JPH0246634B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention improves the viscosity of mineral oils by adding certain saturated ethylene copolymers that provide superior low temperature viscosity properties compared to other ethylene copolymer viscosity index improvers to mineral oils of lubricating viscosity. Concerning improving properties. Recently, ethylene-propylene copolymers have become widely used as viscosity improvers in lubricating oils due to their low processing levels and improved viscosity properties. However, on the market there are various thickening effects (usually
There is a need for different molecular weight grades with different densities (referred to as consistency enhancement or TE). Although the production of each such copolymer grade can be accomplished by direct synthesis, different molecular weight grades can be produced by degradation of the ethylene-propylene copolymer to produce lower molecular weight variants. It can be manufactured by It is advantageous to use degradation methods. This is because large quantities of copolymer are produced in large scale polymer plants, the copolymer product is then used as a base stock, and the base stock is then converted to meet market demands for viscosity index improvers. This is because it is economical to decompose it into lower molecular weight grades. In order to achieve such degradation, (a) the amorphous rubber-like ethylene-propylene copolymer is heated at 260 to 420° C. with the exclusion of air;
(b) heating the ethylene copolymer for ~30 minutes until it first melts at 150-280°C, then excluding air;
heating and extruding at a temperature of 300-500℃, and
(c) oxidatively and mechanically degrading an ethylene-propylene copolymer (preferably free of other monomers such as dienes) in an oxygen-containing environment, such as by kneading. There is a way. Ethylene terpolymers containing dienes such as 5-vinyl-2-norbornene or ethylene quaternary polymers containing both 1,4-hexadiene and 2,5-norbornadiene are kneaded in the presence of air or oxygen. It is known that it is not suitable for mechanical degradation such as oxidation. This is because this degradation technique produces excessive amounts of oil-insoluble polymer gel particles. This problem,
C ₃ to C ₁₆ higher α-olefin and 1 to 25% by weight
A breakthrough was made by the use of ethylene copolymers that also contained _C8 - _C28 alkylnorbornenes (October 1978).
(see German DOS 28 15 427, published 19 May). It has been introduced for a variety of reasons, including as a means of introducing branching into ethylene polymers and as a means of cross-linking the polymers by introducing a proportion of diene-reactive cross-linking agents. There is a large body of patent literature dealing with ethylene terpolymers and quaternary polymers containing one or more dienes (see, for example, British Patent No. 1195625). However, only a limited number of these patents deal with ethylene terpolymers and quaternary polymers added to mineral oils as viscosity index modifying additives and are best exemplified by U.S. Pat. No. 3,790,480. Ru. This US patent teaches ethylene terpolymers and quaternary polymers containing ethylene, a _C3 to _C18 higher α-olefin such as propylene, and two dienes based on the relative polymerizability of each double bond. In one group of dienes (such as represented by 1,4-hexadiene) only one of the two bonds is readily polymerizable, whereas in the other group (such as represented by 2,5-norbornadiene), only one of the two bonds is readily polymerizable. (such as the one typified by), both double bonds are easily polymerizable. Here, ethylene polymer viscosity index modifying additives for mineral oils contain dienes of both groups rather than prior art ethylene terpolymers containing dienes of the group having only one easily polymerizable double bond. It has been taught that ethylene terpolymers containing ethylene terpolymers are superior. Introducing a second diene comonomer with two easily polymerizable double bonds into the terpolymer results in a negligible increase in intrinsic viscosity (column 8,
(see lines 23-30) and because it provides a meaningful increase in bulk polymer viscosity without reducing the properties of the terpolymer that provides the viscosity index improvement for mineral oils.
It is believed that the above-mentioned excellence can be achieved. The only discussion of the low temperature viscosity properties of mineral oil solutions containing this type of ethylene terpolymer is given in columns 10, lines 1-3, and is shown to be satisfactory for those 10W30 multigrade lubricants. It is said that it gave good results. U.S. Pat. Nos. 3,499,741 and 3,681,302 contain small amounts of nonconjugated dienes and provide pour point depressants for "fuel oils, diesel oils, middle distillates, and other viscous hydrocarbon oils." (See Column 1, Section 1 of the specification). The above terpolymers are also useful as gasoline additives for modifying deposits in induction system systems (No.
