METHOD FOR OXIDATIVELY SHEARING A POLYOLEFIN

Abstract: A method for oxidatively shearing an olefinic polymer accompanied by introduction into the sheared polymer of carbonyl groups which comprises oxidising the olefinic polymer in a solvent such as a lubricating oil in the presence of an alkali or alkaline earth metal added in the form of either the elemental metal or a compound other than a benzene sulphonic acid salt. The oxidised sheared polymer so-produced can be used without further modification as a viscosity index improver additive in lubricating oil composi­ tions or can be modified by reaction with functional group-­ containing compounds to introduce multifunctional proper­ ties.

Description: METHOD FOR OXIDATIVELY SHEARING AN OLEFINIC POLYMER. The present invention relates to a method for oxidatively shearing an olefinic polymer accompanied by introduction into the sheared polymer of carbonyl groups, to lubricating compositions containing the oxidised sheared polymer so-produced and to lubricating compositions containing the oxidised sheared polymer post-reacted with functional group-containing compounds. Lubricating oils are normally classified in terms of their viscosity at a particular temperature but equally important is a property known as the viscosity index, which is an empirical number giving a measure of the extent to which the viscosity of an oil decreases as the temperature is raised. An oil which satisfies viscosity requirements at both extremes of the temperature range to which it may be subjected is said to have a high viscosity index. This property can be controlled to some extent by refining, but in recent years the trend has been towards multi-grade#oils, of extremely high viscosity index, containing olefinic polymer additives as viscosity index improvers. While the olefinic polymers are undoubtedly effective in improving lubricant oil temperature viscosity relationships, their resistance to molecular weight degradation by mechanical or oxidative means, otherwise referred to as their shear stability, is rather low, resulting in curtailment of the viscosity index improver life. In this connection it is known that the shear stability of an olefinic polymer is a function of its carbon backbone chain length, i.e. its number average molecular weight (#i#), and that higher molecular weight olefinic polymers when mechanically sheared (i.e. by mastication) and/or chemically sheared (e.g. by air oxidation), although degraded in molecular weight, become somewhat improved in shear stability. It is also advantageous to introduce carbonyl groups into the sheared polymer because such groups can be further reacted with functional group-containing compounds such as, for example amines, to produce condensation products which exhibit multifunctional properties such as for example both viscosity index improver and dispersancy properties. Such oxidative shear of the olefinic polymers can be accomplished by mastication of the polymer in a Banbury Mixer in the presence of air or by sparging an oxygen-containing gas (e.g. air) into a solution of the polymer in hexane, xylene or a lubricating oil at elevated temperature and atmospheric or elevated pressure, optionally in the presence of a free-radical initiator and optionally also in the presence of metal catalysts such as metals of the platinum-palladium group and compounds (e.g. salts) containing one or more of the metals copper, iron, cobalt, cadmium, manganese, vanadium and the like metal oxidation catalysts. Such oxygen-sparging oxidation methods applied to the olefinic polymers are described in the prior art, for example in US Patent Nos. 2,982,728; 3,316,177; 3,153,025; 3,365,449 and 3,544,520. We have confirmed the results reported in for example USP 4,145,493 that whilst such methods do cause substantial shear, in order to achieve desirable shear stabilities and a sufficiency of carbonyl groups in the sheared polymer it is generally necessary to prolong the oxidation, which results in unacceptable discolouration of the sheared polymer solution, at least in lubricating oil solutions thereof. In those cases in which a lubricating oil is used as the solvent there is a marked tendency for the lubricating oil itself to suffer random oxidation leading to undesirable oxidation products. Some at least of the problems associated with the prior art processes are claimed to be overcome by the process described in the aforesaid USP 4,145,493, using a spraying technique. USP 4,011,380 describes the oxidation of copolymers of ethylene and olefinic monomers in the presence of from about 