A B C D E F I ₂ (g / 10min) 5.0 3.3 1.0 1.72 1.1 0.50 Density (g / cm 3) 0.870 0.878 0.870 0.860 0.870 0.868 I ₁₀ / I ₂ ratio 7.38 7.99 8.13 6.06 7.37 M _w / M _n 1.92 1.96 2.36 1.90 2.03 OSMF critical shear rate (sec ^-1 ) 5423 366 1670 105 385

Polymer description Polymer / Characteristics G H I J K I ₂ (g / 10min) 0.50 0.47 0.3 0.64 2.0 Density (g / cm 3) 0.863 0.860 0.870 0.855 0.974 I ₁₀ / I ₂ ratio 7.30 8.85 6.10 10.5 9.5 M _w / M _n 2.00 1.91 1.95 2.62 3.1 OSMF critical shear rate (sec ^-1 ) 101 134 58 90 - ^{* *} Not available

Example 1-8

Seven SLEP were tested as VI enhancers in crude oil A (FN1365 100N available from Exxon Chemical Company). A polymer (6 wt% polymer concentration) of each SLEP was prepared by dissolving the polymer in hot (110-120 ° C.) crude oil. Thereafter, the concentrate was added to crude oil and tested. The kinematic viscosity (KV) in centistokes (cSt) was determined for crude oil A and for each blend of crude oil A and SLEP 0.9% by weight. KV values were measured at 40 ° C. and 100 ° C. according to ASTM D-445. The polymer KV contributing to this KV value and KV at 100 ° C. is shown in Table II.

Example polymer KV ＠ 40 ℃ (cSt) KV ＠ 100 ℃ (cSt) Polymer KV (cSt) contributed to ＠ 100 ℃ 1 ^* none 19.87 4.009 N / A 2 A ** 7.361 3.352 3 C 58.08 8.855 4.846 4 D 45.07 8.160 4.151 5 F 56.97 9.656 5.647 6 G 54.59 9.684 5.675 7 H 56.31 9.927 5.918 8 K 32.05 6.179 2.170 ^* Not an embodiment of the present invention ^** not measured

The KV values shown in Table II indicate that SLEP can function as an oil additive and can improve viscosity at high temperatures such as 100 ° C. when added to oily compositions. These KV values also represent the thickening power of the polymer additive and can be further used to calculate the amount to be added to a fully formulated oil, such as 5W-30 motor oil.

Example 9-13

Five SLEPs were tested as VI enhancers in 5W-30 oil formulations. Concentrates (6 wt.%) Of SLEP were prepared as in Examples 2-8. Table III shows the composition of the oil formulation. This formulation was prepared using two different crude oils, Crude Oil A and Crude Oil B (FN1243 150N oil, Exon Chemical Company). Dispersion inhibitor (DI) additive (DI-1) was 8482-A1 (ethyl corporation). The PPD additive (PPD-1) was a developed polyalkyl methacrylate polymer under the trade name XPD-194 (manufactured by Rohm & Haas).

Three tests were conducted on oil formulations containing SLEP as VI enhancer: KV measured at Examples 1-7 (at 100 ° C.); Cold Crank Simulator (CCS) measured at −25 ° C. according to SAE J300 appendix; And High Temperature Heat Shear (HTHS) measured at 150 ° C. according to ASTM D-4741 and ASTM D-4683. Table III also shows the results of this test.

Example 9 10 11 12 13 ingredient weight% weight% weight% weight% weight% Crude Oil A 68.97 67.94 68.93 71.29 78.25 Crude Oil B 2.49 8.22 8.92 6.23 0.00 DI-1 11.31 11.31 11.31 11.31 11.31 PPD-1 0.30 0.30 0.30 0.30 0.30 Polymer A Concentrate 16.94 - - - - Polymer C Concentrate - 12.23 - - - Polymer F Concentrate - - 10.54 - - Polymer G Concentrate - - - 10.88 - Polymer H Concentrate - - - - 10.15 Test result KV (cSt) 10.69 11.78 10.56 10.66 10.31 CCS (cP) 3,190 3,250 3,180 3,100 3,220 HTHS (cP) 3.11 3.18 2.91 3.04 3.00

The data in Table III all show that the formulations of Examples 9-13 containing SLEP according to the present invention meet the SAE SH classification criteria for 5W-30 lubricant formulations. The criteria are KV of 9.1 to 12.5 cSt, CCS <3500 cp and HTHS> 2.9 cp.