3499741 specification, column 1, lines 23-25).
The nine specific nonconjugated dienes are 2,5-norbornadiene or hiscyclo[2.2.1]hepta-2,5-
Although the present invention includes thermally decomposed unsaturated ethylene-propylene-hexadiene- Only 1,5 and ethylene-propylene-cyclopentadiene terpolymers are specifically exemplified. Unsaturation in polymeric viscosity index improvers is generally undesirable. This is because the unsaturation, or double or triple bonds, in a polymer can cause, for example, a high molecular weight polymer to degrade during engine lubrication into fragments that no longer have viscosity index modifying properties or The desirability of additives such as by cross-binding to molecular weights that are no longer soluble in mineral oil, inducing their precipitation as varnish on engine interior surfaces and/or contributing to engine lube sludge formation. This is because it becomes a means of deteriorating the characteristics. The object of the present invention is a saturated ethylene copolymer viscosity index improver for mineral oils with lubricating viscosity with excellent low temperature viscosity properties, preferably easily oxidatively degraded to low molecular weight to obtain maximum working properties. The goal is to provide what we can. Accordingly, in the present invention, 0.05 to 3.0 preferably
0.05 to 1.5, more preferably 0.1 to 1.0, most preferably 0.2 to 1.5
Ethylene/ _C3 - _C18 α-olefin terpolymer containing 0.8% by weight of 2,5-norbornadiene (bicyclo[2.2.1]hepta-2,5-diene) is saturated and easily reprocessed. capable of providing improved low temperature viscosity properties to mineral oils of lubricating viscosity, being compatible with pour point depressants in solution in the mineral oil, and, if desired, reducing the harmful effects of oil-soluble polymer gel particles. It has been found that the molecular weight can be easily reduced by oxidative degradation without the formation of (Mn) and 1.0 to 3 preferably 1.2
with a consistency increase in the range of ~2.8 and 26-79% by weight
(35-85 mol%) of at least one C3-C18 α-olefin such as ethylene and propylene and 0.05-85 mol% of at least one _C3 - _C18 α-olefin such as ethylene and propylene
1.5 preferably at least a viscosity index improving dose of an oil-soluble ethylene copolymer containing from 0.1 to 1.0 wt. Contains oil pour point depressants. In a preferred embodiment, the ethylene copolymer is heated at a temperature of about 95-260°C, preferably in the presence of air.
Oxidatively and mechanically degraded by kneading for 0.25 to 20 hours, thereby increasing the consistency from a value greater than about 3, e.g. from about 4 to 1.0 to 3.0, preferably 1.2
-2.8, and the oxygen content in the ethylene copolymer is about 0.005-6% by weight, preferably 0.05-3% by weight, based on the total weight of the copolymer. Mechanically degraded and oxidized copolymers can be reacted with polyamines to obtain dispersibility, thereby providing polyfunctionalization, i.e., the copolymers have a The nitrogen content is about 0.005 to 4, preferably 0.05 to 2, by weight. The consistency enhancement (TE) is 12.4 centistokes at 98.9°C for a solvent-extracted neutral mineral lubricating oil (Solvent 150 Neutral) with a viscosity of 150 SUS at 37.8°C, a viscosity index of 105 and an ASTM pour point of -17.8°C. Polyisobutylene with Schausinger molecular weight of 20,000 required to thicken to viscosity (Exxon, New York, New York, USA)
It is defined as the ratio of the weight percent of a test copolymer required to thicken the same oil to the same viscosity at the same temperature. Generally, the amount of copolymer added to the mineral oil is within the range of 0.1 to 15%, preferably 0.2 to 7% by weight, based on the total weight of the lubricating composition. Ethylene quaternary copolymers containing ethylene, longer-chain α-olefins, 1,4-hexadiene, and 2,5-norbornadiene monomers are known as VI improvers for mineral oil compositions, and are known as VI improvers for mineral oil compositions. The quaternary copolymer provides suitable low temperature performance, and even though it is itself an unsaturated copolymer, it is easily processable. In accordance with the teachings of the present invention, 2,5-norbornadiene is a copolymer with an iodine value of less than 0.8 that is indistinguishable from a readily processable saturated copolymer, i.e., a copolymer containing no diolefin with long chain branching. The additive activity of the terpolymer in mineral oil appears to copolymerize with ethylene and _C3 - _C18 higher α-olefins to form a copolymer, thereby providing excellent low-temperature viscosity properties. Moreover, when necessary, the terpolymer can be compounded into a TE that provides improved shear stability of the mineral oil additive. Without wishing to be bound by any theory, it is believed that 2,5-norbornadiene acts to reduce the length of the ethylene bonds in the polymer chain, which ultimately It appears to play many roles in providing long chain branching (which is desirable as noted in the prior art) by reducing meration and lowering oil solution viscosity at low temperatures. It also appears that the 2,5-norbornadiene enters the chain by more than one mechanism, one of which does not result in branching. The absence of residual olefins or unsaturation allows oxidative milling to reduce molecular weight. It appears that only the 2,5-norbornadiene structure is capable of performing these various functions. Both double bonds should be easily polymerizable for the purpose of forming long chain branches and leaving no olefinic residues. For the purpose of reducing the length of ethylene bonds, olefins can be polymerized only with ethylene and polymerized with higher α-
Olefins should be sufficiently sterically hindered that they do not polymerize, and they should polymerize readily with ethylene to produce products with effective reactivity ratios close to zero (reactivity ratios for various structures). For product and dynamic data definitions, please refer to F.P.
