CN1214078A - Substantially linear ethylene/alpha-olefin polymers as viscosity index improvers or gelling agents - Google Patents

Abstract

Substantially linear ethylene polymers, such as ethylene/octene copolymers and ethylene/propylene/diene modified polymers, when added in a viscosity modifying amount to an oleaginous material, such as a lubricating oil, provides the material with a viscosity index that exceeds that of the material alone. The substantially linear ethylene polymers, prepared by constrained geometry catalysis, may be grafted with one or more unsaturated organic compounds, such as maleic anhydride, that contain ethylenic unsaturation. The grafted polymer may be further functionalized by reactions with, for example, an alcohol or an amine compound. The substantially linear ethylene polymers, when subjected to shearing action either before or after addition to an oleaginous material, improve shear stability of the oleaginous material. The substantially li near 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 filling coumpounds and cosmetics. In addition, the substantially linear ethylene polymers provide effective results when blended with other components of conventional oleaginous material compositions.

Description

Substantially linear ethene/alpha-olefinic polymer as viscosity index improver or jelling agent

The application requires U.S. Provisional Application that 1996.8.30 submits to number 60/024,913

The rights and interests of the U.S. Provisional Application of submitting to 1996.3.8. number 60/013,052.

The present invention relates in general to the oily composition that contains at least a ethylene/alpha-olefin interpolymer as viscosity index (being designated hereinafter simply as VI) improving agent or jelling agent.The present invention more specifically relates to such composition, and wherein multipolymer is gone up substantially and is line style, especially has even branching and distributes and narrow molecular weight distributions (MWD).This interpolymer can come modification so that other function to be provided by the further reaction of a step or multistep.One is made us interested especially this reaction and comprises that the olefines unsaturated organic compound as maleic anhydride is grafted on this interpolymer, and resulting graftomer further reacts as amine and so on additional compounds with one or more again.

When the VI improving agent is joined go in the oily composition after, but composition viscosity at high temperature people or improve to some extent more.Improving of high temperature viscosity and do not have other variations to be referred to as VI to improve.

VI is an experience number that is used for measuring lubricant viscosity and temperature stability.High VI be illustrated in heat up or high temperature under resistance rare, low VI then is illustrated in thinning tendency under such temperature.

The performance index of VI improving agent comprise thickening capabilities, shear stability and chemistry and thermo-oxidative stability, and all these are relevant with polymer architecture.Ability that the given VI improving agent of the sticking behavior of institute's phase high temperature side is provided depends on the factor such as polymericular weight, concentration and the chemical structure relevant with the chemical structure of oily composition.Shear stability depends on polymericular weight and MWD to a great extent.

Existing various oil-soluble polymers is used as the VI improving agent of lubricating oil.The illustration polymkeric substance comprises hydrogenated styrene/diene polymer, hydrogenated polyisoprene, polyalkyl methacrylate, and as ethylene/propene copolymer and ethylene/propylene/diene terpolymers and so on ethylene/alpha-olefin copolymer and these copolymers different derivatives with terpolymer.These polymkeric substance can be used to prepare those and satisfy SAE (Society of automotive engineers) high temperature and the sticking multigrade oil (as 10W-30) that requires of low temperature survey simultaneously.

At least some oil-soluble polymers is for also being useful as the thickening material of the oil-containing material of mineral oil, paraffin oil and naphthenic oil or jelling agent as other so that preparation is suitable as the composition that lubricating grease or cosmetic use.

Open based on the also existing document of the VI improving agent of the ethylene alpha olefin copolymer of preparation in the presence of metallocene catalyst, as USP 5,151,204 and USP5,446,221.

Summary of the invention

One aspect of the present invention is the oily composition of the substantially linear ethylene polymers (hereinafter to be referred as SLEP) of a kind of oil-containing material and viscosity modified significant quantity, and this SLEP is characterised in that: (ⅰ) melt flow ratio, I ₁₀/ I ₂〉=5.63; (ⅱ) MWD, M _w/ M _n, by equation M _w/ M _n≤ (I ₁₀/ I ₂)-4.63 definition; (ⅲ) begin to occur the critical shear rate of surperficial melt fracture (hereinafter to be referred as OSMF) at least than similar I is arranged ₂And M _w/ M _nPolymer of linear olefin big by 50% at the critical shear rate of OSMF.

First related fields are that the quantity of polymkeric substance is to make composition be suitable for preparing the effective thickening or the gelling consumption of lubricating grease or cosmetic.

Second related fields be, oily composition also contains a kind of pour point reducer (hereinafter to be referred as PPD), and its consumption is enough to make its cryogenic properties to be improved than the cryogenic properties of the similar composition that does not conform to PPD.

The 3rd related fields are, are substituted by the SLEP that shears modification to small part SLEP, and whereby, the shear stability of oily composition is improved.The polymer-modified suitable method for making of this shearing is: SLEP is applied is enough to improve its melt index (I ₂) shearing action.

The 4th related fields are, this oily composition also comprises at least a polymkeric substance except that comprising SLEP, be selected from hydrogenated polyisoprene, phenylethylene/butadiene block polymer, styrene/isoprene block polymer, hydrogenated styrene/butadiene block polymkeric substance, hydrogenated styrene/isoprene block polymkeric substance, graft phenylethene/butadiene block polymkeric substance, graft phenylethene/isoprene block polymkeric substance, polyalkyl methacrylate, polyalkyl acrylate, ethene polymers and acrylate/methacrylate polymkeric substance.

Each aspect of above-mentioned aspect and related fields comprises that again 3 further related fields (a) are to (c).Aspect (a), the ethylene content among the SLEP is in 20 to 80 weight percentage scopes of polymer weight.Aspect (b), but SLEP is at least the unsaturated organic compound that contains the grafting part of 0.01 weight percentage of SLEP weight after the grafting in the grafting.Aspect (c) contains the grafting SLEP of active part and the compound of hydroxyl or amidine functional group and further reacts.The illustration compound comprises alcohol, and especially aliphatic saturated monohydroxy alcohol, acid and amine is primary amine particularly.

" segmented copolymer " comprises diblock polymer, triblock polymer, radial block or radial block polymer and taper interpolymer.

" ethene polymers " means ethylene/alpha-olefin copolymer or diene modified ethylene/alpha-olefin copolymer.The illustration polymkeric substance comprises ethylene/propene (hereinafter to be referred as EP) multipolymer, ethylene/octene (hereinafter to be referred as EO) multipolymer and ethylene/propylene/diene modification (hereinafter to be referred as EPDM) interpolymer.

" substantial linear " means that per 1000 backbone c atoms are replaced by 0.01 to 3 long-chain branch in the main chain of polymkeric substance.

" long-chain branch " or " LCB " means at least 6 carbon atoms of chain length.At this more than length, carbon-13 nmr (C-13 NMR) no longer can distinguish and definite chain in carbonatoms.In some cases, chain length can be the same with the main polymer chain that it is connected long.

