NL8000141A - LUBRICATION OIL COMPOSITION. - Google Patents

Description

4 * VO 8860

Lubricating oil composition.

The present invention relates to improvements in the viscosity properties of mineral oils of lubricating viscosity suitable by the addition of certain saturated ethylene copolyners which provide the mineral oil with excellent low temperature viscometric properties compared to other viscosity index improvers. based on ethylene copolymers.

For some time, ethylene / propylene copolymers have been widely used as viscosity improvers in lubricating oils because of the small amounts required from these copolymers, and their improved viscometric properties.

However, there is a demand for grades of different molecular weight, which grades have a different thickening capacity, so that they can be used with mineral oils of different viscosities. While such copolymer values can be prepared by direct synthesis, the different molecular weight grades can also be obtained by degradation of an ethylene / propylene copolymer to form lower molecular weight versions. The degradation method offers advantages, since it is more economical to prepare a large amount of copolymer in a large-scale polymerizer and then use this copolymer as a base material, which is broken down to lower molecular grades to meet demand. Degradation can be accomplished in various ways, such as (a) heating an amorphous rubbery ethylene / propylene copolymer for 3-30 min at 2 ° -120 ° C with exclusion of air, (b) extrusion and heating an ethylene copolymer, first at 150 -280 ° C until melted and then at a temperature of 300-500 ° C under exclusion of air, and (c) by oxidative and mechanical 800 0 1 41 ƒ 2 degradation of ethylene / propylene copolymers in an oxygen containing environment, which copolymers are preferably free from other monomers, such as dienes (see U.S. Pat. No. 3 * 769 * 216).

It is known that ethylene terpolymers which serve, such as 5-5 vinyl-2-norbornene, or ethylene tetrapoiymers containing both 1,1-hexadiene and 2,5-norbomadiene are not suitable for mechanical degradation in the presence of air or oxygen, where oxidation occurs, since this degradation technique yields excessive amounts of oil-insoluble polymeric gel particles.

This problem was solved by using an ethylene copolymer, which also contains a C8 -C18 g alkene-1 and 1-25 wt.% Of an alkyl norborne with 8-28 carbon atoms (see German Offenle- gungsschrift 28 15 1 * 27)

The patent literature contains many publications on ethylene tri-15 and tetrapolymers containing one or more types of dienes which have been introduced for various reasons, such as for branching into the ethylene polymer and providing the possibility of cross-linking the polymer by introduction of a cross-linking agent which reacts with a portion of the diene (see, for example, British Patent 1,195,625). However, the number of patents relating to the addition of ethylene tri and tetra polymers to a mineral oil to change the viscosity index is limited in number. A good illustration is U.S. Patent No. 3,790,880, which relates to ethylene ter and tetra polymers of ethylene, a C8 -C18 olefin-1 such as propylene, and two classes of service based on the polymerisability of each of the double bonds. In a class of diene (of which 1,1-hexadiene is a representative example), only one of the double bonds is easily polymerizable, while in the other classes for which 2,5-norbornadiene is representative, both double bonds are easily polymerizable. According to the patent, an ethylene-containing mineral oil polymer additive for changing the viscosity index is superior when it is an ethylene 80 0 0 1 41 i 3 * tetrapolymer containing both classes of service, in contrast to the known ethylene terpolymer, which class of service, which has only an easily polymerizable double bond. Apparently, this superiority is due to the fact that the introduction of the second deencomonomer with two readily polymerizable double bonds into the terpolymer causes a marked increase in the bulk viscosity of the polymer with only a slight increase in the inherent viscosity (see column 8 , lines 23-30) and without deteriorating the ability of the terpolymer to improve the viscosity index of mineral oils. The only place where the low temperature viscometric properties of mineral oils containing this type of ethylene terpolymer is concerned is column 10, lines 1-13, which are said to give satisfactory results for multigrade lubricating oils 10W30.