(See Baldwin and G. Bar. Straight, Rubber Reviewa 44 , 769 (1972)). Gelation in a continuous flow stirred reactor is 1/(2
DPw) (where w is the weight average degree of polymerization in the absence of diene) and this value for the polymers of Example 1 is approximately 0.01% (for these polymers (much larger), so there must be multiple polymerization mechanisms. Presumably, 2,5-norbornadiene enters the chain to form a nortricyclone structure. Similar structures appear to be possible with vinyl-1-cyclohexane, which can also be adapted through experimentation to provide relatively unique and valuable terpolymers. This is because it is obtained with the terpolymer described in the present invention. This chain structure can be as high as 90% 2,5-norbornadiene incorporated into the polymer. Without this double polymerization mechanism, inadequate dienes may be introduced into the polymer to meaningfully affect bond distribution. The long chain α-olefins that can be used alone or in mixtures in preparing the ethylene copolymers used in the practice of this invention include from 3 to about 18
A monomer containing 5 carbon atoms. These α-olefins may be linear,
Alternatively, if branching occurs at three or more carbon atoms away from the double bond, it may be branched.
_C3 to _C18 , although single olefins are preferred
Mixtures of olefins can also be used. However, it is preferred to copolymerize ethylene monomer with propylene. Generally, the copolymers of ethylene, _C3 to _C18 higher alpha-olefins, and 2,5-norbornadiene used in accordance with the present invention contain about 26 to 80% ethylene and about 20 to 74% by weight. of _C3 to _C18 α-olefin and 0.05 to 3.0 preferably 0.05 to 1.5% by weight of 2,
It is derived from 5-norbornadiene, and the latter is the only diene used. Preferably, the copolymer is derived from about 40-65% by weight ethylene, about 35-60% by weight _C3 - _C18 alpha-olefin, and about 0.2-1.0% by weight norbornadiene. The most preferred copolymer is 43% by weight
of ethylene, 56.2% by weight propylene and 0.8% by weight norbornadiene. The copolymers of the present invention can be characterized by the following properties.

[Table] These copolymers are found in elements b of the periodic table,
Catalysts consisting of transition metal compounds from groups b and b, in particular compounds of titanium and vanadium, such as VOCl ₃ , and organometallic reducing compounds from groups a, b and a, called cocatalysts, in particular organoaluminum compounds, such as (C ₂ H ₅ ) ₃ Al ₂ C ₃ . Examples of suitable catalysts and preferred reaction conditions can be found in U.S. Patent No. 3,551,336.
No. The polymerization is carried out using ethylene,
The copolymer can be produced by passing an α-C ₃ to C ₂₈ monoolefin, preferably propylene, 2,5-norbornadiene and hydrogen. The non-reactive reaction medium may be an aromatic hydrocarbon such as toluene, a saturated aliphatic hydrocarbon such as heptane, pentane and hexane, or a chlorohydrocarbon such as tetrachloroethylene. All steps in this reaction should preferably be carried out in the absence of oxygen, moisture, carbon dioxide or other harmful substances. During the polymerization, the reaction mixture is heated at −40 to 100 °C over a period of 1 to 300 minutes, preferably 3 to 60 minutes, optimally 15 minutes.