" interpolymer " is meant at least the polymkeric substance by two kinds of monomer polymerizations.It comprises, for example multipolymer, terpolymer and tetrapolymer.It especially comprises by ethene and at least one comonomer, is typically 3 to 20 carbon atom (C ₃～C ₂₀) the polymkeric substance that makes of the comonomer polymerization of alpha-olefin.The illustration alpha-olefin comprises propylene, butene-1, hexene-1,4-methylpentene-1, heptene-1, octene-1 and vinylbenzene.C ₃～C ₁₀Alpha-olefin be desirable.Preferred multipolymer comprises EP and ethylene-octene copolymer.The illustration terpolymer comprises ethylene/propylene/octene terpolymer and ethene, C ₃～C ₂₀Alpha-olefin with such as Dicyclopentadiene (DCPD), hexadiene-1,4, pentadiene-1,3,5-ethylidene norbornene-2, and so on the terpolymer of diene.

Substantial linear ethylene alpha-olefin interpolymers (" SLEP " or " substantially linear ethylene polymers ") can be by as U.S. Pat P5, and 272,236 and 5,278,272 described preparations, the relevant portion of these two pieces of patents is listed as reference of the present invention.USP5,272,236 (walking to 6 hurdles, 28 row from 5 hurdles 67) have been narrated through use at least one reactor, but fair a plurality of reactors, in the process that enough produces stepless control polymerization production SLEP under the temperature and pressure of the SLEP of phase character to some extent.Polymerization process preferably adopts the solution polymerization of using how much limited catalyst technologies down at 20 to 250 ℃.

The limited catalyzer of suitable geometry is at USP5, and 272,236 6 hurdles 29 walk to 13 hurdles, 50 ranks and go out.Can describe this class catalyzer like this: promptly it comprises a kind of metal complexes, the metal of the 3rd～10 family or group of the lanthanides in this title complex containing element periodictable, and the delocalized pi-bond part of inducing part to replace by a constraint.Title complex has the constrained geometry around atoms metal, and causing between the center of delocalized pi-bond part of replacement and at least one all the other substituting group center with this metal is that the angle on summit lacks this constraint and induces the respective angles of similar title complex of substituent similar π key part little than containing.If such title complex comprises the delocalized pi-bond part more than a replacement, then such part is only arranged is ring-type, the delocalized pi-bond part that replaces to each atoms metal of title complex.Catalyzer also further contains a promotor that plays activation as three (pentafluorophenyl group) borane.USP5,272,236 6 hurdles 57 walk to 8 hurdles, 58 row and USP5, and 278,272 7 hurdles 48 walk to 9 hurdles, 37 row the specific catalyst title complex have been discussed.About the concrete technology of these catalyzer general technologies and these special catalysts is made reference of the present invention by receipts.

If it is narrow comonomer distribution that SLEP is characterised in that the words of its narrow MWD and interpolymer.The feature of SLEP also is it in low residual volume, specifically refers to the residual content of the low-molecular-weight oligomer that produces in relict catalyst, unreacted comonomer and the polymerization process.The further feature of SLEP is the processibility that provides by the control molecular configuration, even if its MWD is narrower than common olefin polymer.

Preferred SLEP has the feature of a series of distinctnesses, and the one, the more preferably ethene of 30 to 70 weight percentage of 20 to 80 weight percentage is arranged in the co-monomer content, all the other then are one or more comonomers.The SLEP co-monomer content can be measured with method B or the ASTM D-3900 of infrared spectra (IR) according to ASTM (American society for testing materials) (hereinafter to be referred as ASTM) D-2238.Co-monomer content also can be determined by C-13 NMR spectrum.

Another distinct characteristic of SLEP comprises I ₂With melt flow than (MFR or I ₁₀/ I ₂).According to ASTM D-1238,190 ℃/2.16Kg condition (condition E originally) down the I2 of desirable interpolymer be 0.01～500g/10min, and serve as better with 0.05～50g/10min.According to D-1238, the MFR of SLEP 〉=5.63, and be advisable with 6.5～15,7～10 is better.Concerning SLEP, I ₁₀/ I ₂Ratio is the sign of LCB degree, so I ₁₀/ I ₂Ratio is big more, and just the LCB degree of polymkeric substance is high more as much as to say.

Another distinct characteristic of SLEP is the MWD (M that it is measured by gel permeation chromatography (GPC) _w/ M _nOr " polydispersity index ").M _w/ M _nDefine by following equation:

M _w/M _n≤(I ₁₀/I ₂)-4.63

Wish MWD＞0 and＜5, particularly between 1.5 to 3.5, be preferably 1.7 to 3.

Surprisingly, evenly the MFR of branching SLEP is irrelevant with its MWD basically.This is to have formed tangible contrast with even branching of common line style and the assorted branching ethylene copolymer of line style, and the latter must increase MWD to improve MFR.

SLEP is further characterized in that the critical shear rate ratio of its OSMF has similar I ₂And M _w/ M _nThe OSMF critical shear speed of polymer of linear olefin big by 50%.

The SLEP that satisfies above-mentioned standard comprises that for example the trade mark is the polyolefin elastomer of ENGAGETM and other the polymkeric substance by how much limited Catalyst Production of road elastomerics limited-liability company of Du Pont usefulness.

SLEP can join in the oily composition under such as grafted modification or unmodified situation.If use graft modification, gained grafting SLEP also can through or without one go on foot or the additional reaction of multistep after join in the oily composition again and go.Also can grafting again after SLEP has joined in the oily composition.

Anyly contain the unsaturated structure of at least one ethylene linkage (at least one two keys) and unsaturated organic compound that can be grafted on the SLEP all can be used to make the SLEP modification.The illustration unsaturated compound comprises heterogeneous ring compound, the vinyl of vinyl ether, vinyl substituted

Azoles quinoline, vinyl amine, vinyl epoxide, unsaturated epoxide, unsaturated carboxylic acid and these sour acid anhydrides, ether, amine or ester.Representational compound comprises the alkylphenol and the glycidyl methacrylate of toxilic acid, fumaric acid, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, tiglic acid and styracin and their acid anhydride, ester or ether derivant, vinyl substituted.Suitable unsaturated amine comprises that those contain the aliphatic series and the heterocycle organic nitrogen compound of at least one two key and at least one amido (at least one one-level, secondary or tertiary amine).Representational example comprises vinyl pyridine and vinyl pyrrolidone.Maleic anhydride is preferred unsaturated organic compound.

The content of unsaturated organic among grafting SLEP house thing be 〉=the 0.0l weight percentage of polymkeric substance and organic compound weight sum, preferably 〉=0.05 weight percentage.The maximum level of unsaturated organic compound may change to some extent, but is typically≤10 weight percentage, be preferably≤5 weight percentage, and≤2 weight percentage are better.

Can use any known technology, such as those at USP3,236,917 and USP5, the technology described in 194,509 is grafted to unsaturated organic compound on the SLEP, these correlation techniques are taken in the part of the present invention as reference of the present invention.At USP3, in 236,917, the polymkeric substance of EP multipolymer and so on joined in the double-roll type mixing machine and under 600 ℃ of temperature mix.Then maleic anhydride and so on unsaturated organic compound is added with benzoyl peroxide and so on radical initiator, and the component mixing is finished until grafting at 30 ℃.