US Pat. Nos. 3,999-7,1 and 3,631,302 describe ethylene terpolymers containing a minor amount of a non-conjugated diene which can be thermally cracked to provide a pour point lowering additive. * 20 additive for "fuel oils, diesel oils, middle distillates and other viscous hydrocarbon oils" (see column 1, first paragraph of both patents). The intended terpolymer can also be used as an additive to gasoline to modify deposits in the loading system (see U.S. Patent No. 3, 3, 99, 7, 1, column 1, lines 23-25). Among the nine unconjugated dienes listed are 2,5-norbomadiene, ie, bicyclo / 2.2.1 / hepta-2,5-diene (see U.S. Pat. No. 3,681,302, column 2, line 36 and U.S. Pat. 3, 99-7, 1, column 2, lines 29-30), although the invention is specifically illustrated only with thermally cracked, unsaturated ethylene / propylene / hexadiene-1,5 and ethylene / propylene / cyclopentadiene terpolymers.

Unsaturation in a polymer additive to improve the viscosity index is generally undesirable, since the unsaturated portion, ie, the double or triple bond of the polymer, allows the desired properties of the polymer to be achieved. the additive deteriorates during engine lubrication, for example, by cleavage of the high molecular weight polymer in fragments which do not have viscosity index improving properties, or by cross-linking the polymer to a molecular weight with which it is no longer soluble in mineral oil so that it precipitates as a paint on internal engine surfaces and / or contributes to the formation of oil sludge.

An object of the invention is to provide a saturated ethylene-containing copolymer viscosity index improving additive for mineral oils having a viscosity suitable for lubrication purposes, which additive has excellent low temperature viscometric properties and is preferably readily oxidative degradable. to a lower molecular weight.

It was found that an ethylene / C 1 -C 2 g olefin-1 terpolymer containing 0.05-3.0 wt. #, Preferably 0.05-1.5 wt. #, Especially 0.1- 1.0% by weight, optimally 0.2-0.8% by weight # 2,5-nororadadiene (bicyclo [2.2.1 / hepta-2,5-diene), is saturated, can be easily processed and imparts improved low temperature viscometric properties to a mineral oil of lubrication viscosity, if solution in the mineral oil is compatible with pour point lowering additives and, if desired, can be easily reduced in molecular weight by oxidative degradation without damaging the formation of oil-insoluble polymeric gel particles occur.

The lubricating oil composition according to the invention contains a mineral oil with a viscosity suitable for lubrication and at least a viscosity index improving amount of an oil-soluble ethylene copolymer with a number average molecular weight of at least 5000, preferably 10,000-100,000, a thickening capacity of 1. 0-3, preferably from 1.2-2.8, and containing 26-79 wt.% (35-35 mol. #) Of ethylene, at least one C 1 -C 4 g keen-: 1, such as propylene and 0.05-1.5 wt.%, preferably 0.1-1.0 wt. # 80 0 0 1 41 4 5 * 2,5-norbomadiene, the sum by weight being 100), and preferably at least a pour point lowering amount of a pour point lowering additive for lubricating oil.

In a preferred embodiment, the ethylene copolymer 5 is oxidatively and mechanically degraded, preferably by mastication, in the presence of air at a temperature of 95-260 ° C for 0.25-20 hours, with the thickening power from a value of more than 3, for example, from about 4, it is reduced to a value between 1.0 and 3.0, preferably 1.2-2.8, and the oxygen content of the ethylene copolymer is 0.005-6, preferably 0.05- 3 wt.%, Based on the total weight of the copolymer.

The mechanically degraded and oxidized copolymer can be reacted with polyamines for dispersibility to provide multifunctionality, and the copolymer typically 0.005 wt.%, Preferably 0.05-2 wt.% Nitrogen based on the total weight of the copolymer.

The thickening power is defined as the ratio of the weight percentage of polyisobutene (sold under the trade name Paratone (5) '20 IJ ^ by Exxon Chemical Co., New York) with a Staudinger molecular weight of 20,000 required for thickening of a solvent extracted neutral mineral lubricating oil with a viscosity of 150 SUS at 37.8 ° C, a viscosity index of 105 and an ASTM pour point of -17.8 ° C (Solvent 150 25 Neutral) to a viscosity of 12, b cSt at 98.9 ° C, up to 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 0.1-15% by weight, preferably 0.2-7% by weight, based on the total weight of the lubricating oil composition.

It is known that ethylene tetrapolymers containing ethylene, a longer chain olefin-1, 1,1-hexadiene and 2,5-norbomadiene monomers can be used as a viscosity index improved 80 0 0 1 41 ΐ 6 additives for mineral oil compositions. Such a tetrapolymer confers suitable low temperature properties and is itself easily processable, despite the fact that it is an unsaturated copolymer.

