COPOLYMERS Of SULPHUR DIOXIDE AND MONOMERS COPOLYMERISABLES BEING APPROPRIATE LIKE ADDITIVES FOR OILS AND OILY COMPOSITIONS WHILE CONTAINING
The present invention relates to additives for hydrocarbon interest to impart to the lubricating oils, when incorporated therein, one or more properties such as viscosity index improvers, the freezing point depression, the spreadability sludge, a greater ability to support the loads, a greater rust-inhibiting, and improved resistance to oxidation and, in the case of residual fuels and heavy distillates, an improvement of their low temperature flow properties. More particularly, the invention relates to such additives for hydrocarbons comprising the copolymers a polar monomer ethylenically unsaturated and sulphur dioxide, which copolymers which may contain one or more additional monomers including substantially linear alpha olefins, cyclic olefins and conjugated diolefins. The products resulting from the polymerization of sulphur dioxide with unsaturated compounds such as alcohols, ethers, esters and unsaturated acids (see the Patent of the United States of America n5 2 114,292), and with olefins and polar compounds ethylenically unsaturated (see the patents of the United States of America n5 2 241,900, 2,645 631, 3,563 961 and 3,684 778) are well known. Copo lymères The of sulfur dioxide and of unsaturated compounds are prepared by various methods, including the bulk polymerization, solution and emulsion. In the patents of the United States of America The patent of the United States of America n5 2,652 368 proves the use of alkylene copolymers sulfone SO ^ and olefins in the lubricating oil composition for improving the high-temperature viscosity in torque converters. These copolymers are made by hydrocarbon polymerization alpha-olefin having from 7 to 24 carbon atoms and Sà the reflux temperature of the latter and in the presence of a catalyst selected from peroxides and nitrates. The patent of the United States of America n9 3,442 790 reveals copolymers of olefins in to, C^e t of sulfur dioxide as modifying agents paraffins the crystallinity. These substances are added to paraffinic petroleum oils, for example, to vary the size and the shape of the wax crystal, so as to allow faster separation of the paraffin during the dewaxing of hydrocarbon oils. Unlike and methods of the prior art, most are directed especially the manufacture of sulphonated polymers comprising the products of the reaction between the sulfur dioxide/olefins and diolefins, it is determined that the sulphonated hydrocarbon-soluble copolymers of a polar ethylenically unsaturated monomer can be advantageously incorporated into lubricating oils to improve the oxidation resistance and/or anti-wear properties. When the ethylenically unsaturated polar monomer has hydrocarbyl groups side having on average from about 6 carbon atoms to about 50 carbon atoms, preferably, of 8 to 30 carbon atoms, the copolymer- lymère sulfone can be added to alter the freezing point and/or the spreadability and/or viscosity index ' and/or the anti-rust property and/or the antiwear and/or the anti-oxidation property lubricating oils and promote the low-temperature flow properties of residual fuels and heavy distillates. One preferred class of these sulfonated copolymers contains an appreciable amount, i.e., up to about 60 mole percent of a third monomer which is not a polar ethylenically unsaturated monomer, for example, a substantially linear alpha olefin of 2 to 50, preferably about 10 to 20 carbon atoms, to replace partially the polar monomer. Sulfones These polymers are readily prepared using the oi ^ Lnduite thermal decomposition of free radical initiators. They can be prepared by methods by load, batchwise, semibatchwise or continuously using methods of solution polymerization or mass. Their number average molecular weight (Mn) is advantageously between about 400 and about 750,000, preferably between about 500 and about 500,000-determined by osmometry using vapor pressures (OPY) between 400 and about 25,000 and by osmometry through a membrane over 25,000). 