SE433228B

Hydrogenated polymers

Abstract

A viscosity index-improver for lubricating oil compositions is disclosed. This viscosity index improver is a hydrogenated star-shaped polymer comprising a poly(poly-alkenyl coupling agent) nucleus and at least four polymeric arms linked to the nucleus wherein the arms are hydrogenated homopolymers and copolymers of conjugated dienes, hydrogenated copolymers of cojugated dienes and monoalkenyl arenes, or mixtures thereof.

SE433228B, drawing sheet 1 — Sheet 1 of 52

Term

No projected expiry on record.

8 claims: 4 independent, 4 dependent

1
Patentkrav claim 1. Smörjoljekomposition innefattande en smörjolja och en stjärnformad polymer av en eller flera konjugerade C^-C^diener och eventuellt styren och/eller ett alkylerat derivat därav, under användning av ett aromatiskt polyalkenyl-kopplingsmedel, kännetecknat därav, att polymeren innefattar en poly(polyalkenylaromatiskt kopplingsmedel)kärna med 4-25 sig därifrån utåt sträckande hydrerade polymerkedjor av en eller flera konjugerade C^-C-^-diener och eventuellt styren och/eller ett alkylerat derivat därav, varvid de hydrerade polymerkedjorna har en talmedelmolekylvikt av 5000-150 000 och innehåller mindre än 50% av sin ursprungliga olefiniska omättnad och varvid mängden stjärnformad polymer är 0,15-30 vikt%, räknat på kompositionen. 1st Lubricating oil composition comprising a lubricating oil and a star-shaped polymer of one or more conjugated C C-CC dienes and optionally styrene and / or an alkylated derivative thereof, using an aromatic polyalkenyl coupling agent, characterized in that the polymer comprises one poly (polyalkenyl aromatic coupling agent) core having from 4 to 25 extensively extending hydrogenated polymer chains of one or more conjugated C 1 -C 2 - dienes and optionally styrene and / or an alkylated derivative thereof, wherein the hydrogenated polymer chains have a number average molecular weight of 5000 150,000 and contains less than 50% of its original olefinic unsaturation and wherein the amount of star-shaped polymer is 0.15-30% by weight based on the composition.
4
Smörjoljekomposition enligt något av kraven 1-3, kännetecknad därav, att de hydrerade polymerkedjorna är hydrerade homopolymerkedjor. 4th Lubricating oil composition according to any one of claims 1-3, characterized in that the hydrogenated polymer chains are hydrogenated homopolymer chains.
6
Smörjoljekomposition enligt något av kraven 1-3, kännetecknad därav, att de hydrerade polymerkedjorna är hydrerade sampolymerkedjor. 6th Lubricating oil composition according to any one of claims 1-3, characterized in that the hydrogenated polymer chains are hydrogenated copolymer chains.
8
Smörjoljekomposition enligt något av kraven 1-7, kännetecknad därav, att minst två olika typer av hydrerade polymerkedjor är närvarande. Eighth Lubricating oil composition according to any one of claims 1-7, characterized in that at least two different types of hydrogenated polymer chains are present.

Independent claims4

278 paragraphs in 4 sections, as filed

(54) Title: Lubricating oil composition comprising a lubricating oil and a hydrogenated star-shaped polymer (56) Published publications: SE 7507958-2, GB 1 025 295, DE 2 030 641 (C08F 8/04), DE 2 045 621 (C08F 8/04 ), DE 2 519 081 (C08F 8/04) .11 .J.

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7614606-7

The present invention relates to a lubricating oil composite comprising a lubricating oil and a star-shaped polymer.

It is known that for oils, e.g. lubricating oils, adding oil-soluble amounts of polymers for the purpose of improving the viscosity and / or flow point properties of the oils. It is clearly economically desirable to use as small an amount of polymer as possible to achieve such properties. In general, such polymers should have high thickening capability and high shear stability. The first property is desirable for the resulting oil compositions to have the required viscosity properties, although small amounts of polymers are added, and the second property is desirable in view of the large shear force the compositions can undergo in use, e.g. such as lubricating oils in internal combustion engines. If such polymers have a low shear stability, they would rapidly degrade, and the oil compositions would lose their required viscosity properties and would no longer be of the correct kind. Furthermore, such polymers should form readily manageable concentrates containing a large amount of polymer, with the oil types they will be used with. This property is desirable because the polymer manufacturers usually transport polymer in the form of concentrates to the blenders, which dilute the cone.

7614606-7 the centers with additional quantities of oil for preparing the oil compositions for use, e.g. lubricating oil compositions. From an economic point of view, it is not attractive to transport large quantities of oil in the concentrate to the mixers, nor is it attractive to the mixers to have to use large quantities of polymer manufacturers' oil in the final oil compositions.

One class of polymers proposed as oil additives are the hydrogenated, substantially linear polymers of conjugated dienes and optionally aromatic monoalkenyl compounds.

Such hydrogenated polymers are prepared by anionic solution polymerization of the monomers, followed by hydrogenation. This process involves polymerization of a conjugated diene and optionally an aromatic monoalkenyl compound in solution and in the presence of an anionic initiator to form an unsaturated living polymer. Those skilled in the art are well versed in the term living polymer, which term is used to designate such polymers having a terminal carbon anionic group. They are referred to as living polymers because they are capable of reacting further with e.g. additional monomer or various modifiers. In the production of hydrogenated, substantially linear polymers, the living polymers are usually deactivated or terminated by addition thereto by chain terminators before they are hydrogenated.

Examples of hydrogenated, substantially linear polymers commercially used as oil additives include hydrogenated styrene /

- butadiene and hydrogenated styrene / isoprene copolymers.

In the case of hydrogenated, substantially linear polymers, it is possible to increase their thickening capacity and therefore possible to use a smaller amount thereof by increasing their molecular weight. However, this has the disadvantage that the shear stability of such polymers generally decreases with increasing molecular weight. Accordingly, the choice of a particular polymer constitutes a compromise between a large amount of a low molecular weight polymer with good shear stability and a small amount of a higher molecular weight polymer with poor shear stability. In addition, it is difficult to prepare oil concentrates of such polymers containing more than about 10% by weight thereof, which, for the reasons stated above, is a further disadvantage of such polymers.