USP5,194,509 disclose a kind of USP3 of being similar to, 236, the patent of the method for 9l7, but its temperature of reaction higher (210 to 300 ℃, preferred 210 to 280 ℃) and need not or the consumption of restraint of liberty base initiator.USP5,194, the 509 special no peroxide grafted that propose unsaturated carboxylic acid, acid anhydride and derivatives thereof can be common as Werner ﹠amp; The ZDSK53 twin screw extruder of Pfleiderer or some other as carrying out in Brabender reactor and so on the common unit.Ethene polymers and treat grafted monomer in case of necessity thoroughly mixes under 140 ℃ or higher temperature, then in high temperature (from 210 to 300 ℃, preferred 210 to 280 ℃, 210 to 260 ℃ better) reaction down.Still this puts unimportant treating monomer that grafting is got on to introduce reactor after before the ethene polymers fusion.The used concentration for the treatment of grafted monomer is 0.01～0.5 weight percentage of weight ethylene polymer, and serves as preferred with 0.05～0.25 weight percentage.

USP4 discloses in 950,541 and a kind ofly substitutes and be preferred grafting method, and its correlation technique is made reference of the present invention.What this alternative method was used is that the twin screw devolatilizing extruder is as mixing device.SLEP and unsaturated organic compound mix in the presence of the melt temperature of reactant and radical initiator and reaction in extruding machine.Preferably unsaturated organic compound is injected in the district that keep-ups pressure of extruding machine.

Second kind of preferred alternate grafting method is USP4,810,754 related solution graftings, and its correlation technique is also as reference of the present invention.This method comprises, in the kind solvent of mineral oil initiator, treat the grafted monomer and, under the temperature of enough initiation grafting reactions, react then as EP polymkeric substance and so on mixed with polymers.A kind of such temperature is 190 ℃.

The SLEP of graft modification can with material modified generation further reaction and then improve and contain grafting go forward side by side dispersiveness, low temperature viscosity and the oxidation/thermostability of oxygenant in the oily composition of SLEP of single step reaction or combustion by-products introducing one or more functional groups.The material modified alcohol that comprises of illustration, long-chain (the highest typical 36 carbon atoms) lipid acid and amine.The example of alcohol includes 〉=aliphatic series and the aromatic alcohol of 2 carbon atoms, be preferred greater than the alcohol of 12 carbon atoms, less than the alcohol of 36 carbon atoms better.Representational pure and mild longer chain fatty acid comprises the pure and mild acid of decyl, lauryl and octadecyl.The example of amine comprise those contain 〉=one-level and/or 〉=secondary and randomly 〉=one aliphatic series and the heterocyclic nitrogen compounds of a tertiary amine.Some amine had both contained aliphatic series such as Triethylenetetramine (TETA), tetren and polyethylene polyamine (such as the Ethyleneamine E-100 of commercially available Dow Chemical Company) and had also contained heterocyclic moiety.Commercially available polyethylene polyamine is typically the blend or the mixture of linearity, branching and heterocycle ethyleneamines.Representational example comprises that polyethylene (as diethylenetriamine), 3-amino-ethyl imidazoles-1, aminoethylpiperazine, 4-(3-aminopropyl) morpholine and polyoxy alkylene polyamine are (as the Jeffamines that is produced by Huntsman chemical company ^TM).USP5,401,427 have applied for the patent of additional alkohol and amine, and particularly 45 hurdles 40 therein walk to 49 hurdles, 29 row, and correlation technique has been introduced into this patent as a reference.

USP5,401,427 disclose other suitable alkylene polyamines, comprise benzylidene amino, ethyleneamines, butylidene amine, propylidene amine, pentylidene amine, hexylidene amine, inferior heptyl amine, octylene amine, other ring and more high-grade homologue such as piperazine, the aminoalkyl substituted-piperazinyl etc. of polymethylene amine, these amine.These amine comprise, quadrol for example, diethylenetriamine, Triethylenetetramine (TETA), propylene diamine, two (heptamethylene) triamine, tri propylidene tetramine, tetren, the trimethylene diamines, penten, two (trimethylene) triamine, 2-heptyl-3-(2-aminopropyl) tetrahydroglyoxaline, the 4-methylimidazole quinoline, 1,3-two (2-aminopropyl) tetrahydroglyoxaline, pyrimidine, 1-(2-aminopropyl) piperazine, 1,4-two (2-amino-ethyl) piperazine, N, N '-dimethylaminopropylamine, N, N '-dioctyl ethamine, N-octyl group-N '-methyl ethylene diamine and 2-methyl isophthalic acid-(the amino butyl of 2-) piperazine.The term polyamines is contained the substituent hydroxyalkyl alkylene polyamine of one or more hydroxyl alkane on the hydroxyalkyl polyamines, particularly nitrogen-atoms.The example of the polyamines that this class hydroxyalkyl replaces comprises N-(2-hydroxyethyl) ethylene diamine, N, and N-two (2-hydroxyethyl) ethylene diamine, 1-(2-hydroxyethyl) piperazine, monohydroxy propyl group replace diethylenetriamine, dihydroxypropyl replaces tetren and N-(3-hydroxyl butyl) tetramethylene-diamine.

USP5, disclosed pure and mild polyvalent alcohol comprises and containing≤aliph polyols of 100 carbon atoms and 2 to 10 hydroxyls in 401,427.As required, these alcohol replace or unsubstituted, be obstructed or be not obstructed or side chain or straight chain.Typical alcohol is as ethylene glycol, propylene glycol, 1, ammediol, butyleneglycol and so on aklylene glycol, and contain the aklylene glycol and the multi alkylidene diol of 2 to 8 carbon atoms as pure and mild other of polybinary of glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, dibutylene glycol, three butyleneglycols and so on.Preferably contain≤Fatty Alcohol(C12-C14 and C12-C18) of 20 carbon atoms comprises glycerine, tetrahydroxybutane, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, glyconic acid, Glycerose, glucose, pectinose, 1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2.5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-trihydroxybutane, 1,2,4-trihydroxybutane, 2,2,6,6-four (methylol) hexalin and 1,10-decane glycol.

After joining the graft modification SLEP of the SLEP of SLEP, graft modification and/or further reaction in different base oils or the oil-containing material, compare with the oil-containing material of the SLEP of the graft modification of SLEP that does not contain this SLEP or this graft modification or this further reaction, at least a index has been improved in VI, dispersiveness, stability and the indexs such as gelling or thickening of this kind oil-containing material.

