US20130281340A1

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Publication number: US20130281340A1
Application number: US13/797,319
Authority: US
Inventors: Rainer Kolb
Original assignee: ExxonMobil Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2012-04-19
Filing date: 2013-03-12
Publication date: 2013-10-24
Also published as: US9012578B2; US20130281641A1; WO2013158253A1; WO2013158254A1

Abstract

Lubricant compositions, as well as processes for their formulation, are provided. The lubricant compositions comprise an oil basestock and one or more blocky ethylene propylene copolymers. The copolymers are preferably prepared using metallocene catalyst systems but without using a chain shuttling agent.

Description

PRIORITY CLAIM

This application claims the benefit of and priority to U.S. Provisional Application Nos. 61/635,650 and 61/635,633, both filed on Apr. 19, 2012, both of which are herein incorporated by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to ethylene propylene copolymers (“EP copolymers”) useful as rheology modifiers. More particularly, the invention relates to lubricating compositions comprising an oil basestock and one or more blocky EP copolymers and to processes for formulating such compositions. The blocky copolymers have semicrystalline ethylene sequences and amorphous or low crystallinity propylene sequences. The polymers may be prepared using metallocene-based catalyst systems and preferably without the use of a chain shuttling agent. The polymers have higher melting temperatures than previously known random copolymers or block copolymers prepared with chain shuttling agents.

BACKGROUND OF THE INVENTION

Lubrication fluids are applied between moving surfaces to reduce friction, thereby improving efficiency and reducing wear. Lubrication fluids also often function to dissipate the heat generated by moving surfaces.

One type of lubrication fluid is a petroleum-based lubrication oil used for internal combustion engines. Lubrication oils contain additives that help the lubrication oil exhibit a certain viscosity at a given temperature. In general, the viscosity of lubrication oils and fluids is inversely dependent upon temperature. When the temperature of a lubrication fluid is increased, the viscosity generally decreases, and when the temperature is decreased, the viscosity generally increases. For internal combustion engines, for example, it is desirable to have a lower viscosity at low temperatures to facilitate engine starting during cold weather, and a higher viscosity at higher ambient temperatures when lubrication properties typically decline.

Additives for lubrication fluids and oils include rheology modifiers, such as viscosity index (VI) improvers. VI improving components, many of which are derived from ethylene-alpha-olefin copolymers, modify the rheological behavior of a lubricant to increase viscosity and promote a more constant viscosity over the range of temperatures at which the lubricant is used. Higher ethylene content copolymers efficiently promote oil thickening and shear stability. However, higher ethylene content copolymers also tend to flocculate or aggregate in oil formulations leading to very viscous and potentially solid formulations. Flocculation typically happens at ambient or subambient conditions of controlled and quiescent cooling. This deleterious property of otherwise advantageous higher ethylene content viscosity improvers is measured by low temperature solution rheology. Various remedies have been proposed for these higher ethylene content copolymer formulations to overcome or mitigate the propensity towards the formation of high viscosity flocculated materials.

One proposed solution is the use of blends of amorphous and semicrystalline ethylene-based copolymers for lubricant oil formulations. The combination of two such ethylene-propylene copolymers allows for increased thickening efficiency, shear stability index, low temperature viscosity performance and pour point. See, e.g., U.S. Pat. Nos. 7,402,235 and 5,391,617, and European Patent No. 0 638 611, the disclosures of which are incorporated herein by reference.

There remains a need, however, for lubricant compositions comprising ethylene and propylene suitable for use in VI improvers which have good thickening efficiency compared to prior compositions while still being equivalent in their beneficial low temperature solution rheology properties. The present invention addresses this by providing blocky ethylene propylene copolymers having amorphous propylene sequences and semicrystalline ethylene sequences together in the same polymer. The copolymers are preferably polymerized without the added complexity and expense of a chain shuttling agent.

SUMMARY OF THE INVENTION

The present invention relates to lubricant compositions and concentrates comprising ethylene propylene copolymer compositions “EP copolymers” having blocky structures that are useful for modifying the rheological properties of the lubricants. The present invention also relates to processes for formulating such lubricant compositions. The blocky EP copolymers comprise from about 50 to about 95 wt. % ethylene and have a melting temperature greater than about 90° C. Preferably, less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene (ODCB).

The performance of ethylene-based rheology modifiers as VI improvers can be measured by the thickening efficiency (TE) and the shear stability index (SSI), and by the ratio of TE to SSI. It is generally believed that the composition of an olefin copolymer at a given SSI largely determines the TE, and that higher ethylene content is preferred because of its TE. While increasing the ethylene content of rheology modifiers can lead to improved TE/SSI ratios, it may also lead to increasing crystallinity of the olefin copolymer. Increasing crystallinity, however, detracts from the performance of a rheology modifier as a VI improver because crystalline polymers tend to flocculate, either by themselves or in association with other components of the lubrication oil, and precipitate out of lubrication oils. These precipitates are apparent as regions (e.g., “lumps”) of high viscosity or essentially complete solidification (e.g., “gels”) and can lead to clogs and blockages of pumps and other passageways for the lubrication fluid and can harm and in some cases cause failure of moving machinery.

While not wishing to be bound by any particular theory, it is believed that rheology modifiers for lubrication fluids comprising blocky ethylene-based copolymers that have amorphous or low crystallinity regions in combination with semicrystalline regions will be less prone to the deleterious effects of macroscopic crystallization in dilute solution, as measured by the change in the rheology of the fluid solution compared to an equivalent amount of a random ethylene-based copolymer of the same average composition as the blocky copolymer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows melting temperature versus ethylene content for ethylene-rich EP copolymers of the invention, as well as for comparative ethylene-rich copolymers.

DEFINITIONS

As used herein, the term “copolymer” includes polymers having two or more monomers, optionally with other monomers, and may refer to interpolymers, terpolymers, etc. “EP copolymer,” as used herein, refers to polymers comprising ethylene-derived and propylene-derived units. The term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof. The term “polymer” as used herein also includes impact, block, graft, random and alternating copolymers. The term “polymer” shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic and random symmetries.

As used herein, the term “monomer” or “comonomer” refers to the monomer used to form the polymer, i.e., the unreacted chemical compound in the form prior to polymerization, and can also refer to the monomer after it has been incorporated into the polymer, also referred to herein as a “[monomer]-derived unit”, which by virtue of the polymerization reaction typically has fewer hydrogen atoms than it does prior to the polymerization reaction. Different monomers are discussed herein, including propylene monomers, ethylene monomers, and other α-olefin monomers. For the purposes of this invention, it is understood that whenever a polymer is referred to as “comprising” an olefin or other monomer, the olefin present in the polymer is the polymerized form of the olefin or other monomer, respectively.

As used herein, “ethylene-rich” or “ethylene-based” refers to polymers comprising greater than 50 wt. % units derived from ethylene.

As used herein, “block” or “blocky” when used to describe copolymers refers to copolymers having statistically significant sequences of the same repeating monomer units. Block (or blocky) copolymers described herein are distinguished from random polymers, i.e., those having random statistical distribution of monomer units. In block copolymers, the average length of sequences of the same repeating monomer unit is greater than in a random copolymer with a similar composition. Within the context of the invention, the term “sequence” describes a number of contiguous olefin monomer residues catenated together by chemical bonds and obtained by a polymerization procedure. Whereas random copolymers often have properties, such as melting temperatures or glass transition temperatures, that are an average of the properties of the homopolymers comprising the copolymer, block copolymers often retain the characteristics of the corresponding homopolymers in each block.