Another class of polymers proposed as oil additives are the hydrogenated branched polymers derived from conjugated dienes and aromatic monoalkenyl compounds. The British ii

7614606-7 patent 1,370,093 suggests e.g. the use of hydrogenated star-shaped multiple-tapered copolymers of a diene having at least 5 carbon atoms and a vinyl aromatic compound. Furthermore, British Patent Specification 1,329,000 also suggests the use of hydrogenated, branched, three-segment copolymers, which are derived from e.g. conjugated dienes and monovinylarene compounds. However, neither publication exemplifies the preparation or use of such hydrogenated, star-shaped or branched polymers. In addition, such polymers have apparently never come into commercial use, probably because they do not offer enough advantages over hydrogenated linear polymers.

A further class of polymers which have been proposed as components of oil compositions are star-shaped polymers produced by coupling live polymers using a particular type of coupling agent, namely a polyalkenyl coupling agent such as divinylbenzene. British Patent Specification 1,025,295 discloses e.g. Such a use of star-shaped polymers, which has been prepared by reacting a live (aromatic monoalkenyl hydrocarbon / conjugated diene) block copolymers with divinylbenzene.

Polyalkenyl type coupling agents are capable of coupling live polymers to form a polymer comprising a poly (polyalkenyl coupling agent) core or center having a plurality of polymer chains or arms extending outwardly therefrom. It is believed that the poly (polyalkenyl coupling agent) core is a cross-linked core. The number of polymer chains is usually from 4 to 25. Due to the configuration of the polymers, they are referred to as star-shaped polymers or radial polymers. A mechanism by which such star-shaped polymers are formed is described in Polymer, 1975, Vol. March 16, p. 180-184. Further information regarding the preparation of star-shaped polymers based on polyalkenyl coupling agents can be found in German Laid-open Specification 2,529,065 and U.S. Patent No. 3,280,084.

However, such star-shaped polymers are not suitable as oil additives because they have little thickening capacity and are thermally unstable.

It has now been found that hydrogenated star-shaped polymers prepared from such polyalkenyl coupling agents are excellent oil additives. It has been found that such polymers, which are novel polymers, have good thickening ability, even when used in small amounts, and good shear stability, although their molecular weights are very high. In addition, oil concentrates may be prepared therefrom, which are

7614606-7 readily manageable although the polymer content of the concentrate exceeds 10% by weight.

Accordingly, the present invention relates to a lubricating oil composition comprising a lubricating oil and a hydrogenated star-shaped polymer comprising a poly (polyalkenyl coupling agent) core having a plurality thereof extending hydrogenated polymer chains of one or more conjugated dienes and optionally one or more aromatic compound. The lubricating oil composition is further defined in claim 1.

The preparation of the hydrogenated star-shaped polymer comprises the following reaction steps:

(a) polymerizing one or more conjugated dienes and optionally one or more aromatic monoalkenyl compounds in solution and in the presence of an anionic initiator to form a living polymer; (b) reacting the living polymer with a polyalkenyl coupling agent to form a star-shaped polymer and (c) hydrogenating the star-shaped polymer to form a hydrogenated, star-shaped polymer.

The living polymers prepared in reaction step (a) of the process of the invention are the precursor compounds of the hydrogenated polymer chains extending outwardly from the poly (polyalkenyl coupling agent) core.

As is well known, living polymers can be prepared by anionic solution polymerization of conjugated dienes and optionally aromatic monoalkenyl compounds in the presence of an alkali metal or an alkali metal hydrocarbon, e.g. the sodium precipitate, such as anionic initiator. The preferred initiator is lithium or a monolithium hydrocarbon. Suitable lithium hydrocarbons include unsaturated compounds such as allyllithium and metal lithium, aromatic compounds such as phenyllithium, tolyllithium, xylyllithium and naphthyllithium and in particular alkyllithium compounds, Sec-butyllithium is the preferred initiator. The initiators may be added to the polymerization mixture in two or more steps, optionally together with additional monomer. The living polymers are olefinic and

7614606-7 possibly aromatically unsaturated.

The living polymer obtained by reaction step (a) and forming linear, unsaturated living polymers is prepared from one or more conjugated C 2dienes and optionally one or more aromatic monoalkenyl compounds which are constituted by styrene and / or an alkylated derivative thereof.

Specific examples of suitable conjugated dienes include butadiene (1,3-butadiene) isoprene 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, 1-phenyl-1 , 3-butadiene,

1,3-hexadiene and 4-ethyl-1,3-hexadiene, with butadiene and / or isoprene being preferred. In addition to one or more conjugated dienes, the living polymers may also be partially derived from styrene and / or an alkylated derivative thereof, such as o-, m- and p-methylstyrene, α-methylstyrene and tert-butylstyrene.

Styrene is the preferred aromatic monoalkenyl compound.

The living polymers may also be partially derived from small amounts of other monomers, such as monovinyl pyridines, alkyl esters of acrylic and methacrylic acids (e.g., methyl methacrylate, dodecyl methacrylate, octadecyl methacrylate), vinyl chloride, vinylidene chloride, monovinyl esters of carboxyl acid ). Preferably, the living polymers derive exclusively from hydrocarbon monomers. If an aromatic monoalkenyl compound is used in the preparation of the living polymers, it is preferred that the amount thereof be below 50% by weight, preferably below 25% by weight, based on the weight of the diene used.

The living polymers can be live homopolymers, live copolymers, live terpolymers, live tetrapolymers, etc. The live homopolymers can be illustrated by the formula AM where M is a carbon anionic group, e.g. lithium, and A is polybutadiene or polyisoprene. Living polymers of isoprene are the preferred living homopolymers. The living copolymers can be illustrated by the formula ABM, where AB is a segmented, randomly constructed or tapered copolymer such as poly (butadiene / isoprene), poly (butadiene / styrene) or poly (isoprene / styrene). Without further restrictions, such formulas do not limit the placement of the monomers in the living polymers. Living poly (isoprene / styrene) copolymers can e.g. be living polyisoprene-polystyrene block copolymers, live polystyrene-polyisoprene copolymers, live randomly constructed poly (isoprene / styrene) copolymers, live tapered poly (isoprene / styrene) copolymers or live poly (isoprene / styrene / isoprene) 76

block copolymers. Examples of a living terpolymer are living poly (butadiene / styrene / isoprene) terpolymers.