The oil-containing material or the base oil that are suitable in the lubricant formula can comprise with coming from not refining, refining and (regeneration) oil of re-refining that make in natural and synthetic source.Illustration oil-containing material comprises different hydrocarbon ils, the lubricating oil based on alkylene oxide polymer and derivative thereof, diprotic acid ester oil or the silicon-based oil of any formation present composition.These oil natural or synthetic, comprise lubricating oil and fuel oil.The example of suitable oil comprises the oil that kerosene, paraffin lubricating oil, cycloalkanes lubricating oil and paraffin-naphthenic mixed type lubricating oil, coal or shale refines, poly-(alpha-olefin) oil, vegetables oil, animal oil, by polyoxyalkylene polymers or multipolymer, poly-alkyl, the poly-aryl of one or more oxyethane, propylene oxide or butylene oxide ring, tetrahydrofuran (THF) preparation, gather alkoxyl group or poly-aryloxy silicone oil and silicic acid ester oil.Also can use these oily blends.USP5,446,221 8 hurdles 47 walk to the Additional Information that 10 hurdles, 34 row have disclosed different oil-containing materials, and this is also as reference of the present invention.

Be that not grafted, grafting or grafting are gone forward side by side the SLEP of single step reaction when being used as VI properties-correcting agent in the oily composition when no matter, composition also can contain the additive of several dissimilar increases to the characteristic that material requires that contains this composition.These additives can comprise traditional VI improving agent, generally comprise dispersion agent, washing composition, antioxidant, anti-wear additive and withstand voltage dose, friction modifiers, PPD, corrosion inhibitor, ashless dispersant (containing boron derivative as polyisobutenyl succinimide and its) and antifoaming agent.The general amount that exists of these additives is 0.001 to 20 weight percentage with respect to weight of oil.Tradition VI improving agent comprises high molecular hydrocarbon polymer, polyalkyl methacrylate and contains unsaturated C ₃To C ₈The polyester of the copolymerization units of monobasic and di-carboxylic acid.Additive can enriched material or dispersion liquid in oil or the adding of undiluted form.

In preparation formulated oil formulation, the additive of introducing is the form that contains active ingredient concentration 5 to 80 weight percentage in the oil usually.Adopt enriched material to make differing materials deal with dissolving or the dispersion of the less and short additive of difficulty in formulation.

PPD can reduce lubricating oil and flow or dumpable temperature.Such PPD is that everybody is familiar with.Those additives that typically can be used for improving the lubricating oil low-temperature fluidity are dialkyl fumarate vinyl acetate copolymer, polymethacrylate (USP2,091,627 and 2,100,993) and naphthalene wax (USP2,174,246).

When preparation lubricating grease, be applied to the electric wire and cable head with material or thixotroping jelling agent in no matter be not grafted, grafted or connect skill go forward side by side single step reaction SLEP when joining in the oily composition as thickening material or jelling agent, it can be defined in those adopts enriched material as what use in the lubricating oil oily composition, and any or all additive is used in combination.The electric wire and cable head purposes of illustration comprise common use such as potting material, water-proof material and insulating material.These are used optical cable is particularly important.

When such polymkeric substance being joined in the oily composition as thickening material or jelling agent with the time as makeup, ointment or externally applied agent, they can with other be used in combination as spices, tinting material, dyestuff, stablizer, tensio-active agent, tenderizer and oil (such as Oleum Cocois).

Oily composition with improved cryogenic properties comprises the SLEP of oil-containing material, PPD and improvement viscosity significant quantity.When SLEP be essentially no setting (it can contain≤6% degree of crystallinity, be advisable with 3%, more preferably≤1% but 〉=0 better) time, as long as the beginning Tc (T of contained wax in the oil-containing material _c) T of institute's content of wax in SLEP not _cIn the scope, can use any common PPD.When SLEP is hypocrystalline (degree of crystallinity 6 to 25% serves as preferred with 6 to 20%, and 6 to 16% is better), add certain preferred PPD, promptly the multipolymer of fumaric acid di n-alkanyl ester and vinyl acetate just can obtain satisfied cryogenic properties.Multipolymer as PPD is suitable for by USP4, and 839,074 described preparations, related content also joins the present invention as a reference.

USP4, a part of content in 839,074 is carried, earlier diprotic acid esterification such as fumaric acid, and then with as vinyl acetate and so on polymerisable monomer compound react or copolymerization, adopt traditional radical polymerization technique to obtain unregulated polymer.Suitable polymerization is carried out under inert hydrocarbon solvent (as hexane or heptane), oxygen-free environment (as nitrogen atmosphere) and 65-150 ℃ of temperature.Though preferably with the complete esterification of all carboxyls of diacid monomer, the partial esterification esterifying carboxyl group esterification of 70 molecular fractions (but 〉=) is also enough.Typical esterification is carried out with alcohol mixture, used pure a little branching, but with straight chain C ₁To C ₂₀Fatty Alcohol(C12-C14 and C12-C18) be preferred, C ₆To C ₂₀Fatty Alcohol(C12-C14 and C12-C18) is better.

It is believed that, hypocrystalline SLEP can be used effect fine with fumaric acid di n-alkanyl ester/vinyl acetate copolymer, its (measuring with differential scanning calorimetric (DSC)) peak crystallization temperature is different from this temperature of institute's content of wax in the oil-containing material, thereby contained wax will as expectation cocrystallization not take place in SLEP and the oil-containing material.Because the peak crystallization temperature of oil-containing material is because of obviously changing such as factors such as wax contents, every kind of combination of oil-containing material, hypocrystalline SLEP and fumaric acid di n-alkanyl ester/vinyl acetate copolymer must be accepted the evaluation to its cryogenic properties.

Composition of the present invention is modification (as grafting, the laggard single step reaction of grafting or not further reaction) or unmodified SLEP to be joined in oil or the oily composition with common blending technology form.Polymkeric substance can add separately or with the oil concentrate form.Generally, the scope of the amount of polymers that adds is 0.1 to 20 weight percentage (dry polymeric) of weight of oil of being modified, 0.2 modification is preferred to viscosity to the dry polymeric of 5 weight percentage, when doing thickening or gelling and using then the dry polymeric of 5-15 weight percentage for preferred.

In the batching of preparation lubricating oil, additive normally adds with the enriched material form of active ingredient in hydrocarbon ils (as mineral lubricating oils) or some other suitable solvents.The active component content of typical case's enriched material is 5 to 80 weight percentage of enriched material gross weight.In the process of refining lubricant of allotment such as crankcase motor oil, the normally every weight part additive of enriched material is with 3 to 100 weight parts, dilutes with the lubricating oil of 5 to 40 weight parts sometimes.Used enriched material makes the operation of different additive become more or less freely, thereby makes additive form solution or dispersion system easily in final lubricant.As an example, typical VI improving agent is to use at the enriched material of lubricating oil 5 to 20 weight percentage.