As used herein, a “catalyst system” is a combination of different components that, taken together, provide the active catalyst. A catalyst system may therefore comprise at least a transition metal compound (also referred to herein as “catalyst,” “precatalyst,” or “catalyst precursor,” these terms being identical in meaning and used interchangeably herein) and an activator. An activator is also sometimes referred to as a “co-catalyst” (these terms are again identical in meaning and used interchangeably herein). The activator activates the transition metal compound and converts it into its catalytically active form. For example, an activator converts a neutral metallocene compound into its cationic form, which is the catalytically active species. When the term “catalyst system” is used to describe a catalyst/activator pair before activation, it refers to the unactivated catalyst (i.e., the precatalyst) together with an activator. When this term is used to describe a catalyst/activator pair after activation, it refers to the activated catalyst and the charge-balancing anion derived from the activator or other charge-balancing moiety. In the scientific and commercial literature the term “catalyst” is sometimes used to refer to the non-activated (i.e., neutral and stable) metallocene, which still has to be converted to its respective charged form in order to react with the monomers to produce polymer. The components of the catalyst system may, either separately or jointly, be supported on a solid support, such as alumina or silica.

A “scavenger” is a compound that is typically added to facilitate polymerization by scavenging impurities (poisons that would otherwise react with the catalyst and deactivate it). Some scavengers may also act as activators, and they may also be referred to as co-activators. A co-activator may be used in conjunction with an activator in order to form an active catalyst.

The terms “radical,” “group,” and “substituent” are used interchangeably herein and indicate a group that is bound to a certain atom as indicated herein. A “substituted” group is one in which a hydrogen has been replaced by a hydrocarbyl, a heteroatom or a heteroatom containing group. For example, methyl cyclopentadiene is a cyclopentadiene substituted with a methyl group.

The term “hydrocarbyl” is used herein to refer to any hydrocarbon-derived substituent or group and thus is understood to include, without limitation, linear, branched or cyclic alkyl, alkylene, alkene, alkyne, as well as aryl groups. Any of these groups may be substituted or unsubstituted.

The term “alkyl” is used herein to refer to an aliphatic, branched or linear, non-cyclic or cyclic substituent, typically with a certain number of carbon atoms as individually specified. Unless specified otherwise herein, “alkyl” specifically includes aliphatic groups having from 1 to 20, or from 1 to 10, or from 1 to 5 carbon atoms, and specifically methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, pentyl, n-pentyl, isopentyl, cyclopentyl, hexyl, n-hexyl, isohexyl, cyclohexyl, heptyl, n-heptyl, isohexyl, cycloheptyl, octyl, n-octyl, isooctyl, cyclooctyl, nonyl, n-nonyl, isononyl, decyl, n-decyl, iso-decyl, and the like. The same definition applies for the alkyl in an alkoxy substituent.

The term “aryl” is used herein to refer to an aromatic substituent, which may be a single aromatic ring or multiple aromatic rings, which are fused together, covalently linked, or linked to a common group such as a methylene or ethylene moiety. The common linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether. The aromatic ring(s) may include phenyl, naphthyl, fluorenyl, indenyl, biphenyl, diphenylether, tolyl, cumyl, xylyl, and benzophenone, among others. Unless specified otherwise herein, the term “aryl” specifically includes those having from 5 to 30, or from 5 to 25, or from 5 to 20, or from 5 to 15 carbon atoms, alternately the aryl may have 6 to 15 carbon atoms or may have 5 or 6 carbon atoms. “Substituted aryl” refers to aryl as just described in which one or more hydrogen atoms to any carbon are, independently of each other, replaced by one or more groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalogen, such as hydroxyl-, phosphino-, alkoxy-, aryloxy-, amino-, thio- and both saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or ethylene moiety. The linking group may also be a carbonyl such as in cyclohexyl phenyl ketone. The term “aryl” also includes aromatic groups containing one or more heteroatoms, such as nitrogen, oxygen, phosphorus, or sulfur. Non-limiting examples of such hetero-atom containing aromatic groups are furanyl, thiophenyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, benzofuranyl, pyrazinyl, pyrimidinyl, pyridazinyl, chinazolinyl, indolyl, carbazolyl, oxazolyl, thiazolyl, and the like.

The term “ring system” refers to any system or combination of aliphatic and/or aromatic rings that are fused to each other via shared ring member atoms, that are covalently linked to each other, or that are linked via a common linking group, such as an alkylene group or a hetero-atom containing group such as carbonyl. One or more of the aliphatic and/or aromatic rings of the ring system may also contain one or more heteroatoms, such as nitrogen, oxygen, phosphorus or sulfur. Any of the aliphatic and/or aromatic rings of the ring system may be substituted by one or more groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalogen, such as hydroxyl-, phosphino-, alkoxy-, aryloxy-, amino-, thio- and both saturated and unsaturated cyclic hydrocarbons. For the aromatic or aliphatic rings of the ring system, the above-provided definitions for “aryl” and “alkyl” regarding the number of carbon atoms apply as well. A ring system in the context of the present invention contains at least two rings. A “ring carbon atom” is a carbon atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring carbon atoms and para-methylstyrene also has six ring carbon atoms.

The term “amino” is used herein to refer to the group —NQ¹Q², where each of Q¹and Q²is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

As used herein, the term “complex viscosity” means a frequency-dependent viscosity function determined during forced small amplitude harmonic oscillation of shear stress, in units of Pascal-seconds, that is equal to the difference between the dynamic viscosity and the out-of-phase viscosity (imaginary part of complex viscosity).

As used herein, the numbering scheme for the Periodic Table Groups is as published in Chemical and Engineering News, 63(5), 27 (1985).

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to lubricant compositions (including concentrates) comprising rheology modifying blocky EP copolymers and to processes for formulating such compositions. In particular, the blocky EP copolymers have semicrystalline ethylene sequences and amorphous or low crystallinity propylene sequences. The polymers are preferably prepared using metallocene catalyst systems but without the use of a chain shuttling agent. The polymers have higher melting temperatures than previously known random copolymers or blocky copolymers prepared with chain shuttling agents and having similar comonomer contents.

The presence of blocky characteristics in the polymers can be shown by their high melting temperature when compared to random copolymers having the same comonomer composition. Further indication of blockiness can be found in the poor solubility of the polymers in multiple solvents, including xylene and ortho-dichlorobenzene (ODCB).

Test Methods

The following test methods are used to determine the properties reported herein.

Gel Permeation Chromatography (GPC)—Techniques for determining the molecular weight (Mn, Mw and Mz) and MWD may be found in U.S. Pat. No. 4,540,753 (Cozewith, Ju and Verstrate), incorporated by reference herein, and references cited therein, and in Macromolecules, 1988, Vol. 21, p. 3360 (Verstrate et al.), which is incorporated by reference herein, and references cited therein. For example, molecular weight may be determined by size exclusion chromatography (SEC) by using a Waters 150 gel permeation chromatograph equipped with the differential refractive index detector and calibrated using polystyrene standards.