As indicated above, the living copolymers may be live block copolymers, live randomly built up copolymers or live tapered copolymers. The living block copolymers can be prepared by stepwise polymerization of the monomers, e.g. by polymerization of isoprene to form live polyisoprene, followed by addition of the second monomer, e.g. styrene, to form a living block copolymer of the formula polyisoprene-polystyrene-M, or the styrene can first be polymerized to form live polystyrene, followed by the addition of isoprene to form a live block copolymer of the formula polystyrene-polyisoprene-M.

The live randomly constructed copolymers can be prepared by gradually adding the most reactive monomer to the polymerization reaction mixture, which includes either the less reactive monomer or a mixture of the monomers, so that the molar ratio of the monomers present in the polymerization mixture is maintained at a controlled level; it is also possible to achieve this by gradually adding a mixture of the monomers intended for copolymerization to the polymerization mixture. live randomly constructed copolymers can also be prepared by performing the polymerization in the presence of a so-called random generator. Random generators are polar compounds which do not deactivate the catalyst and. provides the propensity for random copolymerization. Suitable random generators are tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, tri-n-propylamine, tri-n-butylamine, dimethylaniline, pyridine, quinoline, N-ethylpiperidine and N-methylmorpholine, thioethers such as dimethylsulfide, diethylsulfide, diethylsulfide, , di-n-butyl sulfide and methyl ethyl sulfide and. in particular ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, dioctyl ether, dibenzyl ether, diphenyl ether, anisole, 1,2-dimethyloxyethane and o-dimethoxybenzene, and cyclic ethers such as tetrahydrofuran.

Live tapered copolymers are prepared by polymerizing a mixture of monomers and are the result of the difference in reactivity between the monomers. For example, monomer A is more reactive than monomer B, the composition of the copolymer is gradually changed from the composition of near pure poly-A to the composition of near pure poly-B. Therefore, in each living copolymer molecule one can distinguish three regions which gradually transition into each other and which do not exhibit any

7614606-7 sharp boundaries. One of the outer regions consists almost exclusively of units derived from monomer A, and. containing only small amounts of units derived from monomer B, in the intermediate region, the relative amount of units derived from monomer B increases greatly and the relative amount of units derived from monomer A decreases while the the second outer region consists almost exclusively of units derived from monomer B, and contains only small amounts of units derived from monomer A. Live tapered copolymers of butadiene and isoprene are the preferred live tapered polymers.

Since the living polymers generated in reaction step (a) in the above process constitute precursor compounds to the hydrogenated polymer chains extending outwardly from the poly (polyalkenyl coupling moiety) core, it will be appreciated that the preferred hydrogenated polymer chains are hydrogenated polybutadiene-hydrogenated, ) chains, hydrogenated poly (butadiene / styrene) chains and hydrogenated poly (isoprene / styrene) chains.

The solvents in which the living polymers are formed are inert liquid solvents such as hydrocarbons, e.g. aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclohexane or methylcyclohexane or aromatic hydrocarbons, e.g. benzene, toluene, ethylbenzene, xylenes, diethylbenzenes or propylbenzenes. Cyclohexane is preferred. Mixtures of hydrocarbons, e.g. lubricating oils, can also be used.

The temperature at which the polymerization is carried out can vary widely, such as from -50 ° C to 15 ° C, preferably from 20 ° C to 80 ° C. The reaction is conveniently carried out in an inert atmosphere such as nitrogen and can be carried out under pressure, e.g. at a pressure of 0.5-10 bar.

The concentration of the initiator used to prepare the living polymer may also vary widely and is determined by the desired molecular weight of the living polymer.

The number average molecular weight of the living polymers prepared in reaction step (a) can range from 5000 to 150,000, with number average molecular weights of 15,000 - 100,000 being preferred. Accordingly, the number average molecular weight of the hydrogenated polymer chains in the final star-shaped polymer may also vary within these limits.

The living polymers generated in reaction step (a) are then reacted in reaction step (b) with a polyalkenyl coupling agent. Polyalkenyl coupling agents capable of forming star-shaped polymers are

7614606-7 well known to those skilled in the art. They are usually compounds with at least two non-conjugated alkenyl groups. Such groups are usually bonded to the same or different electron-attracting groups, e.g. an aromatic core. Such compounds have the property that at least two of the alkenyl groups are capable of independently reacting with various living polymers and differ in this respect from conventional, conjugated polymerizable diene monomers such as butadiene, isoprene, etc. Pure polyalkenyl coupling agents or technical grade ones may be used. Such compounds may be aliphatic, aromatic or heterocyclic. Examples of aliphatic compounds include polyvinyl and polyallylacetylenes, diacetylenes, phosphates and phosphites as well as dimethacrylates, e.g. ethylene dimethacrylate. Examples of suitable heterocyclic compounds include divinylpyridine and divinylthiophene. The preferred coupling agents are the aromatic polyalkenyl compounds, and the most preferred are the aromatic polyvinyl compounds. Examples of such compounds include such aromatic compounds, e.g. benzene, toluene, xylene, anthracene, naphthalene and dure, which are substituted by at least two alkenyl groups, which are preferably directly linked thereto. Examples include the polyvinylbenzene, e.g. divinyl, trivinyloch tetravinylbenzenes, divinyl, trivinyl and tetravinyl ortho, meta and para-xylenes, divinylnaphthalene, divinylethylbenzene, divinylbiphenyl, diisobutenylbenzene, diisopropenylbenzene and diisopropenylbenzene. The preferred aromatic compounds are those which can be illustrated by Formula A wherein A is an optionally substituted aromatic nucleus and x is an integer of at least 2. Divinylbenzene, especially methadivinylbenzene, is the most preferred aromatic compound. Pure divinylbenzene or technical grade divinylbenzene (containing various amounts of other monomers such as styrene and ethylstyrene) may be used. The coupling agents can be used in admixture with small amounts of added monomers which increase the size of the core, e.g. styrene or alkylated styrene. In this case, the core can be described as a poly (dialkenyl coupling agent / aromatic monoalkenyl compound) core, e.g. a poly (divinylbenzene / aromatic monoalkenyl compound) core. From the above it is clear that the term divinylbenzene when used for the description of the core means either purified divinylbenzene or technical grade divinylbenzene.