The 2,5-norbornadiene has been found to copolymerize with ethylene and the C18 -C18 olefins-1 in such a way that an easily processable saturated copolymer is obtained which has an iodine value of less than 0.8 and cannot be distinguished from the copolymer, which does not contain a long chain branching alkadiene, wherein the activity of the terpolymer in mineral oil provides excellent low temperature viscometric properties, yet, if necessary, this terpolymer can be masticated to such a thickening capacity that improved shear stability of the mineral oil additive is obtained.

Although it is not intended to bind the invention to any theory, the 2,5-norbomadiene appears to perform various roles by providing long chain branching, which is desirable, as shown in the literature, and by reducing the length of ethylene series in the polymer chain, ultimately reducing agglomeration and lowering the viscosity of oil in which the polymer is dissolved at low temperature. Probably 2,5-norbomadiene enters the chain through more than one mechanism, none of which leads to branching. The absence of unsaturation allows oxidative mastification to reduce molecular weight.

Only the 2,5-norbomadiene structure appears to be able to fulfill these different functions. Both double bonds should be easily polymerizable in order to achieve long chain branching and not leave olefinic residues. To reduce these lengths of the ethylene series, the olefin must be sterically hindered enough to polymerize only with ethylene and not higher olefins, and easily polymerize with ethylene with an effective reactivity ratio product near zero (see Rubber Reviews , M + (1972) 709 for a definition of the reactivity ratio product and for kinetic data for different structures). Since gelling in a continuous flow stirred reactor should occur after incorporation of a diene mole fraction equal to 1 / (2DPw) (where DPw represents the 5 degree average polymerization degree in the absence of diene) and this value for the polymers of Example I is about 0.01 $, which value is far exceeded by these polymers, more polymerization mechanisms must play a role. Probably 2,5-norbornadiene enters the chain to form a nortricyclon structure. This chain structure can have as much as 90% of the 2,5-norbornadiene present in the polymer. Without these two polymerization mechanisms, insufficient diene would be incorporated into the polymer to significantly affect series distribution. The longer chain olefins-1, which can be used individually or as a mixture for the preparation of the ethylene copolymers of the invention, are monomers of 3-18 carbon atoms. The olefins-1 may be linear or branched if the branching occurs three or more carbon atoms from the double bond. Although a single olefin 20 is preferred, mixtures of C 1 -C 20 g olefins can also be used. Preferably, however, the ethylene monomer is copolymerized with propylene. Generally, the ethylene / C 1 -C 2 g olefin-1 / 2,5-norbornadiene copolymers of the invention are derived from 26-80 wt.% Ethylene, 20-7 wt.% Of one or more C 2 -C. 25 g olefins-1 and 0.05-3.0 wt.%, preferably 0.05-1.5 wt.% 2.5-norbornadiene, which is the only diene used.

Preferably, the copolymers are derived from bO-65 wt. Ethylene, 35-60 wt.% From a C 1 -C 2 g olefin-1 and 0.2-1.0 wt.% Norboradadiene. Most preferred copolymers are derived from 43% ethylene, 6.2% propylene and 0.8% norbomadiene.

The copolymers according to the invention can be characterized by the properties listed in Table A.

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00 d h d o o to ft H

ft O d ft ft> "ft <8 ftM-KSJ-KtO Ή Λ« · Η c Λ d yard ft «h c >> dd g k c <v Aidd ^ so

ft ft: o> d ft * d C

d c a 12 d ft jG Η C Ο ft d S ϋ d Xi d ft 5-i ft ft d ft d d ft H, ¾ ft X SO s yard

o fi d ft> ΐ G

S ft Ο H

d to ft ο ο o to isfl C ft ft CO 5-1 G · Η 0 ft c o 3 ft d d c

> d Λ ft I

G Λ d ITS

-¾¾ T) ft CN ft 2 *

-¾¾ ft Η · Η S OJ

. d d O 3. > ft ft H 3 ft

Ih U s SO ft O d G d SO -¾¾. Ο · Η C ^ J4 ea S3 <u SO OO N yard cn * o ft O <A t— -¾- dr * t— ft 5-1 · 13 in * Η II> H dw Ο Ό Η IOO in SO H ft ft ft