Differential Scanning calorimetry (DSC)—DSC procedures for determining peak melting temperature (Tm), crystallization temperature (Tc), and heat of fusion (Hf) include the following. The polymer is pressed at a temperature of from about 200° C. to about 230° C. in a heated press, and the resulting polymer sheet is hung, under ambient conditions, in the air to cool at room temperature (approximately 23° C.). About 6 to 10 mg of the polymer sheet is removed with a punch die. This 6 to 10 mg sample is annealed at room temperature for about 80 to 100 hours. At the end of this period, the sample is placed in a DSC (Perkin Elmer Pyris One Thermal Analysis System) and cooled to about −70° C. The sample is heated at 10° C./min to attain a final temperature of about 200° C. The sample is kept at 200° C. for 5 minutes and a second cool-heat cycle is performed. Events from both cycles are recorded. The thermal output is recorded as the area under the melting peak of the sample, which typically occurs between about 0° C. and about 200° C. It is measured in Joules and is a measure of the Hf of the polymer.

Comonomer Content—The ethylene content of ethylene/propylene copolymers was determined using FTIR according to the following technique. A thin homogeneous film of polymer, pressed at a temperature of about 150° C., was mounted on a Perkin Elmer Spectrum 2000 infrared spectrophotometer. A full spectrum of the sample from 600 cm⁻¹to 4000 cm⁻¹was recorded and the area under the propylene band at ˜1165 cm⁻¹and the area under the ethylene band at ˜732 cm⁻¹in the spectrum were calculated. The baseline integration range for the methylene rocking band is nominally from 695 cm⁻¹to the minimum between 745 and 775 cm⁻¹. For the polypropylene band the baseline and integration range is nominally from 1195 to 1126 cm⁻¹. The ethylene content in wt. % was calculated according to the following equation:

ethylene content(wt.%)=72.698−86.495X+13.696X²,

where X=AR/(AR+1) and AR is the ratio of the area for the peak at ˜1165 cm⁻¹to the area of the peak at ˜732 cm⁻¹.

Temperature Rising Elution Fractionation (TREF)—The TREF data reported herein were measured using an analytical size TREF instrument (Polymerchar, Spain), with a column of the following dimensions: inner diameter (ID) 7.8 mm, outer diameter (OD) 9.53 mm, and column length of 150 mm. The column was filled with steel beads. 0.5 mL of a 4 mg/mL polymer solution in ortho-dichlorobenzene (ODCB) containing 2 g butylated hydroxyl-toluene (BHT)/4 L were charged onto a the column and cooled from 140° C. to −15° C. at a constant cooling rate of 1.0° C./min. Subsequently, ODCB was pumped through the column at a flow rate of 1.0 mL/min, and the column temperature was increased at a constant heating rate of 2° C./min to elute the polymer. The polymer concentration in the eluted liquid was detected by means of measuring the absorption at a wavenumber of 2941 cm⁻¹using an infrared detector. The concentration of the ethylene-α-olefin copolymer in the eluted liquid was calculated from the absorption and plotted as a function of temperature.

Fractionation—Copolymers were fractionated using the TREF method described above. In order to obtain individual fractions in sufficient quantity for additional analysis, solvent with polymer eluting at the following three temperature ranges was collected: 15° C. to 0° C.; >0° C. to +10° C.; and >10° C. to 130° C. The solvent was evaporated and the dried polymers collected at these ranges were further analyzed by DSC for thermal properties and by IR spectroscopy for ethylene content.

Thickening Efficiency (TE) was determined according to ASTM D445.

Shear Stability index (SSI) was determined according to ASTM D6278 at 30 and 90 cycles using a Kurt Orbahn (KO) machine.

Ethylene-Rich Blocky Copolymers

Provided herein are rheology modifying EP copolymers comprising propylene and ethylene, wherein the copolymer comprises from about 50 to about 95 wt. % ethylene, the copolymer has a melting temperature greater than about 90° C., and less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene.

The EP copolymers may comprise from about 50 to about 95 wt. %, or from about 52 to about 93 wt. %, or from about 55 to about 90 wt. %, or from about 57 to about 87 wt. %, or from about 60 to about 85 wt. %, or from about 65 to about 85 wt. %, or from about 70 to about 85 wt. %, or from about 75 to about 85 wt. % ethylene derived units.

The EP copolymers may have a melting temperature of from about 90° C. to about 200° C., or from about 95° C. to about 200° C., or from about 100° C. to about 180° C., or from about 105° C. to about 180° C., or from about 110° C. to about 180° C., or from about 112° C. to about 160° C., or from about 114° C. to about 160° C., or from about 115° C. to about 160° C.

The EP copolymers may have a weight-average molecular weight (Mw) in g/mol, determined using GPC, of from about 10,000 to about 500,000, or from about 25,000 to about 125,000, or from about 40,000 to about 115,000, or from about 45,000 to about 110,000, or from about 50,000 to about 100,000, or from about 50,000 to about 80,000.

The EP copolymers may have a number-average molecular weight (Mn) in g/mol, determined using GPC, from about 4,000 to about 40,000, or from about 5,000 to about 35,000, or from about 6,000 to about 30,000, or from about 7,000 to about 30,000, or from about 8,000 to about 30,000, or from about 10,000 to about 30,000, or from about 12,000 to about 28,000.

The EP copolymers may have a z-average molecular weight (Mz) in g/mol, determined using GPC, from about 50,000 to about 300,000, or from about 75,000 to about 275,000, or from about 100,000 to about 250,000, or from about 110,000 to about 225,000, or from about 115,000 to about 200,000, or from about 115,000 to about 175,000.

The EP copolymers may have a molecular weight distribution (MWD), Mw/Mn, from about 2.0 to about 10.0, or from about 2.0 to about 9.0, or from about 2.0 to about 8.0, or from about 2.5 to about 7.0, or from about 2.5 to about 6.5, or from about 2.5 to about 6.0, or from about 2.0 to about 5.0, or from about 2.5 to about 5.0.

The EP copolymers may have a density in the range of from 0.85 g/cc to 0.97 g/cc, or in the range of from 0.86 g/cc to 0.94 g/cc, or in the range of from 0.86 g/cc to 0.91 g/cc, or in the range of from 0.86 g/cc to 0.90 g/cc.

The fraction of the EP copolymer that is soluble in xylene or ODCB is less than about 15 wt. %, or less than about 10 wt. %, or less than about 7.5 wt. %, or less than about 5 wt. %, or less than about 4 wt. %, or less than about 3 wt. %. The melting temperature of the soluble fraction may be greater than about 90° C., or greater than about 95° C., or greater than about 100° C., or greater than about 105° C., or greater than about 110° C., or greater than about 115° C.

Processes for Preparing Blocky EP Copolymers

Also provided herein are processes for preparing the rheology modifying EP copolymers. Such processes may comprise polymerizing propylene and ethylene in a solution process and in the presence of a catalyst system comprising a catalyst and an activator where the catalyst comprises a metallocene compound as described in further detail below, and the activator comprises a cationic component and an anionic component, each also described in further detail below. In one or more embodiments, the copolymers of the present invention are prepared without the use of a chain shuttling agent.

The cationic component of the activator may correspond to either formula (1A) or formula (2A):

[R₁R₂R₃NH]⁺, (1A)

where R₁and R₂are together a —(CH₂)_a— group, where a is 3, 4, 5, or 6 and R₁and R₂form a 4-, 5-, 6-, or 7-membered non-aromatic ring together with the nitrogen atom to which one or more aromatic or heteroaromatic rings may optionally be fused via adjacent ring carbon atoms; and R₃is a C₁-C₅alkyl group; or

[R₃NH]⁺, (2A)

where all R are identical and are C₁-C₃alkyl groups.