The polyalkenyl coupling agent should be added to the living polymer after the polymerization of the monomers has been substantially completed, ie. the agent should be added only after being essentially

7614606-7 all monomers have been converted to living polymers.

The amount of polyalkenyl coupling agent added can vary widely, but preferably at least 0.5 mole per mole of unsaturated living polymer is used. Preferred amounts are from 1 to 15 moles, in particular from 1.5 to 5 moles. The amount, which can be added in two or more steps, is usually such that it can convert at least 80 or 85% by weight of the living polymers into star-shaped polymers.

The reaction step (b) can be carried out in the same solvent as the reaction step (a). A list of suitable solvents has been given above. The temperature of reaction step (b) can also vary widely, e.g. from 0 to 150 ° C, preferably from 20 ° to 120 ° C. The reaction may also take place in an inert atmosphere, e.g. nitrogen, and under pressure, e.g. at a pressure of 0.5-10 bar.

The star-shaped polymers produced in reaction step (b) are characterized by having a compact center or core of cross-linked poly (polyalkenyl coupling agent) and a plurality of arms of substantially linear, unsaturated polymers extending outwardly therefrom. The number of arms can vary considerably but usually amounts to between 4 and 25, e.g. 7-15 · Star-shaped homopolymers can be illustrated by the formula Ax (A)n, and star-shaped copolymers can be illustrated by the formula ABx —..... · - (BA)nwherein n is an integer, usually between 3 and 24, and x is the poly (polyalkenyl coupling agent) core.

From the above it can be seen that x is preferably a poly (aromatic polyvinyl coupling agent) core and in particular a poly (divinylbenzene) core. As can be seen above, it is assumed that the cores are cross-linked.

Such star-shaped polymers, which are still alive ", can then be deactivated or terminated in known manner by the addition of a compound which reacts with the carbon anionic end group. Examples of suitable deactivators include compounds having one or more active hydrogen atoms such as water, alcohols (e.g. methanol, ethanol, isopropanol, 2-ethylhexanol) or carboxylic acids (e.g. acetic acid), compounds having an active halogen atom, e.g. .ex. a chlorine atom (e.g. benzyl chloride, chloromethane), compounds with an ester group and carbon dioxide. If deactivation is not done in this way, the live star-shaped polymers will be terminated in the hydrogenation step (c).

However, the live, star-shaped polymers, before termination, can be reacted with additional amounts of monomers such as

7614606-7 same or different diets and / or aromatic monoalkenyl compounds of the above types. The effect of this additional step, apart from increasing the number of polymer chains, is to generate a further living, star-shaped polymer with at least two different types of polymer chains. A live, star-shaped polymer derived from live polyisoprene may e.g. is reacted with additional isoprene monomer to form a further live, star-shaped polymer with polyisoprene chains exhibiting different number average molecular weights. Alternatively, the live, iron-shaped polyisoprene homopolymer can be reacted with styrene monomer to form an additional live, star-shaped copolymer with both polyisoprene and polystyrene homopolymer chains. From what has just been stated, it is evident that different polymer chains are meant chains having different molecular weights and / or chains having different structures. These additional polymerizations may take place under substantially the same conditions as described above for the reaction step (a) of the process of the invention. The additional chains may be homopolymer chains, copolymer chains, etc., as described above.

The molecular weight of the star-shaped polymer intended for hydrogenation in reaction step (c) may vary widely, suitable molecular weights are from 25,000 to 1,000,000, molecular weights from 100,000 to 750,000 are preferred, and molecular weights from 250,000 to 650,000 are particularly preferred. . Conveniently, the molecular weights are expressed as peak molecular weights as determined by C-PC on polystyrene shells.

In step (c), the star-shaped polymers can be hydrogenated by any suitable technique. Suitably, at least 50%, preferably at least 70%, especially at least 90%, and especially at least 95% of the olefinic unsaturation are hydrogenated. If the star-shaped polymer is partially derived from an aromatic monoalkenyl compound, the possible amount of aromatic unsaturation which is hydrogenated depends on the hydrogenation conditions used. Preferably, however, less than 10% and in particular less than 5% of such aromatic unsaturation are hydrogenated. If the poly (polyalkenyl coupling agent) core is a poly (aromatic polyalkenyl coupling agent) core, the aromatic unsaturation of the core may or may not be hydrogenated, depending on the hydrogenation conditions used. The molecular weights of the hydrogenated star-shaped polymers correspond to the molecular weights of the non-hydrogenated star-shaped polymers.

The hydration can be carried out in any desired manner. A hydrogenation catalyst can be used, e.g. a copper or molybdenum compound. Compounds containing precious metals or precious metals for compounds may. used as hydration catalysts. Preferably, catalysts containing a base metal or a compound thereof belonging to Group VIII are used in the periodic system, e.g. iron, cobalt and especially nickel. Examples include Raney nickel and nickel on diatomaceous earth. Particularly, hydrogenation catalysts obtained by reacting metal hydrocarbyl compounds with organic compounds of any of the metals of iron, cobalt or nickel belonging to Group VIII are preferred, the latter compounds containing at least one organic compound which is bonded to the metal atom via an oxygen atom, such as e.g. . is described in the British patent specification. 1 030 306. Particularly preferred are hydrogenation catalysts obtained by reacting trialkyl aluminum (e.g. triethyl aluminum or triisobutyl aluminum) with a nickel salt of an organic acid (e.g. nickel diisopropyl salicylate, nickel naphthenate, nickel 2-ethylhexanoate, nickel di-tert-butyl benzoate, nickel salts of saturated monocarboxylic acids obtained by reacting olefins with 4-20 carbon atoms in the molecule with carbon monoxide and water in the presence of acid catalysts or catalysts or acid catalysts or (e.g., nickelacetonylacetonate or the nickel salt of butylacetphenone).