0.01 to about 5.0 weight percent or higher based on copolymer/oil solution, of an oil-soluble benzene sulphonic acid or salt therecf. Sodium or calcium salts are reported to promote the oxidation reaction but worsen product colour and magnesium salts are reported to promote the oxidation reaction and provide lighter products. We have now found that compounds of alkali and alkaline earth metals other than sulphonic acid salts, and indeed the metals themselves, are effective in promoting oxidative shear of olefinic polymers and that the oxidation products can be used as viscosity index improver additives in lubricating oil compositions. Accordingly, the present invention provides a method for oxidatively shearing an olefinic polymer accompanied by introduction into the sheared polymer of carbonyl groups which method comprises oxidising the olefinic polymer in a solvent in the presence of an alkali or alkaline earth metal added in the form of either the elemental metal or a compound other than a benzene sulphonic acid salt. The term "olefinic polymer as used throughout this specification refers to polymers derived from olefinically unsaturated hydrocarbon monomers. The polymer may be either a homopolymer, a copolymer, which term includes random, block and tapered copolymers, and terpolymers, tetrapolymers, etc. Suitable homopolymers include polybutenes, such as polyisobutene having an Mn in the range 5,000 to 60,000, preferably in the range 10,000 to 45,000. Suitable copolymers include ethylene copolymers, such as ethylene/propylene e.g. ethylene/propylene copolymers containing from about 20 to about 65, preferably from about 35 to about 45 mole percent propylene and having an Mn in the range 20,000 to 200,000, preferably from 20,000 to 70,000 and copolymers of a vinyl aromatic monomer, e.g. styrene, alphamethylstyrene and vinyl naphthalene and a conjugated diene monomer, e.g. butadiene and isoprene, of which hydrogenated block and tapered copolymers containing from about 10 to 40, preferably from 15 to 35 weight percent of the vinyl aromatic monomer and having an Mn in the range 25,000 to 125,000, preferably from 50,000 to 125,000, are preferred. Such polymers are described in for example US Patents Nos: 3994815; 3775329; 3668125 and 3763044. Suitable random copolymers are described in, for example US Patents Nos: 3,554,911; 3,630,905; 3,752,767 and 3,772,169. Suitable terpolymers include terpolymers of ethylene, a C3 to C8 straight-or branched-chain alpha-olefin, e.g. propylene, and a non-conjugated acyclic or alicyclic diolef in, e.g. 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,4-cyclohexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, containing from 30 to 85, preferably from 40 to 70 mole percent ethylene, from 15 to 70, preferably from 20 to 58 mole percent alpha-olefin and from 0.5 to 20 mole percent, preferably from 1 to 15, even more preferably from 2 to 10 mole percent diene and having an Mn in the range from about 15,000 to about 200,000, preferably from 20,000 to about 70,000. Preferred terpolymers are terpolymers of ethylene, propylene and 1,4-hexadiene or 5-ethylidene-2-norbornene. Suitable tetrapolymers include tetrapolymers of ethylene, a C3 to C8 straight-or branchedchain alpha-olefin and two non-conjugated acyclic or alicyclic diolefins. The preparation of the terpolymers, using Ziegler-Natta catalysts, is described for example in US Patents Nos: 2,933,4890, 3,000,866 and 3,093,621. These terpolymers and tetrapolymers, which are primarily produced for use in elastomeric compositions, are characterised by the absence of chain or backbone unsaturation and contain sites of unsaturation in groups which are pendant to or in cyclic structures outside of the main polymer chain. It is an advantage of the present invention that oxidative shear occurs substantially on the main backbone chains of the polymers in preference to the groups pendant to or outside the backbone chain. Mixtures of polymers may also be used, if so desired, in the process of the invention. Thus blends may be formulated to provide desirable properties, e.g. improved low temperature thickening. Suitable mixtures of polymers include mixtures of two or more ethylene/propylene copolymers having different ethylene/propylene ratios and/or molecular weights and mixtures of an ethylene/propylene copoymer and a polyisobutene. Although a wide range of solvents may be employed suitable solvents include hydrocarbon solvents such as linear paraffins, e.g. hexane, cyclic paraffins, e.g. cyclohexane, aromatic solvents, e.g. xylene, low molecular weight liquid