The present invention partly relates to VI improved oil-containing or oil compositions, particularly comprises lubricating oil and as the oil compositions of the SLEP of VI improving agent.Compare with the oil compositions that does not contain such VI improving agent, the high temperature viscosity that contains the oil compositions of such VI improving agent has improved.Being set out by the VI improving agent also to derive other character or function, as the dispersiveness to fuel oil and lubricating oil composition.Derived polymers comprises such as (pressing as above and USP5,346,963 3 hurdles 67 walk to that 4 hurdles 24 row is described to be prepared) maleic anhydride grafted SLEP and so on grafting SLEP, it can further react with alcohol or amine, such as USP3,702,300 (4 hurdles 56 walk to 5 hurdles 60 row and relate to alcohol mixture and making such as containing the esterification that maleic anhydride interpolymer and so on contains the carboxyl interpolymer, then with the polyamines residual carboxyl that neutralizes); USP4,089,794 (3 hurdles 37 walk to 4 hurdles 59 row and relate to alkene class unsaturated carboxylic acid materials, as maleic anhydride by solution graft copolymerization on ethylene/alpha-olefin polymer such as EP multipolymer, use polyamines and grafting then polymer reaction); USP4,160,739 (the capable afterreactions that relate to by the carboxyl that reaction provided of non-polymerization polyamines and Malaysia acid or anhydride grafts of 6 hurdle 35-52); Or USP4,137,185 (7 hurdle 4-17 are capable relate in solution grafting the reaction of carboxylic acid material, as the maleic anhydride grafting the reaction of ethylene/alpha-olefin polymer and many (primary amines)); Or as USP4, the grafting shown in 068,056 SLEP of nitrogen compound (4 hurdles 47 walk to hydrocarbon polymer that 5 hurdles 23 row relates to ziegler-natta catalyzed in the presence of oxygen-containing gas with amine compound in 130 ℃ to the 300 ℃ reactions under mixing condition); USP4,146,489 (2 hurdles 49 walk to 3 hurdles 15 row, relate to pyridine of C-vinyl or W-vinyl pyrrolidone by free yl graft polymerization on EP rubber or EPDM rubber; And USP4,149,984 relate to polymerizable heterogeneous ring compound such as vinylpyridine or V-Pyrol RC graft on a kind of in polyolefin polymer solution methacrylic acid C ₈～C ₁₈On the polymkeric substance that the alcohol polyisocyanate polyaddition forms).The relevant technologies of these patents is as reference of the present invention.

The following examples are in order to explanation the present invention, no matter are clearly or implicit restriction but the present invention is not subjected to them.Unless mention in addition, all umber and percentage ratios all are meant for gross weight.

Embodiment

8 kinds of 11 kinds of basic polymkeric substance that are used for embodiment are represented the present invention, and polymer B, E and I do not represent the present invention.Used polymkeric substance is:

A: the ethylene/octene (ethylene content 61.7 weight percentage) that commercially available road elastomerics limited-liability company of Du Pont produces, trade(brand)name EG8200;

B: the ethylene/butylene copolymers that commercially available Exxon chemical company produces, trade(brand)name EXACT ^TM4024;

C: the ethylene/octene (ethylene content 68.2 weight percentage) that commercially available road elastomerics limited-liability company of Du Pont produces, trade(brand)name EG8100;

D: the ethylene/propylene/ethylidene norbornene terpolymer (ethylene content 57 weight percentage) of road elastomerics limited-liability company of Du Pont development;

E: the EP multipolymer TAFMER that commercially available Mitsui petro-chemical corporation produces ^TMP-0480;

F: ethylene/octene (the ethylene content 64.7 weight percentage) EG8150 that commercially available road elastomerics limited-liability company of Du Pont produces;

G: ethylene/octene (the ethylene content 61.0 weight percentage) EG8180 that commercially available road elastomerics limited-liability company of Du Pont produces;

H: the EP multipolymer (ethylene content 53.1 weight percentage) of road elastomerics limited-liability company of Du Pont development and production;

I: the EP multipolymer TAFMER that commercially available Mitsui petro-chemical corporation produces ^TMP-0480;

J: the EP multipolymer (ethylene content 34.7 weight percentage) of road elastomerics limited-liability company of Du Pont development;

K: the ethylene/styrene multipolymer (ethylene content 60 weight percentage) of Dow Chemical Company's development.

Table I A and IB have listed the physical property data of basic polymer A～K.

Table I A

Polymkeric substance/character	??A	??B	????C	???D	??E	??F
							I 2(g/10min) density (g/cm 3) I 10/I 2Compare M w/M nThe critical shear rate of OSMF (second -1)	?5.0 ?0.870 ?7.38 ?1.92 ?5423	?3.3 ?0.878 ?5.8 ?1.95 ?250	?1.0 ?0.870 ?7.99 ?1.96 ?366	?1.72 ?0.860 ?8.13 ?2.36 ?1670	?1.1 ?0.870 ?6.06 ?1.90 ?105	?0.50 ?0.868 ?7.37 ?2.03 ?385

Table I B-polymkeric substance is described

Polymkeric substance/character	??G	???H	???I	??????J	??K
						I 2(g/10min) density (g/cm 3) I 10/I 2Ratio M w/M nThe critical shear rate of OSMF (second -1)	?0.50 ?0.863 ?7.30 ?2.00 ?101	?0.47 ?0.86 ???0 ?8.85 ?1.91 ?134	??0.3 ??0.87 ???0 ??6.10 ??1.95 ??58	????0.64 ????0.855 ????10.5 ????2.62 ????90	?2.0 ?0.974 ?9.5 ?3.1 ?-*

* do not obtain embodiment 1～8

Tested the VI improving agent of 7 kinds of SLEP as base oil A ( the FN1365 100N of Exxon chemical company ) .The enriched material of every kind of SLEP ( polymer concentration 6 weight percentage ) is by making in the base oil that polymkeric substance is dissolved in heat ( 110～120 ℃ ) .Join enriched material in the base oil then and test.The every kind of combination Yi Li ( centistokes is called for short cSt ) that has measured the SLEP of base oil A and base oil A and 0.9 weight percentage is the kinematic viscosity ( KV ) of unit.The KV value is measured according to ASTM D-445 under 40 ℃ and 100 ℃, and the table II has been listed the contribution to the KV under 100 ℃ of these KV values and polymkeric substance.

The table II

The embodiment numbering	Polymkeric substance	KV under 40 ℃ (cSt)	KV under 100 ℃ (cSt)	Polymkeric substance is to the contribution (cSt) of 100 ℃ of following KV
					????1*	Do not have	????19.87	????4.009	????-
????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

* non-embodiments of the invention; * does not have measurement

KV value shown in the table II shows that SLEP can play a kind of oil additives function, makes be improved as the viscosity under 100 ℃ the high temperature after joining it in the oily composition.These KV values also show the thickening capabilities of polymeric additive, and can further be used for calculating the amount that joins as in 5W-30 motor oil and so on full formula lubricating oil.Embodiment 9～13

Carry out the test of 5 kinds of SLEP as the VI improving agent of 5W-30 formulated oil.SLEP enriched material (6 weight percentage) equally prepares by embodiment 2-8.The table III shows the composition of formulation.Use two kinds of different base oils, promptly base oil A and base oil B (the FN1243 150N oil of Exxon chemical company) prepare these formulations.Scattered inhibitor (DI) additive (DI-1) usefulness be the 8482-A1 of ethyl corporation.PPD additive (PPD-1) usefulness be Rohm ﹠amp; Hass exploitation name polyalkylmethacrylatpolymer polymer for XPD-194.

Carry out three tests with the formulation that contains SLEP VI improving agent: 100 ℃ the KV value of being measured as embodiment 1-7; According to the mensuration (CCX) in the bent axle low temperature simulator of SAE J300 appendix under-25 ℃; And measure 150 ℃ of elevated temperature heat shearings (HTHS) down according to ASTM D-4741 and D-4683.The table III also shows the result of these tests.