The hydrogenation of the star-shaped polymer is advantageously carried out in solution in a solvent which is inert during the hydrogenation reaction. Saturated hydrocarbons and mixtures of saturated hydrocarbons are very suitable, and it is advantageous to carry out the hydrogenation in the same solvent in which the polymerization has been carried out.

The hydrogenated star-shaped polymer can be recovered in solid form from the solvent in which it is hydrogenated by any suitable technique, such as by solvent evaporation. For preparing a lubricating oil composition according to the invention, a lubricating oil can be added to the solution and the solvent is evaporated from the mixture thus formed to produce concentrate. Easily manageable concentrates are obtained even if the amount of hydrogenated star-shaped polymer therein exceeds 10% by weight. Suitable concentrates contain 10-25% by weight of the hydrogenated star-shaped polymer.

The hydrogenated star-shaped polymers are used to prepare lubricating oil compositions of the present invention. Examples of lubricating oils include synthetic lubricating oils, e.g. an ester oil, but preferably mineral lubricating oils. The concentration of the hydrogenated star-shaped polymers in such oils varies in the range of 0.15-10 wt%, especially 0.1-5 wt% and in particular 0.5-2.5 wt% are common. The amounts are calculated on the weight of the composition.

7614606-7

The lubricating oil composition of the invention may also include other additives such as anti-corrosion additives and / or antioxidants and / or a detergent and / or an EP additive and / or one or more additional V1 enhancing additives and / or floating point depressants. . _ _ ---------------.......

In case the oil composition is a lubricating oil composition for use in internal combustion engines, it is preferred that the oil to which the polymer is added has a viscosity index of at least 80, preferably of 90-145 and especially of 90-120.

The invention is further illustrated by the following embodiments, wherein the temperatures indicated are degrees of Oelsius.

In Examples 1-19, which relate to the preparation of the hydrogenated star-shaped polymers, a 5-liter reaction vessel was used, and the polymerizations were carried out under nitrogen. In reaction step (a) of these examples, the polymerization reaction mixtures at 35 ° C were first purified by adding thereto of sec-butyllithium before the polymerizations were initiated. In all polymerizations, the conversion of monomer was substantially complete. In reaction steps (a) and (b) of these examples, solutions of sec.butyllithium and divinylbenzene (methadivinylbenzene, technical grade) refer to solutions in cyclohexane. In addition, unless otherwise indicated, the number average molecular weights were determined by GPC, and the peak molecular weights were determined by GPC. In reaction step (b) of these examples, the live, star-shaped polymers were terminated by the addition of a 20% molar excess of 2-ethylhexanol, based on the amount of sec-butyllithium used in reaction (a). In reaction step (c) of these examples, the percentage of hydrogenation refers to the percentage of hydrogenated olefinic bonds in the polymer chains, which hydrogenation rates were determined by ozone analysis after the hydrations.

Example 1 (a) A live polyisoprene homopolymer was prepared by polymerizing 250 g of isoprene in 1750 g of cyclohexane solution. The polymerization was initiated by adding to the solution of 50 ml of a 100 mmol / l solution of sec-butyllithium. The reaction was continued for 5 hours at 50 °. The live polyisoprene homopolymer had a number average molecular weight of 46,000 and a peak molecular weight of 76,000.

(b) The living polymer solution thus prepared was cooled to about 25 °, after which 76.1 ml of a 197 mmol / l solution of divinylbenzene was added. The temperature was raised to 60 °, and the reaction was allowed to proceed for 5 hours, after which the live, star-shaped polymer was texminated. He found that more than 92% of the living polymer had been converted to star-shaped polyisoprene.

(c) The reaction vessel was then purged with hydrogen, and a hydrogenation catalyst prepared by mixing at 40 ° of 44.1 ml of a 0.0728 molar solution of Ni (octoate) was added.2 in cyclohexane and 30.9 ml of a 0.22 molar solution of Al (Et) in cyclohexane. The star-shaped polyisoprene solution was then hydrogenated (more than 95%) at a temperature of 65 ° and a hydrogen pressure of 30 kg / 2 cm. The hydration catalyst was then extracted by washing the solution at about 70 ° with aqueous citric acid solution (1% by weight) and with water. The peak molecular weight of the hydrogenated star-shaped polyisoprene was 520,000 (on polystyrene scale) and 270,000 (on hydrogenated, linear polyisoprene scale).

Example 2 (a) Example 1 (a) was repeated with the differences that the amount of isoprene and cyclohexane was 340.5 g and 1362 g respectively and that the polymerization was initiated with 80.5 ml of a 94 mmol / l solution of sec. butyl lithium. the polymerization was continued for 2.5 hours at 50 ° C. The number average molecular weight of the living polyisoprene homopolymer was 44,000.

(b) The living polymer solution thus prepared was reacted with J 4, 1 ml of a 650 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. It was found that 95% of the living polymers had been converted to star-shaped polyisoprene.

(c) The solution of star-shaped polyisoprene thus prepared was hydrogenated (99.4%) using the procedure of Example 1 (c). The peak molecular weight of the hydrogenated, star-shaped polyisoprene was 540,000.

Example 3 (a) Example 2 (a) was repeated with the differences that the amount of cyclohexane was 1451 g and that the polymerization was initiated with 76.4 ml of a 92 mmol / l solution of sec-butyllithium. The number average molecular weight of the living polyisoprene homopolymer was 43,000.

(b) The living polymer solution thus prepared was reacted with 66.7 ml of a 481 mmol / l solution of divinylbenzene, preheated to a temperature of 72 °, for 2.5 hours at 80 °, after which

7614606-7 the live, star-shaped polymer was terminated. It was found that 92 ° / o of the living polymers had been converted to star-shaped polyisoprene.

(c) The thus prepared star-shaped polyisoprene solution was hydrogenated (98.9%) using the procedure of Example 1 (c). The peak molecular weight of the hydrogenated, star-shaped polyisoprene was 474,000.

Example 4 (a) Example 2 (a) was repeated with the differences that the amounts of isoprene and cyclohexane were 400 g and 1600 g, respectively, and that the polymerization was initiated with 124.2 ml of a 92 mmol / l solution of sec-butyllithium. The number average molecular weight of the living polyisoprene homopolymer was 34,000.