polyolefins, e.g. polyisobutene and mineral oils of lubricating viscosity derived from petroleum, such as the solvent neutral oils. The solvent may suitably be present in an amount in the range from 20 to 99%, preferably from 50 to 95%, even more preferablly from 70 to 90% by weight, based on the weight of the olefinic polymer. Since the principal application of the oxidatively sheared polymer product is as a lubricating oil additive or as an intermediate in the preparation of lubricating oil additives it is preferred to use a lubricating oil as solvent, thereby avoiding solvent separation and recycle steps. It is an advantage of the method of the present invention that the olefinic polymer can be oxidised in preference to the lubricating oil. The oxidation is carried out in the presence of an alkali or alkaline earth metal, preferably an alkali metal, added in the form of either the elemental metal or a compound of the metal other than the benzene sulphonic acid salt. It is preferred to employ a compound of the metal. Of the alkali metals, lithium, sodium and potassium are preferred. Suitable metal compounds include oxides, hydroxides, carbonates, bicarbonates, alkyls, alkoxides and peroxy compounds such as peroxides and peroxycarbonates. Thus lithium hydroxide, potassium hydroxide, potassium carbonate, butyl lithium, sodium hydroxide, potassium ethoxide and potassium peroxycarbonate are specific examples of compounds which may be employed. Whilst the peroxy compounds may be added as such it is particularly preferred to form them 'in situ' during the oxidation reaction. Thus the peroxycarbonate, for example, may be formed by reacting potassium hydroxide with carbon dioxide during the oxidation reaction. Alternatively potassium and sodium catalysts may be activated by treatment with carbon dioxide prior to the oxidation. Only very small amounts of the alkali or alkaline earth metal are necessary to achieve satisfactory shear stabilities and carbonyl group concentrations. Thus amounts as small as 0.01% by weight based on the elemental metal may be used, though it is preferred to use greater than 0.05% by weight. It is advantageous to use as small an amount as possible because for most applications of the oxidatively sheared polymer the presence of metallic residues in the polymer is undesirable and the use of excessive amounts unnecessarily complicates subsequent filtration for the removal of such residues. The alkali or alkaline earth metal or compound thereof may be unsupported or supported on a high surface area inert support such as silica and may be either dispersed in the solvent or used in the form of a fixed bed. The olefinic polymer may suitably be oxidised by contacting a solution of the polymer under suitable conditions of temperature and at atmospheric, subatmospheric or elevated pressures with an oxidising agent such as air or free oxygen, or any oxygen-containing material capable of releasing oxygen under the oxidation conditions. The oxidation may be carried out by methods generally known in the art as represented by, for example. US Patents Nos. 2,982,728, 3,316,177, 3,153,025, 3,365,499, 3,544,520 and 3,864,268. Generally, the oxidation can be carried out over a wide temperature range, though temperatures within the range 100 to 2500 C, preferably 120 to 200 C, will usually be found suitable. Further, oxidation may suitably be conducted at atmospheric or superatmospheric pressures. Oxidation of the olefinic polymers dissolved in a solvent such as mineral oil is conveniently carried out, either in batches or continuously, in a stirred reactor with air, or air prediluted with an inert gas such as nitrogen or carbon dioxide, preferably carbon dioxide, so as to minimise explosion hazards. Stirring may be accomplished by any form of high-speed stirrer, such as for example, a turbomixer. The air, or diluted air, is preferably introduced into the polymer solution in a finely divided state, by for example a Robojet" mixer. The reaction time will depend amongst other thinks upon the particular olefinic polymer, the nature of the alkali or alkaline earth metal compound and its particular form and the desired end-use of the oxidised sheared polymer. The progress of the oxidation may be monitored for example by measuring the viscosity of the polymer solution. At any desired viscosity the oxidation may suitably be terminated by blanketing the reactor with nitrogen. At the completion of the oxidation reaction it may be necessary to filter the sheared polymer product. The sheared olefinic polymer may then be used as a viscosity index improver