The anionic component of the activator may correspond to formula (3A):

[B(R₄)₄]⁻, (3A)

where R₄is an aryl group or a substituted aryl group having one or more substituents, wherein the one or more substituents are identical or different and are selected from alkyl, aryl, halogenated aryl, or haloalkylaryl groups or a hydrogen atom, as further described in U.S. Pat. No. 7,985,816.

Transition Metal Compounds

Any transition metal compound capable of catalyzing a reaction such as a polymerization reaction, upon activation of an activator as described herein is suitable for use in the present invention. Transition metal compounds known as metallocenes are preferred compounds according to the present invention. Useful metallocene compounds are described in greater detail in U.S. Publication No. 2010/0029873, which is incorporated herein by reference in its entirety.

Preferably, the transition metal compound is represented by the formula: T(L₁)(L₂)M(X₁)(X₂), wherein the metal (M) is a Group 4 metal, specifically, titanium, zirconium, or hafnium, and the indenyl (L) is unsubstituted or may be substituted by one or more substituents selected from the group consisting of a halogen atom, C₁to C₁₀alkyl, C₅to C₁₅aryl, C₆to C₂₅arylalkyl, and C₆to C₂₅alkylaryl. More preferably, the metal is zirconium or hafnium, L₁and L₂are unsubstituted or substituted indenyl radicals. T may be a dialkylsiladiyl, and X₁and X₂are both halogen or a C₁to C₃alkyl. Preferably, these compounds are in the rac-form. In the formula above, T is bound to L₁and L₂; L₁and L₂are each bound to M to form a cyclic structure; and X₁and X₂are each bound to M. Preferably the transition metal compound is a dimethylsilylbis(indenyl)metallocene where X₁and X₂are both halogen or a C₁to C₃alkyl.

Illustrative, but not limiting examples of preferred stereospecific metallocene compounds are the racemic isomers of dimethylsilylbis(indenyl)metal dichloride, -diethyl or -dimethyl, wherein the metal is titanium, zirconium or hafnium, preferably hafnium or zirconium. It is particularly preferred that the indenyl radicals are not substituted by any further substituents. The two indenyl groups may be, independently of each other, indenyl, 2-methyl-4-phenylindenyl; 2-methyl indenyl; 2-methyl,4-[3′,5′-di-t-butylphenyl]indenyl; 2-ethyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-n-propyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-iso-propyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-iso-butyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-n-butyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-sec-butyl-4-[3′,5′-di-t-butylphenyl]indenyl; 2-methyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-ethyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-n-propyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-iso-propyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-n-butyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-sec-butyl-4-[3′,5′-di-phenylphenyl]indenyl; 2-tert-butyl-4-[3′,5′-di-phenylphenyl]indenyl; and the like. Further illustrative, but not limiting examples of preferred stereospecific metallocene compounds are the racemic isomers of 9-silafluorenylbis(indenyl)metal dichloride, -diethyl or -dimethyl, wherein the metal is titanium, zirconium or hafnium. Again, unsubstituted indenyl radicals are particularly preferred. In some embodiments, however, the two indenyl groups may be replaced, independently of each other, by any of the substituted indenyl radicals listed above.

Particularly preferred metallocenes as transition metal compounds for use in the catalyst systems of the present invention together with the activators include a cation of formula (1A) or (2A) defined above for use in polymerizing olefins are rac-dimethylsilylbis(indenyl)hafnocenes or -zirconocenes, rac-dimethylsilylbis(2-methyl-4-phenylindenyl)hafnocenes or -zirconocenes, rac-dimethylsilylbis(2-methyl-indenyl)hafnocenes or -zirconocenes, and rac-dimethylsilylbis(2-methyl-4-naphthylindenyl)hafnocenes or -zirconocenes, wherein the hafnium and zirconium metal is substituted, in addition to the bridged bis(indenyl) substituent, by two further substituents, which are halogen, preferably chlorine or bromine atoms, or alkyl groups, preferably methyl and/or ethyl groups. Preferably, these additional substituents are both chlorine atoms or both methyl groups. Particularly preferred transition metal compounds are dimethylsilylbis(indenyl)hafnium dimethyl, rac-dimethylsilylbis(indenyl)zirconium dimethyl, rac-ethylnylbis(indenyl)zirconium dimethyl, and rac-ethylnylbis(indenyl)hafnium dimethyl.

Illustrative, but not limiting examples of preferred non-stereospecific metallocene catalysts are: [dimethylsilanediyl(tetramethylcyclopentadienyl)-(cyclododecylamido)]metal dihalide, [dimethylsilanediyl(tetramethylcyclopentadienyl)(t-butylamido)]metal dihalide, [dimethylsilanediyl(tetramethylcyclopentadienyl)(exo-2-norbornyl)]metal dihalide, wherein the metal is Zr, Hf, or Ti, preferably Ti, and the halide is preferably chlorine or bromine.

In preferred embodiments, the transition metal compound is a bridged or unbridged bis(substituted or unsubstituted indenyl)hafnium dialkyl or dihalide.

Activators and Activation Methods

The transition metal compounds described herein are activated to yield a catalytically active, cationic transition metal compound having a vacant coordination site to which a monomer will coordinate and then be inserted into the growing polymer chain. In the process for polymerizing the EP copolymers described herein, an activator of one of the following general formulas (1) or (2) may be used to activate the transition metal compound:

[R¹R²R³AH]⁺[Y]⁻, (1)

where [Y]⁻ is a non-coordinating anion (NCA) as further illustrated below, A is nitrogen or phosphorus, R¹and R²are hydrocarbyl groups or heteroatom-containing hydrocarbyl groups and together form a first, 3- to 10-membered non-aromatic ring with A, wherein any number of adjacent ring members may optionally be members of at least one second, aromatic or aliphatic ring or aliphatic and/or aromatic ring system of two or more rings, wherein said at least one second ring or ring system is fused to said first ring, and wherein any atom of the first and/or at least one second ring or ring system is a carbon atom or a heteroatom and may be substituted independently by one or more substituents selected from the group consisting of a hydrogen atom, halogen atom, C₁to C₁₀alkyl, C₅to C₁₅aryl, C₆to C₂₅arylalkyl, and C₆to C₂₅alkylaryl, and R³is a hydrogen atom or C₁to C₁₀alkyl, or R³is a C₁to C₁₀alkylene group that connects to said first ring and/or to said at least one second ring or ring system; or

[R_nAH]⁺[Y]⁻, (2)

where [Y]⁻ is a non-coordinating anion (NCA) as further illustrated below, A is nitrogen, phosphorus or oxygen, n is 3 if A is nitrogen or phosphorus, and n is 2 if A is oxygen, and the groups R are identical or different and are a C₁to C₃alkyl group.

Both the cation part of formulas (1) and (2) and the anion part, which is a NCA, are described in further detail in U.S. Publication No. 2010/0029873, which is incorporated by reference herein in its entirety. Any combinations of cations and NCAs disclosed therein are suitable to be used in the processes of the present invention.

Preferred activators of formula (1) in the catalyst systems used in the polymerization processes are those where A is nitrogen, R¹and R²together are a —(CH₂)_a— group with A being 3, 4, 5, or 6, and R³is C₁, C₂, C₃, C₄or C₅alkyl, and [Y]⁻ is [B(R⁴)₄]⁻, with R⁴being an aryl group or a substituted aryl group, of which the one or more substituents are identical or different and are selected from the group consisting of alkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups, and preferably R⁴is a perhalogenated aryl group, more preferably a perfluorinated aryl group, more preferably pentafluorophenyl, heptafluoronaphthyl or perfluorobiphenyl. Preferably, these activators are combined with a transition metal compound (such as a metallocene) to form the catalyst systems of the present invention.