OliOHH yard C · - '> Ο Η ft. ea ft ft ft »d η \ 0 Η Η" -Ï Ο ft Μ ft yard ft ft

ft yard O O H

H Ih & «NOC

m O d ft S -ft 3 O O d * ft

Ph ft & h d ^ d ft

^ £ h d ft O

ft. d ft to • n ft · S f * • H ft g! >> * 3 H d d H +3 yard 65. ft ft ft Ο efl £ -¾¾. d ft U ft d s O to 0 5-i5-i G · d> 3. g G 5h O d

(U ^ tOOO dddO

dd t— O O to ft ft ft ft> 1 SO in co co <ft ft G ft d o d

d «III 'ft C ft to O

SC Cs H O 'la O ö «_ · η ft

H t— I H d d C C

<I in dftdftdd ιό O ft C ft ft ft CM «ft d N SO rj

O yard o C yard C

S3 ft «ft 3

Sn ft ft SO d> Ο O d ft ft ft> -Η ft d sa d u c 3 d a ft OflftNÊftft

h coaSnftftC

ajft d l> dd -P d ftsl ft A ft> ddft ded 5-1 «C a ^ Nd

SO in P CMddO S U

d so d ftft cod dto 9 a d G a e ft aj ft O 3ftd3S * ^ S.

-ft ft a ^ ft ft ^ eo dftd eo H d SO O ft ftsdft 0 ddftftCOoo hcc a «3 -Hftftd yard 5h -ο 3! >>? -. G d ft ft ft 0 ft 00 3 H ft d ft -P ft dftHll 5h ed o g sa G 3 d

SOinHOO ft CddftCftN

aodHH a dft.HNdOd <u d -P d eoft ft ¢ 3 ft d I and X X! 2 d ft A ft, ft

ft «5 *,„ C. “> -K

ft CM ft IS 12 -K -K

80 0 0 1 41 X _ ..... 9

These copolymers can be prepared using a catalyst composition, which contains as a major constituent a transition metal compound with the Groups IVb, Vb and VTb of the Periodic Table, in particular compounds of titanium p and vanadium, for example V0Cl3 and as co-catalysts reducing organometallic compounds of metals from the Groups Ila,

Ilb and lilac, in particular organoaluminum compounds, for example ethylaluminum sesquichloride, (C 1 H 3) 3 ^ 01 01. Examples of suitable catalysts and preferred reaction conditions are described in U.S. Patent 3,551,336.

The copolymerization can be carried out by supplying ethylene, C 1 -C 4 alkene-1, preferably propylene, 2,5-norbornadiene and hydrogen in a liquid inert diluent-solvent-reaction medium, which is the catalyst and the co-catalyst in catalytic amounts. As the non-reactive reaction medium, an aromatic hydrocarbon, such as toluene, a saturated aliphatic hydrocarbon, such as heptane, pentane and hexane, or a chlorinated hydrocarbon, such as tetrachloroethene, can be used. All steps of the reaction are preferably conducted in the absence of oxygen, moisture, carbon dioxide and other harmful materials.

The reaction medium can be stirred during the polymerization and at temperatures from - ^ 0 ° C to 100 ° C, preferably -10 ° C

25 to 70 ° C and optimally about 30 ° C and kept under an overpressure of 2 2 2 0-70 kg / cm, preferably 0-21 kg / cm 'optimally, 2 kg / cm for 1-300 min, preferably 3-60 min and optimally 15 min. At the end of this period, the reaction mixture can be worked up to separate the product copolymer, while the mixture can also be used as such for degradation.

It has been found that these copolymeric viscosity index improving additives according to the invention can be easily degraded, ie decreased in molecular weight, by aastication * in air, for example, using a mechanical shear 80 0 0 1 41 fc 10 such as a Banbury mixer . This results in shear stable copolymers which, when added to lubricating oils, provide "stay-in-grade" behavior, well behavior is important, if not essential for the lubrication of modern high performance engines.

That these materials can be masticated in a high shearing device, surprisingly, since commercially available terpolymers containing more than 1 wt% cyclic alkadiene, e.g., Vistalon 250k, are marketed 10 by Exxon Chemical, Houston, Texas (ethylene / propylene / 2-ethylidene-5-norbornene terpolymer) or tetra polymers with more than 1 wt.% Linear alkadiene, such as Hordei 1320, sold by EI duPont de-Nemours, Wilmington, Delaware (tetrapolymer of ethylene / propylene / 1,1-hexadiene / 2,5-norbornadiene) in air mastication to form an oil-insoluble gel. This gel formation is not acceptable because the oxidized-masticated terpolymers are insoluble in mineral oil and are no longer useful as viscosity modifying additives.