(b) The living polymer solution thus prepared was reacted with 165.3 ml of a 205 mmol / l solution of divinylbenzene under

2.5 hours at 80 °, after which the live, star-shaped polymer was terminated. It was found that 93% of the living polymers had been converted to star-shaped polyisoprene.

(c) The solution of star-shaped polyisoprene thus prepared was hydrogenated (99.3%) using the procedure of Example 1 (c). The peak molecular weight of the hydrogenated, star-shaped polyisoprene was 400,000.

Example 5 (a) A live polyisoprene homopolymer was prepared by polymerizing 170.25 g of isoprene in a solution of 1362 g of cyclohexane. The eolymerization was initiated by the addition of 63 ml of a 90 mmol / l solution of sec-butyllithium. The reaction was continued for 2 hours at 50 °. Additional amounts of sec-butyllithium solution (63 ml of a 90 mmol / l solution) and 170.25 g of isoprene were then added to the reactor and allowed to react for an additional 2 hours at 50 ° Εθη thus produced live polyisoprotein homopolymer exhibited two different number average molecular weights. namely 15,000 and 45,000 respectively.

(b) The living polymer solution thus prepared was reacted with 70.5 ml of a 625 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live polymer was terminated. It was found that 94% of the living polymers had been converted to star-shaped polyisoprene.

7614606-7 (c). The peak molecular weight of the hydrogenated, star-shaped polyisoprene was 41,000.

Example 6 (a) Example 2 (a) was repeated.

(b) The solution of living polyisoprene homopolymer thus obtained was reacted with a mixture of 34.5 ml of a 625 mmol / l solution of divinylbenzene, which also contained additional styrene (24.8 g), at 80 ° below 2.5 hours, after which the live, star-shaped polymer was terminated. It was found that 91% of the living polymers had been converted to star-shaped polyisoprene.

(c) The thus prepared star-shaped polyisoprene solution was hydrogenated (99.5%) using the procedure of Example 1 (c). The peak molecular weight of the hydrogenated, star-shaped polyisoprene was 5? 4,000.

Examples 7-10 (a) Four live tapered poly (isoprene / butadiene) copolymers (ad) were prepared by polymerizing a mixture of 139.5 6 isoprene and 110.6 g of butadiene in a solution of 1790 g of cyclohexane. The amounts of sec-butyllithium used are given in Table 1 below, as well as the molecular weights of the tapered poly (isoprene / butadiene) produced.

copolymers.

Table 1

<td>Live polymer</td><td>Solution of sec. butyllithium (100 mmol / liter) (ml)</td><td>Number average</td><td>The peak molecular weight</td>

<td></td><td colspan="2">(b) Seeds produced in seed</td><td>four solutions of</td>

<td colspan="4">more reacted with different amounts of divinylbenzene solutions</td>

live polyuns using the procedure of Example 1 (b). The reaction conditions used and the amounts of divinylbenzene as well as the percentage of living polymers that had been converted to star-shaped tapered poly (isoprene / butadiene) copolymers are presented in Table 2 below.

(c) The star-shaped copolymers thus prepared were hydrogenated (over 95%) using the procedure of Example 1 (c). The peak molecular weights for the hydrogenated, star-shaped tapered poly7614606-7 (isoprene / butadiene) copolymers are also presented in Table 2.

Table 2

<td>Example</td><td>Use live polymer</td><td>Solution of divinylbenzene (197 mmol / liter) (Ml)</td><td>Temp. (° C)</td><td>Time (Hrs.)</td><td>Conversion rate (%)</td><td>The peak molecular weight</td>

Example 11 (a) A live, randomly constructed poly (isoprene / butadiene) copolymer was prepared by polymerization, under a pressure of

5.2 abs, of a mixture of JO g of isoprene and 270 g of butadiene in 1200 g of cyclohexane in the presence of J5 wt% diethyl ether. The polymerization was initiated by adding to the solution of 70.2 ml of a 95 mmol / l solution of sec-butyllithium. The reaction was continued for 2.5 hours at 45 °. The live, randomly constructed poly (isoprene-butadiene) copolymer's peak molecular weight was 86,000.

(b) The living polymer thus prepared was reacted with J1, J ml of a 625 mmd / L solution of divinylbenzene at 45 ° for 2.5 hours and then with the same amount at the same temperature for an additional 2.5 hours, the live, star-shaped polymer was terminated. It was found that 90% of the living polymers had been converted to star-shaped, randomly constructed poly (isoprene / butadiene) copolymers.

(c) The solution of star-shaped copolymers thus prepared was hydrogenated (97Λ%) using the procedure of Example 1 (c). The hydrogenated, randomly formed, star-shaped poly (isoprene / butadiene) copolymer's peak molecular weight was 6J4,000.

Example 12 (a) A live poly (styrene / isoprene) block copolymer of the polystyrene-polyisoprene-Li structure was prepared by polymerizing J4.0 g of styrene in a solution of 1 622 g of cyclohexane. The polymerization was initiated by adding to the solution of 75.7 ml of a 90 mmol / l solution of sec-butyllithium. The reaction was continued for 2 hours at 50 °. The living polystyrene homopolymer solution was then reacted with J06.5 g of isoprene for an additional 2 hours at 50 °. The number average molecular weight of the live poly (styrene / isoprene) block copolymer was 49,600.

7614606-7 (b) The living polymer solution thus prepared was reacted with 51.0 ml of a 625 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. He found that 93% of the living polymers had been converted to star-shaped poly (styrene / isoprene) block copolymers.

(c) The thus-prepared star-shaped copolymer solution was hydrogenated (99.5%) using the procedure of Example 1 (c). The hydrated star-shaped poly (styrene / isoprene) block copolymer weight was 504,000.

Example 13 (a) A live poly (isoprene / styrene) block copolymer of the polyisoprene-polystyrene-Li structure was prepared by polymerizing 310.2 g of isoprene in a solution of 1362 g of cyclohexane. The polymerization was initiated by the addition of 79.6 ml of a 95 mmol / l solution of sec-butyllithium. The reaction was continued for 2.5 hours at 50 °. The live polyisoprene homopolymer solution (number average molecular weight 41,000) was then reacted with 30.3 g of styrene for an additional 2.5 hours at 50 °. The number average molecular weight of the live poly (isoprene / styrene) block copolymer was 45,000.