The table III

The embodiment numbering

??9

??10

???11

???12

???13

Component	Weight percentage	Weight percentage	Weight percentage	Weight percentage	Weight percentage
						Base oil A	????68.97	????67.94	????68.93	????71.29	????78.25
Base 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
						The polymer A enriched material	????16.94	????-	????-	????-	????-
Polymkeric substance C enriched material	????-	????12.23	????-	????-	????-
						Polymkeric substance F enriched material	????-	????-	????10.54	????-	????-
Polymkeric substance G enriched material	????-	????-	????-	????10.88	????-
						Polymkeric substance H enriched material	????-	????-	????-	????-	????10.15
Test-results	????-	????-	????-	????-	????-
						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 of table III show that embodiment 9～13 contains the SAE SH criteria for classification that satisfies the 5W-30 formulated oil according to the formulation of SLEP of the present invention.This standard is, KV is 9.1 to 12.5cSt, CCS＜3500 cP (centipoise, down with) and HTHS＞2.9cP.Embodiment 14～21

To mix with polymkeric substance G (ethylene/octene) and D (ethylene/propylene/ethylidene norbornene terpolymer) solvent neutral oil (SN) and hydrocrackates base oils such as (HC) preparation formulation 5W-30 (embodiment 14,15,18 and 19) (embodiment 16 with 10W-30,17,20 and 21) performance is assessed.The SN base oil is base oil A and B.The HC base oil is the 100R RLOP oil (base oil C) and 240R RLOP oil (base oil D) of ChevronUSA Products Co., Ltd.DI (DI-2) is Paramins ^TMPDN2977, PPD are PPD-1.Polymkeric substance G and D are to add as 6 weight percentage enriched materials among the embodiment 2～8.The test-results that the table IV shows group component and tests equally as embodiment 9～13.The SAE SH criteria for classification of 10W-30 formulated oil is-20 ℃ of mensuration except CCS, and all the other are all the same with 5W-30 formulation standard.

The table IV

The embodiment numbering	?14	???15	??16	?17	????18	????19	??20	??21
									The formulation kind	5W-30 ?SN	?5W-30 ???HC	?10W- ??30 ??SN	10W- ?30 ?HC	?5W-30 ???SN	?5W-30 ????HC	?10W- ??30 ??SN	?10W- ??30 ??HC
Component	Weight percentage	Weight percentage	Weight percentage	Weight percentage	Weight percentage	Weight percentage	Weight percentage	Weight percentage
									Base oil A	74.87	?-	?0.07	??-	?78.71	??-	?7.03	???-
Base oil B	3.65	?-	?82.10	??-	???-	??-	?72.15	???-
									Base oil C	-	?74.40	???-	?48.23	???-	?77.59	???-	?53.03
Base 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
									Polymkeric substance G enriched material	11.40	?11.04	?7.72	?8.15	???-	???-	???-	???-
Polymkeric substance D enriched material	?-	??-	???-	???-	?11.17	?12.14	?10.71	?11.44
									Test-results
KV(cSt)	10.65	?10.52	?10.65	?10.48	?9.24	?9.55	?10.78	?10.49
									-25 ℃ CCS (cP)	3,210	?3,365	???-	???-	?3,600	?3,600	???-	???-
-20 ℃ CCS (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 of table IV show that according to the SAE SH classification fiducial mark of 10W-30 lubricating oil composition, all polymkeric substance and base oil A, B, C and D allotment effect are fine.Polymkeric substance G satisfies all SAE SH criteria for classifications of 5W-30 lubricating oil composition in base oil A, and in base oil B, polymkeric substance G satisfies all standards except HTHS.In base oil A and B, polymkeric substance D only satisfies the KV standard of 5W-30.The author believes that a skilled worker can carry out formulation optimization to satisfy all SAE SH standards of 5W-30 formulation to embodiment 15,18 and 19 easily.Embodiment 22～25

Repeat embodiment 14～21 just wherein letter adopt base oil C and D, DI changes into the Hitec that (among the embodiment 22 and 24) obtains from ethyl corporation ^TM1117 (DI-3) or just wherein only employing (among the embodiment 23 and 25) from the OLOA9250RXA1736 (DI-4) that Oronite company obtains, the trade mark that PPD uses commercially available Exxon chemical company instead is ParaminsParaflow ^TM392 dialkyl fumarate.The table V shows amounts of components and test-results.

The table V

The embodiment numbering	??22	????23	????24	???25
					The formulation kind	?5W-30	???5W-30	?10W-30	?10W-30
Component	Weight percentage	Weight percentage	Weight percentage	Weight percentage
					Base oil C	?72.40	????72.69	?43.13	?34.41
Base 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
Polymkeric substance G enriched material	?11.39	????12.34	?8.01	?8.75
					Test-results
????KV(cSt)	?10.67	????10.53	?10.56	?10.43
					-25 ℃ CCS (cP)	?3,130	????2,960	????-	???-
-20 ℃ CCS (cP)	???-	??????-	?2,700	?2,760
					????HTHS(cP)	?3.11	????3.08	?3.16	?3.14

Data show shown in the table V, and substantially linear ethylene polymers of the present invention all can satisfy the two SAE SH criteria for classification of 5W-30 and 10W-30, and the function as the VI improving agent of lubricating oil is all arranged.Embodiment 26～28

Repeat the preparation procedure of embodiment 1～7, just use the mixture of one of polymkeric substance G and three kinds of other polymkeric substance instead, its amount is shown in the table VII.Three kinds of other polymkeric substance are that the trade mark of polymkeric substance D (embodiment 26), commercially available Exxon chemical company is Paratone ^TMThe trade mark of 8452 EP multipolymer (embodiment 27) and commercially available shell chemical company is ShellVis ^TM250 styrene block copolymer (embodiment 28).Equally measure the contribution to the KV under 100 ℃ of the KV value of 40 ℃ and 100 ℃ and polymkeric substance according to embodiment 1～7 fully, test-results is shown in the table VI together with the result of embodiment 1.

The table VI

The embodiment numbering	Component	Weight percentage	40 ℃ KV (cSt)	100 ℃ KV (cSt)	Polymkeric substance is to the contribution (cSt) of the KV under 100 ℃
						????1*	Base oil A	?100	?19.87	?4.009	????-
????26	Base oil A polymkeric substance G polymkeric substance D	?99.1 ?0.36 ?0.54	?48.78	?8.802	????4.973
						????27	Base oil A polymkeric substance G Paratone TM????8452	?99.1 ?0.36 ?0.54	?65.23	?11.24	????7.231
????28	Base oil A polymkeric substance G ShellVis TM250	?99.1 ?0.36 ?0.54	?47.45	?8.687	????4.678

* non-embodiments of the invention

The digital proof of table shown in the VI, SLEP particularly EPDM SLEP can with other polymer blendings, and still have function as the effective oil additive that improves high temperature viscosity.Embodiment 29～32

Repeat embodiment 22～25, just the blend with a polymkeric substance G and an additional polymer comes replace polymeric G.This additional polymer is commercially available Rohm ﹠amp; The trade mark of Hass is Acryloid ^TMThe trade mark of the polymkeric substance of 954 polymethyl acrylic acid (embodiment 29), commercially available road elastomerics limited-liability company of Du Pont is Nordel ^The trade mark of 4523 ethylene/propylene/hexadiene terpolymer (embodiment 30 and 32) and commercially available road elastomerics limited-liability company of Du Pont is Nordel ^4549 ethylene/propylene/hexadiene terpolymer (embodiment 31).Acryloid ^TMThe 954th, the 40% enriched material form in the deep fat made adds, Nordel ^4523 and Nordel ^4549 is as polymkeric substance G, and 6% enriched material of making in the deep fat adds form.Table VII A and VII B have listed group component and test-results respectively.