For the purposes of the invention, the mechanical oxidative degradation of the ethylene copolymer can be carried out in a single device or in steps. Preferably, work is done in the absence of solvent or flux oil so that the ethylene copolymer is easily exposed to the air (see French Patent Application 75.23806). Examples of suitable devices are anbury mixers and adjustable-opening mills, which devices may be jacketed through which a heating medium may be passed, for example, superatmospheric steam or heated Dowtherm®.

When the degradation has reached a desired level, as can be seen from the oxygen uptake and the thickening reduction, a flux oil can be added to the degraded copolymer. Sufficient oil is usually added to obtain a concentration of the degraded copolymer of 5-50% by weight, calculated as 80 0 0 1 41 11 by weight of the total solution. The resulting oil solution can be marketed as an additive for lubricating oils or can be incorporated directly into the lubricating oil.

Suitable temperatures for the mechanical oxidative degradation of the ethylene copolymers are between 95 and 260 ° C. The time required to obtain satisfactory results depends on the type of degradation or mastication equipment, the temperature at which the degradation is performed, and in particular the rotational speed, if a paddle mixer is used as the demolition or mastication device. In this regard, the Bramley Brooks Blade Mixer has proved particularly suitable for obtaining the desired degree of mastication or grinding and oxidative degradation in a single device. This mixer, which is provided with a variable speed drive, has two rollers, which are equipped with helically arranged blades and which are driven in such a way that one roller rotates at half the speed of the other. The rollers are arranged with a jacketed reactor, which has two semicircular halves on the underside adapted to the 20 jets of the two rollers. Overheated steam or heated Dovtherm® can be passed through the jacket to obtain the desired temperature. With this mixer, within the temperature range of 95-260 ° C, a satisfactory reduction in thickening power can be obtained in 0.25-20 hours.

Instead of a flux oil, other inert solvents can also be used to prepare a solution of the ethylene copolymer. Examples of inert solvents are liquid hydrocarbons, such as naphtha, hexane, cyclohexane, dodecane, mineral oil, biphenyl, xylene or toluene, a "solvent neutral" type lubricating oil, a white lubricating oil, chlorinated solvents, such as dichlorobenzene, and of such.

The amount of solvent is not critical as long as a sufficient amount is used to obtain a liquid solution of the ethylene copolymer to facilitate mechanical oxidative degradation. Such a solution, as previously described, usually contains 50-95% by weight of solvent.

The oil-soluble copolymer additives, including the oxygen and nitrogen-containing derivatives of the invention, are incorporated in lubricating oil compositions, for example, automotive or diesel engine crankcase lubricating oils, in at least the viscosity index improving amounts and generally in concentrations of 0.1- 15 wt%, preferably 0.2-7 wt% of the total composition.

Furthermore, the oil-soluble degraded copolymeric viscosity index improvers of the invention can be derivatized into multifunctional viscosity index improvers by adding sludge dispersing activity.

This is easily accomplished by reaction with amine-15 compounds or inoculation of amine compounds to the copolymers of the invention.

Suitable amine compounds for the introduction of sludge dispersing activity are mono- and polyamines with a total of 2-60 carbon atoms, for example 3-20 carbon atoms and 1-12 nitrogen atoms, for example 2-6 nitrogen atoms in the molecule, which amines can be hydrocarbylamines or hydrocarbylamines containing other groups, for example, hydroxy groups, alkoxy groups, amide groups, imidazoline groups and the like. Preferably saturated aliphatic amines are used, including those of general formulas 1 and 2 (see formula sheet), wherein R, R 'and R "independently of one another are hydrogen, C 1 -C 6 branched or straight chain alkyl groups, C 1 -C Koxy-C8-C8 alkylene groups, C8-C18 hydroxy or aminoalkylene groups or alkylene soap bars are a number 30 with a value of 2-6, preferably 2-k, and t a number with a value of 0-10, preferably from 2-6.