Preferred activators in the catalyst systems of formula (2) in the catalyst systems used in the polymerization process are those wherein A is nitrogen, n is 3, all groups R are identical and are methyl, ethyl or isopropyl, and [Y]⁻ is [B(R⁴)₄]⁻, with R⁴being an aryl group or a substituted aryl group, of which the one or more substituents are identical or different and are selected from the group consisting of alkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups, and preferably R⁴is a perhalogenated aryl group, more preferably a perfluorinated aryl group, more preferably pentafluorophenyl, heptafluoronaphthyl or perfluorobiphenyl. Preferably, these activators are combined with a transition metal compound (such as a metallocene) to form the catalyst systems.

In the polymerization process, in addition to the preferred activators of formula (1) mentioned in the preceding paragraph also the activators of formula (2) wherein A is nitrogen and all groups R are identically methyl or ethyl, and wherein [Y]⁻ is defined as in the preceding paragraph are preferably used. Again, these activators are preferably combined with a metallocene (e.g. as explained herein below) to form the catalyst systems used in the polymerization process.

Catalyst Systems

Preferred combinations of transition metal compound and activator in the catalyst systems for olefin polymerization comprise a metallocene compound and an activator comprising a cationic component and an anionic component. In one or more embodiments, the metallocene compound is preferably a dialkylsilyl-bridged bis(indenyl)metallocene, wherein the metal is a group 4 metal and the indenyl is unsubstituted, or if substituted, is substituted by one or more substituents selected from the group consisting of a C₁to C₁₀alkyl, C₅to C₁₅aryl, C₆to C₂₅arylalkyl, and C₆to C₂₅alkylaryl; more preferably dimethylsilylbis(indenyl)metal dichloride or -dimethyl, ethylenylbis(indenyl)metal dichloride or -dimethyl, dimethylsilylbis(2-methyl-4-phenylindenyl)metal dichloride or -dimethyl, dimethylsilylbis(2-methyl-indenyl)metal dichloride or -dimethyl, and dimethylsilylbis(2-methyl-4-naphthylindenyl)metal dichloride or -dimethyl, wherein in all cases the metal may be zirconium or hafnium.

In one or more embodiments, the cationic component is of the formula [R¹R²R³AH]⁺, where preferably A is nitrogen, R¹and R²are together a —(CH₂)_a— group, wherein a is 3, 4, 5 or 6 and form, together with the nitrogen atom, a 4-, 5-, 6- or 7-membered non-aromatic ring to which, via adjacent ring carbon atoms, optionally one or more aromatic or heteroaromatic rings may be fused, and R³is C₁, C₂, C₃, C₄or C₅alkyl, more preferably N-methylpyrrolidinium or N-methylpiperidinium; or of the formula [R_nAH]⁺, where preferably A is nitrogen, n is 3 and all R are identical and are C₁to C₃alkyl groups, more preferably trimethylammonium or triethylammonium.

In one or more embodiments, the anionic component is [Y]⁻ which is an NCA, preferably of the formula [B(R⁴)₄]⁻, with R⁴being an aryl group or a substituted aryl group, of which the one or more substituents are identical or different and are selected from the group consisting of alkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups, preferably perhalogenated aryl groups, more preferably perfluorinated aryl groups, and more preferably pentafluorophenyl, heptafluoronaphthyl, or perfluorobiphenyl.

Preferably, the activator for use in any of the polymerization processes according to the present invention is trimethylammonium tetrakis(pentafluorophenyl)borate, N-methylpyrrolidinium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(heptafluoronaphthyl)borate, or N-methylpyrrolidinium tetrakis(heptafluoronaphthyl)borate. The metallocene is preferably rac-dimethylsilyl bis(indenyl)zirconium dichloride or -dimethyl, rac-dimethylsilyl bis(indenyl)hafnium dichloride or -dimethyl, rac-ethylnyl bis(indenyl)zirconium dichloride or -dimethyl or rac-ethylnyl bis(indenyl)hafnium dichloride or -dimethyl.

Any catalyst system resulting from any combination of the preferred metallocene compound, preferred cationic component of the activator, and preferred anionic component of the activator mentioned in the preceding paragraphs shall be explicitly disclosed and may be used in accordance with the polymerization of one or more olefin monomers. Also, combinations of two different activators can be used with the same or different metallocene(s).

Scavengers or Additional Activators

The catalyst system may contain, in addition to the transition metal compound and the activator described above, additional activators or scavengers. A co-activator is a compound capable of alkylating the transition metal complex, such that when used in combination with an activator, an active catalyst is formed. Co-activators include alumoxanes and aluminum alkyls. An alumoxane is preferably an oligomeric aluminum compound represented by the general formula (R^x—Al—O)_n, which is a cyclic compound, or R^x(R^x—Al—O)_nAlR^x₂, which is a linear compound. Common alumoxanes are a mixture of cyclic and linear compounds. In the general alumoxane formula, R^xis independently a C₁-C₂₀alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and the like, and “n” is an integer from 1-50. More preferably, R^xis methyl and “n” is at least 4. Methyl alumoxane (MAO) as well as modified MAO, referred to herein as MMAO, containing some higher alkyl groups to improve the solubility, ethyl alumoxane, iso-butyl alumoxane and the like are useful herein. Particularly useful MAO can be purchased from Albemarle in a 10 wt. % solution in toluene. Co-activators are typically only used in combination with Lewis acid activators and ionic activators when the pre-catalyst is not a dihydrocarbyl or dihydride complex.

In some embodiments, scavengers may be used to “clean” the reaction of any poisons that would otherwise react with the catalyst and deactivate it. Typical aluminum or boron alkyl components useful as scavengers are represented by the general formula R^xJZ₂where J is aluminum or boron, R^xis a C₁-C₂₀alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl, and isomers thereof, and each Z is independently R^xor a different univalent anionic ligand such as halogen (Cl, Br, I), alkoxide (OR^x) and the like. More preferred aluminum alkyls include triethylaluminum, diethylaluminum chloride, ethylaluminium dichloride, tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, trimethylaluminum, and combinations thereof. Preferred boron alkyls include triethylboron. Scavenging compounds may also be alumoxanes and modified alumoxanes including methylalumoxane and modified methylalumoxane.

The catalyst systems of the present invention can be prepared and supported according to methods known in the art. In particular, methods for preparing the catalyst systems described herein, as well as suitable supports and methods for supporting the catalyst systems are described in detail in U.S. Publication No. 2010/0029873, which is incorporated by reference herein in its entirety.

Polymerization Processes

The process for polymerizing ethylene and propylene may comprise contacting ethylene and propylene under polymerization conditions with a catalyst system comprising an activator of formula (1) or formula (2) as defined above.

In particular, the polymerization processes exclude the use of or are substantially free from the use of a chain shuttling agent during polymerization. Known shuttling agents include, but are not limited to, diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide), n-octylaluminum di(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxide). By “exclude the use of” and “substantially free of” is meant that, while there is the potential that small amounts of chain shuttling agent may be present as an impurity in the polymerization process, no chain shuttling agent is deliberately added to the reactor or reactors before or during the polymerization process. In one or more embodiments, the concentration of shuttling agent is less than about 1000 ppm, or less than about 750 ppm, or less than about 500 ppm, or less than about 250 ppm, or less than about 100 ppm.