additive to provide a finished lubricating oil composition. In another aspect therefore the invention also provides a finished lubricating oil composition comprising a base oil of lubricating viscosity and a viscosity index improving amount of the sheared olefinic polymer containing carbonyl groups produced by the method as hereinbefore described. A wide variety of mineral oils having a broad range of viscosity and origin may be used as the base oil. The mineral oils may be straight-run distillates in the lubricant range, e.g. boiling above 3150C, or may have been further refined by deasphalting, dewaxing, solvent extraction, sorbent treatment or hydrogenation. Also suitable are synthetic hydrocarbon oils in the lubricating range by, for example, polymerisation oligomerisation and alkylation of aromatics with olefins. Oxidation of the olefinic polymer in lubricating oil as solvent produces a sheared olefinic polymer which may be incorporated in the finished lubricating oil without removal of the lubricating oil used as solvent. In the case of oxidation in other solvents it may be necessary to separate the solvent from the 8heared polymer before this can be incorporated in the finished oil composition. The finished lubricating composition may suitably contain from 0.01 to 90X, preferably from 0.5 to 40X by weight of the sheared olefinic polymer. Alternatively the sheared olefinic polymer itself may be used as a lubricating oil. In addition to the sheared olefinic polymer the finished lubricating oil composition may also contain other additives commonly employed in the art, such as other viscosity index improvers, dispersants, detergents, corrosion inhibitors, antiliear agents etc. It is believed that the carbonyl groups introduced into the polymer, or at least the ethylene/propylene copolymers, by the oxidative method of the present invention tend to be ketocarbonyl groups rather than aldehydocarbonyl and carboxylic acid-carbonyl groups. Ketocarbonyl groups are favoured for the further chemical conversion of the sheared polymer. The sheared olefinic polymers may be reacted through their carbonyl groups with a variety of other reagents, e.g. hydrogen or nitrogen, oxygen, sulphur, boron and/or phosphorus-containing compounds, to form multifunctional products. It is preferred to react the sheared olefinic polymer with one or more non-tertiary nitrogen-containing compounds such as ammonia, primary and secondary amines, diamines and, in particular, polyalkylene polyamines having the formula: EMI8.1 wherein R1 is either hydrogen or a C1 to C6 alkyl group, preferably hydrogen, and x is an integer in the range from 2 to 10, preferably in the range from 2 to 5, to form an imine product having both viscosity index improver and dispersancy properties. Examples of suitable nitrogen-containing compounds include 1,2-diaminoethane; 1,3t3-diaminopropane; 11,4-diaminobutane; 1, 6-diaminohexane; diethylene triamine, triethylene tetramine, tetraethylene pentamine; 1,2-propylene diamine; di-(1,2-propylen) triamine, di-(1,3-propylene) triamine; N,N-dimethyl-1 , 3-diaminopropane; N,N-di-( 2-aminoethyl) ethylene diamine; N,N-di-(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropyl-amine; N-dodecyl-1,3-propane diamine; tris-hydroxymethyl aminomethane, diisopropanolamine and diethanolamine. Other useful amines include alicyclic diamines such as 1,4-bis-Caminomethyl) cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkyl piperazines. Commercial mixtures of amine compounds may advantageously be used. There may also be used the mono-succinimide or the bis-succinimide, preferably the mono-succinimide, formed by reacting an alkenylsuccinic anhydride such as polyisobutene succinic anhydride with either a diamine or a polyalkylene polyamine having the formula (I). The reaction of the sheared polymer with the nitrogen-containing compound, for example the polyalkylene polyamine of formula (I), may also be conducted in the presence of an aldehyde, e.g. a formaldehyde-yielding reactant, to form a Mannich condensation product exhibiting both viscosity index improver and dispersant/detergent properties. Suitable examples of formaldehyde-yielding reactants include formalin, paraformaldehyde, other linear and cyclic formaldehyde polymers and gaseous formaldehyde. The reaction conditions for the reaction of carbonyl groups with nitrogen-containing compounds both in the presence and absence of aldehydes are well-known in the art and require no further elaboration herein. Thus, for example, the condensation of oxidised rubbery polymers containing a plurality of ketocarbonyl