Examples of suitable amine compounds are mono-, di- and tritallow amines, 1,2-diaminoethane, 1,3-diaminopropane, 1,1-diaminobutane, 1,6-diaminohexane, diethylene triamine, tri-80 0 0 1 41 * 13 ethylene tetramine , tetraethylene pentamine, 1,2-propylenediamine, di- (1,2-propylene) triamine, di- (1,3-propylene) triamine, N, IT-dimethyl-1,3-diaminopropane, NH-di- ( 2-aminoethyl) ethylenediamine, II, N-di- (2-hydroxyethyl) -1,3-propylenedimine, 3-dodecyloxypropyl-5-amine, N-dodecyl-1,3-propanediamine, trishydroxymethylmethylamine, diisopropanolamine and diethanolamine.

Other suitable amine compounds are alicyclic diamines, such as 1,1 + -di- (aminomethyl) cyclohexane, and heterocyclic nitrogen compounds, such as imidazolines and Sr-aminoalkylpipera-10 zines of the general formula 3, wherein Z is oxygen or NG, wherein G is hydrogen or a J-aminoalkylene group having 1-3 carbon atoms, and p is an integer of 1-1 +. Examples of such amines are 2-pentadecylimidazoline, N- (2-aminoethyl) piperazine, N- (3-aminopropyl) piperazone, N, H-di-15 (2-aminoethyl) piperazine and n-propylaminomorpholine.

Advantageously, commercially available mixtures of amine compounds can be used. For example, alkylene amines can be prepared by reacting an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, resulting in a complex mixture of alkylene amines, in which pairs of nitrogen atoms are joined by alkylene groups, and compounds such as diethylene triamine, triethylene tetramine, tetraethylene pentamine and isomeric piperazines. Cheap poly (ethylene amines) having a composition approaching that of tetraethylene pentamine are commercially available under the trade name Polyamine 1 + 00 (PA-1 + OO), sold by Jefferson Chemical Co., Hev York. Similar materials can be prepared by the polymerization of aziridine, 2-methylaziridine and acetidine.

Other amines with heteroatom chains, such as polyethers or sulfides, can also be used.

The introduction of sludge dispersing activity can take place in various ways. For example, the oil-soluble ethylene copolymer can be reacted with an oxygen 800 0 1 41 ƒ

I "containing gas and the amine compound at a temperature of 130-300 ° C under mechanical degradation of the copolymer and formation of an anion of the oxidized ethylene copolymer, then reacting this anion with acrylonitrile and then derivatizing the reaction product with amines The reaction product can be used in lubricating oil compositions, mainly consisting of a mineral oil with a viscosity suitable for lubrication purposes, optionally in combination with other viscosity index improvers. If desired, the copolymers can be used in combination with other additives, such as pour point lowering agents, ash-free dispersants, such as the reaction product of polyisobutenyl succinic anhydride and tetraethylene pentamine, detergents such as calcium nonyl sulfurized phenate and magnesium phenyl sulfonate, zinc antioxidants such as dialkyl dithiophosphate, and the like.

By mineral oils of a viscosity suitable for lubrication purposes are meant the materials which can be obtained by distillation of crude oil under vacuum or by synthesis, whereby lubricating oils are obtained, which are suitable for the lubrication of engines, with internal combustion and for hydraulic purposes. Although it would be possible to classify these lubricating viscosity mineral oils according to the SAS J 300d viscosity classification, the mineral oil for the purposes of the invention has a viscosity range at -18 ° C of 600-9600 cPs, at preference of 1200-2000 cPs, measured according to ASTM Procedure D 2602, and a viscosity range at 99 ° C of 5.7-22.7 cSt, measured according to ASTM Procedure D UU5.

A particular aspect of the invention is that a significant improvement in the low temperature viscometric properties can be obtained without the pour point being undesirably affected if a pour point depressant is present in the oil composition. This improvement can be observed in particular when the lubricating oil composition is 80 0 0 1 41 15.

Contains point reduction agent in an amount of 0.1-1.0 wt%, preferably of 0.1 wt%. Examples of suitable pour point depressants which may be present in the compositions of the invention are the chlorinated paraffin / naphtha boron condensates as disclosed in U.S. Pat. No. 2,1lh.2b6, C 1 -C 4 g alkyl methacrylate polymers, as disclosed in U.S. Pat. Nos. 2,091,627 and 2,100,993, C1Q-C1g alkyl acrylates, copolymers of di-n-alkyl fumarate and vinyl acetate, as described in U.S. Patent 2,936,300, ethylene / vinyl acetate copolymers, and copolymers of styrene and olefins-1 and copolymers of styrene and maleic anhydride.