Example 14-21

Polymers G (ethylene / octene copolymer) and D (ethylene / propylene / ethylidene norbornene terpolymers) were prepared from 5W-30 (Example 14, 15) prepared from solvent neutral (SN) and hydrocracking (HC) crude oils. , 18 and 19) and 10W-30 (Examples 16, 17, 20 and 21) oil formulations. SN crude oil was crude oil A and B. HC crude oil was sold by Chevron USA Products Company as 100R RLOP oil (crude C) and 240R RLOP oil (crude D). DI (DI-2) was Paramins® PDN2977 and PPD was PPD-1. Polymers G and D were added as 6 wt% concentrates as in Examples 2-8. Table IV shows the amounts of components and test results using the same test as in Examples 9-13. The SAE SH classification criteria for the 10W-30 lubricant blend were the same as for the 5W-30 blend except that the CCS was measured at -20 ° C.

Example 14 15 16 17 18 19 20 21 Formulation Type 5W-30 SN 5W-30 HC 10W-30 SN 10W-30 HC 5W-30 SN 5W-30 HC 10W-30 SN 10W-30 HC ingredient weight% weight% weight% weight% weight% weight% weight% weight% Crude Oil A 74.84 - 0.07 - 78.71 - 7.03 - Crude Oil B 3.65 - 82.10 - - - 72.15 - Crude Oil C - 74.40 - 48.23 - 77.59 - 53.03 Crude oil D - 4.44 - 33.51 - 0.17 - 25.42 DI-2 9.91 9.91 9.91 9.91 9.91 9.91 9.91 9.91 PPD-1 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Polymer G Concentrate 11.40 11.04 7.72 8.15 - - - - Polymer D Concentrate - - - - 11.17 12.14 10.71 11.44 Test result KV (cSt) 10.65 10.52 10.65 10.48 9.24 9.55 10.78 10.49 CCS at 25 ° C. (cP) 3,210 3,365 - - 3,600 3,600 - - CCS at 20 ° C. (cP) - - 3,145 2,760 - - 3,245 2,770 HTHS (cP) 2.91 2.81 2.94 2.92 2.83 2.76 3.20 3.01

The data in Table IV show that both polymers work well with crude oils A, B, C and D in terms of SAE SH classification criteria for the 10W-30 lubricant composition. In crude oil A, polymer G meets all SAE SH classification criteria for 5W-30 lubricant compositions, while in crude oil polymer G meets all criteria except HTHS. In crude oils A and B, polymer D meets only the 5W-30 KV criteria. One skilled in the art believes that the formulations of Examples 15, 18 and 19 can be easily optimized to meet all SAE SH criteria for the 5W-30 formulation.

Example 22-25

Hitec® 1117 (DI-3) (Examples 22 and 24), or Oronite Company, using only crude oils C and D, and DI purchased from Ethyl Corp. Was changed to OLOA 9250R XA1736 (DI-4) (Examples 23 and 25) and PPD (PPD-3) was purchased from Exxon Chemical Company by Paramins Paraflow (registered). It was carried out as in Examples 14-21 except that it was changed to a commercially available dialkyl fumarate as 392. The amounts of ingredients and test results are shown in Table V.

Example 22 23 24 25 Formulation Type 5W-30 5W-30 10W-30 10W-30 ingredient weight% weight% weight% weight% Crude Oil C 72.40 72.69 43.13 34.41 Crude oil D 5.17 6.02 37.81 48.28 DI-3 10.84 - 10.85 - DI-4 - 8.76 - 8.75 PPD-3 0.20 0.20 0.20 0.20 Polymer G Concentrate 11.39 12.34 8.01 8.75 Test result KV (cSt) 10.67 10.53 10.56 10.43 CCS at 25 ° C. (cP) 3,130 2,960 - - CCS at 20 ° C. (cP) - - 2,700 2,760 HTHS (cP) 3.11 3.08 3.16 3.14

The data shown in Table V indicate that the substantially linear ethylene polymers of the present invention meet both 5W-30 and 10W-30 SAE SH classification criteria and can function as VI enhancers for lubricating oils.

Example 26-28

The methods of Examples 1-7 were used except that Polymer G was mixed with one of three other polymers in the amounts shown in Table VI. Three different polymers were prepared from Polymer D (Example 26), EP copolymer commercially available as Paratone® 8452 (Example 27) from Exxon Chemical and Shell from Shell Chemical. It was a styrene block polymer sold as ShellVis (R) 250 (Example 28). Both polymer KVs contributing to KV values measured at 40 ° C. and 100 ° C. and KV at 100 ° C., measured as in Examples 1-7, are shown in Table VI along with the results of Example 1.