1. The monomers A. Sulfurous anhydride Given that has easily of sulfur dioxide, the sulfones copolynères interest according to the invention are obtained from the sulfur dioxide. The sulfone copolymer obtained by the reaction of SO2 and a polar monomer ethylenically unsaturated can be considered as a block copolymer containing alternating substantially equal molar amounts of sulfur dioxide and the ethylenically unsaturated monomer. It is to signal while, in some cases, the respective molar amounts of the polar monomer, including the content of the olefinic monomer, and sulphur dioxide present in the copolymer, are not necessarily the same. For example, in the presence, of a suitable polymerization catalyst as described below, would be expected that there is a certain homopolymerization of the polar monomer or dql' olefin used to replace a portion of the polar monomer, thereby giving a copolymer comprising more than 50 mole percent of the polar monomer and, if present, the olefinic monomer. Therefore, the present invention contemplates the use of a sulfonated copolymer comprising from about 50 to about 70 mole percent of polar monomer and olefin monomer and about 30 {/ about 50 mole percent of sulfur dioxide. B. Ethylenically unsaturated polar Monomers The polar monomers useful in the practice of the invention are mono- éthyléniquernent polar monomers which are copolymerizable with unsaturated SO ^, which have the total of 8 to 52, preferably from 10 to 32 carbon atoms and which generally comprise carbon, hydrogen and one or more oxygen atoms, nitrogen, halogen or sulfur. Preferably, these polar monomers can be represented by the general formula: wherein R 'and R ", taken independently of one another, represent hydrogen, halogen, such as methyl alkyl to; Q' is a carboxyl group (-C00H), cyano (-CN), methyl hydroxy (C-^-OH) or carboalkoxy (- C00R " ") (wherein R" "represents a straight-chain or branched to Calkyl bond, , arylalkyl or cycloalkyl), an alkoxy radical methyl (-CK ^-O-R" ') hydrocarbyl or methyl ketone (-CH ^-CO-R " ") (wherein R" " is as defined above), a hydrocarbyl radical ketone (-0-R "') (wherein R" 'is as defined above) and g " represents hydrogen, a carboxyl radical (-C00H), cyano (-CR) or carboalkoxy (- C00R "') (wherein R" ' has the meaning given above). Particularly preferred are the esters or acyclic c alicydic to C "_ acrylic acid, esters which are * Another preferred sub-class of polar monomers suitable for the preparation of the sulfonated copolymer comprises (a) ester or amide fumaric acid, (b) a maleic acid derivative (c) or a maleate ester alkyl C ^ C^à • In particular, the members of the subclass are fumaric esters, maleic esters, maleic anhydride and methyl maleic anhydride (known as citraconic anhydride). Another preferred sub-class of polar monomer comprises vinyl aromatic compounds halogénométhylés in , V 0^to C^g which are illustrated by the general formula CH CH CH-R ^ ^-X where rT is an arylene radical having from 1 to 3 cycles and X is halogen, such as chlorine, bromine or iodine. As non-limiting examples include the following: 3-chloromethyl-1-styrene, 4-chloro-methyl-styrene, 1-vinyl-4-naphthalene chloromethyl, bromoethyl 4-styrene, 5-chloromethyl-4-methyl styrene, 3-methoxy-4-chloromethyl styrene. C. Olefinic Monomers The olefin monomers suitable for carrying out the invention to give the sulphonated copolymers comprise the essentially linear monoolefins to having a structure of the type R-CH ^ H ^ (type I), a structure of the type R-CH = CHRhas (type II) and the outermost structure hardly copolyméri sand R (R,) = C CH " (wherein R, R and R are each hydrogen, a straight or branched chain alkyl group, .aryl, alkylaiyle , arylalkyl or eycloalkyle) (type III). The olefin monomers of the type I, II and III may contain up to about 30 mole percent of dienes. Examples noijlimitatifs of olefins of the type I, include: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 4, 4-dimethyl-1-pentene, 1-dodecene, 1-octadecene, styrene, 4-methyl styrene, the 3-phenyl-1-propene, vinyl cyclohexane, 2-vinyl norbornene and vinyl naphthalene. Examples of the type II are the 2-butene, 2-pentene, 3-hexene, 4-octene, the 5-octene, norbornene, cyclohexene and cyclopentene. As non-limiting examples of olefins of the type III include: isobutylene, the 2, 3-dimethyl-1-butene, 2, 4, 4-trimethyl-1-pentene, 2, 6-dimethyl-1-octene, 4-isopropenyl toluene, 1 'isopropenyl cyclohexane; 1' alpha-methyl styrene. The The conjugate dienes include the non-conjugated diene s and acyclic straight-chain or branched and alicyclic. As non-limiting examples of conjugated diolefins, preferably acyclic conjugated diolefins in C^à C ^ which can be interpolymerized with the polar monomers and olefinic, include: the butadiene, isoprene, piperylene cis and trans, the 2, 3-dimethyl -1, 3-butadiene, 1, 3-hexadiene, 3, 7-dimethyl -1, 3-octadiene and 3-(4- méthylpenty1)-1, 3-butadiene. Since non-limiting illustrative examples of non-conjugated diolefins include: A. The straight chain acyclic dienes such as 1, 4-hexadiene, 1, 5-heptadiene and the 1, 6-octadiene. B. The branched chain acyclic dienes such as 5-methyl -1, 4-hexadiene, 3, 7-dimethyl 1, 6-octadiene, 3, 7-dimethyl 1, 7-ene and mixed octadi leg4somères dihydromyrcène dihydroocimène of the and the. C. The alicyclic dienes to a single cycle as the 1, 4-cyclohexadiene, 1, 5-cyclooctadiene, 1, 5-cyclododecadiene, the 3- allylcyclopentène , the 4-allyl-cyclohexene and the 1-isopropenyl 4 (4-butenyl) cyclohexane. D. The alicyclic dienes multi-cycle non-abutting as the 4.4 '- dicyclopentényl and 4.4' - dicyclohexényl dienes. E. The alicyclic dienes more fused ring and bridged as the tétrahydroindène , methyl tétrahydroindène , dicyclopentadiene, bicyclo (2.2.1) hepta 2, 5-diene, the alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-6-methyl-2-norbornene, 5-methylene -6, 6-dimethyl-2-norbornene, 5-propenyl-2-norbornene, 5-(3-cyclopentenyl)-2-norbornene and 5- cyelohexylidène -2-norbornene. Sulfones The copolymers may contain in total of about 5 to about 68, preferably about 10 to about 40 mole percent of the olefin monomer units; however, its diolefinic monomer units represent a total of up to about 6 mole percent of the copolymer. 2. conolymères Production of the sulfones In general, the sulfonated copolymers are prepared by dissolving the monomers, i.e., the polar monomer and, optionally, the olefin monomer, in a solvent, and then saturating the resulting solution by means of sulfur dioxide gas and while keeping the flow of SO2 in the reaction system by adding a catalyst. Preferably, the catalyst is added, in the form of a solution, to the reaction system, at time intervals and by aliquots. The temperature of the polymerization medium is controlled and maintained below the temperature limit of the monomers, i.e. the temperature above which the monomers polymerize not. If desired, the monomers may be added in part or in whole with the catalyst solution or very shortly after its introduction into the polymerization system. The inert solvent used for the reaction may be selected from four general types, c % is to say from hydrocarbons, hydrocarbons haiogénés , glycol ethers and alkyl esters. Examples of the first group, include: benzene, n-hexane, naphtha, kerosene, etc; in the second group include perchloroethylene, methylene chloride, the trichlorobenzene, carbon tetrachloride, etc; the third group includes diethylene glycol, dimethyl ether, diethylene glycol, ether, dimethyl ether ethylene glycol, etc; and the fourth group comprises ethyl acetate, ethyl butyrate, propyl acetate, andc. The polymerization catalyst which can be used in this process is preferably of the radical type. Examples of catalysts, include generally all conventional catalysts, such as, those of the peroxide or azo. An illustrative as an example the kind of catalysts that are suitable for use in this reaction peroxide benzoyl peroxide, di-tert butyl, diacetyl peroxide, diethyl the peroxycarbonate and hydroperoxides preferred as a 1' hydroperoxide and tert-butyl hydroperoxide 2-2-phenyl propane (eumène hydroperoxide). The catalysts of the azo type are characterized by the presence of the group in their molecule-N=N connected to one or two organic radicals, preferably at least one of the links connecting a tertiary carbon atom. Suitable catalysts of the azo type are exemplified by the alpha-alpha azodiisobutyronitrile , the fluoroborate p-bromobenzene-diazonium, N-nitroso-p-bromoacetanilide, 1' azo-methane, halides phényldiazonium , the diazoaminobenzène , hydroxide and p- broraobenzènediazonium p- tolyldiazoaminobenzène. The polymerization catalyst is used in small amounts which are generally smaller than 2 weight percent based on the monomer. An appropriate quantity is often between 0.05 and 0.5 percent by weight. Since the temperature of the reaction must not exceed the limit temperature polar monomers or olefins, the temperature is substantially between about 100 and about -50e C, preferably between about 30 and -309 C. The polymerization pressure may be between about 1 and 30 atmospheres. The reaction duration can vary widely, according to the reactivity of the particular monomers, and the catalyst concentrations according to the reaction temperature. Therefore, the polymerization times can vary between 1 minute and 15 hours, the preferred time is between 5 minutes and 3 hours. The preferred polymerization technique of the invention involves dissolution of the one or more monomers in the inert solvent before introducing the free radical catalyst. The concentrations customary of the monomers in the solvent are between 10 and 60 percent by weight. The sulfone copolymer which is dissolved in the solvent at the end of the polymerization reaction can be readily separated by distillation from said solvent. Another aspect would be to precipitate the copolynière by mixing the solvent containing the sulfonated copolymer with a non-miscible solvent, for example the inéthanol. After precipitation in the solvent, the sulfonated copolymer can be easily separated and dried. Sulphonated The copolymers soluble in oils or hydrocarbons produced according to the invention can be incorporated satisfactorily in compositions as liquid hydrocarbon, for example, in lubricating oils for motor casings of automobiles or diesel engines, to provide one or more additional properties such as anti-wear properties, extreme pressure, viscosity index improving, oxidation resistance, corrosion-inhibiting, andc. These copolymers which can be primed to impart these properties are advantageously dissolved additive in an amount sufficient to obtain one or more of these properties and, preferably, at concentrations of from about 0.01 and 20 weight percent. For example, they may be added in the following proportions: 1 to 20 percent by weight for improving the viscosity index; preferably 0.01 to 10 weight percent for improving dispersability; to about 0.05-5 weight percent for improving rust-preventing properties; to improve antioxidant properties, preferably about 0,001 to 2 weight percent j to lower the freezing point, preferably about 0,005 to 2 percent by weight and for extreme pressure properties (improving the ability to support loads) the proportion is between about 0.05 and 10 weight percent. The products of the invention are suitable for use, not only for the hydrocarbon lubricating oils derived from oil, but for the synthetic lubricants such as alkyl esters of diacids, the complex esters obtained by esterification of diacids, ^ pol glycols, monoacid and alcohols, esters and phosphoric acids, carboxylic esters of polyglycols, andc. The residual fuels oils which are treated by means additives sulphonated copolymers of the invention to improve their low temperature flow properties are petroleum oils with paraffins having an initial boiling point greater than about 3405 C. The residual oils or the heavy distillais modified according to the invention generally require the incorporation for improving the low temperature flow, an amount of from about 0,001 and 2.0 weight percent, preferably between 0,005 and 0.1 percent by weight of the copolymer sülfoné in either of these oils, thereby improving the low-temperature fluidity. Preferably the number average molecular weight (Mn) of these copolymers is between about 800 and about 500,000. Sulphonated The copolymers of the invention can be used in the traditional methods of solvent dewaxing. Preferably these copolymers have an Mn of between 500 and 500,000. Advantageously mixtures of the copolymer, of the solvent dewaxing and oil containing the wax are processed by cooling the mixture in an appropriate manner to a paraffin precipitation temperature. The resulting precipitated paraffin may then be removed by conventional means, for example by centrifugation or filtration (preferably the latter). Dewaxing operations are ordinarily conducted at a temperature range of about In general, the sulfonated copolymers are useful, according to the invention, with hydrocarbyl groups side 6 to 50 carbon atoms. It is possible to clean these copolymers as indicated above, in order to enhance their utility as an additive by adjusting the average carbon content of hydrocarbyl groups and/or the ratio of carbon and sulfur of these copolymers to obtain greater affinity as an additive in the particular system and/or hydrocarbon in lubricant which is admixed with the sulfonated copolymer. When the latter is added for use in extreme pressure lubricants such as lubricating oil, side the hydrocarbyl group preferably contains on average from about 8 to about 30 carbon atoms and better still from 10 to 18 carbon atoms. For a dispersion effect, anti-oxidation, rust-inhibiting and viscosity index improvers, side the hydrocarbyl groups preferably contain on average to 1S 6 carbon atoms, and more preferably from 8 to 16 carbon atoms and for improving the low temperature flow residual oils, side the hydrocarbyl groups preferably contain an average of from 10 to 26 carbon atoms, and better still from 17 to 24 carbon atoms. Examples after 1 to 4 and 6 to 8, a polar monomer containing all illustrate the invention. The example 5, without polar monomer, illustrates the prior art. Example 1 . Sulfonated Copolvmère SO ^ and allyl alcohol Is dissolved 29 grams (0.5 mole) allyl alcohol in 100 ml of ethyl acetate contained in a lease n reaction 1 litre. The saturates the sulfur dioxide solution and maintained in an atmosphere of sulphur dioxide during the polymerization at a pressure which is slightly above atmospheric pressure. Periodically is added 0.5 gram of t-butyl hydroperoxide dissolved in 40 ml of ethyl acetate in two aliquots of 10 ml and four fractions of 5 ml to the solutioq & éactionnelle within about 2 hours. The container is kept in a water bath, thereby keeping the temperature between about 5 and about 19e C. The consumes about 31 grams (0.5 mole) of SO2 in the reaction " resulting in a sulfonated copolymer which is precipitated out of the solution. After the polymerisation reaction is completed, the system is purged with nitrogen and the polymer is precipitated in normal hexane. The yield is 58.8 grams of polymer (about 96.4 percent having a greyish white appearance. Example 2 . Sulfonated copolymer of SO2 and allyl acetate, tetradecene- 1-hexadecene and 1 Is used the general method described in the example 1, except that the proportion of monomers, the introduction and the nature of the catalyst solution and the temperature are modified as follows: 92 ml of benzene is dissolved in 19.6 grams (0.1 mole) of 1-tetradecene (purity greater than 90 percent), 22.4 grams (0.1 mole) of 1-hexadecene (purity greater than 90 percent) and 2.1 grams (0,021 mole) allyl acetate. 11.7 The consumes' grams (0.18 mol) of SO2 during the polymerization. Is periodically inserted 0.9 gram of t-butyl hydroperoxide (dissolved in 80 ml of benzene} in three aliquots of 10 ml aliquots of 20 ml and 2 within 85 minutes of reaction and maintains the temperature and 4 Example 3 . Sulfonated Copolvmère SO ^. allyl alcohol and hexene -1 Is performed as described in example 2 except that the monomers and the method are the following Example 4 . Sulfonated copolymer of SO2, allyl acetate and a mixture alpha olefins in the Are performed generally described in exempie 2 changes to the following monomers, and to a method: is dissolved in 125 ml of cyclohexane 23.4 grams (0.08 mol) of a mixture of Al pha-key thin to C32 (distributed as follows: 90.3 weight percent of alpha olefins are in C^g to C2g, which 8 weight percent C^g , 2.2 percent by weight of C. ^, i7, 4pour weight percent < ^ 20, 23.1 percent by weight of Example 5 (comparative example) Sulfone Copùlvmère SO ^ . dodecene -1 and octadéoène -1 Is performed as described in the example 2 but with the following modifications on the monomers and the method 54.2 Oq & issout in grams of benzene, 18 grams (0,106 mole) of 1-dodecene (97 percent purity) and 36.2 grams (0.14 mole) of octadecene -1 (97 percent purity). It has 45 grams (0.7 mole) of SO2 during the polymerization. Is dissolved 0.5 gram of t-butyl hydroperoxide in 50 ml of benzene to form the solution of the catalyst and the reaction is carried out for about one hour between 10 and 215C. The copolymer is precipitated in methyl alcohol and efficiency can be achieved 61.6 grams of a sulfonated copolymer having a (Mn) of 10,673. Example 6 . Sulfonated copolymer of SO2, allyl alcohol, 1-dodecene and 1-octadecene Is performed as described in the example 5 with the following modifications on the monomers and the temperature: Is dissolved, in 50 ml of benzene, 17.1 grams (0.10 mol) of 1-dodecene (purity of about 99 percent), 34.3 grams (0,133 mole) of octadecene -1 (purity of $ enviroi 9 percent) and 1.25 gram (0,022 mole) allyl alcohol. Consumes for the polymerization The 16.3 grams (0.26 mole) of SO2 and the temperature is maintained between 6 and 20 SC. The yield is approximately 100 percent of sulfone copolymer. Example 7 . Sulfone copolymer of SO2, allyl acetate, dodecene -1 and d * octadécone -1 Is performed as described in the example 6 with the following modifications as to the monomers: Is dissolved, in 58 ml of benzene, 18.0 grams (0,107 mole) of 1-dodecene (purity of about 99 percent), 36.2 grams (0,143 mole) of octadecene -1 (purity of about 99 percent) and 2.5 grams (0,025 mole) allyl acetate. The polymerization is consumed to 15.8 grams (0.25 mol) of SO2. The yield is 66.9 grams (90 percent of theoretical yield) of a copolymer having a Mn of 10,329. Example 8. Sulfonated copolymer of SO2 and allyl esters dodécanoîque octadéeanoïque acids and Is prepared in the following manner the aliphatic esters and aliphatic C^g C^2 of allyl alcohol: Is reacted a molar excess of 20 percent allyl alcohol in separate reactions with the corresponding aliphatic acid in cyclohexane. Esterifications are each The catalyzed by para-toluene sulfonic acid. Esterification The temperature of each is between 70 and 805C and kept at this value for a period of about 3 to 4 hours in which the water of esterification is expelled by distillation by maintaining a reduced pressure. Each solution resulting product is neutralized by sodium bicarbonate, washed with water three times, thereafter adding 25 ml of cyclohexane and the system is allowed to stand for 16 hours in the presence of magnesium to obtain the corresponding esters. Furthermore, each system is subjected Copolymers are obtained by the method of the example 3 with the following modifications as to the monomers, and to a method: Is dissolved in 50 ml of benzene 23.6 grams (0.10 mole) dodecanoic ester of allyl alcohol and 22.2 grams (0,068 mole) octadecanoic ester of allyl alcohol. Consumes during the polymerization The 3.5 grams (0.06 mole) of SO2 and polymerization is continued for about 50 minutes. The yield is 18.6 grams (32.9 percent of theoretical yield) of a sulfonated copolymer having a (Mn) of 1129. The utility of the additives according to the invention is demonstrated in part by the results given below which are derived from assays showing the effect obtained on the freezing point depression lubricating oils, to improve the flow of a residual fuel oil and on the lubrication under high pressure. The table I given as comparative illustrative and the effect on the freezing point lubricating oils. TABLE I The activity for a residual fuel oil figure at II. table on see the effect resulting from the addition of 0.15 weight percent of the additive to a residual fuel oil known as a fuel of FVT 343 TABLE II The properties of the extreme pressure additive for lubricating the sulfonated copolymers according to the invention are illustrated at table III. The results are obtained by attempting to lubricating oils modified by the addition of sulfonated copolymers in a machine " Falex " test lubricants and which is provided by the Company Fairlie- LeValley Corp. of Chicago, Illinois. The machine spindle in (steel lubricated by the lubricant to be tested) in a chuck provided with two aluminum members cooperating each other for resting on a part of the pin. The assay is stopped upon breakage of the pin. The test conditions are 2 minutes at 250 rpm, and 500 rpm to break. The oil under test is a mineral oil containing-the additive in an amount from 0.5 percent by weight based on the weight of the oil. TABLE III Duration the test additive minutes to 500 rev/min until breaking Probe (not. additive) 1.5 example 2,13 of the example 5 (comparative example) 0.5 example 6,14 of the These results demonstrate the ability to the extreme pressure lubrication lubricating oils treated according to the invention with respect to untreated oils or treated with a copolymer of SO ^ and alpha olefins (example 5). Briefly, sulphonated interest the copolymers according to the invention are obtained by the polymerization of about 30 to about 50 mole percent of sulfur dioxide, of about 2 to about 70 mole % of a polar monomer ethylenically unsaturated (preferably monoethylenically unsaturated) to 52 having 8 carbon atoms and mixtures of these polar monomers, from about 0 to about 68 mole percent of a monoolefin in to and mixtures and monoolefins of 0 to about 6 mole percent of a diolefin or mixtures of diolefins, said copolymer having an Mn of 400 to 750,000. Sulfone copolymeric oil additives having utility as a lubricating oil pour point depressant, viscosity index improver, dispersant, load carrying agent, rust inhibitor and/or antioxidant, or as a cold flow improver for heavy distillates and residual fuels, comprise the hydrocarbon soluble copolymers of an ethylenically unsaturated polar monomer and sulfur dioxide. This sulfone copolymer may contain one or more additional monomers including: C2 to C50, preferably at least C6, substantially linear alpha olefins; C2 to C12, preferably C2 to C9, cyclic olefins; and, C4 to C6 conjugated diolefins. 1. Hydrocarbon composition, characterized in that it comprises a major proportion of a hydrocarbon oil such as a lubricating oil or a fuel oil and dissolved therein in an amount of 0.01 to 20 weight percent of the total weight of the composition, of a sulfone copolymer soluble in the oil of: a) of about 30 to about 50 mole percent of sulfur dioxide b) of about 20 to about 70 mole % of a polar ethylenically unsaturated monomer and copolymerizable with sulphur dioxide and which has a total of 52 to 8 carbon atoms and represented by the general formula: R' wherein R ' and R " are independently of one another hydrogen, halogen, alkyl C^à C. ^, Q1 radical is - C00H , -CH, -CH2 0:00, PARTICI-" ', -CH2 -0-r " ', -Ch2 -c0-r"1 or-0-R " 'and Q" is hydrogen, a radical-C 00H , -CH or-COOR "' , the symbol R" ' is an alkyl radical, straight or branched chain C C^à ^, arylalkyl or cycloalkyl- c) of about 0 to about 68 mole percent of a monoolefin in C2 cj-q and to d) of about 0 to about 6 mole percent of a diolefin, said copolymer having a number average molecular weight (Mn) of between about 400 and about 750,000 and improving one or more properties of the hydrocarbon oil. 2. A composition according to claim 1, characterized in that R ', R "and Q" are each hydrogen and Q' is-CH, , OH or-CH2 0R "R 'or" ' is C^à C, , ^. 3. A composition according to claim 2, characterized in that Q ' is a radical- 0Η , , 0Η so that the formula to claim 1 is that of allylic 1*alcool. 4. A composition according to claim 2, characterized in that Q 'is a radical-CILs, OR " *, which fa' it that the formula to claim 1 is that an allyl ester. 5. Composition according to any one of claims 1 to 4, characterized in that the copolymer has a Mn of about 500 to about 500,000 and that the polar monomer has at total of about 10 to about 32 carbon atoms and average hydrocarbyl groups side about 8 to about 30 carbon atoms. 6. Composition according to any one of claims 1 to 7. Composition according to any one of claims 1 to 6, characterized in that the polar monomer is allyl alcohol and that the olefinic monomer consists of one or more monoolefins to alpha 0^ 8. Composition according to any one of claims 1 to 6, characterized in that the polar monomer is the allyl ester of a carboxylic acid of 1 to 18 carbon atoms and that the olefinic monomer is a mixture of one or more alpha monoolefins. ^ C2 TO C^2 * SN 75 SN 150 SN 330 SN 450 Base oil as it is -18 -15 -9 -9 Example s additive added 5 -34 -34 -26 -26 7 -29 -32 -29 -32 8 -23 -23 -26 -26 46 5C 54 C^ 5 as such residuum 41 41 41 41 Residuum + copolymer of the example 4 21 21 21' 13-