It can be stirred and maintained at a temperature of preferably -10 to 70°C, optimally about 30°C. At the end of this period, the reaction mixture can be treated to separate the product copolymer, or the mixture can be used as is for degradation. These additives for improving the viscosity index of ethylene copolymers of the present invention can be easily degraded, that is, their molecular weight can be reduced by kneading them in air using a mechanical shearing machine, such as a Banbury mixer. I found out that it can be done. This process produces "stay-in-grade" performance when formulated into lubricating oils, which is important, if not essential, for the lubrication of modern high-performance engines. yields a shear-stable ethylene copolymer that provides This discovery that these materials can be mixed in a high shear machine is surprising. That is,
Commercially available terpolymers having greater than 1% by weight of cyclic diolefins, such as Vistalon 2504 (ethylene-
propylene-2-ethylidene-5-norbornene terpolymers) or quaternary polymers having more than 1% by weight linear diolefins, such as those sold by E.I. DuPont, Wilmington, Del. “Nordel 1320”
(Tetrapolymer of ethylene, propylene, 1,4-hexadiene, and 2,5-norbornadiene)
This is because it produces an oil-insoluble gel when kneaded in air. This gel formation is unacceptable since the oxidized milled quaternary polymers are respectively insoluble in mineral oil and are no longer useful as viscosity modifiers. For the purposes of the present invention, the mechanical-oxidative degradation of ethylene copolymers can be carried out in a single piece of equipment or can be carried out in stages. It is preferred to operate in the absence of solvents or fluxing oil so that the ethylene copolymer is easily exposed to air as taught in French Patent Application No. 7,523,806.
Useful equipment includes Banbury mixers and mills with adjustable gaps, which are equipped with jackets through which a heating medium such as overpressure steam or heated DOWTHERM can pass. It can also be sealed in a container. Fluxing oil can be added to the degraded ethylene copolymer when the desired level of degradation is reached, as measured by oxygen uptake and reduction in consistency enhancement (TE) as described above. usually,
About 5-50% by weight based on the weight of the total solution obtained
Sufficient oil is added to provide a degraded copolymer concentration within the range of . The resulting oil solution can then be used commercially as a lubricating additive or easily incorporated into lubricating oils. Useful temperatures for mechanical-oxidative degradation of ethylene copolymers are within the range of about 95-260°C. The time required to achieve a satisfactory result will depend on the type of reduction or kneading equipment, the temperature of the reduction, and especially the rotational speed of the blade mixer, if used as reduction or kneading equipment. In this regard, to provide the desired degree of kneading or milling and oxidative degradation in a single unit, Bramley Becken
Blade mixers have been found to be particularly useful. This mixer is equipped with a variable speed device and has two rolls with geared knives arranged around them so that one roller rotates at half the speed of the other roller. These rollers are journaled in a jacketed reactor that has two hemispheres at the bottom (corresponding to the radii of the two rollers). Superheated steam or heated "dowtherm" can be circulated through the jacket to provide the desired temperature. When using this mixer, approximately 95~
A satisfactory reduction in consistency can be obtained in a temperature range of 260°C for 0.25-20 hours. Instead of using fluxing oil, other inert solvents can be used in preparing fluid solutions of ethylene copolymers, including naphtha, hexane, cyclohexane, dodecane, mineral oil, biphenyl , liquid hydrocarbons such as xylene or toluene, solvent-neutral lubricating oils, white lubricating oils, chlorinated solvents such as dichlorobenzene, and the like. The amount of solvent is not critical as long as a sufficient amount is used to provide a fluid solution of the ethylene copolymer to facilitate mechanical-oxidative degradation. Such solutions as described above typically contain from about 50 to about 95 weight percent solvent. The oil-soluble ethylene copolymer additives containing the oxygen- and nitrogen-containing derivatives of the present invention are present in lubricating oil compositions, such as automotive or diesel crankcase lubricants, in at least a viscosity index-enhancing amount and generally throughout the entire composition. About 0.1-15% by weight of the product preferably 0.2