A series of ethylene / propylene copolymers were prepared with varying ethylene, propylene and / or norbomadiene content. These copolymers 15 are referred to as EPNBD 1-5. These EPNBD copolymers were prepared from ethylene, propylene and norbornadiene by varying the feed ratio of the three comonomers during the polymerization, which was carried out for the copolymer EPNBD 1 as follows: 3.0 wt. parts of ethylene, 6.8 wt. parts of propene, 0.006 parts by weight of norbornadiene and ppm of hydrogen, were charged with 100 parts by weight of n-hexane, 0.009 parts by weight of vanadium oxychloride and 0.032 parts by weight of ethyl aluminum sesquichloride. The catalyst exhibited a Al / V molar ratio of k. The residence time was about 13 minutes, the polymerization temperature 32 ° C and the overpressure U, 2 kg / cm 2. Steam distillation provided the solvent-free ethylene copolymer of the invention. The copolymers EPNBD 2-6 were prepared by an appropriate change in the feed ratio. The specific compositions are listed in the table below: 8 0 0 0 1 41 iV '16 EPNBD Wt.% Wt.% Wt.% Copolymer ethylene propylene norbomadiene 1 1 + 5 5b, 9 0.1 2 1 + 3 56, 8 0.2 5 3 1 + 3 5 * +, 8 0.2 b 1 + 1 + 55.6 0.1+ 5 1 + 3 56.2 0.8 6 1 + 3 56.2 0.8

For comparison, an ethylene / propylene copolymer containing 1 + 6 wt.% Ethylene was used. This commercially available copolymer was prepared in the manner described in U.S. Pat. No. 3,697.1 + 29 and is further referred to as EPC 1.

Example

In this example, the properties of a reference oil, which always contains one of the copolymers EPHBD 2-6 according to the invention, are compared with the properties of the same oil, which contains the known copolymer EPC 1. The reference oil is a composite test oil, consisting of "solvent neutral" oils and a pour point depressant, which test oil has a viscosity at 99 ° C of about 6.7 cSt. Table B shows the effect of both types of copolymers on the properties of the reference oil when sufficient copolymer has been added to obtain a viscosity at 98.9 ° C of about 1 + 0 cSt.

N

80 0 0 1 41

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The data in Table B show that it is possible to prepare a series of 2,5-norbomadiene-containing ethylene terpolymers, which exhibit the bulk viscosity properties of the tetrapolymers of U.S. Pat. 1 * hexadiene is represented, and further that these terpolymers of the present invention impart useful and surprising low temperature viscosity properties to mineral oils having a viscosity suitable for lubrication purposes, as compared to the properties imparted by ethylene / propylene copolymers. These low temperature properties have hitherto only been achieved by incorporation of the class of dienes, which leave residual unsaturation in the known polymers (terpolymers and tetrapolymers of ethylene, as described in U.S. Pat. No. 3,790-80) or no significant long chain branching as in the ethylene tip polymer, which contains an alkyl norborne phenomenon, as described above.

The copolymers are added to mineral oils of a viscosity suitable for lubrication purposes in at least viscosity improving amounts, generally 0.1-15 wt. for lubricating oil compositions; however, when the copolymer is marketed as a concentrate in the mineral oil, the copolymer content is 6-b5 wt% (all weight percentages are based on the total weight of the composition or concentrate). In summary, the concentration of the copolymer (including the oxidized type) of the invention in the mineral oil is 0.1% to 5% by weight of the copolymer in a major amount of the mineral oil with a lubricity suitable for use. viscosity, generally 55-99 wt.

800 0 1 41

Claims (12)