groups with a primary or secondary amine to an aminated ketocarbonyl compound useful as a lubricating oil additive is described in USP 3,864,268. The condensation of an oxidised rubbery copolymer with both an aldehyde and a primary or a secondary amine is described in USP 3,872,019. As an alternative to reacting the sheared olefinic polymer recovered from the oxidation reaction with the nitrogen-containing compound, the nitrogen-containing compound, and in particular the mono-succinimide, may be added at any time during the oxidation reaction. In a similar manner derivatives of the sheared olefinic polymer may be formed by reaction with oxygen-containing compounds, sulphur compounds, boron compounds and/or phosphorus compounds. In yet another aspect the invention also provides a finished lubricating oil composition comprising a major proportion of a base oil of lubricating viscosity and a minor proportion of the further-reacted sheared olefinic polymer. The invention will now be more particularly described by reference to the following Examples. The apparatus employed in Examples 4 to 7 is illustrated in the accompanying Figure. With reference to the Figure, 1 is a 2 litre-capacity glass reaction vessel, 2 is a heating mantle, 3 is a Silverson mixer, 4 is a thermocouple, 5 is a temperature control unit, 6 isvan air sparge tube, 7 is an air flow rotameter, 8 is a flow rate control valve and 9 is a pull-apart fixed catalyst bed with wire gauze basket for holding the catalyst. Example 1 135 g of a 15% by weight solution of ORTHOLEUM 2052 (an ethylene propylene/1,4-hexadiene terpolymer) in 100SN base oil having a viscosity measured at 1000C of 4500cS and a shear stability index as measured by the procedure of DIN 51382 of 34 was heated in the presence of 0.15 g lithium metal to 19000 under a nitrogen blanket. The mixture was stirred using a paddle stirrer whilst blowing air through for 3 hours at a rate of 15cm3/minute. At the end of this period the viscosity at 10000 was 700cS, the shear stability index was 23 and the colour as measured by ASTN D1500 was 2.5. In addition there was a sharp peak in the IR spectrum at 1720 cm¯l indicating the presence in the sheared polymer of ketocarbonyl groups. Comparison Test 1 Example 1 was repeated except that lithium metal was not added. The results were as follows: Viscosity at 10000 = 2100cS Shear stability index = 39 Colour = greater than 8.0 The IR spectrum showed a broad band at 1700 to 1740 cm¯1 indicating the presence of ketocarbonyl, aldehydic carbonyl and carboxylic acid carbonyl groups. Example 2 Example 1 was repeated except that the lithium metal was replaced by 0.5 g lithium hydroxide monohydrate. The results were: Viscosity at 100 C = 1800cS Shear stability index = 28 Colour = 2 Sharp peak at 1720 cm¯1 indicative of ketocarbonyl group. Example 3 The product of Example 1 was reacted with 5 g diethylene triamine (DETA) at 18000 under nitrogen for 2 hours. The product was then vacuum stripped to remove excess DETA. The nitrogen content of the product was 0.23X w/w. The carbonyl peak in the IR spectrum at 1720 cm¯1 had been removed. The product acted as a dispersant and VI improver in bench tests. Example 4 With reference to the Figure a 13.2X by weight solution of Ortholeum 2035 in 100SN base oil (1000 g) was placed in vessel 1 and heated to 18000 whilst mixing with a paddle stirrer. On reaching the temperature the paddle stirrer was removed and the Silvers on mixer 3 with pump head and catalyst bed 9 (containing 10 g NaOH as a fixed bed) were placed in position. The mixer was switched on to circulate the polymer solution. Air was introduced through the air sparge tube 6 under the head of the mixer at a rate of 5 litres/hour so that much of the air was drawn through the mixer with the polymer solution. The viscosity of the polymer solution was measured at intervals and the oxidation continued until the desired viscosity was reached. The viscosity readings were as follows: Time Viscosity at 1000C (cSt) Initial 6834 After 2 hours 2693 After 3 hours 1311 After 3+ hours 785 The IR spectrum showed a sharp peak at 1720 cm¯1 indicating the presence of ketocarbonyl groups in the sheared polymer. Example 5 Example 4 was repeated on a 13.5X by weight solution of Ortholeum 2035. The viscosity measurements were as follows: Time Viscosity at 1000C (cSt) Initial 8921 After 1 hour 6431 After 2 hours 5149 After 3 hours 3609 After 4 hours 2918 After 5 hours 2058 The IR spectrum of the sheared polymer indicated the presence of ketocarbonyl groups. Comparison Test 2 Example 4 was repeated in the absence of a catalyst. The viscosity measurements were as follows: Time Viscosity at 1000C (cSt) Initial 7268 After 1 hour 7228 After 3 hours 5515 After 6 hours 3039 This is not an example according to the invention because no catalyst was used and is included only for the purpose of comparison. Example 6 Example 4 was repeated except that only 100 g polymer solution was used and the catalyst was 5 g NaOH. The viscosity measurements were as follows: Time Viscosity at 1000C (cSt) Initial 6821 After 1 hour 3705 After 2 hours 2068 After 2+ hours 1637 The IR spectrum indicated the presence of ketocarbonyl groups in the sheared polymer. Example 7 Example 5 was repeated except that the 100SN base oil was replaced by Lavera base oil and only 5 g NaOH catalyst was used. The viscosity measurements were as follows: Time Viscosity at 1000C (cSt) Initial 5809 After 1 hour 2586 After 2 hours 745 After 3 hours 99.6 The IR spectrum indicated the presence of ketocarbonyl groups in the sheared polymer. Examples 4 to 7 and Comparison Test 2 demonstrate that the use of a fixed catalyst bed considerably reduces the oxidation time. The product of Comparison Test 2 was much darker than the products of Examples 4 to 7. Example 8 Into a 1 inch internal diameter 1 metre length glass column having an outer jacket containing refluxing decalin (1900C) and packed with + inch spurs was added a 13.5X by weight solution of ORTHOLEUM 2035 containing 0.15% by weight potassium carbonate at a temperature of about 1400C. The solution was added in such a manner that the top of the column was flooded in order to provide an even distribution of liquid across the top of the column. The solution was allowed to pass down the column under gravity at a flow rate of 250 ml her¯1. Air was passed into the column at the bottom at a flow rate of 5 1 her¯1, rose through the column countercurrent to the direction of liquid flow and bubbled out through the top. The solution was allowed to flow through the column for a period of 4 hours and collected (1 litre). The results were as follows: Initial viscosity of the solution measured at 1000C = 8053 cS Final viscosity of the product solution at 1000C = 2780 cS Example 9 Example 8 was repeated. The results were as follows: Initial viscosity of solution at 1000C = 8053 cS Final viscosity of solution at 1000C t 2840 cS Example 10 The procedure of Example 8 was repeated except that the air flow rate was increased to 10 1 hr'l, The results were as follows: Initial viscosity of solution at 1000C = 8053 cS Final viscosity of solution at 1000C = 2790 cS Example 11 The product solution from Example 8 was passed through the column in the manner described in Example 8 except that no further potassium carbonate was added. The results were as follows: Initial viscosity of solution at 1000C = 2780 cS Final viscosity of solution at 1000C r 1580 cS The colour of the solution visibly deteriorated. Example 12 The product solution from Example 9 was passed through the column in the manner described in Example 8, ie 0.15% by weight potassium carbonate was added to the intial solution. The results were as follows:- Initial viscosity of solution at 1000C = 2840 cS Final viscosity of solution at 1000C = 1630 cS No colour deterioration of the solution was observed. Example 13 The procedure of Example 8 was repeated except that instead of adding the potassium carbonate as a solution it was coated on pumice from aqueous solution and the column was packed with the coated pumice. In addition the liquid flow rate was reduced to 60 ml hr'l. The results were as follows: Initial viscosity of solution = 8053 cS Final viscosity of solution 1 2820 cS Example 14 Using the procedure of Example 1, 500 g of a 13.5X by weight solution of ORTHOLEUM 2035 containing 0.15X wt/wt potassium carbonate was oxidised using air at the rate of 6 dm3 hr¯ over 3 hours at a temperature of 1800C. The results were as follows: Initial viscosity of solution - 6000 cS Final viscosity of solution - 600 cS Example 15 Example 14 was repeated except that carbon dioxide was admixed with the air supply in a 1:1 volume ratio such that the total gas flow was 12 dm3ht#l. The same viscosity loss was achieved in 1.5 hours. Example 16 Example 14 was repeated except that carbon dioxide was admixed with air supply in a 2:1 volume ratio Cie 7X 02) such that the total gas flow was 18 dm3hr'l. The same viscosity loss was achieved in 1 hour. Example 17 Example 14 was repeated except that the air supply was reduced to 1.5 dm3hr¯1 and carbon dioxide was added at 12 dm3hr¯l (ie 2.5X 02). The same viscosity loss was achieved in 4 hours.