It is formulated at a concentration within the range of ~7% by weight. Additionally, these oil-soluble degraded ethylene copolymer improving materials of the present invention can be derivatized into multitubular performance improvers by the addition of sludge dispersing activity. This is easily accomplished by reacting or grafting an amine compound to the ethylene copolymer material of the present invention. Amine compounds useful for introducing sludge dispersion activity include mono- and polyamines having about 2 to 60, e.g., 3 to 20, total carbon atoms and about 1 to 12, e.g., 2 to 6 nitrogen atoms in the molecule. and these amines may be hydrocarbyl amines or hydrocarbyl amines containing other groups such as hydroxy groups, alkoxy groups, amido groups, imidazoline groups and the like. Preferred amines have the general formula [In the above formula, R, R' and R'' are hydrogen, _C1 - _C25 straight chain or branched alkyl group, _C1 - _{C12 alkoxyC2-
C6} alkylene groups, _C2 - _C12 hydroxy or aminoalkylene groups and _C1 - _C12 alkylamino _C2 - _C6
each selected from the group consisting of alkylene groups,
s is a number from 2 to 6, preferably from 2 to 4; and t is a number from 0 to 10, preferably from 2 to 6. Examples of suitable amine compounds include mono-, di- and tritallowamines, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, diethylenetriamine, tritallowamine, Ethylenetetramine, tetraethylenepentamine, 1,2-propylene diamino, di-(1,2-propylene)triamine, di(1,3-propylene)triamine, N,N-dimethyl-1,3-diaminopropane, N , N-di(2-aminoethyl)ethylenediamine, N,N
-di(2-hydroxyethyl)-1,3-propylenediamine, 3-dodecyloxypropylamine, N-dodecyl-1,3-propanediamine,
Mention may be made of trishydroxymethylmethylamine, diisopropanolamine and diethanolamine. Other useful amine compounds include cycloaliphatic diamines such as 1,4-di(aminomethyl)cyclohexane and imidazolines and the general formula [wherein Z is oxygen or NG, G is selected from the group consisting of hydrogen and Ω-aminoalkylene groups of 1 to 3 carbon atoms, and p is an integer of 1 to 4]. Heterocyclic nitrogen compounds such as N-aminoalkylpiperazine are mentioned.
Examples of such amines include, but are not limited to, 2
-Pentadecylimidazoline, N-(2-aminoethyl)piperazine, N-(3-aminopropyl)
Piperazine, N,N'-di-(2-aminoether)
Includes piperazine and n-propylaminomorpholine. Commercial mixtures of amine compounds can also be used with advantage. For example, one method for making alkylene amines is to prepare alkylene dihalides (such as ethylene dichloride or propylene trichloride).
and ammonia to form a complex mixture of alkylene amines in which nitrogen pairs are linked by alkylene groups, thus forming compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and piperazine isomers. includes doing. A low cost poly(ethylene amine) compound having a composition similar to tetraethylene pentamine is commercially available under the trade name "Polyamine 400 (PA-400)" by the Freuderson Chemical Company of New York, New York, USA. are available on the market. Similar materials can also be made by polymerization of aziridine, 2-methylaziridine and azetidine. Still other amines separated by heteroatom chains such as polyethers or sulfides can be used. Introduction of sludge dispersion activity can be accomplished by various means, such as mechanically degrading oil-soluble ethylene copolymers with oxygen-containing gases and amine compounds from about 130 to about
reacting at a temperature of 300° C. to form an anion of said oxidized ethylene copolymer and reacting said anion with acrylonitrile, followed by derivatization of the reaction product with an amine, and from a mineral oil of lubricating viscosity. This can be achieved by reacting the oxidized ethylene copolymer with the amine alone (these can be used in combination with other viscosity index improvers) in the main lubricating oil composition. can. If desired, the copolymer may contain other additives such as preferably pour point depressants,
ashless dispersants, such as the reaction product of polyisobutenylsuccinic anhydride and tetraethylenepentamine;
detergent type additives such as calcium nonyl sulfurized phenate and magnesium phenyl sulfonate;
It can be used in combination with zinc antioxidants such as dialkyldithiophosphates. Mineral oils of lubricating viscosity are those obtained by distilling crude oil under vacuum or otherwise synthesized to provide a lubricating oil suitable for the lubrication of internal combustion engines and hydraulic applications. means a substance. These mineral oils of lubricating viscosity are certified by the Society of Automotive Engineers SAE J
Although it is possible to classify according to the viscosity classification method of "300d", for the purpose of this specification, the mineral oil has a viscosity of 9600 preferably
Viscosity range from 1200 to 2400 centipoise and ASTM
It has a viscosity range of 5.7 to 22.7 centistokes at 99°C as measured by the D445 procedure. A feature of the present invention is that significant improvements in low temperature viscosity properties can be achieved without undesirably affecting pour point when pour point depressants are present in the formulated oil. This improvement can be particularly noted when the lubricating composition contains the pour point depressant in an amount of 0.1 to 1.0% by weight, preferably 0.4% by weight.