The catalyst systems described above are suitable for use in a solution, bulk, gas, or slurry polymerization process or a combination thereof, preferably solution phase or bulk phase polymerization process. Preferably, the process is a continuous process. By “continuous”, it is meant a system that operates without interruption or cessation. For example, a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

One or more reactors in series or in parallel may be used. Catalyst precursor and activator may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor. A preferred operation is two solutions, for example, one catalyst precursor solution and one activator solution, activated in-line. Methods to introduce multiple catalysts into reactors are further described in U.S. Pat. No. 6,399,722, and PCT Publication No. WO 01/30862A1. While these references may emphasize gas phase reactors, the techniques described are equally applicable to other types of reactors, including continuous stirred tank reactors, slurry loop reactors, and the like. Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator, scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series. The catalyst compounds can be added to the first reactor in the series. The catalyst component may also be added to both reactors, with one component being added to first reaction and another component to other reactors.

Preferably, the polymerization processes using activators of formula (1) or (2) in combination with a transition metal compound, preferably a metallocene, are solution processes, where polymerization is conducted at a temperature of at least about 50° C., or at least about 60° C., or at least about 70° C., or at least about 80° C., or at least about 90° C.

Preferably, the polymerization processes using activators of formula (1) and/or (2) in combination with a metallocene as described above are run with a monomer conversion of from 5 to 95%, or from 5 to 90%, or from 5 to 85%, or from 5 to 80%, or from 5 to 75%, or from 5 to 70%, all percentages based on a theoretically possible 100% conversion. The conversion is calculated on a weight basis (the actual amount (weight in gram) polymer obtained, divided through the theoretically possible amount (again weight in gram) of polymer if all monomer was converted into polymer). As an example, as propylene has a density of 0.52 g/mL, if 100 mL propylene monomer is fed into the reactor, theoretically 52 g polypropylene could be obtained (assuming a theoretical 100% conversion). The % conversion achieved in a particular polypropylene reaction run with 100 mL of propylene is feed is therefore calculated as follows: conversion [%]=(actual weight (g) polypropylene recovered/52 g)×100%. So, for example, if 5.2 g of polymer is recovered, the conversion would be 10%.

Lubricant Compositions and Concentrates

Lubricating oil compositions comprising the blocky EP copolymers described herein and one or more base oils (or basestocks) are also provided. The basestock can comprise natural or synthetic oils of lubricating viscosity, whether derived from hydrocracking, hydrogenation, other refining processes, unrefined processes, or re-refined processes. The basestock can comprise used oil. Natural oils include animal oils, vegetable oils, mineral oils, and mixtures thereof. Synthetic oils include hydrocarbon oils, silicon-based oils, and liquid esters of phosphorus-containing acids. Synthetic oils may be produced by Fischer-Tropsch gas-to-liquid synthetic procedures as well as other gas-to-liquid procedures.

The basestock may comprise a polyalphaolefin (PAO) including a PAO-2, PAO-4, PAO-5, PAO-6, PAO-7 or PAO-8 (the numerical value relating to Kinematic Viscosity at 100° C. (ASTM D 445)). Preferably, the polyalphaolefin is prepared from dodecene and/or decene. Generally, polyalphaolefins suitable as oils of lubricating viscosity have a viscosity less than that of a PAO-20 or PAO-30 oil.

In one or more embodiments, the basestock can be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. For example, the basestock can comprise an API Group I, II, III, IV, or V oil or mixtures thereof.

In one or more embodiments, the basestock may include oils or blends thereof that are conventionally employed as crankcase lubricating oils. For example, suitable basestocks may include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like. Suitable basestocks may also include those oils conventionally employed in and/or adapted for use as power transmitting fluids such as automatic transmission fluids, tractor fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids, and the like. Suitable basestocks may also comprise gear lubricants, industrial oils, pump oils and other lubricating oils.

The basestock can include not only hydrocarbon oils derived from petroleum, but also synthetic lubricating oils such as esters of dibasic acids; complex esters made by esterification of monobasic acids, polyglycols, dibasic acids and alcohols; polyolefin oils, etc. Thus, the lubricating oil compositions described can be suitably incorporated into synthetic base oil basestocks such as alkyl esters of dicarboxylic acids, polyglycols and alcohols; polyalphaolefins; polybutenes; alkyl benzenes; organic esters of phosphoric acids; polysilicone oils; etc. The lubricating oil composition can also be utilized in a concentrate form, such as from 1 wt. % to 49 wt. % in oil, e.g., mineral lubricating oil, for ease of handling.

The lubricant compositions may include a basestock and one or more blocky EP copolymers as described herein. The lubricant compositions may further optionally comprise a pour point depressant.

The lubricant compositions may have a thickening efficiency (TE) greater than or equal to about 1.0, or 1.5, or 1.7, or 1.9, or 2.0, or 2.1, or 2.2. The lubricant compositions may have a TE less than or equal to about 4.0, or 3.5, or 3.3, or 3.1, or 3.0, or 2.8.

The lubricant compositions may have a shear stability index (SSI) greater than or equal to about 7.5%, or 10.0%, or 12.5%, or 15%, or 17.5%, or 20%. The lubricant compositions may have an SSI less than or equal to about 32.5%, or 30%, or 27.5%, or 25%, or 22.5%. Alternatively, the lubricant compositions may have an SSI greater than or equal to about 20%, or 22%, or 24%, or 25%, or 26%, or 27%, or 28%, or 29%, or 30%.

The lubricant compositions may have a complex viscosity at −35° C. of less than 500, or less than 450, or less than 300, or less than 100, or less than 50, or less 20, or less than 10 centistokes (cSt).

The compositions can have a Mini Rotary Viscometer (MRV) viscosity at −35° C. in a 10W-50 formulation of less than 60,000 cps according to ASTM 1678.

The compositions may have any combination of desired properties. For example, an exemplary lubricant composition may have a thickening efficiency greater than about 1.0 or greater than about 2.0, a shear stability index of less than 55 or less than 35 or less than 25, a complex viscosity at −35° C. of less than 500 cSt or less than 300 cSt or less than 50 cSt, and/or a Mini Rotary Viscometer (MRV) viscosity at −35° C. in a 10W-50 formulation of less than about 60,000 cps according to ASTM 1678.

The lubricant compositions may comprise less than about 3.0 wt. %, or about 2.5 wt. %, or about 1.5 wt. %, or about 1.0 wt. % or about 0.5 wt. % of one or more blocky EP copolymers as described herein, based upon the weight of the composition. In some embodiments, the amount of the EP copolymer in the lubricant composition can range from a low of about 0.25 wt. %, 0.5 wt. %, 0.75 wt. %, 1.0 wt. %, or about 1.25 wt. % to a high of about 1.75 wt. %, 2.0 wt. %, 2.25 wt. %, 2.5 wt. %, 2.75 wt. %, or 3.0 wt. %, based upon the weight of the composition.

Oil Additives

The lubricant compositions can optionally contain one or more conventional additives, such as, for example, pour point depressants, antiwear agents, antioxidants, other viscosity-index improvers, dispersants, corrosion inhibitors, anti-foaming agents, detergents, rust inhibitors, friction modifiers, and the like.

Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricant composition. Illustrative corrosion inhibitors include phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C₂to C₆olefin polymer such as polyisobutylene, with from 5 to 30 wt. % of a sulfide of phosphorus for ½ to 15 hours, at a temperature in the range of 66° C. to 316° C. Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner known by those skilled in the art.