Table VII A

The embodiment numbering	????29	????30	?????31	?????32
					Prescription	????5W-30	????5W-30	????5W-30	????10W-30
Component/weight percentage
					Base oil C	????76.13	????74.04	????76.56	????35.21
Base oil D	????1.89	????0.80	????0.05	????45.80
					????DI-3	????10.84	????10.84	????10.85	?????-
????DI-4	?????-	????-	??????-	????8.75
					????PPD-3	????0.20	????0.20	????0.20	????0.20
Polymkeric substance G enriched material	????9.85	????5.67	????4.93	????6.02
					????Acryloid TM954	????1.09	????-	??????-	?????-
????Nordel 4523	?????-	????8.45	??????-	????4.03
					????Nordel 4549	?????-	????-	????7.42	?????-

Table VII B

The embodiment numbering	????29	????30	??31	??32
					Test-results
KV(cSt)	????10.76	????10.58	?10.46	10.57
					-25 ℃ CCS (cP)	????3,170	????3,330	?3,230	???-
-20 ℃ CCS (cP)	???????-	??????-	??-	?2,825
					HTHS(cP)	????3.08	????3.06	?3.06	?3.11

Digital proof in the table VII (A and B), the blend polymer that contains SLEP can play the function of the VI improving agent of the composition lubricating oil that satisfies 5W-30 and 10W-30 SAE SH criteria for classification.Embodiment 33～36

Repeat embodiment 22～25, just use DI-3 or PPD-3 (embodiment 34 and 36) or PPD-1 (embodiment 33 and 35) and or the enriched material (embodiment 33 and 34) of polymkeric substance G or the enriched material (embodiment 35 and 36) of polymkeric substance J instead.In addition, the physical properties test comprises mensuration scanning Brookfield (SB) temperature under 30,000 cP according to ASTMD-5133.The SAE SH standard of 5W-30 formulation comprises that the SB temperature is-30 ℃.Table VIII A and VIII B have listed group component and test-results.

Table VIII A

The embodiment numbering	????33	????34	????35	????36
					Allotment	????5W-30	????5W-30	????5W-30	????5W-30
Component/weight percentage
					Base oil C	????72.44	????72.40	????75.71	????75.72
Base oil D	????5.14	????5.17	????0.56	????0.56
					????DI-3	????10.85	????10.84	????10.86	????10.86
????PPD-1	????0.20	??????-	????0.20	??????-
					????PPD-3	??????-	????0.20	??????-	????0.20

Table VIII B

The embodiment numbering	????33	???34	???35	??36
					Polymkeric substance G enriched material	????11.38	?11.39	???-	???-
Polymkeric substance J enriched material	??????-	????-	?12.67	?12.66
					Test-results
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

Data shown in the table VIII show, improved low temperature viscosity (embodiment 34 and 36) with the PPD that has added dialkyl fumarate, though, both of these case PPD is produced satisfied result with more remarkable than with EP multipolymer (embodiment 36) of the effect (embodiment 34) of POE.Because the formulation of embodiment 33 has satisfied the every other SAESH standard of 5W-30, those skilled in the art should be able to revise the prescription of embodiment 33 to satisfy this SB standard.Embodiment 37 and 38

Repeat the process of embodiment 1～7, adopt (embodiment 38) of shearing and (embodiment 37) polymkeric substance H and the base oil A that does not shear.I before polymkeric substance H shears ₂Be 1.72g/10min, shearing the back is 4.20g/10min.Polymkeric substance changes with per minute 200 in two-spool super mixer (Haake), shears 20min in 250 ℃.Also available other known mechanisms such as forcing machine replace super mixer.Measure the shear stable index (SSI) of each example.SSI is according to formula S SI=100 * (V ₀-V _s) (V ₀-V _b) determine, the V in the formula ₀Be the KV value of solution before 100 ℃ are tested down, V _sBe the KV value of testing back solution down at 100 ℃, V _bIt is the KV value of base oil.It is low that SSI value representation polymkeric substance-the oil solution shear stability is more stable than the polymkeric substance-oil solution of high SSI value.The KV of base oil is 4.009 (embodiment 1) before the test.The V of embodiment 37 ₀Be 6.55cSt, V _sBe 5.81cSt, SSI is 29.1.The V of embodiment 38 ₀Be 5.94cSt, V _sBe 5.64cSt, SSI is 15.5.

Embodiment 37 and 38 digital proof are in joining oil and carry out before the shear stability test of resulting polymers-oil solution SLEP being sheared the shear stability (reducing the SSI of solution) that will strengthen solution earlier.

After forming polymkeric substance-oil solution, shear other SLEP of polymerization image are the same with the oil-containing material, but the phase obtains 1～38 similar result with embodiment.All these have disclosed in the above.Embodiment 39

G presses USP5 polymkeric substance, 346,963 described process maleic anhydride grafting.Specifically, polymkeric substance G being sent to the Werner-PfleidererZSK70 conrotatory with the speed of 750 pounds of polymkeric substance per hour changes in the twin screw extruder.Forcing machine is at extrusion screw speed 260rpm and barrel zone temperature: operate under the condition of district 1=water-cooled, district 2=370 (188 ℃), district 3=380 (193 ℃), district 4=430 (221 ℃), district 5=410 (210 ℃), district 6=410 (210 ℃), district 7=410 (210 ℃), district 8=430 (221 ℃), district 9=410 (210 ℃), district 10=345 (174 ℃), district 11=345 (174 ℃) and mouth mould=360 (182 ℃), it is the polymer melt of 446 (230 ℃) that temperature is provided.Maleic anhydride (MAH) be by district's 1 end of forcing machine inject nozzle with volume pump per hour 14.5 pounds metering speed add.The trade mark of Atochem produce and market is LUPERSOL ^TM130 peroxidase 12,5-two (t-butyl peroxy) hexin-the 3rd, of district's 4 ends by forcing machine inject nozzle with volume pump per hour 1.5 pounds metering rate add.Forcing machine remains on 〉=and the vacuum level of 26 inch of mercury pressure to be to promote removing of solvent, unreacted MAH and other impurity.The MAH percentage ratio that joins among the polymkeric substance G is 1.2%.Material by forcing machine output descends granulation through the granulation underwater method at 60 °F (16 ℃).