Exemplary pour point depressants that may be present in the compositions of the present invention include chlorinated wax/naphthalene condensates, such as those described in U.S. Pat. No. 2,174,246; like
_C10 - _C18 alkyl methacrylate polymers, copolymers of di-n-alkyl fumarates and vinyl acetate as described in U.S. Pat. No. 2,936,300, ethylene-
Examples include vinyl acetate copolymers, styrene and α-olefin copolymers, and styrene and maleic anhydride copolymers. In the following examples, all parts are by weight unless otherwise specified. A series of ethylene-propylene copolymers were prepared with varying ethylene, propylene and/or norbornadiene contents. These copolymers (of which there are five examples) are hereinafter referred to as EPNBD-1-5. These EPNBD copolymers are prepared from the above three comonomers by varying the feed ratios of ethylene, propylene and norbonadiene in a polymerization process carried out essentially as follows.
EPNBD-1 copolymer is produced under these specific conditions. That is, 100 parts n-hexane, 0.009 parts vanadium oxychloride, and 0.032 parts by weight.
3.0 parts with ethylaluminum sesquichloride
1 part ethylene, 6.8 parts propylene, 0.006 parts norbornadiene and 45 ppm hydrogen were introduced into the reactor. The catalyst composition was characterized by an Al/V molar ratio of 4. The residence time was approximately 13 minutes.
The polymerization temperature was 32°C and the pressure was 60 psig. The solvent-free ethylene copolymers of the invention were produced by steam distillation. copolymer
EPNBD2-6 were produced by varying the feed ratio appropriately. Specific compositions are shown below.

Table: For comparison purposes, an ethylene-propylene copolymer with an ethylene content of 46% by weight was used. This commercially available copolymer was made in accordance with US Pat. No. 3,697,429 and is referred to herein as EPC-1. Example 1 In this example, the copolymers of the present invention, namely EPNBD2~
The oil mixing properties of a reference oil containing EPC-1 were compared to an oil sample containing a prior art ethylene-propylene copolymer, EPC-1. The reference oil is a formulation test oil consisting of a solvent neutral oil and a pour point depressant to provide a mixture having a viscosity of about 6.7 centistokes at 99°C. Table 2 illustrates the effect of both types of ethylene copolymers on the blending properties of the reference oil when sufficient copolymer is added to provide a 98.9° C. viscosity of about 40 centistokes.

[Table] None
(1) All oils were formulated to have a viscosity of 12.4 centistokes at 99°C as measured in an Utsbelohde viscometer. (2) ASTM Committee D-2RDD and C
A Kuett-type viscometer as described by
It was operated at a shear stress of 100Pa. MRV = mini rotary viscometer. Pa·s means Pascal seconds. (3) State College, Pennsylvania, USA;
A Quetzt-type viscometer available from Common Instrument Company, P.O. Box 16, was operated at approximately 0.01 MPa. CCS = cold
Cranking Simulator ASTM D-
Measured using test method 2607-72. (4) Before λ - After λ / Before λ x 100 (λ is the viscosity measured at 99℃ using an Utsbelohde viscometer) (5) Measured as 1/3 of the tensile viscosity at a stress of approximately 1 KPa (the bar straight , Double You
Mr. Glasley's Rubber Chem.Technol. ).
Representative quaternary polymers of U.S. Pat. No. 3,790,480 such as "Nodel 2522" were tested in this test.