(b) The solution of live polymer thus prepared was reacted with 34.6 ml of a 625 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. It was found that 90% of the living polymers had been converted to star-shaped poly (isoprene / styrene) block copolymers.

(c) The thus prepared solution of co-shaped copolymer was hydrogenated (98.5%) using the procedure of Example 1 (c). The hydrogen molecularly star-shaped poly (isoprene / styrene) block copolymer weight was 499,000.

Example 14 (a) A live tapered poly (isoprene / styrene) copolymer was prepared by polymerizing a mixture of 360.0 g of isoprene and

40.2 g of styrene in 2050 g of cyclohexane. The polymerization was initiated by adding to the solution of 93.6 ml of a 95 mmol / l solution of sec-butyllithium. The reaction was continued for 2.5 hours at 50 °. The number average molecular weight of the live tapered poly (isoprene / styrene) copolymer was 4J 400.

(b) The solution of living polymer thus prepared

7614606-7 was reacted with 4-1.8 ml of one. 625 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. MAN. found that 94% of the living polymers had been converted to star-shaped tapered poly (isoprene / styrene) copolymers.

(c) The thus prepared star-shaped copolymer solution was hydrogenated (98.2%) using the procedure of Example 1 (c). The hydrogenated star-shaped tapered poly (isoprene / styrene) copolymer's peak molecular weight was 4-89,000.

Example 15 (a) A live, randomly constructed poly (isoprene / styrene) copolymer was prepared by polymerizing 102.2 g of isoprene and 34.2 g of styrene in 1208 g of cyclohexane. The polymerization was initiated by the addition of 79.6 ml of a 95 mmol / l solution of sec-butyllithium. Immediately after initiation, a solution of 204 g of isoprene and 156 g of cyclohexane was pumped into the reaction vessel at a constant rate for 45 minutes. The reaction temperature was 50 °, and the total reaction time was 3.25 hours. The live, randomly constructed poly (isoprene / styrene) number average molecular weight of the copolymer was 42,200.

(b) The living copolymer solution thus prepared was reacted with 33.9 ml of a 578 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. It was found that 92% of the living polymers had been converted to star-shaped, randomly constructed poly (isoprene / styrene) copolymers.

(c) The thus prepared star-shaped copolymer solution was hydrogenated (98.9%) using the procedure of Example 1 (c). The hydrogenated star-shaped randomly constructed poly (isoprene / styrene) copolymer top molecular weight was 451,000.

Example 16 (a) A live poly (isoprene / styrene / isoprene) block copolymer was prepared by polymerizing 151.5 g of isoprene in a solution of 1362 g of cyclohexane. The polymerization was initiated by the addition of

79.5 ml of a 95 mmol / l solution of sec.butyllithium. The reaction was continued for 2.5 hours at 50 °. The thus-formed solution of live polyisoprene (number average molecular weight 25600) was then reacted with 37.9 g of styrene, and the reaction was continued for another 2.5 hours at 50 °. The solution of living poly (isoprene / styrene) block copolymer thus formed (number average molecular weight 31,200) was then reacted with an

Isoprene (151.5 g), and the reaction is continued for an additional 2.5 hours at 50 °. The number average molecular weight of the live poly (isoprene / styrene / isoprene) segment polystyrene was 54,400.

(b) The living polymer solution thus prepared was reacted with 37.1 ml of a 578 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours, after which the live, star-shaped polymer was terminated. It was found that 94% of the living polymers had been converted to star-shaped poly (isoprene / styrene / isoprene) block copolymers.

(c) The star-shaped polymer solution thus prepared was hydrogenated (98.5 ° fi) using the procedure of Example 1 (c). The hydrogenated star-shaped poly (isoprene / styrene / isoprene) segment molecular weight of the copolymer was 585,000.

Example 17 (a) A live polyisoprene homopolymer was prepared by polymerizing 170 g of isoprene in a solution of 2097 g of cyclohexane. The polymerization was initiated by the addition of 44.7 ml of a 95 mmol / l solution of sec-butyllithium. The reaction was continued for 2 hours at 50 °. The number average molecular weight of the living polyisoprene homopolymer was 41,000.

(b) (i) The living polymer solution thus prepared was reacted with 20 ml of a 625 mmol solution of divinylbenzene at 80 ° for 2.5 hours. It was found that 91% of the living polymers had been converted to star-shaped polyisoprene.

(ii) The resulting solution of live star-shaped polyisoprene homopolymer was then reacted with 42.1 g of styrene at 50 ° for an additional 2 hours, after which the live star-shaped mixed polyisoprene / polystyrene copolymer was terminated.

(c) The thus prepared star-shaped ampolymer solution was hydrogenated (97.8%) using the procedure of Example 1 (c). The hydrated star-shaped blended polyisoprene / polystyrene copolymer tops molecular weight was 484,000.

Example 18 (a) A live polyisoprene homopolymer was prepared by polymerizing 149.8 g of isoprene in a solution of 1867 g of cyclohexane. The polymerization was initiated by the addition of 39.4 ml of a 95 rimol / l solution of sec-butyllithium. The reaction was continued for 2 hours at 50 °. The number average molecular weight of the living polyisoprene homopolymer was 39,800.

(b) (i) The living polymer solution thus prepared is reacted with 17.6 ml of a 625 nmd / L solution of divinylbenzene at

7614606-7

80 ° for 2.5 hours. It was found that 93% of the living yolymers had been converted to star-shaped polyisoprene.

(ii) The solution of live star-shaped polyisoprene thus prepared was reacted with 5.4 g of styrene at 5θ ° for 0.25 hours.

(iii) The live star-shaped blend polyisoprene / polystyrene copolymer thus prepared was reacted with 4-5.1 g of isoprene at 50υ for 2.5 hours, after which the live star-shaped mixed polyisoprene / polystyrene / polyisoprene copolymer was terminated.

(c) The star-shaped copolymer solution was hydrogenated (99.1%) using the procedure of Example 1 (c). The hydrogen molecular, star-shaped mixed polyisoprene / polystyrene / polyisoprene copolymer's peak molecular weight was 388,000.

Example 19 (a) A live polyisoprene homopolymer was prepared by polymerizing 300 g of isoprene in a solution of 1500 g of cyclohexane. The polymerization was initiated by the addition of 83.3 ml of a 90 mmol / l solution of sec-butyllithium and continued for 2 hours at 50 °. The number average molecular weight of the living polyisoprene homopolymer was 42,000.

(b) (i) The living polymer solution thus prepared was reacted with 35 ml of a 625 mmol / l solution of divinylbenzene at 80 ° for 2.5 hours. It was found that 95% of the living polymers had been converted to star-shaped, living polyisoprene.

(ii) The thus prepared solution of live star-shaped polyisoprene was reacted with an additional amount of isoprene (20.8 g) at 50 ° for 2 hours to produce a live star-shaped polyisoprene homopolymer with additional chains derived from said additional amount of isoprene. Then the polymer was terminated.

(c) The thus-prepared star-shaped homopolymer solution was hydrogenated (98.9%) using the procedure of Example 1 (c). The hydrogenated star-shaped polyisoprene homopolymer had a η peak molecular weight of 456,000.

The hydrogenated star-shaped polymers prepared according to Examples 1-19 are characterized by poly (divinylbenzene) cores, which are believed to be cross-linked, with the exception of the hydrogenated, star-shaped polymer of Example 6, which is characterized by a poly (divinylbenzene / styrene) core. They are also characterized by a variety of hydrogenated polymer chains of one or more conjugated dienes, and optionally a monoalkenyl compound, which chains extend outwardly therefrom. In most cases, the number of hydrogenated polymer chains was between 7 and 15 ·

7614606-7

Example 20

The solutions of the hydrogenated star-shaped polymers prepared according to Examples 1-19 were diluted with Quatar Marine HVI 60 base lubricating oil, and the cyclohexane was evaporated to make oil concentrates containing 10-25% by weight of the polymers.

Examples 21-42 '' Multi-grade lubricating oil compositions were prepared from the hydrogenated star-shaped polymer concentrates described in Example 20. The concentrates were added to a Quatar Marine HVI 60 base oil (viscosity index 95) together with 0.5% by weight of a floating point lowering polymethacrylate and 10.1% by weight of a commercial lub-oil package containing a polyalkylsuccinimide and / or polyalkylsuccinate and a zinc dialkyl dithiophosphate. The amounts of polymer present, based on the weight of the compositions, are given in Table 5 below.

The kinematic viscosities of the compositions at 150 ° G, 99 ° C and 58 ° C (ASTM D445), the dynamic viscosities at -18 ° C (ASTM) D2602), the viscosity index (extrapolated, V1-g) and the shear stability (DIN 51582) determined. The results are presented in Table 5 below.

Particular emphasis is placed on the finding that the shear stability of the polymers is very good, especially in light of the high molecular volts of the polymers, that small amounts of the polymers have good thickening capacity (see _ results) and that V4 Λ -REK99 The C ^150 ° C results are good.

For comparison, a method of multi-grade lubricating oil compositions containing polymers described below was prepared and tested in the manner described above. The results are also presented in Table 3 below.

The polymers tested were:

(a) a hydrogenated, tapered styrene / butadiene copolymer having a peak molecular weight of 100,000;

(b) a hydrogenated styrene / isoprene block copolymer having a peak molecular weight of 140,000;

7614606-7 aa.

iii '

Table 5

7614606-7

111 '> ra · η -P p ΕΟ, Ο <D rj β cö -P 44 -Η -P · Η <J> fl' Λ H

B II I! II II II It II II II II II II

0) ra • rl

Pi oo

CO> O.

O

O σ '

M CQ i> O

<td>queue</td><td>la</td><td>σ \</td><td>cow</td><td></td><td></td><td>LA</td><td></td><td>cow</td><td></td><td>II</td>

Table 5 (cont

CQ o

d> HM <D

n it II II II II

It II

II II II II II

II II

II II II II

7614606-7 ay

Contents4

30 members in 17 offices

This recordMember, by publication datePriority claim7 more offices are in the list below

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Document	Office	Kind	Date
521276	United Kingdom	A	1976-02-10
521276	United Kingdom	A	1976-02-10
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BE850336A	Belgium	A	1977-07-13
DK1077A	Denmark	A	1977-08-11
SE7614606L	Sweden	L	1977-08-11
NL7700168A	Netherlands (Kingdom of the)	A	1977-08-12
JPS5296695A	Japan	A	1977-08-13
DE2700294A1	Germany	A1	1977-08-18
FR2340959A1	France	A1	1977-09-09
ZA7719B	South Africa	B	1977-11-30
ATA3477A	Austria	A	1978-02-15
AU2110077A	Australia	A	1978-07-13
US4116917A	United States of America	A	1978-09-26
AT345952B	Austria	B	1978-10-10
US4156673A	United States of America	A	1979-05-29
AU507379B2	Australia	B2	1980-02-14
ATA161478A	Austria	A	1980-02-15
SU719512A3	Soviet Union (until 1991)	A3	1980-02-29
GB1575507A	United Kingdom	A	1980-09-24
AT358817B	Austria	B	1980-10-10
FR2340959B1	France	B1	1981-01-09
AR222626A1	Argentina	A1	1981-06-15
CA1110396A	Canada	A	1981-10-06
CH631725A5	Switzerland	A5	1982-08-31
SE433228BThis record	Sweden	B	1984-05-14
JPS6150120B2	Japan	B2	1986-11-01
DK151035B	Denmark	B	1987-10-12
DK151035C	Denmark	C	1988-05-02
DE2700294C2	Germany	C2	1990-02-01
IT1241565B	Italy	B	1994-01-18
NL191264B	Netherlands (Kingdom of the)	B	1994-11-16
NL191264C	Netherlands (Kingdom of the)	C	1995-04-18

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Hydrogenated polymers

Abstract

Term

O

II II II II II

II II

II II II II

Priority claims4

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