Oxidation inhibitors, or antioxidants, reduce the tendency of mineral oils to deteriorate in service, as evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces, and by viscosity growth. Such oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having C₅to C₁₂alkyl side chains, e.g., calcium nonylphenate sulfide, barium octylphenate sulfide, dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurized or sulfurized hydrocarbons, etc. Other oxidation inhibitors or antioxidants useful in this invention include oil-soluble copper compounds, such as described in U.S. Pat. No. 5,068,047.

Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids. Representative examples of suitable friction modifiers are described in U.S. Pat. No. 3,933,659, which describes fatty acid esters and amides; U.S. Pat. No. 4,176,074 which describes molybdenum complexes of polyisobutenyl succinic anhydride-amino alkanols; U.S. Pat. No. 4,105,571 which describes glycerol esters of dimerized fatty acids; U.S. Pat. No. 3,779,928 which describes alkane phosphonic acid salts; U.S. Pat. No. 3,778,375 which describes reaction products of a phosphonate with an oleamide; U.S. Pat. No. 3,852,205 which describes S-carboxyalkylene hydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl succinamic acid and mixtures thereof; U.S. Pat. No. 3,879,306 which describes N(hydroxyalkyl)alkenyl-succinamic acids or succinimides; U.S. Pat. No. 3,932,290 which describes reaction products of di-(lower alkyl)phosphites and epoxides; and U.S. Pat. No. 4,028,258 which describes the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl)alkenyl succinimides. Preferred friction modifiers are succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis-alkanols such as described in U.S. Pat. No. 4,344,853.

Dispersants maintain oil insolubles, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts. Suitable dispersants include high molecular weight N-substituted alkenyl succinimides, the reaction product of oil-soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof. High molecular weight esters (resulting from the esterification of olefin substituted succinic acids with mono or polyhydric aliphatic alcohols) or Mannich bases from high molecular weight alkylated phenols (resulting from the condensation of a high molecular weight alkylsubstituted phenol, an alkylene polyamine and an aldehyde such as formaldehyde) are also useful as dispersants.

Pour point depressants, otherwise known as lube oil flow improvers, lower the temperature at which the fluid will flow or can be poured. Any suitable pour point depressant known in the art can be used. For example, suitable pour point depressants include, but are not limited to, one or more C₈to C₁₈dialkylfumarate vinyl acetate copolymers, polymethyl methacrylates, alkylmethacrylates and wax naphthalene.

Foam control can be provided by any one or more anti-foamants. Suitable anti-foamants include polysiloxanes, such as silicone oils and polydimethyl siloxane.

Anti-wear agents reduce wear of metal parts. Representatives of conventional antiwear agents are zinc dialkyldithiophosphate and zinc diaryldithiosphate, which also serves as an antioxidant.

Detergents and metal rust inhibitors include the metal salts of sulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil soluble mono- and dicarboxylic acids. Highly basic (e.g., overbased) metal sales, such as highly basic alkaline earth metal sulfonates (especially Ca and Mg salts) are frequently used as detergents.

Compositions containing these conventional additives can be blended with the basestock in amounts effective to provide their normal attendant function. Thus, typical formulations can include, in amounts by weight, a viscosity index (VI) improver (from about 0.01% to about 12%); a corrosion inhibitor (from about 0.01% to about 5%); an oxidation inhibitor (from about 0.01% to about 5%); depressant (from about 0.01% to about 5%); an anti-foaming agent (from about 0.001% to about 3%); an anti-wear agent (from about 0.001% to about 5%); a friction modifier (from about 0.01% to about 5%); a detergent/rust inhibitor (from about 0.01 to about 10%); and a base oil, based upon the weight of the formulation.

When other additives are used, it may be desirable, although not necessary, to prepare additive concentrates that include concentrated solutions or dispersions of the VI improver (in concentrated amounts), together with one or more of the other additives. Such a concentrate is typically referred to as an “additive package”, whereby several additives can be added simultaneously to the basestock to form a lubrication oil composition. Dissolution of the additive concentrate into the lubrication oil can be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The additive package can be formulated to contain the VI improver and optional additional additives in proper amounts to provide the desired concentration in the final formulation when the additive package is combined with a predetermined amount of base oil. For example, the VI improver may be present in a lubricant concentrate composition or additive package in an amount from about 2.5 to 25 wt. %, or about 5 to 20 wt. %, or about 7.5 to 15 wt. %, or about 10 to 12.5 wt. %, based on the total weight of the lubricant concentrate.

Blending with Basestock Oils

Conventional blending methods are described in U.S. Pat. No. 4,464,493, which is incorporated by reference herein. Conventional processes include passing the polymer through an extruder at elevated temperature for degradation of the polymer and circulating hot oil across the die face of the extruder while reducing the degraded polymer to particle size upon issuance from the extruder and into the hot oil. The pelletized, solid EP copolymers of the present invention, as described above, can be added by blending directly with the base oil. The solid copolymers can be dissolved in the basestock without the need for additional shearing and degradation processes.

The EP copolymers may be soluble at room temperature in lube oils at from about 7.5 to about 15 wt. %, in order to prepare a rheology modifier concentrate. Such concentrates, including eventually an additional additive package including the typical additives used in lube oil applications as described above, are generally further diluted to the final concentration (usually around 1 to 2%) by multi-grade lube oil producers. In this case, the concentrate will be a pourable homogeneous solid free liquid.

The invention may be further described with reference to the following embodiments.

Embodiment A: A lubricant composition comprising an oil basestock and from about 0.5 to about 2.5 wt. %, based on the total weight of the lubricant composition, of copolymer of propylene and ethylene, wherein the copolymer comprises from about 50 to about 95 wt. % ethylene, the copolymer has a melting point greater than about 90° C., and less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene.

Embodiment B: The lubricant composition of Embodiment A, wherein the copolymer comprises from about 65 to about 90 wt. % ethylene.

Embodiment C: The lubricant composition of any of Embodiments A through B, wherein the copolymer has a melting point greater than about 100° C.

Embodiment D: The lubricant composition of any of Embodiments A through C, wherein the melting point of the soluble fraction of the copolymer is greater than about 100° C.

Embodiment E: The lubricant composition of any of Embodiments A through D, wherein the lubricant composition has a thickening efficiency from about 1.5 to about 3.5.

Embodiment F: The lubricant composition of any of Embodiments A through E, wherein the lubricant composition has a shear stability index from about 15% to about 25%.

Embodiment G: The lubricant composition of any of Embodiments A through E, wherein the lubricant composition has a shear stability index greater than or equal to about 24%.

Embodiment H. The lubricant composition of any of Embodiments A through G, wherein the copolymer is not synthesized in the presence of a chain shuttling agent.

Embodiment I: A lubricant composition comprising an oil basestock and from about 7.5 to about 15.0 wt. %, based on the total weight of the lubricant concentrate, of a copolymer of propylene and ethylene, wherein the copolymer comprises from about 50 to about 95 wt. % ethylene, the copolymer has a melting point greater than about 90° C., and less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene.

Embodiment J: The lubricant composition of Embodiment I, wherein the copolymer comprises from about 65 to about 90 wt. % ethylene.

Embodiment K: The lubricant composition of any of Embodiments I through J, wherein the copolymer has a melting point greater than about 100° C.

Embodiment L: The lubricant composition of any of Embodiments I through K, wherein the melting point of the soluble fraction of the copolymer is greater than about 100° C.

Embodiment M: The lubricant composition of any of Embodiments I through L, wherein the copolymer is not synthesized in the presence of a chain shuttling agent.