It has a viscosity of 7MPa・s. The data in Table 2 shows a series of 2,5-norbornadiene-containing ethylene tripolymers that exhibit the bulk viscosity properties of the quaternary polymers of U.S. Pat. No. 3,790,480 in the absence of dienes of the group represented by 1,4-hexadiene. It is further demonstrated that these terpolymers of the present invention exhibit useful and surprising low temperature viscosity properties comparable to those provided by ethylene-propylene copolymers. Indicates that it provides a mineral oil with a lubricating viscosity. Until now,
Such low temperature properties leave residual unsaturation in prior art polymers (both terpolymers and quaternary polymers of ethylene such as those described in U.S. Pat. No. 3,790,480) or It could only be obtained by incorporating a group of dienes that do not provide significant long chain branching, such as in ethylene terpolymers containing ₁ to _C21 alkylnorbornene. The copolymers are incorporated into mineral oils of lubricating viscosity at least in viscosity-enhancing doses, generally from 0.1 to 15% by weight, based on the lubricating oil composition. However, when the copolymer is marketed as a concentrate in mineral oil, the copolymer content is in the range of 6 to 45% by weight (all weight percentages are based on the total weight of the composition or concentrate). . Thus, in summary, the amount of the copolymer of the present invention (including the oxidized form) in mineral oil is 0.1 to 45% in the majority (generally 55 to 99% by weight) of mineral oil of lubricating viscosity. Within the range of % by weight.

Claims (1)

[Scope of Claims] 1. A major amount of mineral oil having lubricating viscosity and an ethylene content of 26 to 79% by weight (35 to 85 mol%), C ₃ to C ₁₈
higher α-olefin and 0.05 to 3.0% by weight of 2,
1.0 to 3 when compared to polyisobutylene having a number average molecular weight (Mn) of at least 5000 and a viscosity average molecular weight (Mv) of 20000.
0.1 to 15% by weight of an oil-soluble oxidatively and mechanically degraded saturated ethylene copolymer having a consistency increase in the range of . 2. The lubricating oil composition of claim 1, wherein 2,5-norbornadiene is present in an amount within the range of 0.05 to 1.5% by weight and is the only diene present. 3 Ethylene copolymer has a consistency increase rate of 1.2 to 2.8 and
(Mn) of 10000-100000, and 2,5
A lubricating oil composition according to claim 1 or 2, characterized in that - norbornadiene is present in an amount of 0.2 to 0.8% by weight. 4. The lubricating oil composition according to any one of claims 1 to 3, wherein the higher olefin is propylene. 5. The lubricating oil composition according to any one of claims 1 to 4, wherein the ethylene copolymer has an oxygen content of 0.005 to 6% by weight based on the total weight of the copolymer. . 6 Claims 1 to 5 in which the ethylene copolymer has an oxygen content of 0.05 to 3% by weight
The lubricating oil composition according to any one of paragraphs. 7. Claim 1 also comprising at least a pour point depressing dose of a lubricating oil pour point depressant.
The lubricating oil composition according to any one of items 1 to 6. 8 The general formula [formula] [formula] and [In the above formula, R, R' and R'' are hydrogen, _C1 - _C25 straight chain or branched alkyl group, _C1 - _{C12 alkoxyC2-}
each selected from the group consisting of a _C6 alkylene group, a _C2 - _C12 hydroxyalkylene group, a _C2 - _C12 aminoalkylene group, a _C1 - _C12 alkylamino _C2 - _C6 alkylene group, and Z is O or NG. (wherein G is selected from the group consisting of hydrogen and Ω-aminoalkylene groups having 1 to 3 carbon atoms), s is a number from 2 to 6, and t is a number from 0 to 10. and p is an integer from 1 to 4] in an amount sufficient to provide the copolymer with a nitrogen content of 0.01 to 0.5% by weight. The composition according to any one of claims 5 to 7, which comprises: 9. The composition of claim 8, wherein the amine compound is an alkylene polyamine containing 2 to 6 nitrogens per molecule. 10 The ethylene copolymer has an ethylene content of 26 to 79% by weight, 20 to 79% by weight of _C3 to _C18 α-olefin, and 0.05 to 1.5% by weight of 2,5-norbornadiene and is greater than 3.0 10. The composition according to claim 5, which is a reaction product obtained by kneading an ethylene copolymer with increased consistency in air.