Example ingredient weight% KV ＠ 40 ℃ (cSt) KV ＠ 100 ℃ (cSt) Polymer KV contributed to 100 ° C (cSt) 1 ^* Crude Oil A 100 19.87 4.009 N / A 26 Crude A Polymer G Polymer D 99.10.360.54 48.78 8.802 4.793 27 Crude A polymer GParatone® 8452 99.10.360.54 65.23 11.24 7.231 28 Crude A polymer GShellVis® 250 99.10.360.54 47.45 8.687 4.678 ^* Not an embodiment of the invention

The data shown in Table VI demonstrate that SLEP, in particular EPDM SLEP, can be blended with other polymers and can function as an effective oil additive by imparting improved viscosity at high temperatures.

Example 29-32

The same procedure was followed as in Examples 22-25, except that a blend of Polymer G and additional polymer was used instead of Polymer G. Additional polymers are polymethacrylate polymers, commercially available from Rohm & Haas as Acryloid® 954 (Example 29), DuPont Dow E. L.C. Ethylene / propylene / hexadiene terpolymer, commercially available from Elastomers LLC as Nordel 4523 (Examples 30 and 32), and Nordel from Dupont Dow Elastomers L.C. (Trademark) 4549 (Example 31) was an ethylene / propylene / hexadiene terpolymer. Acryloid® 954 was prepared and added as a 40% concentrate in hot oil. Nordel (R) 4523 and Nordel (R) 4549 were prepared as polymer G and added as a 6% concentrate in hot oil. The amounts of ingredients and test results are shown in Tables VIIA and VIIB, respectively.

Example 29 30 31 32 Formulation 5W-30 5W-30 5W-30 10W-30 Ingredient / weight% Crude Oil C 76.13 74.04 76.56 35.21 Crude oil D 1.89 0.80 0.05 45.80 DI-3 10.84 10.84 10.85 N / A DI-4 N / A N / A N / A 8.75 PPD-3 0.20 0.20 0.20 0.20 Polymer G Concentrate 9.85 5.67 4.93 6.02 Acryloid (trademark) 954 1.09 N / A N / A N / A Nordel (R) 4523 N / A 8.45 N / A 4.03 Nordel (R) 4549 N / A N / A 7.42 N / A

Example 29 30 31 32 Test result KV (cSt) 10.76 10.58 10.46 10.57 CCS at 25 ° C. (cP) 3,170 3,330 3,230 N / A CCS at 20 ° C. (cP) N / A N / A N / A 2,825 HTHS (cP) 3.08 3.06 3.06 3.11

The data shown in Tables VII (A and B) demonstrate that polymer blends containing SLEP can function as VI enhancers in lubricating oil compositions that meet the 5W-30 and 10W-30 SAE SH classification criteria.

Example 33-36

In DI-3, and either PPD-3 (Examples 34 and 36) or PPD-1 (Examples 33 and 35), and in Polymer G (Examples 33 and 34) or Polymer J (Examples 35 and 36). As in Examples 22-25, except that one concentrate was used. The physical property test results also included a scanning Brookfield (SB) temperature measured at 30,000 centipoises (cP) according to ASTM D-5133. SAE SH criteria for the 5W-30 blend include an SB temperature of -30 ° C. The amounts of ingredients and the test results are shown in Tables VIIIA and VIIIB.

Example 33 34 35 36 Formulation 5W-30 5W-30 5W-30 5W-30 Ingredient / weight% Crude Oil C 72.44 72.40 75.71 75.72 Crude oil D 5.14 5.17 0.56 0.56 DI-3 10.85 10.84 10.86 10.86 PPD-1 0.20 N / A 0.20 N / A PPD-3 N / A 0.20 N / A 0.20

Example 33 34 35 36 Polymer G Concentrate 11.38 11.39 N / A N / A Polymer J Concentrate N / A N / A 12.67 12.66 Test result KV (cSt) 10.76 10.58 10.43 10.43 CCS (cP) 3,170 3,330 3,570 3,570 HTHS (cP) 3.08 3.06 3.01 3.01 SB (℃) -26.1 -30.1 -35.3 -35.5

The data in Table VIII show that low temperature viscosity improved by PPD including dialkyl fumarate (Examples 34 and 36) is obtained and results are satisfactory for either PPD but the effect is due to the EP copolymer (Example 36). More pronounced by the ethylene octene copolymer (Example 34). When all other criteria for the SAE SH 5W-30 classification are met by the formulation of Example 33, those skilled in the art should be able to modify the formulation of Example 33 so that it also meets the SB criteria.

Examples 37 and 38

The methods of Examples 1-7 were carried out using polymer H sheared (example 38) and not sheared (example 37), and crude oil A. Polymer H had I ₂ of 1.72 g / 10 min (min) before shear and 4.20 g / 10 min after shear. The polymer was sheared at 200 revolutions per minute (rpm) for 20 minutes at 250 ° C. in a high speed mixer (Haake) in a paired rotor. Instead of the high speed mixer, other known mechanical devices such as extruders were used. In each example, the shear stability index (SSI) was also measured. SSI was measured according to the following equation.

SSI = 100 x (V _o -V _s ) (V _o -V _b )

Where V _o is the KV of the solution before testing at 100 ° C., V _s is the KV of the solution after testing at 100 ° C., and V _b is the KV of crude oil. Low SSI values are considered as an indicator that the polymer-oil solution has higher shear stability than polymer-oil solutions with higher SSI values. The crude oil had a KV of 4.009 before the test (Example 1). Example 37 had V _o of 6.55 cSt, V _s of 5.81 cSt and SSI of 29.1. Example 38 had V _o of 5.94 cSt, V _s of 5.64 cSt, and SSI of 15.5.

The data of Examples 37 and 38 demonstrate that shear stability testing of the polymer-oil solution formed by shearing before adding SLEP to oil improves the shear stability of the solution (lower SSI).

As described above, similar results as shown in Examples 1 to 38 can be expected when the polymer is sheared after blending the polymer-oil solution as well as other SLEP and oily materials.

Example 39

Polymer G was grafted with maleic anhydride using the method shown in US Pat. No. 5,346,963. In particular, polymer G was fed at a rate of 750 pounds per hour on a Werner-Pfleiderer ZSK70 co-rotating twin screw extruder. Extruder the following zone barrel temperature at the extruder screw speed of 260 rpm: zone 1-water cooling; Zone 2 = 370 ° F. (188 ° C.); Zone 3 = 380 ° F. (193 ° C.); Zone 4 = 430 ° F. (221 ° C.); Zone 5 = 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 die = 360 ° F. (182 ° C.) to provide a polymer melt temperature of 446 ° F. (230 ° C.). Maleic anhydride (MAH) was fed by means of a metering pump to the end of zone 1 of the extruder through an injection nozzle at a rate of 14.5 pounds per hour. Peroxide, LUPERSOL® 130, manufactured and sold by Atochem at 1.5 pounds per hour by metering pump with (2.5-di (t-butyl peroxy) hexin-3 Feed through the injection nozzle to the end of zone 4 of the extruder The extruder was maintained at a vacuum level of mercury ≧ 26 inch to facilitate devolatization of solvents, unreacted MAH and other contaminants MAH into polymer G The incorporation rate of was 1.2% The extrudate from the extruder was pelleted through water pelletization at a temperature of 60 ° F. (16 ° C.).

The MAH-grafted SLEP was then reacted by blending with a development monofunctional amine terminated polybutylene oxide compound having an M _w of 1500 and manufactured by Dow Chemical Company. Blending and reaction took place in a Werner-Pfleiderer ZSK-30 co-rotating twin screw extruder operated at a screw speed of 150 rpm, a throughput of 20 lb / hour and an extrusion temperature of 190 ° C. An amine compound was added to the polymer grafted with a ratio of amine compound to polymer of 0.15 to 1.

The grafted and reacted polymer formed was tested as a VI enhancer using the same crude oil and method as in Examples 1-8. KV values are as follows: 60.45 cSt at 40 ° C. and 9.706 cSt at 100 ° C. The polymer KV, which contributed to KV at 100 ° C., was 5.611 cSt.

Example 39 provides satisfactory results when SLEP is grafted with unsaturated organic compounds such as maleic anhydride and then used as VI enhancers for oily compositions when further reacted with functionalized compounds such as amine terminated compounds. Indicates.

Examples 2 to 39 all show that addition of SLEP improves oil composition VI. Other oily composition properties can be optimized by blending changes. Similar results can be expected with other SLEP, unsaturated organic compounds and functionalized compounds, all of which have been described above.

Claims (24)

a) melt flow rate, I ₁₀ / I ₂ ≧ 5.63; b) molecular weight distribution defined by the following formula (1), M _w / M _n ; And <Equation 1> M _w / M _n ≤ (I ₁₀ / I ₂ ) -4.63 c) substantially characterized by having a critical shear rate at the onset of surface melt fracture that exceeds 50% of the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having similar I ₂ and M _w / M _n . Oily composition which consists of linear ethylene polymer viscosity adjustment effective amount and oily substance. The method of claim 1 wherein the substantially linear ethylene polymer is used in place of the substantially linear ethylene polymer and grafted to at least about 0.01% by weight (based on the weight of the grafted ethylene polymer) with at least one ethylenically unsaturated organic compound. Oily composition, which is the basic raw material of the grafted polymer. The oily composition of claim 1 or 2, wherein the graft polymer has an ethylene content of 20 to 80% by weight based on the polymer weight. The oily composition of claim 1 or 2, wherein the substantially linear ethylene polymer is further characterized as being a copolymer of ethylene and a C ₃ -C ₂₀ α-olefin. The oily composition of claim 1 or 2 wherein the substantially linear ethylene polymer is an interpolymer consisting of copolymerized units of ethylene, C ₃ -C ₂₀ α-olefins and one or more diene monomers. The oily composition of claim 5 wherein the diene monomer is selected from dicyclopentadiene, 1,4-hexadiene, piperylene and 5-ethylidene-2-norbornene, 1,7-octadiene and vinyl norbornene. . The oily composition of claim 1 or 2, wherein the molecular weight distribution is less than 5. The oily composition of claim 1 or 2, wherein the melt flow ratio is 6.5 to 15. The unsaturated organic compound of claim 2, wherein the unsaturated organic compound is a carboxylic acid, carboxylic anhydride, carboxylic acid ester, carboxylic acid ether, carboxylic acid amine, carboxylic acid amide and succinimide, unsaturated epoxy compound, vinyl substitution. Oily composition selected from heterocyclic compounds, vinyl amines, vinyl oxazolines and vinyl epoxies. The oily composition of claim 9 wherein the unsaturated organic compound is a carboxylic acid selected from maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, α-methyl crotonic acid and cinnamic acid. 10. The oily composition of claim 9 wherein the unsaturated organic compound is maleic anhydride. The oily composition according to any one of claims 9 to 11, wherein the unsaturated organic compound is further reacted with a reactant which is an acid, an amine or an alcohol. The substantially linear ethylene polymer of claim 12 wherein the reactant is an amine selected from aliphatic and heterocyclic organic nitrogen compounds containing at least one primary amine and / or at least one secondary amine, and optionally at least one tertiary amine group. Oily composition that will react with. The oily composition of claim 13, wherein the amine is selected from cyclic or higher homologs of polyethylene polyamines, alkylene polyamines, alkylene polyamines, amine terminated polyoxyalkylene compounds and hydroxyalkyl polyamines. 13. The oily composition of claim 12, wherein the alcohol is an aliphatic polyhydric alcohol having 100 or less carbon atoms and hydroxyl groups 2 to 10. The oily composition of claim 15, wherein the alcohol is alkylene glycol, polyglycol, or an aliphatic alcohol having up to 20 carbon atoms. 10. The oily composition of claim 9 wherein the unsaturated organic compound is vinylpyridine or n-vinyl-2-pyrrolidone. The oily composition according to claim 1 or 2, wherein the oily material is selected from hydrocarbon oils, alkylene oxide polymers and derivatives thereof based lubricants, oils of esters of dicarboxylic acids, and silicon based oils. 19. The oil-based material according to claim 18, wherein the oily substance is liquefied petroleum, paraffinic, naphthenic and mixed paraffinic-naphthenic type lubricants, oils derived from coal and shale, poly (α-olefin) oils, vegetable oils, animal oils. Oily composition selected from polyoxyalkylene polymers prepared from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils, and silicate oils. The oily composition of claim 1 or 2, wherein the amount of substantially linear ethylene polymer is gelled or thickened, making it suitable for use in preparing greases, cable filling compounds or cosmetic materials. The oily composition of claim 1 or 2, further comprising an amount of the pour point depressant sufficient to enhance the low temperature properties of the composition as compared to similar compositions lacking the pour point depressant. 3. Hydrogenated polyisoprene, styrene / butadiene block polymer, styrene / isoprene block polymer, hydrogenated styrene / butadiene block polymer, hydrogenated styrene / isoprene block polymer, grafted styrene / butadiene block polymer, grafted styrene Oily composition further comprising at least one polymer selected from isoprene block polymer, polyalkylmethacrylate, polyalkylacrylate, ethylene polymer, and acrylate / methacrylate copolymer. The oily composition of claim 1 wherein at least a portion of the substantially linear ethylene polymer is replaced with a substantially linear ethylene polymer that is shear modified to increase shear stability. An oil addition concentrate composition consisting of a mineral oil diluent and from 5 to 60% by weight of the substantially linear ethylene polymer of claim 1.