Claims: Claims: 1. A method for oxidatively shearing an olefinic polymer accompanied by introduction into the sheared polymer of carbonyl groups which method comprises oxidising the olefinic polymer in a solvent in the presence of an alkali or alkaline earth metal added in the form of either the elemental metal or a compound other than a benzene sulphonic acid salt. 2. A method according to claim 1 wherein the olefinic polymer is a polyisobutene having an Na in the range 5,000 to 60,000. 3. A method according to claim 1 wherein the olefinic polymer is an ethylene/propylene copolymer-containing from 20 to 65 mole percent propylene and having an Na in the range 20,000 to 200,000. 4. A method according to claim 1 wherein the olefinic polymer is a copolymer of a vinyl aromatic monomer and a conjugated diene monomer containing from 10 to 40 weight percent of the vinyl aromatic monomer and having an En in the range 25,000 to 125,000. 5. A method according to claim 1 wherein the olefinic polymer is a copolymer of ethylene, a C3 to C8 straight-or branched-chain alpha-olefin and one or more non-conjugated acyclic or alicyclic diolefins containing from 30 to 85 mole percent ethylene, from 15 to 70 mole percent alpha-olefin and from 0.5 to 20 mole percent diene and having an Mn in the range from 15,00 to 200,000. 6. A method according to claim 5 wherein the alpha-olefin is propylene and the diolefin is one or more of 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,4-cyclohexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene. 7. A method according to claim 5 wherein the olefinic polymer is a terpolymer of ethylene, propylene and either 1,4-hexadiene or 5-ethylidene-2-norbornene. 8. A method according to any one of the preceding claims wherein the solvent is a mineral oil of lubricating viscosity. 9. A method according to any one of the preceding claims wherein the oxidation is carried out in the presence of a compound of an alkali or alkaline earth metal. 10. A method according to claim 9 wherein the compound is an oxide, a hydroxide, a carbonate, a bicarbonate, an alkyl, an alkoxide or a peroxy compound. 11. A method according to claim 10 wherein the peroxy compound is a peroxycarbonate, a peroxysulphate or a peroxysulphite. 12. A method according to claim 10 wherein the peroxy compound is formed 'in situ' during the oxidation reaction. 13. A method according to claim 12 wherein the peroxy compound is peroxycarbonate formed during the oxidation from potassium hydroxide and carbon dioxide. 14. A method according to any one of claims 9 to 13 wherein the compound is a compound of lithium, sodium or potassium. 15. A method according to any one of the preceding claims wherein the alkali or alkaline earth metal or compound thereof is employed in the form of a fixed bed. 16. A method according to any one of the preceding claims wherein the olefinic polymer is oxidised by contacting a solution of the polymer at a temperature in the range 100 to 2500C and either atmospheric or superatmospheric pressure with an oxidising agent selected from air, free oxygen or an oxygen-containing material capable of releasing oxygen under the oxidation conditions. 17. A method according to claim 16 wherein the solvent is a mineral oil and the oxidising agent is either air or air prediluted with nitrogen or carbon dioxide. 18. A method according to any one of the preceding claims wherein the oxidatively sheared polymer is reacted with one or more non-tertiary nitrogen-containing compounds. 19. A method according to claim 18 wherein the non-tertiary nitrogen-containing compound is a polyalkylene polyamine having the formula: EMI17.1 wherein R1 is either hydrogen or a C1 to C6 alkyl group and x is an integer in the range from 2 to 10. 20. A method according to any one of the preceding claims wherein the oxidatively sheared olefinic polymer is reacted with the mono- or bis-succinimide formed by reacting an alkenyl succinic anhydride with either a diamine or a polyalkylene polyamine having the formula (I). 21. A method according to claim 20 wherein the oxidatively sheared olefin polymer is reacted with the mono-succinimide formed by reacting a polyisobutene succinic anhydride with a polyalkylene polyamine having the formula (I). 22. A method according to any one of claims 18 to 21 wherein the reaction of the oxidatively sheared olefin polymer with the nitrogen-containing compound is conducted in the presence of an aldehyde to form a Mannich condensation product. 23. A method according to any one of claims 1 to 17 wherein the oxidatively sheared olefinic polymer is reacted with an oxygen-containing compound, a sulphur compound, a boron compound and/or a phosphorus compound. 24. A method according to any one of claims 1 to 17 wherein a mono-succinimide is added at any time during oxidation of the olefinic polymer. 25. A finished lubricating oil composition comprising a base oil of lubricating viscosity and a viscosity index improving amount of the sheared olefinic polymer containing carbonyl groups produced by the process as claimed in any one of the claims 1 to 17. 26. A finished lubricating oil composition comprising a major proportion of a base oil of lubricating viscosity and a minor proportion of the product of the method claimed in any one of claims 18 to 24.

Inventors: BRANKLING, DAVID, CRAWFORD, JOHN
Applicants: OROBIS LIMITED
Application year: 1981
Main classification: C08F8
IPC codes: C10M143, C10M159, C08F8