Then the end capped polybutylene oxide compound of the monofunctional amines of MAH grafted SLEP and a kind of trial-production is carried out blend and reaction, the weight-average molecular weight M of described polybutylene oxide _wBeing 1500, is the preparation of Dow Chemical formula.Blend and reaction are changeed in the twin screw extruder in the Werner-PfleidererZSK-30 conrotatory and are carried out, and the screw speed of forcing machine is 150rpm, and through-put is per hour 20 pounds, and extrusion temperature is 190 ℃.Amine compound is with amine compound the ratio 0.15 to 1 of polymkeric substance to be joined in the polymers grafted to go.

The grafting of gained and the polymkeric substance that reacted are carried out the test of VI improving agent by embodiment 1～8 used same base oil and program.The KV value is 40 ℃ of following 60.45cSt, 100 ℃ of following 9.706cSt.Polymkeric substance is 5.611cSt to the contribution of 100 ℃ of following KV.

Embodiment 39 shows, when with carrying out grafting as maleic anhydride and so on unsaturated organic compound, and then with as the further SLEP of reaction of the end capped compound of amido and so on functional compound, during as the VI improving agent of oily composition, can provide satisfied result.

Embodiment 2～39 shows that adding SLEP has improved the VI of oily composition.Other character of oily composition can be optimized by adjusting prescription.SLEP, unsaturated organic compound and functional compound expection with other also can obtain similar result.All these all disclose in the above.

Claims (24)

1. One kind what comprise oil-containing material and viscosity modification significant quantity is the oily composition of linear ethylene polymer basically, it is characterized in that: a) melt flow compares I ₁₀/ I ₂〉=5.63; B) molecular weight distribution M _w/ M _nBy equation M _w/ M _n≤ (I ₁₀/ I ₂)-4.63 definition; And c) begins to occur the critical shear rate of surperficial melt fracture at least than having similar I ₂And M _w/ M _nPolymer of linear olefin to begin to occur the critical shear rate of surperficial melt fracture big by 50%.
2. 2. the composition of claim 1, wherein be that linear ethylene polymer is the raw material of graftomer basically, this graftomer is used for substituting linear ethylene polymer basically, described graftomer grafting be at least the unsaturated organic compound that contains at least one unsaturated ethylene linkage of 0.01 weight percentage of grafted ethylene polymer weight.
3. 3. claim 1 or 2 composition, the ethylene content of wherein said graftomer is in 20 to 80 weight percentage scopes of polymer weight.
4. 4. claim 1 or 2 composition, wherein said is that the another of linear ethylene polymer is characterised in that it is ethene and C basically ₃～C ₂₀The multipolymer of alpha-olefin.
5. 5. claim 1 or 2 composition, wherein said is that linear ethylene polymer is to comprise ethene, C basically ₃～C ₂₀Alpha-olefin and the interpolymer of the copolymerization units of at least a diene monomers.
6. 6. the composition of claim 5, wherein said diene monomers is selected from Dicyclopentadiene (DCPD), hexadiene-1,4, pentadiene-1,3 and 5-ethylidene norbornene-2, octadiene-1,7 and vinyl norbornene.
7. 7. claim 1 or 2 composition, wherein molecular weight distribution is less than 5.
8. 8. claim 1 or 2 composition, wherein the melt flow ratio is 6.5 to 15.
9. 9. the composition of claim 2, wherein said unsaturated organic compound is selected from heterogeneous ring compound, vinyl amine, Yi Xi oxazolin class and the vinyl epoxide of carboxylic acid, carboxylic acid anhydride, carboxylicesters, ether carboxylic acid, carboxylic acid amine, carboxylic acid amide and succinimide class, unsaturated epoxy compound, vinyl substituted.
10. 10. the composition of claim 9, wherein said unsaturated organic compound is the carboxylic acid that is selected from toxilic acid, fumaric acid, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, tiglic acid and styracin.
11. 11. the composition of claim 9, wherein said unsaturated organic compound is a maleic anhydride.
12. 12. the composition of claim 9～11, wherein said unsaturated organic compound also further react with acid, amine or alcohol reactant.
13. 13. the composition of claim 12, wherein said reactant be can with grafting after be basically that linear ethylene polymer reacts, be selected from and contain at least one one-level and/or at least one w secondary, and the randomly aliphatic series of at least one tertiary amine group and the amine of heterocycle organic nitrogen compound.
14. 14. the composition of claim 13, wherein said amine are selected from ring-type or higher homologue, the end capped polyoxyalkylene compounds of amido and the hydroxyalkyl polyamines of polyethylene polyamine, alkylene polyamine, alkylene polyamine.
15. 15. the composition of claim 12, wherein said alcohol contain maximum 100 carbon atoms, and the aliphatic polyol of 2 to 10 hydroxyls is arranged.
16. 16. the composition of claim 15, wherein said alcohol are aklylene glycol, polyglycol or the fatty alcohol that contains maximum 20 carbon.
17. 17. the composition of claim 9, wherein said unsaturated organic compound are vinyl pyridine or N-vinyl pyrrolidone-2.
18. 18. the composition of claim 1 or 2, wherein said oil-containing material are selected from hydrocarbon ils, the lubricating oil based on alkylene oxide polymer and derivative thereof, di-carboxylic acid ester oil and silicon-based oil.
19. 19. the composition of claim 18, wherein said oil-containing material are selected from kerosene, paraffin lubricating oil, cycloalkanes lubricating oil and paraffin-cycloalkanes mixed type lubricating oil, the oil by coal or shale refinement, poly-(alpha-olefin) oil, vegetables oil, animal oil, the polyalkylene oxide polymkeric substance by oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) preparation, poly-alkyl, poly-aryl, gather alkoxyl group or poly-aryloxy silicone oil and silicic acid ester oil.
20. 20. the composition of claim 1 or 2, wherein said is that the consumption of linear ethylene polymer is to make composition be suitable for preparing the generation gelling of lubricating grease, cable filling composite material or cosmetics material or the amount of thickening basically.
21. 21. the composition of claim 1 or 2, wherein composition also comprises the pour point reducer of sufficient amount, so that its cryogenic properties is improved than the analogous composition that does not conform to pour point reducer.
22. 22. the oily composition of claim 1 or 2, wherein it also comprises at least a polymkeric substance that is selected from hydrogenated polyisoprene, phenylethylene/butadiene block polymer, styrene/isoprene block polymer, hydrogenated styrene/butadiene block polymkeric substance, hydrogenated styrene/isoprene block polymkeric substance, graft phenylethene/butadiene block polymkeric substance, graft phenylethene/isoprene block polymkeric substance, polyalkyl methacrylate, polyalkyl acrylate, ethene polymers and acrylate/methacrylate multipolymer.
23. 23. the oily composition of claim 1, thereby wherein at least a portion is that the substantially linear ethylene polymers that linear ethylene polymer is sheared modification substitutes the shear stability that increases oily composition basically.
24. 24. an oil additive concentrate composition, it comprise mineral oil thinner and 5 to 60 weight percentage claim 1 or 2 be linear ethylene polymer basically.