1. Lubricating oil composition, characterized by a predominant amount of mineral oil having a lubricity suitable viscosity and a viscosity index improving amount of an oil soluble saturated ethylene copolymer having an ethylene content of 26-5 T9% # (35-85 mol) #), one or more olefins-1 and 0.05-3.0 wt. # 2,5-norbomadiene, which ethylene copolymer has a get as the average molecular weight of at least 5000 and has a thickening power of 1.0-3, compared to polyisobutene with a viscosity average molecular weight of 20,000. Lubricating oil composition according to claim 1, characterized in that the 2,5-norbomadiene is present in an amount of 0.05-1.5%. # and forms the only diene present. Lubricating oil composition according to claims 1-2, characterized in that the ethylene copolymer has a thickening capacity of 1.2-2.8 and a number average molecular weight of 10,000-100,000, and the 2,5-norboradiene is present. in an amount of 0.2-0.8 wt. #. Lubricating oil composition according to claims 1-3 », characterized in that the olefin-1 is propylene. Lubricating oil composition according to claims 1 to 4, characterized in that the copolymer is an oil-soluble, oxidative and mechanically degraded ethylene copolymer, with an oxygen content of 0.005-6 wt. #, calculated pp the total weight of the copolymer. Lubricating oil composition according to claims 1-5, characterized in that the ethylene copolymer has an oxygen content of 0.05-3% by weight. Lubricating oil composition according to claims 1-6, characterized in that a pour point-lowering amount of a pour-point reducing agent for lubricating oil is also present. 8. Composition according to claims 5-7, characterized in that the degraded copolymer is derivatized with an amount of an amine compound of formula 1, 2 or 3 (see formula sheet), wherein R, R 'and R "independently of each other is hydrogen C 1 -C 8 branched or unbranched alkyl groups, C 1 -C 6 alkoxy C 2 -C 8 alkylene groups, 9000141 ........ "....... 20 hydroxyalkylene groups, C 2" C 12 α-nalic3rleenSRUPS or ci "c2 a ^ rl" represent amino-Crt-C ^ alkylene groups, Z represents oxygen or JTG, wherein G is hydrogen or a amino-aminoalkylene group with 1-3 carbon atoms, s is a whole number with a value of 2-6, t represent an integer value 0-10 and p represent an integer value 1-4, which amount of amine is sufficient for a polymer nitrogen content of 0.01-0.5 wt . #. Composition according to claim 8, characterized in that the amine compound is an alkylene polyamine with 2-6 nitrogen atoms per 10 molecule. A composition according to claims 5-9, characterized in that the ethylene copolymer is the reaction product obtained by mastication in air of an ethylene copolymer with an ethylene content of 26-79 wt.%, 20-79 wt. g olefins-1 and 0.05-1.5 wt. # 2,5-norborna-15 diene, and has a thickening capacity of more than 3 * 0. 11. Saturated ethylene copolymer, characterized by a number average molecular weight of at least 5000, an iodine number of less than 0.8 and a thickening power of 1.0-3 as compared to polyisobutylene having a viscosity average molecular weight of 20,000.20 obtained by copolymerization of at least three comonomers consisting essentially of 26-79 wt.% ethylene, a C 1 -C 4 g and 0.05-3.0 wt. # 2,5-norbornadiene. 12. Ethylene copolymer according to claim 11, characterized in that the number average molecular weight is 10,000-100,000 and the thickening power is 1.2-2.4, the olefin-1 consists of propylene and the norbomadiene content 0.05-1.5 wt. # is. Ethylene copolymer according to claims 10-12, characterized by an oxygen content of 0.005-6% by weight and a nitrogen content of 0.01-0.5% by weight. 30 l4. Concentrate, characterized by a predominant amount of mineral oil of viscosity suitable for lubrication and 6-1 * 5 wt% of an oil-soluble saturated ethylene copolymer having an ethylene content of 26-79 wt% » (35-85 mol #), a C 1 -C-5 alkene-1 and 0.05-3.0 wt. #, Preferably 0.05-1.5 wt. # 2,5-norbornadiene, 800 O 1 41 sheet of ethylene copolymer has a number average molecular weight of at least 5000 and a thickening power of 1.0-3 compared to polyisobutene with a viscosity average molecular weight of 20,000 * Process for preparing a fully saturated ethylene terpolymer containing a non-conjugated diene, characterized in that a mixture of 26-79 parts by weight ethylene, 0.05-3.0 parts by weight, preferably 0.05-1.5 parts by weight of 2,5-norbornadiene, and the balance contains a C 1 -C 2 g alkene-1 in sufficient quantity to obtain a mixture of a total of 100 parts by weight , is polymerized in the presence of a catalyst. 80 0 0 1 41 rnr 'R * 2 R — H— (CH2) s —p N- (CH2} s J— N - RI · ί 3 NH2 (CH2) p— yl \ h2-CH2 80 0 0 1 41 Exxon Research and Engineering Company