Embodiment N: The lubricant composition of any of Embodiments I through M, wherein the oil basestock comprises one or more oils and a pour point depressant.

Embodiment O: The lubricant composition of any of Embodiments I through N, wherein the lubricant composition has a thickening efficiency from about 1.5 to about 3.5.

Embodiment P: The lubricant composition of any of Embodiments I through O, wherein the lubricant composition has a shear stability index from about 15% to about 25%.

Embodiment Q: The lubricant composition of any of Embodiments I through O, wherein the lubricant composition has a shear stability index greater than or equal to about 24%.

Embodiment R. A process for making a lubricant composition comprising: combining (a) an oil basestock, and (b) from about 0.5 to about 2.5 wt. %, based on the total weight of the lubricant composition, of a copolymer of propylene and ethylene, wherein the copolymer comprises from about 50 to about 95 wt. % ethylene, the copolymer has a melting point greater than about 90° C., and less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene; preferably where the copolymer is prepared by:

- polymerizing propylene and ethylene in a solution process and in the presence of a catalyst system comprising a catalyst and an activator to form a copolymer of propylene and ethylene; wherein the catalyst comprises a metallocene compound, the activator comprises a cationic component and an anionic component; wherein the cationic component of the activator corresponds to the formula:

[R¹R²R³NH]⁺, i.

- where R¹and R²are together a —(CH₂)_a— group, where a is 3, 4, 5, or 6 and R¹and R²form a 4-, 5-, 6-, or 7-membered non-aromatic ring together with the nitrogen atom to which one or more aromatic or heteroaromatic rings may optionally be fused via adjacent ring carbon atoms, and R³is a C₁-C₅alkyl group, or

[R₃NH]⁺, ii.

- where all R are identical and are C₁-C₃alkyl groups; and
- wherein the anionic component of the activator corresponds to the formula [B(R⁴)₄]⁻, where R⁴is an aryl group or a substituted aryl group having one or more substituents, wherein the one or more substituents are identical or different and are selected from alkyl, aryl, halogenated aryl, or haloalkylaryl groups or a hydrogen atom.

Embodiment S. The process of Embodiment R, wherein the copolymer is prepared in the absence of a chain shuttling agent.

Embodiment T. The process of any of Embodiments R through S, wherein the copolymer comprises from about 65 to about 90 wt. % ethylene.

Embodiment U. The process of any of Embodiments R through T, wherein less than about 5 wt. % of the copolymer, based upon the total weight of the copolymer, is soluble in xylene or ortho-dichlorobenzene.

Embodiment V. The process of any of Embodiments R through U, wherein the metallocene compound is a dialkylsilyl-bridged bis(indenyl)metallocene.

Embodiment W. The process of any of Embodiments R through V, wherein the cationic component of the activator is selected from N-methylpyrrolidinium, N-methylpiperidinium, trimethylammonium, or triethylammonium; and the anionic component of the activator is selected from tetrakis(pentafluorophenyl)borate or tetrakis(heptafluorophenyl)borate.

Embodiment X. The process of any of Embodiments R through W, where from about 0.5 to about 2.5 wt. % of the copolymer, based on the total weight of the lubricant composition, is combined with the oil basestock.

Embodiment Y. The process of any of Embodiments R through W, where from about 7.5 to about 15.0 wt. % of the copolymer, based on the total weight of the lubricant composition, is combined with the oil basestock.

ExamplesPreparation and Properties of Ethylene-Rich Copolymers

Five ethylene-propylene copolymers were prepared using a catalyst system comprising a dimethylsilyl bis(indenyl)hafnium dimethyl transition metal compound and a trimethyl anilinium tetrakis(pentafluorophenyl)borate activator. The copolymers have ethylene contents between about 75 and about 85 wt. %. Inventive copolymers are identified in Table 1, below, as polymers 1 through 5. Five comparative copolymers, prepared using a chain shuttling agent, diethyl zinc, are also listed in Table 1 and are identified as polymers C1 through C5. Properties of the comparative polymers are taken from PCT Publication No. WO2009/012216 (Table 2). Representative properties for the inventive and comparative polymers, including ethylene contents, melting temperatures, and molecular weight data, are given in Table 1.

TABLE 1

			Amorphous	Second	High T	Mn,	Mw,	Mw/Mn,
Sample	C₂,	Tm, ° C.	Fraction, %	Peak, ° C.	Peak, ° C.	g/mol	g/mol	g/mol
No.	wt. %	(DSC)	(TREF)	(TREF)	(TREF)	(GPC)	(GPC)	(GPC)

1	77.1	114.4	57.1	77.6	81.7	8617	52572	6.10
2	81.9	117.8	29	74.5	88	14223	58027	4.08
3	75.6	115.6	62	76.2	87	21517	75976	3.50
4	80.4	117.1	—	—	—	20775	61843	2.98
5	85.4	119.5	—	—	—	25840	98553	3.81
C1	71.4	73.7	—	—	—	70800	157600	2.2
C2	71.5	38.8	—	—	—	48040	92530	1.9
C3	71.2	37.0	—	—	—	66140	133700	2.0
C4	69.0	42.0	—	—	—	65770	153600	2.3
C5	69.6	41.4	—	—	—	63940	145800	2.3

Inventive polymer 2, having an ethylene content of 81.9 wt. %, was fractionated using ortho-dichlorobenzene (ODCB) according to the fractionation procedure described previously. Three fractions were obtained. Properties of each of the fractions are given in Table 2, below.

TABLE 2

Fraction	Solvent	Fraction	Wt.	Cumulative	C₂,	Tm,
No.	Temp, ° C.	(mass/g)	%	Wt. %	wt. %	° C.

1	0.0	33.0	8.1	8.1	71.7	110.25
2	10.0	92.0	22.5	30.6	74.5	117.13
3	130.0	282.0	69.1	99.8	80.4	122.14

As shown in Table 2, all three fractions obtained from polymer 2 show at least one melting temperature above 110° C., which indicates that all of the fractions comprise long ethylene sequences. These melting temperatures are at least about 20° C. higher than those of random ethylene-propylene copolymers having similar ethylene contents. Further, the melting temperatures are also at least about 20° C. higher than those of blocky ethylene-propylene copolymers prepared using a chain shuttling agent, as reported in PCT Publication No. WO2009/012216. These properties are illustrated graphically inFIG. 1, which shows melting temperature versus comonomer content for the polymers in Tables 1 and 2.

Preparation of Lubricant Compositions (Prophetic)

EP copolymers corresponding to Polymers 1 through 5 above are dissolved in STS ENJ102 oil (available from ExxonMobil Chemical Company) at a concentration of 1.5 wt. %, so as to resemble commercially available lubricant formulations.

	TABLE 3

	VI Improver	VI Improver Wt. %

	Polymer 1	1.5
	Polymer 2	1.5
	Polymer 3	1.5
	Polymer 4	1.5
	Polymer 5	1.5
	Paratone 8900	1.5

Preparation of Lubricant Concentrate Compositions (Prophetic)

Lubricant concentrate compositions are prepared by dissolving 11.3 wt. % of each of Polymers 1 through 5 in an SAE 10W40 base oil comprising 14.8 wt. % of a detergent inhibitor package, 0.3 wt. % of a pour point depressant, 58 wt. % Chevron 100 oil, and 42 wt. % Chevron 220 oil. Chevron 100 and Chevron 220 are both available from Chevron Corporation.

Certain embodiments and features have been described herein using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, any patents, test procedures, or other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby.