MXPA01001137A - Selectively hydrogenated polymer compositions:polybutadiene-isoprene-polybutadiene - Google Patents

Abstract

The invention provides dispersants and dispersant viscosity index improvers which include polymers of conjugated dienes which have been hydrogenated, functionalized, optionally modified, and post treated. The dispersant substances include a copolymer of two different conjugated dienes, such as butadiene-isoprene-butadiene. The polymers are selectively hydrogenated to produce polymers which have highly controlled amounts of unsaturation, permitting highly selective functionalization.Also provided are lubricant fluids, such as mineral and synthetic oils, which have been modified in their dispersancy and/or viscometric properties by means of the dispersant substances of the invention. Also provided are methods of modifying the dispersancy and/or viscometric properties of lubricating fluids such as mineral and synthetic lubricating oils. The dispersant substances may also include a carrier fluid to provide dispersant concentrates.

Description

SELECTIVELY HYDROGENATED IMERIC PO COMPOSITIONS; POLYBUTADIENE-ISOPRENE-POLYBUTADIENE Description This invention relates to dispersants, dispersants with improved machinery performance, dispersants with viscosity index of improved properties (VI), and improvers. of viscosity index of dispersant from polymers of ^ functionalized diene, and methods of its use. More particularly, the invention relates to dispersants, dispersants with improved viscosity index properties, and dispersant viscosity index improvers from copolymers selectively hydrogenated prepared using conjugated dienes. The invention is further directed to dispersants, dispersants with viscosity index improvement properties, and viscosity index improvers of dispersants from - ^ fc chemically modified derivatives of the previous polymers.

Liquid elastomers are well known and are used in several applications. For example, many liquid functionally terminated polybutadiene elastomers are known. These materials are generally very unsaturated and often form the base polymer for polyurethane formulations. The preparation and application of the hydroxy-terminated polybutadiene is detailed by J.C. Brosse et al., In Hydroxyl - terminated polymers obtained by free radical polymerisation - Synthesis, characterization and applications, Advances in Polymer Science 81, Springer - Verlag, Berlin, Heidelberg, 1987, p. 167-220. Also, liquid polymers that process acrylate, carboxy or mercapto terminals are known. In addition to butadiene, it is known how to use isoprene as the base monomer for liquid elastomers. The liquid elastomers may contain additional monomers, such as styrene or acrylonitrile, to control compatibility in mixtures with polar materials, such as epoxy resins. Prior art non-functionalized liquid hydrocarbons of pure hydrocarbons are also known in the prior art. These liquid elastomers - which contain varying degrees of unsaturation for use in vulcanization. Typical of the highly unsaturated liquid elastomers is polybutadiene, for example, that sold under the name RICON by Ricon Resins, Inc. A liquid polyisoprene that has been hydrogenated to saturate 90 percent of its original double bonds is sold as LIR-290 by Kuraray Isoprene Chemical Co. Ltd. Even more saturated are the liquid butyl rubbers available from Hardman Rubber Co., and Truene, a liquid ethylene-propylene-diene rubber (EPDM) available from Uniroyal Chemical Co. The most highly saturated liquid elastomers exhibit good oxidation and ozone resistance properties.

Falk, Journal of Polymer Science: PART Al, 9: 2617-23 (1971), the entire content which is incorporated herein by reference, discloses a method of hydrogenating 1,4-polybutadiene in the presence of 1,4-poly. -isoprene. More particularly, Falk describes the hydrogenation of the 1,4-polybutadiene block segment in the block copolymer of 1,4-polybutadiene-1,4-polyisoprene-1,4-polybutadiene and in random copolymers of butadiene and isoprene. , both as polymerized monomers having predominantly 1,4-microstructure. The hydrogenation is carried out in the presence of hydrogen and a catalyst made by the reaction of organic aluminum or lithium compounds with transition metal salts of 2-ethylhexanoic acid. Falk, Die Angewandte Chemie, 21 (286): 17-23 (1972), the content of the whole of which is also incorporated herein by reference, describes the hydrogenation of 1,4-polybutadiene segments in a block copolymer of 1,4-polybutadiene-1,4-polyisoprene-1,4-polybutadiene. Hoxmeier, European patent application published 88202449. 0, filed on November 2, 1988, Publication No. 0 315 280, published on May 10, 1989, describes a method for selectively hydrogenating a polymer made from at least two different conjugated diolefins. One of the two diolefins is more substituted at 2, 3 and / or 4 carbon atoms than the other diolefin and produces tri or tetra-substituted double bond after polymerization. The selective hydrogenation is carried out under such conditions as to hydrogenate the ethylenic unsaturation incorporated in the polymer from the minor substituted conjugated diolefin, at the same time as • leaving unsaturated at least a portion of the tri or tetra-substituted unsaturation incorporated in the polymer by the more substituted conjugated diolefin. Mohajer et al., Hydrogenated linear block copolymers of butadiene and isoprene: Effects of variation of composition and sequence archi tecture on properties, Polymer 23: 1523-35 (1982) essentially describes essentially completely hydrogenated butadiene-isoprene-butadiene (HBIB), HIBI and HBI block copolymers in which the butadiene has predominantly a 1,4 microstructure. Kuraray K K, the Japanese patent application published No. JP-328 729, filed December 12, 1987, published July 4, 1989, discloses a resin composition comprising 70-99 weight percent of a polyolefin (preferably polyethylene or polypropylene). ) and 1-30 weight percent of a copolymer obtained by the hydrogenation of at least 50 percent unsaturated bond of isoprene / butadiene copolymer. Ashless dispersants are additives to lubricating fluids such as fuels and lubricating oils that improve the dispersibility of fluids or improve their viscometric properties. Typically, these dispersants are modified polymers, which have a central structure of oleophilic polymer to ensure good solubility and to maintain particles suspended in the oil, and polar functionality to bind or bind to the oxidation and sedimentation products. The dispersants generally have an oleophilic (hydrophobic) solubilizing tail and a polar head (hydrophilic) forming micelles when they are actively bound to the sediment. Common dispersants include polyisobutenes that have been modified by the reaction to include groups Functional agents such as succinimides, hydroxyethyl imides, succinate esters / amides, and oxazolines. Other dispersants include Mannich base derivatives of polybutenes, ethylene propylene polymers, and acrylic polymers. Traditionally, the dispersants have been polybutenes functionalized at a site in the molecule pathway a reaction with maleic anhydride followed by imidization with a polyamine. The polybutenes typically 500-2,000 in molecular weight, and because ^ k to the polymerization process used in its manufacture, they have only one double bond per molecule of polybutene. In accordance with the above, the number of potential functional groups per chain is limited to approximately one. Typically, this site is in the terminal portion of the molecule. Moreover, it is generally accepted that, in order to obtain beneficial dispersing properties, a molecule must have at least one functional group per approximately 2,000 molecular weight. Consequently, the molecular weight of traditional polybutene dispersants can not exceed 2,000 if the desired ratio of functionality / hydrocarbon has to be maintained. In addition, traditional dispersants have had 5 molecular structures that have limited the placement of functional groups, which generally require these groups to be placed in the terminal regions of the molecules. The polymerization process for traditional butene polymers has also generated products that have an unacceptably broad distribution of molecular weights, that is, an unacceptably high proportion of weight average molecular weight (Mw) against the number average molecular weight (MN) Typically, these distributions are MW / MN > 2.5, producing compositions whose dispersing properties are not well defined. Moreover, functionalization reactions in these polymers have typically produced substantial amounts of undesirable byproducts such as modified insoluble polymers of variant molecular weight. The reactions of Functionalization can also result in compounds containing undesirable chemical fractions such as chlorine. U.S. Patent No. 4,007,121, to Holder et al., Discloses lubricating additives including polymers such as ethylene propylene polymers (EPT) having N-hydrocarbylcarboxamide groups. U.S. Patent Nos. 3,868,330 and 4,234,435, to Meinhardt et al., Describe carboxylic acid acylating agents for the modification of lubricant additives. Modified polyalkenes are described as substituted poly (isobutene-succinic acylating agents having MN of 1300-5000 and MW / MN of 1.5-4. These processes employ chlorination to provide greater functionality. Hitherto, the technique has failed to produce dispersants and viscosity index improvers of dispersants that have selective and controllable amounts of polar functionality in their polymer structure. Thus, the art has failed to provide some means of developing dispersant viscosity index dispersants and improvers having higher molecular weights and / or higher amounts of functionalization per molecule. The technique has also failed to provide dispersing polymers having desirably narrow molecular weight distributions to avoid the presence of ? Byproducts that degrade dispersant performance. The technique has also failed to provide dispersant and viscosity index improving compositions that exhibit good thermal stability. In accordance with the foregoing, it is a purpose of this invention to provide dispersant viscosity index dispersants and improvers having polymeric structures that allow highly selective control of the degree of unsaturation and consequent functionalization. Unique materials can also be obtained by chemical modification of the polymers of this invention since the polymers can be selectively modified at controllable sites, such as at random sites or at the terminal ends of the molecules. It is a further purpose of this invention to provide a method for the production of dispersant viscosity index dispersants and improvers from polymers having controlled amounts of randomly incorporated unsaturation in an otherwise saturated core structure. In contrast to the dispersants based on EPDM, the level of unsaturation can be controlled cheaply and easily, for example, from 1 percent to 50 percent, to provide a wide variation in functionality. It is another purpose of the invention to provide dispersants and viscosity-enhancing polymers that have narrow molecular weight distributions and a concomitant lack of undesirable byproducts, thereby providing custom-made dispersants with precision and / or index improving properties. of viscosity. It is still another purpose of this invention to provide dispersants that have improved machine performance. The invention provides dispersant and dispersant viscosity index improvers that include conjugated dienes polymers that have been hydrogenated, functionalized, optionally modified, and post-treated. The dispersion and improvement properties of the viscosity index of the compositions of the invention can be controlled by controlling the size of the polymers and the degree and distribution of their functionalization. In accordance with the above, these substances are referred to in the following as "dispersing substances". In one embodiment of the invention, a dispersing substance is provided for modifying the dispersion or the viscometric properties of a lubricating fluid, in which the dispersing substance includes a copolymer of two different conjugated dienes. In this case, the first conjugated diene includes at least one relatively more substituted conjugated diene having at least 5 carbon atoms and the formula: R 1 -C-C-C-R 6 (1) lili R 2 R 3 R 4 R 5 where R 1 -R6 each is hydrogen or a hydrocarbyl group, with the proviso that at least one of R1-R6 is a hydrocarbyl group, and also with the proviso that, after polymerization, the unsaturation of the polymerized conjugated diene of formula ( 1) have the formula: R1 R1 - C = R (2) RIV where Rt, R11, R111 and RIV each is hydrogen or a hydrocarbyl group, with the proviso that either both R1 and R11 are hydrocarbyl groups or both R111 and RIV are hydrocarbyl groups. The second conjugated diene in the dispersing substances of this embodiment includes at least one less substituted conjugated diene that is different from the first conjugated diene and has at least 4 carbon atoms and the formula: R7-C-C-C-R12 ( 3) R8 R9 R10 R11 wherein R-R12 each is hydrogen or a hydrocarbyl group, with the proviso that, after polymerization, the unsaturation of the polymerized conjugated diene of formula (3) has the formula: RVI Rv - C = C - RVI11 (4) Rvn where Rv, RVI, RVI1 and RVI11 each is hydrogen or a hydrocarbyl group, with the proviso that one of Rv or RVI is hydrogen, one of RVI1 and RVI11 is hydrogen, and at least one of Rv, RVI, RVI1 and RVI11 is a hydrocarbyl group. After the polymerization the diene copolymer is selectively hydrogenated and subsequently functionalized to provide a functionalized copolymer having at least one polar functional group. The functionalized copolymer is optionally modified by reaction with a Lewis base selected from the group consisting of monoamine, polyamine, polyhydroxy compound, reactive polyether, or a combination thereof. The copolymer is post-treated with a post-treatment substance, for example, a compound containing boron. In a preferred embodiment, the dispersing substance includes a polymer in which the first and second conjugated dienes are polymerized as a block copolymer that includes at least two alternative blocks: (I) x- (B) i (B) y- ( I) X or (B) and - (I) x - (B) z In this case, block (I) includes at least one polymerized conjugated diene of formula (1), while block (s) (B) includes at least one polymerized conjugated diene of formula (3). In addition, x is the number of monomer units polymerized in block (I) and is at least 1, and is 15 the number of monomer units polymerized in block (B) and is at least 25 and z is the number of units of polymerized monomer in block (B) and is the same or different as y. It should be understood that in all of this, x, y, z are defined in relation to the blocks in a linear block copolymer or blocks in a branch arm or segment of a branched or branched copolymer in which the arm or segment has substantially linear structure. Preferably, in the block copolymers of this embodiment, x is from 1 to 600, and is from 30 to 4,000, more preferably x is from 1 to 350, and is from 30 to 2,800. Although the larger values for x and y are generally related to higher molecular weights, the polymers that have multiple blocks ^ fc and star-branched polymers will typically have molecular weights that are not well represented in the values of x e and for each block. Alternatively, the dispersing substance includes the first and second conjugated dienes polymerized as a random copolymer. The dispersing substance may include the first and second conjugated dienes polymerized as a ^ branched or branched star copolymer. The copolymers useful according to this embodiment typically have a molecular weight of at least 2,000. Preferably, the molecular weight of the polymers is from 2,000 to 1,000,000, more preferably from 5,000 to 500,000. The molecular weight of a polymer of the invention is generally associated with the physical properties that it exhibits when employed as a dispersant or dispersant viscosity index improver. Typically, polymers having lower molecular weights are used as dispersants, while relative viscosity index and strength improving properties are associated with polymers having higher molecular weights and correspondingly higher viscosity. For discussion purposes, the polymers of the invention having molecular weights in the range of 2,000 to 20,000 can be classified as dispersants, polymers having molecular weights of from 20,000 to 50,000 can be classified as dispersants with improved index properties. viscosity, and the polymers that have • Molecular weights of 50,000 or more can be classified as dispersant viscosity index improvers. In the dispersing substances of the invention, the copolymer is preferably selectively hydrogenated. It is preferred that the unsaturation of formula (4) be substantially completely hydrogenated, whereby substantially none of the original unsaturation of this type is retained, while the unsaturation of formula (2) is substantially retained (i.e., unsaturation) residual after hydrogenation), at least an amount that is sufficient to allow functionalization of the copolymer. After the hydrogenation reaction, the number of iodine for the residual unsaturation of the formula (2) is generally from 50 percent to 100 percent of the number of iodine before the hydrogenation reaction. More preferably, after hydrogenation, the iodine number for the residual unsaturation of the formula (2) is 100 percent of the number of iodine before the hydrogenation reaction. After the hydrogenation reaction, the iodine number for the residual unsaturation of formula (4) is from 0 percent to 10 percent of the number of iodine before the hydrogenation reaction. More preferably, after the hydrogenation reaction, the number of iodine for the residual unsaturation of the formula (4) is from 0 percent to 0.5 percent of the number of the iodine before the hydrogenation reaction. More preferably, after the hydrogenation reaction, the iodine number for the residual unsaturation of the formula (4) is from 0 percent to 0.2 percent of the number of iodine before the hydrogenation reaction. The conjugated diene of the formula (1) preferably includes a conjugated diene such as isoprene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadie-no, 4-methyl-l, 3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-l, 3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1, 3- pentadiene, 2-hexyl-l, 3-butadiene, 3-methyl-l, 3-hexadiene, 2-benzyl-l, 3-butadiene, 2-p-tolyl-l, 3-butadiene, or mixtures thereof. More preferably, the conjugated diene of formula (1) includes isoprene, myrcene, 2,3-dimethylbutadiene or 2-methyl-1,3-pentadie-no. Still more preferably, the conjugated diene of formula (1) includes isoprene. Preferably, the conjugated diene of formula (3) includes 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2, 4 -octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decanediene, 2,4-decanediene, 3,5-decanediene, or mixtures thereof . More preferably, the conjugated diene of the formula (3) includes 1,3-butadiene, 1,3-pentadiene, or 1,3-hexadiene. Still more preferably, the conjugated diene of formula (3) includes 1,3-butadiene. Generally, when the conjugated diene includes substantial amounts of 1,3-butadiene, the polymerized butadiene includes a mixture of 1.4- and 1.2 units. The preferred structures contain at least 25 percent of the 1.2 units. More preferably, the structures contain from 30 percent to 90 percent of the 1.2 subunits. More preferably, the structures contain from 45 percent to 65 percent of the 1.2 units. To provide dispersion, the hydrogenated polymer is selectively chemically modified (functionalized) to provide a polymer having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxy, amino, nitrile, mercapto, imido, carboxy , and sulfonic acid groups of combinations thereof. The functionalized polymers can be further modified to give a more desired type of functionality. In a preferred case, the hydrogenated polymer is selectively functionalized by a method that includes: reacting the hydrogenated polymer selectively with a carboxylic acid (or derivative thereof), such as maleic anhydride) to provide an acylated polymer, and then reacting the acylated polymer with a monoamine, a polyamine, a polyhydroxy compound, a reactive polyether, or a combination thereof. The modified polymer is contacted with one or more post-treatment agents. ^ fc Any of the dispersing substances of the invention may include a functionalized polymer of the invention distributed in a carrier fluid such as synthetic or mineral oil, to provide a dispersing concentrate. Dispersant concentrates generally include the polymer in an amount of from 5 weight percent to 90 weight percent, more preferably 10 weight percent to 70 weight percent, of the dispersing substance, depending on the molecular weight of the polymer. The dispersing substances may also include at least one additive selected from the group consisting of anti-oxidants, pour point depressants, detergents, dispersants, friction modifiers, anti-wear agents, anti-foaming agents, corrosion and rust inhibitors, and viscosity index improvers. The invention further provides a method for modifying the dispersion or the viscometric properties of a Fluid such as a lubricant. The method includes mixing with a fluid an amount of a dispersing substance of the invention which is sufficient to provide a modified dispersant fluid having dispersion or viscometric properties that are altered from the original fluid. Preferably, the The method involves mixing the dispersing substance in an amount of from 0.001 weight percent, up to 20 weight percent, more preferably from 0.1 weight percent up to 10 weight percent, and more preferably 0.5 weight percent • up to 7 percent by weight, of the modified dispersant fluid. Typically, the method of the invention is used to modify lubricating oils and usually liquid fuels; such as engine oils, transmission fluids, hydraulic fluids, gear oils, aviation oils, and the like. In addition, the method may further include mixing with the fluid at least one additive such as anti-oxidants, pour point depressants, detergents, dispersants, friction modifiers, anti-wear agents, anti-foaming agents, corrosion inhibitors. and rust, viscosity index improvers, and the like. The invention also provides a modified dispersant fluid, such as a hydrocarbon fluid, having modified dispersion or modified viscometric properties.

A In this embodiment, the modified dispersion fluid typically includes a mineral or synthetic oil and a dispersing substance of the invention. Preferably, the modified dispersion fluid of the invention includes a dispersing substance in an amount of from 0.001 weight percent up to 20 weight percent, more preferably from 0.1 weight percent up to 10 weight percent, and more preferably from 0.5 for weight percent up to 7 weight percent of the modified lubricating fluid. The modified dispersing fluid preferably includes a mineral or synthetic lubricating oil or a liquid fuel normally; such as motor oils, transmission fluids, hydraulic fluids, gear oils, aviation oils, and the like. These modified dispersant fluids may further include at least one additive such as anti-oxidants, pour point depressants, detergents, dispersants, friction modifiers, anti-wear agents, anti-foaming agents, corrosion and rust inhibitors, and viscosity index improvers. The polymers are prepared under anionic polymerization conditions. After polymerization, the polymers of the invention are selectively hydrogenated to provide a controlled amount and controlled degree of residual unsaturation.

After the selective hydrogenation reaction, the hydrogenation catalyst is removed from the polymer and the polymer is chemically modified or functionalized to impart desirable characteristics to the dispersing substances of the invention. In accordance with the foregoing, as a result of the In accordance with the invention, dispersants, dispersants with viscosity index improver properties, and dispersant viscosity index improvers prepared by the polymerization of conjugated dienes are provided, followed by selective hydrogenation and functionalization. These dispersing substances of the invention possess numerous advantages, including improved machine performance, controlled molecular weight, controlled molecular weight distribution, controlled polymer structure, variable and controlled quantities and functionality distribution, superior thermal stability, potentially allowing reduced treatment levels and producing benefits such as improved viscometric properties . These and other advantages of the present invention will be appreciated from the detailed description and examples presented therein. The detailed description and examples increase the understanding of the invention, but are not intended to limit the scope of the invention. The polymeric dispersants of the invention, typically having lower molecular weights, can be employed in a lubricant or fuel composition that requires a dispersant to control the deposition of sediment particles in, for example, machine parts. Other polymeric substances of the invention, typically those having higher molecular weights, may be employed for their viscosity index improvement properties in any lubricating fluid which may benefit from a modification of its viscometric properties. These compounds can also find a variety of uses in addition to lubricant additives, such as adhesives, sealants, impact modifiers, and the like. As noted above, traditional dispersants have been functionalized polybutenes via a maleic anhydride reaction followed by imidization with a polyamine. Polybutenes typically have 500 to 2,000 molecular weight. With an olefin per molecule of polybutene, the number of potential functional groups per chain is limited to one. Accordingly, the molecular weight of polybutene may not exceed 2,000 if the desired functionality / hydrocarbon ratio is to be maintained. In contrast, with this invention, the amount of residual unsaturation can be controlled variably. As a result, the amount of functionality that one wishes to incorporate is quite flexible. In addition, the molecular weight of the polymer backbone is not limited to 2,000. Polymers with higher molecular weight can be prepared and functionalized so that the same proportion of functionality / hydrocarbon found in the traditional dispersant is maintained if desired. Moreover, with this invention, the position of the functionality is not limited to the end of the polymer chain as is the case with polybutenes. Instead, a variety of options are now available, including, for example, randomly along the central structure, at one end, at both ends, or at the center, of the polymer chain. If a polymer according to the invention has sufficiently high molecular weight (for example, 20,000-50,000), it will exhibit an increased thickening power and an improvement in viscosity index (viscosity index improvement properties, as well as dispersion capacity of Thus, the use of these materials can allow the reduction in use of both traditional dispersants and the viscosity index.If materials with central structures having a molecular weight of 50,000 are prepared, the functionalized versions can be Classify as dispersant viscosity index improvers or viscosity index improvers with dispersing properties Their dispersing capabilities are outstanding for dispersant viscosity index improvers In one embodiment, the present invention provides polymers that include at least two different conjugated dienes , where one of the dienes is more substituted in the positions 2, 3, and / or 4 carbon than the other diene. The most substituted diene produces vinylidene, tri- or tetra-substituted double bonds after polymerization. Hydrogenation ^ fc of the material is selectively made to saturate the less substituted olefins, which mainly arise from the less replaced, while leaving a portion of the more substituted conjugated olefins behind for functionalization. In this embodiment, the most substituted conjugated diene will have at least five (5) carbon atoms in the following formula: 5 Ri _ CC - CC - CC - CC - RR66 (1) 1 1 R "'2 R''a3 RR44 RR l 5s5 where R ^ R6 each is hydrogen (H) or a hydrocarbyl group, with the proviso that at least one of R1-R6 is a hydrocarbyl group. After polymerization, the polymerized conjugated diene unsaturation of formula (1) has the following formula: R11 A R1-C = C-R111 (2) 1 • 5 i » where R1, R11, R111 and RIV each is hydrogen or a hydrocarbyl group, with the proviso that either both R1 and R11 are hydrocarbyl groups or both R111 and RIV are hydrocarbyl groups. Examples of the conjugated dienes of formula 1 include isoprene, 2,3-dimethylbutadiene, 2-methyl-l, 3-pentadiene, myrcene, and the like. Isoprene is greatly preferred. ^ The less substituted conjugated diene in this embodiment differs from the other diene in that it has at least four (4) carbon atoms and the following formula: R7 - C - C - C - R12 (3) R8 R9 R10 R11 where R7-R12 each is hydrogen or a hydrocarbyl group. After the polymerization, the unsaturation in the polymerized conjugated diene of formula (3) has the following formula: Rv Rv C = C - R VIII (4) Rvn • where Rv, RVI, RVI1 and RVI11 each is hydrogen (h) or a hydrocarbyl group, with the proviso that one of Rv and RVI is hydrogen, one of RVI1 or RVI11 is hydrogen, and at least one of Rv, RVI, RVI1 and RVI11 is a hydrocarbyl group. Examples of the conjugated diene of formula (3) include 1,3-butadiene, 1,3-pentadiene, ^^ 2, 4-hexadiene, and the like. A highly preferred conjugated diene of formula 3 is 1,3-butadiene. An exception to this scheme would be when a diene Tetra-substituted, for example, 2,3-dimethylbutadiene, is used for the most substituted component. When this occurs, a tri-substituted olefin, for example, isoprene, can be used for the less substituted component, such that one or both of Rv and RVI are hydrogen and both of RVI1 and RVI11 are hydrocarbyl. It will be apparent to those skilled in the art that the ^^ original unsaturation of the formula (2) R1, R11, R111 and RIV the four can be hydrocarbyl groups, while the original unsaturation of the formula (4) at least one of Rv, RVI, RVI1 and RVI11 must be a hydrogen . The hydrocarbyl group or groups in the formula (1) to (4) are the same or different and are alkyls, alkenyls, cycloalkyls, cycloalkenyls, aryls, alkaryls, or substituted or unsubstituted aralkyls, or isomers thereof.

Copolymers of this embodiment are prepared by anionically polymerizing a diene of formula (1) at a level of from 0.5 weight percent to 25 weight percent, and a diene of formula (3) at a level of from 75 percent up to 99.5 per 5 weight percent, in a hydrocarbon solvent using an alkyl lithium catalyst. The two monomers can be polymerized in a block, in a reduced block, or in a random manner. Since the polymerization is anionic, the molecular weight distribution of those copolymers is typically very narrow, ^ varying generally from 1.01 to 1.20, and the molecular weight is determined by the ratio of the monomer of the initiator and / or with the presence of coupling agents. The monomers (1) and (3) can be polymerized either simultaneously or stepwise depending on the desired position of the remaining unsaturation after hydrogenation. If the random placement of the unsaturation is desired, both monomers are reacted together to give a random copolymer. If it is desirable to have the ^ k functionality at only one end, then the monomers are reacted in a staggered manner, the Order as desired to provide a di-block copolymer. If the functionality is needed at both ends, then the conjugated diene of formula (1) is polymerized first, followed by a diene of formula (3). For the living anion, a coupling agent, for example, phenyl benzoate or benzoate of Methyl is then added to produce a desired tri-block copolymer. Alternatively, a diene of formula (1) can be added to the living di-block to give a tri-block, ^ fc A fourth approach would be to allow functionality to be placed in the center of the polymer chain. In this case, a diene of formula (3) is polymerized first, followed by a diene of formula (1). A tri-block is then formed by the addition of a coupling agent or by the addition of more diene of formula (3). In addition, combinations of the above approaches can be employed. The invention may include polymers of different microstructures. The presence of the polar modifier increases the activity of the catalyst and, therefore, increases the level of the microstructure 1,2 on the microstructure 1,4 in the polybutadiene, for example. The percentage of vinyl obtained is directly proportional to the concentration of the modifier used. Since the temperature of the reaction also represents a function for determining the micro structure of the polybutadiene, the level of the modifier must be chosen taking into account the combined effects. Antrowiak et al., Temperature and Concentration Effects on Polar -modified Alkyl Li thium Polymer i zations and Copolymer izations, Journal of Polymer Science: Part Al, 10: 1319-34 (1972), incorporated herein by reference have presented a way to quickly determine conditions suitable for the preparation of any 1.2 micro-structure contained within the range of 10 percent to 80 percent. The use of this method or any other method to achieve the desired microstructure will be known to anyone of skill in the art. Dispersants and viscosity index improvers of the dispersant of the invention may include different polymer macrostructures. The polymers can be prepared and used having linear and / or non-linear macro-structures, for example, branched star. The star-branched polymers can be prepared by ^ addition of divinyl benzene or the like for the living polymer anion. The lowest levels of branching can be obtained through the use of tri-functional or tetra-functional coupling agents, such as tetrachlorosilane. In all the modalities of this invention, provided that In a reference to the "original double bond" or the "original unsaturation" of the block or random polymer (or copolymer), it is understood that the double bond (s) in k means the polymer before the hydrogenation reaction. In contrast, the terms "bond or residual double bonds" and "0 residual unsaturation", as used herein, refer to the unsaturated group or groups, typically excluding the aromatic unsaturation, present in the copolymer after the reaction of selective hydrogenation. The molecular structure of the original or residual double bonds can be determined in any conventional manner, as is known to those skilled in the art, for example, by infrared (IR) or nuclear magnetic resonance (NMR) analysis. In addition, the total or total residual unsaturation of the polymer can be quantified in any conventional manner, for example, by reference to the iodine number of the polymer. In any polymer of any of the embodiments of this invention, the micro structure of the polymerized conjugated diene of formula (3) must be such that the polymer is not ^ P excessively crystalline after the selective hydrogenation reaction. That is, after the selective hydrogenation reaction the polymer must retain its elastomeric properties, for example, the polymer should contain no more than 10 percent polyethylene crystallinity. Generally, the problems of crystallinity occur only when the polymer includes polymerized 1,3-butadiene. The limitation of the polymer crystallinity can be carried out in several ways. By ML example, this is carried out by introducing side branches in the polymerized conjugated dienes of the formula (1) and / or (3), for example, controlling the microstructure of 1,3-butadiene if it is the predominant monomer in the diene of formula (3); using a diene mixture of formula (3), containing less than the predominant amounts of 1,3-butadiene; or using a single diene of formula (3), other than 1,3-butadiene. More particularly, if the conjugated dienes of formula (3) is predominantly (at least 50 percent per mole) 1,3-butadiene, the side branches are introduced into the polymer ensuring that the polymerized diene of formula ( 3) contains a sufficient amount of the 1,2 units to prevent the selectively hydrogenated polymer from being excessively crystalline. Thus, if the conjugated diene of formula (3) is predominantly (at least 50 percent by mole, eg, 100 percent by mole) 1,3-butadiene, the polymerized diene of formula (3), before the selective hydrogenation reaction, you must A) contain no more than 75 weight percent, preferably 10 weight percent to 70 weight percent, and more preferably 35 weight percent to 55 weight percent of the 1.4 units, and when less 25 weight percent, preferably 30 weight percent to 90 weight percent, and more preferably of 45 weight percent to 65 weight percent of 1,2 units. If the polymerized die (s) of formula (3) contain less than 50 percent per mole of 1,3-butadiene, for example, ML 1, 3-pentadiene is used as the sole diene of formula (3), the micro structure of the polymerized diene of formula (3) before The selective hydrogenation reaction is not critical since, after hydrogenation, the resulting polymer will contain substantially no crystallinity. In all embodiments of the invention, the diene mixtures of formula (1) or (3) can be used to prepare block copolymers (I) x- (B) or any of the random block copolymers or block polymers star or random polymers of the invention. Similarly, mixtures of L-olefin substituted by aryl can also be used to prepare block, random, or branched 5-star copolymers of this invention. In accordance with the foregoing, whenever a reference is made herein to a diene of formula (1) or (3), or to an olefin substituted by aryl, it may encompass more than one diene of formula (1) or (3) , respectively, and more than one olefin substituted by aryl. ^ P The block copolymers of this invention comprise two or more alternative blocks, identified above. Linear block copolymers having two blocks and copolymers having three or more blocks are contemplated herein. The block polymers useful according to the invention typically include at least one block which is substantially completely saturated, but also ML include at least one block containing controlled levels of unsaturation that provides a hydrocarbon elastomer with unsaturation selectively placed for subsequent functionalization. For copolymers prepared from two different conjugated dienes, it has been found that the two dienes in the copolymers are hydrogenated at different speeds, allowing selective control of the placement of the residual unsaturation.

The different variations in compositions, molecular weight, molecular weight distribution, block lengths Relative ML, micro-structure, branching, and Tg (glass transition temperature) achievable with the use of anionic techniques used in the preparation of our polymers will be obvious to our experts in the art. Although it is not desired to limit the molecular weight range of the liquid elastomers prepared according to our invention, the minimum molecular weight for these liquid polymers ^ P is at least 2,000, preferably 2,000 to 100,000, and more preferably 5,000 to 35,000. The star-block, block and random copolymers of this invention can have substantially higher molecular weights and still retain liquid properties. The minimum weight for solid polymers of this invention is at least 50,000 to 1,000,000. The block copolymers of this invention are functionalizable. Without wishing to adhere to any operability theory, it is believed ML that can be functionalized in a controllable way through the unsaturated groups in terminal blocks or blocks to provide dispersants and dispersant viscosity index improvers having at least uniform molecular weight distribution. The star and linear branch versions of the random copolymers and homopolymers of this invention are also functionalizable. All the numerical values of molecular weight given in this specification and the drawings are of a number average molecular weight (Mn). ML The invention will be described hereafter in terms of the embodiments thereof summarized above. However, it will be apparent to those skilled in the art that the invention is not limited to these particular embodiments, but, instead, covers all embodiments encompassed by the broader scope of the description of the invention. Copolymers of At Least Two Different Conjugated Dienes ^ P In this embodiment of the invention there are provided copolymers of two different conjugated dienes, preferably isoprene and 1,3-butadiene. The two monomers can be polymerized by anionic polymerization process either in a block, in a lowered block, or in a random manner. The copolymer of this embodiment includes a first conjugated diene having at least five (5) carbon atoms and the following for: ML R1 - C - C - C - R6 (1) W l i l i 20 R2 R3 R4 R5 where R1-R6 each is hydrogen or a hydrocarbyl group, with the proviso that at least one of R1-R6 is a hydrocarbyl group, and further provided that, when polymerized, the structure of the double bond in the Polymerized conjugated diene of for (1) has the following for: R1 R1 - C = C - R111 (2) R? V where R1, R11, R111 and RIV each is hydrogen or a hydrocarbyl group, with the proviso that either both R1 and R11 are hydrocarbyl groups or both R111 and RIV are hydrocarbyl groups. In the double bond of the polymerized conjugated diene of the for (2), R1, R11, R111 and RIV can all be hydrocarbyl groups. The polymers of this embodiment also include a second conjugated diene, different from the first conjugated diene, having at least four (4) carbon atoms and the following for: R7-C-C-C-C-R12 (3) R8 R9 R10 R11 wherein R7-R12 each is hydrogen or a hydrocarbyl group with the proviso that the double bond structure in the polymerized conjugated diene of for (3) has the following for: RVI Rv - C = C - RVI11 (4) Rvn where Rv, RVI, RVI1 and RVI11 are hydrogen (H) or a hydrocarbon -lo group, with the proviso that one of Rv or RVI is hydrogen, one of Rvn Q Rv? N is hydrogen, and at least one of Rv, RVI, RVI1 and RVI11 is hydrocarbyl group.

After polymerization of the diene copolymer of this embodiment, it is preferably functionalized by a method ML which includes selectively hydrogenating the copolymer to provide a selectively hydrogenated copolymer, followed by functionalizing the hydrogenated copolymer selectively to provide a functionalized copolymer having at least one polar functional group. The polymers of this embodiment include a first conjugated diene of formula (1) in an amount of 0.5 percent ^ by weight, at 30 percent by weight, and a second conjugated diene in an amount from 70 weight percent to 99.5 weight percent. Preferably, a first conjugated diene is included in an amount of from 1 weight percent to 25 weight percent, and a second conjugated diene in an amount of from 75 percent to 99 percent by weight. More preferably, a first conjugated diene is included in an amount of from 5 weight percent to 20 weight percent, and a second conjugated diene is included in an amount of 80 weight percent to 95 weight percent. The polymers of this embodiment include block copolymers having at least two alternative blocks: (I) x- (B) I (B) and- (I) X In this case, the polymer includes at least one block (I) : block (I) is a block of at least one polymerized conjugated diene of formula (1) as described. These block polymers also include at least one polymerized block (B). Block (B) is a block of at least one polymerized conjugated diene of formula (3) as previously described. The polymers of this embodiment also include block copolymers having at least three alternative blocks: (B) and- (I) X- (B) _ In this case, the polymer includes at least one block (I): the block ( I) is a block of at least one polymerized conjugated diene of formula (1) as described. These block copolymers also include at least two polymerized blocks (B). The block or blocks (B) are blocks of at least one polymerized conjugated diene of formula (3) as described. In the block copolymers of this embodiment, x is at least 1, preferably from 1 to 600, and more preferably from 1 to 350. The above definition of x means that each of the blocks (I) is polymerized from at least 1 , preferably 1-600, and more preferably 1-350, monomer units. In the block copolymers of this embodiment, and is at least 25, preferably from 30 to 4,000, more preferably from 30 to 2,800. The above definition of y means that each of the blocks (B) is polymerized from at least 25, preferably from 30-4,000, and more preferably 30- 2,800, monomer units. In the block copolymers of . ^ this mode, z is an equal or different number of y. The block copolymer comprises from 0.5 to 25 percent by 5 percent, preferably from 1 to 20 percent by weight of the blocks (I) and from 80 to 99.5 percent, preferably 80 to 99 percent by weight of the blocks (B) . In any of the copolymers of this embodiment, the double bond structures defined by formula (2) and fP (4) are necessary to produce copolymers that can be selectively hydrogenated in the manner described herein, to selectively produce the block hydrogenated and the random copolymers of this invention. The hydrocarbyl group or groups in the formula (1) and (2) are the same or different and are substituted or unsubstituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, or aralkyl groups, or any isomer thereof.

ML Suitable hydrocarbyl groups are alkyl of 1 to 20 carbon atoms, alkenyl with 1 to 20 carbon atoms, cycloalkyl of 5 to 20 carbon atoms, aryl of 6 to 12 carbon atoms, alkaryl of 7 to 20 carbon atoms or aralkyls of 7 to 20 carbon atoms. Examples of suitable alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, methyl-decyl or dimethyl-decyl. Examples of Suitable alkenyl groups are ethenyl, propenyl, butenyl, pentenyl or hexenyl. Examples of suitable cycloalkyl groups are cyclohexyl or methylcyclohexyl. Examples of suitable cycloalkenyl ML groups are 1-, 2-, or 3-cyclohexenyl or 4-methyl-2-cyclohexenyl. Examples of suitable aryl groups are phenyl or diphenyl. Examples of suitable alkaryl groups are 4-methyl-phenyl (p-tolyl) or p-ethyl-phenyl. Examples of suitable aralkyl groups are benzyl or phenethyl. Convenient conjugated dienes of formula (1) used to polymerize block (I) are isoprene, 2,3-dimethyl-butadiene, 2-methyl-1, 3- ^ P pentadiene, myrcene, 3-methyl-1, 3- pentadiene, 4-methyl-l, 3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2, 3-dimethyl-1, 3-pentadiene, 2-hexyl-l, 3-butadiene, 3-methyl-l, 3-hexadiene, 2-benzyl-l, 3-butadiene, 2-p-tolyl-1,3-butadiene, or mixtures thereof themselves, preferably isoprene, myrcene, 2,3-dimethyl-butadiene, or 2-methyl-1,3-pentadiene, and more preferably isoprene. The hydrocarbyl group or groups in the formula (3) can ML or not be the same as in the formula (4). These hydrocarbyl groups are the same as those described above along with the discussion of the hydrocarbyl group of formula (1) and (2). Suitable monomers of block (B) are 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 2-heptadiene, 1,3-octadiene, 2, 4-octadiene, 3, 5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, 3,5-25 decadiene, or mixtures thereof, preferably, 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, or 1,3-hexadiene, and more preferably is 1,3-butadiene. It is generally preferred that each of the blocks (B) is polymerized from a single monomer. The scope of this embodiment, and of any other embodiment of the invention wherein the block (B) is used, also encompasses polymers wherein the block (B) may comprise copolymers of one or more conjugated dienes of formula (3) and controlled (0.3 to 30 mole percent) of an aryl-substituted olefin, for example, styrene or other suitable monomers (such as alkylated styrene, vinyl naphthalene, or alkylated naphthalene vinyl) incorporated for the control of glass transition temperature ( Tg), density, solubility parameters and refractive index. Similarly, the approach to this embodiment also encompasses polymers wherein the block (B) may be composed of copolymers of one or more conjugated dienes of the formula (3) and any other anionically polymerizable monomer capable of polymerizing with the conjugated diene of the formula (3) . Similar considerations also apply in the case of the block (s) (I), which may include similar styrene-diene copolymers. The copolymer is polymerized by anionic polymerization, discussed in detail below. As will be apparent to those skilled in the art, the block copolymer of this embodiment contains at least two alternative blocks, (I) - (B) or (B) - (I), referred to herein as di-blocks. The block copolymer of this embodiment may contain three alternative blocks, for example, (I) - (B) - (I), referred to herein as tri-blocks or tri-block units, but may contain an unlimited number of blocks. The functionalization of any of these copolymers is carried out in a conventional manner and is described below. After the copolymer (I) - (B) is polymerized, it would undergo a selective hydrogenation reaction during which the polymerized conjugated dienes of formula (3) of the copolymer are selectively hydrogenated to the extent that they contain substantially none of the unsaturation original while the polymerized conjugated dienes of formula (1) of the copolymer retain a sufficient amount of their original unsaturation to allow for functionalization. Usually, for a copolymer wherein the conjugated dienes of formula (1) and (3) are polymerized to provide unsaturation of formula (2) and (4), respectively, as discussed above, the number of iodine for the unsaturation of formula ( 2) after the selective hydrogenation reaction is from 20 percent to 100 percent, preferably from 50 percent to 100 percent, and more preferably 100 percent, of the number of iodine before the selective hydrogenation reaction; and for the unsaturation of formula (4) is from 0 percent to 10 percent, preferably from 0 percent to 0.5 percent, and more preferably from 0 percent to 0.2 percent, of the number of iodine before the reaction of selective hydrogenation. The iodine number, as is known to those skilled in the art, is defined as the theoretical number of grams of iodine which would add the unsaturation to 100 grams of olefin and is a quantitative measure of the unsaturation. In this embodiment of the invention, although the micro-structure of the blocks (I) is not critical and may consist of 1,2-, 3,4- and / or 1,4 units, schematically shown below for the blocks of polyisoprene, when a polar compound is used during the polymerization of block (I), blocks (I) mainly comprise (at least 50 weight percent) 3, -units, the remainder being mainly (less than 50 percent) by weight) 1, 4-units; when the polar compound is not used during the polymerization of block (I), blocks (I) mainly comprise (approximately 80 weight percent) 1,4-units, the remainder being mainly 1,2- and 3,4- units. CH H CH 3 1 1 -CH 2 -C-CH 2 -C - CH 2 -C = CH- CH 2 1,2- 3, 4 - 1, 4 - The micro-structure of the blocks (B), when the monomer predominantly used to polymerize the blocks (B) is 1, 3-butadiene, should be a mixture of 1.4- and 1.2-units schematically shown below for the blocks of ML polybutadiene: CH3 5 I CH2 1,2- 1,4- ^^ since the hydrogenation of the micro-structure predominantly 1.4- produces a segment of crystalline polyethylene. The microstructure of blocks (I) and (B) (as well as of the polymerized conjugated dienes of formula (1) or (3) in any polymer of this invention) is controlled in a conventional manner, for example, by controlling the quantity and the nature of polar compounds used during the polymerization reaction, and the temperature of the reaction. In a particularly preferred embodiment, block (B) contains 50 percent of the microstructure of 1,2 and 50 percent of the 1,4 microstructure. If block (B) is poly-1,3-butadiene, the hydrogenation of segment 5 (B) containing 50 percent to 60 percent of the content of the 1,2-microstructure produces an elastomeric center block on the which is a substantially an ethylene-butene-1 copolymer having substantially no crystallinity. If block (B) is polymerized from 1,3-pentadiene, the microstructure is not critical.

The terms "1,2-", "1,4-", and "3,4-microstructure" or "units" as used in this application refers to the polymerization products obtained by the addition mode of monomer units of 1,2-, 1,4- and 3,4-, respectively. Surprisingly we have discovered that the polymerized conjugated dienes of formula (3), for example, the dienes used in the blocks (B), of the polymers of this invention are selectively hydrogenated in our hydrogenation process much faster than the polymerized conjugated dienes of formula (1), for example, the dienes used in blocks (I). This is not evident from the teachings of Falk, discussed above, because Falk teaches that the double bonds of the di-substituted 1,4-polybutadiene units are selectively hydrogenated in the presence of double bonds of the tri-substituted units of 1, 4-polyisoprene (which is hydrogenated very slowly). Surprisingly we discovered that the di-substituted double bonds of the 1, 4-polybutadie-units are not hydrogenated together with the mono-substituted double bonds of the 1,2-polybutadiene units, while the double and substituted bonds of the 3, 4-polyisoprene units are hydrogenated at a much slower rate than the aforementioned polybutadienes. Thus, in view of the description of Falk it is surprising that the di-substituted double bonds of the 1,4-polybutadiene units are selectively hydrogenated in the presence of the di-substituted double bonds of the 3, 4-polyisoprene units . This is also surprising in view of the ML teachings of Hoxmeier, published European nt application, publication No. 0 315 280, which discloses that the di-substituted double bonds of the 1,4-polybutadiene units, the mono-double bonds substituted of the 1, 2-polybutadiene units and the di-substituted double bonds of the 3,4-polyisoprene units are simultaneously hydrogenated at substantially the same rates. For example, for the block copolymers of this The invention, when the block (I) is polyisoprene and the block (B) is polybutadiene, the infrared Fourier transform analysis of the selectively hydrogenated block copolymers of the invention, such as the polymers of tri-block IBI , indicates that the hydrogenation of the double bonds of the units 1, 2-polybutadiene proceed more rapidly, followed by hydrogenation of the double bonds of the 1,4-polybutadiene units. The infrared absorptions caused by these groups ML disappear before the appreciable hydrogenation of the polyisoprene units. 20 In accordance with the above, controlling the quantity and placement of 1,2-versus 1, 4-micro-structure, as well as the quantity and placement of the poly-isoprene units, it is now possible to control the quantity and the placement of the remaining unsaturation and polymers after hydrogenation. HE It follows that the amount and placement of the functionalization of the polymeric dispersants of the invention is also controllable to a degree not previously possible. After the block copolymer is prepared, it is subjected to a selective hydrogenation reaction to hydrogenate mainly the block (s) (B). The selective hydrogenation reaction and the catalyst are described in detail below. After the hydrogenation reaction is complete, the selective hydrogenation catalyst is removed from the block copolymer, and the polymer is isolated by conventional methods, for example, alcohol flocculation, solvent vapor division, or non-aqueous solvent evaporation. . An anti-oxidant, for example, Irganox 1076 (from Ciba-Geigy), is usually added to the polymer solution prior to polymer isolation. Random Copolymers The random copolymers of this invention have random amounts of unsaturation incorporated randomly in an otherwise saturated core structure. In contrast to EPDM, the level of unsaturation can be easily controlled, for example, to produce polymers having an iodine number of from 5 to 100, to provide a wide variety in the degree of functionalization. In one embodiment, the block copolymers are polymerized from the same monomers used to polymerize the block copolymers (I) X- (B), described elsewhere herein. In particular, random copolymers can be made by polymerizing at least one conjugated diene of formula (1) with at least one conjugated diene of formula (3), both defined above. This random copolymer contains from 1.0 percent to 40 percent, preferably from 1.0 percent to 20 percent, per mole of the polymerized conjugated diene of formula (1) and from 60 percent to 99 percent, preferably 80 percent a 99 percent by mol of the polymerized conjugated diene of formula (3). The convenient conjugated diene of formula (1) is exemplified above. The most preferred conjugated diene of formula (1) for the copolymerization of these copolymers is isoprene. Convenient conjugated dienes of formula (3) are also exemplified above. 1,3-butadiene is the most conjugated diene Preferred of formula (1) for the polymerization of the random copolymer of this embodiment. Thus, more preferably, in this embodiment, the random copolymer is polymerized from t isoprene and 1,3-butadiene and contains from 1 percent to 20 percent by weight of the isoprene units and from 80 percent to 99 weight percent of the butadiene units. The isoprene units have mainly (i.e., 50 weight percent to 90 weight percent) the 3.4 microstructure. The random copolymers are subjected to the selective hydrogenation reaction discussed above for the block copolymers, during which the polymerized conjugated diene units of the formula (3) are substantially completely hydrogenated, while the conjugated diene units of the formula (1) ) are hydrogenated to a lesser degree substantially, ie, to the extent that they retain a sufficient amount of their original unsaturation to functionalize the copolymer, whereby dispersants and viscosity index improvers of dispersant having a random unsaturation proportional to the unsaturation in polymerized dienes of formula (1). For example, for the random copolymer polymerized from a diene of formula (1) and a different diene of formula (3), the number of iodine before selective hydrogenation for the polymer is 450. After selective hydrogenation, the number of iodine for the polymer is 10 to 50, with more than the unsaturation contributed by the diene of formula (1). The hydrogenated polymers are functionalized in the same manner as presented for the block copolymers. Star-branched Polymers The invention is also directed to star block and random polymers. Star-block block polymers are made from any combination of blocks (I) and (B) defined above. Star block (I) - (B) block polymers comprise 0.5 weight percent to 25 weight percent, preferably from 1 weight percent to 20 weight percent, of the blocks (I) and from 75 weight percent to 99.5 weight percent, preferably from 80 weight percent to 99 weight percent of the blocks (B). The star-block block polymers are selectively hydrogenated in the selective hydrogenation process of this invention to the extent that the blocks (B) contain substantially none of the original unsaturation, while each of the blocks (I) respectively retains a sufficient amount of the original unsaturation of the conjugated dienes present in these blocks to functionalize the block polymers branched star. Thus, for the star-branched block polymer (I) - (B), after the selective hydrogenation reaction, the iodine number for the blocks (I) is from 10 percent to 100 percent, preferably from 25 percent to 100 percent, more preferably 50 percent to 100 percent, and more preferably 100 percent of the number of iodine before the selective hydrogenation reaction; and for blocks (B) it is from 0 percent to 10 percent, preferably from 0 percent to 0.5 percent, of the number of iodine before the selective hydrogenation reaction. Star-branched random polymers are made of any combination of at least one diene of formula (1) and at least one diene of formula (3), different from the diene of formula (1), or of any combination of at least one olefin substituted by aryl and at least one diene of formula (1) or (3), all of which are the same as those discussed above. The branched star random polymers of the dienes of formula (1) and (3), which should be different from each other, comprise 0.5 weight percent to 25 weight percent, preferably 1 weight percent to 20 weight percent. weight percent of the diene of formula (1), and 75 weight percent to 99.5 weight percent, preferably 80 weight percent to 99 weight percent, of the diene of formula (3). The star-branched random polymers of the aryl-substituted olefin and the diene of formula (1) or (3) comprise 0.5 weight percent to 50 weight percent, preferably 1 weight percent to 25 weight percent. weight, of the aryl substituted olefin and from 50 percent to 99.5 percent by weight, preferably from 65 percent by weight to 99 percent by weight, of the diene of formula (1) or (3). The star-branched random diene polymers are also selectively hydrogenated in the selective hydrogenation process of this invention to the extent that the polymerized dienes of formula (3) contain substantially none of the original unsaturation, while the polymerized dienes of formula (1) ) retain a sufficient amount of original unsaturation to functionalize the star-branched random polymers. Thus, for the random star-branched polymer of the conjugated diene of formula (1) and a different diene of formula (3), both identified above, the iodine number for the polymerized diene of formula (1), after the selective hydrogenation reaction, from 10 percent to 100 percent, preferably from 25 percent by ML percent to 100 percent, more preferably 50 percent to 100 percent, and most preferably still 100 percent, of the number of iodine before the selective hydrogenation reaction; and for the polymerized diene of formula (3) is from 0 percent to 10 percent, preferably from 0 percent to 0.5 percent, of the number of iodine before the selective hydrogenation reaction. fl) Polymerization Reaction The polymers of this invention are polymerized by any known polymerization process, preferably by an anionic polymerization process. Anionic polymerization is well known in the art and is used in the production of a variety of commercial polymers. An excellent comprehensive review of anionic polymerization processes appears in the text Advances in Polvmer Science 56, ML Anionic Polymerization, pages 1-90, Springer-Verlag, Berlin, Heidelberg, New York, Tokyo 1984 in a monograph entitled Anionic Polymerization of Non-polar Monomers Involving Lithium, by R.N. Young, R.P. Quirk and L.J. Fetters The anionic polymerization process is carried out in the presence of a suitable anionic catalyst (also known as an initiator), such as n-butyl-lithium, sec-butyl-lithium, t-butyl-25-lithium, sodium naphthalide or , cumyl potassium. The amount of the catalyst and the amount of the monomer in the polymerization reaction dictate the molecular weight of the polymer. The polymerization reaction ML is carried out in solution using an inert solvent as the polymerization medium, for example, aliphatic hydrocarbons, such as hexane, cyclohexane, or heptane, or aromatic solvents, such as benzene or toluene. In certain cases, inert polar solvents, such as tetrahydrofuran, may be used alone as a solvent, or in a mixture with a hydrocarbon solvent. The polymerization process will be exemplified below for the polymerization of one of the embodiments of the invention, for example, a tri-block of polyisoprene-polybutadiene-polyisoprene. however, it will be apparent to those skilled in the art that the same process principles are can be used for the polymerization of all polymers of the invention. The process, when a lithium-based catalyst is used, comprises forming a solution of isoprene monomer in an inert hydrocarbon solvent, such as cyclohexane, or modified by the presence therein of one or more polar compounds selected from the group it consists of ethers, thioethers, and tertiary amines, for example, tetrahydrofuran. The polar compounds are necessary to control the microstructure of the butadiene core block, ie the content of structure 1,2 thereof. The greater the content of polar compounds, the greater the content of structure 1,2 in these blocks. Since the presence of the polar compound is not essential in the formation of the first block of polymer with many initiators unless a high content of structure 3,4 of the first block is desired, it is not necessary to introduce the polar compound in this step. , since it can be introduced just before or together with the addition of butadiene in the second stage of polymerization. Examples of polar compounds that can be used are dimethyl ether, ether diethyl, ethylmethyl ether, ethyl propyl ether, dioxane, diphenyl ether, dipropyl ether, tripropyl amine, tributyl amine, trimethyl amine, triethyl amine, and N-N-N '-N' -tetramethyl ethylene diamine. Mixtures of the polar compounds can also be used. The amount of the polar compound depends on the type of The polar compound and the polymerization conditions will be apparent to those skilled in the art. The effect of the polar compounds on the polybutadiene micro structure is _ ^ k details in Antkowiak et al. The polar compounds also accelerate the speed of polymerization. If others monomers other than 1,3-butadiene, for example, pentadiene, is used to polymerize the central blocks (B), polar compounds are not necessary to control the microstructure because these monomers will inherently produce polymers that do not possess crystallinity after the hydrogenation. When the lithium-alkyl-based initiator, a polar compound and an isoprene monomer are combined in an inert solvent, the polymerization of the isoprene proceeds to produce the first terminal block as molecular weight is determined by the proportion of the isoprene with the initiator. The living poly-isoprenyl anion formed in this first step is used as the catalyst for the subsequent polymerization. At this time, the butadiene monomer is introduced into the system and the block polymerization of the second block follows, the presence of the polar compound now influences the desired degree ^ P of branching (structure 1,2) in the polybutadiene block. The resulting product is a living di-block polymer having a terminal anion and a lithium counter ion. The living di-block polymer serves as a catalyst for the growth of the final isoprene block, formed when the isoprene monomer is again is added to the reaction vessel to produce the final polymer block, resulting in the formation of the tri-block I-B-I. After completing the polymerization, the live anion, now ? present in the term of the tri-block, is destroyed by the addition of a proton donor, such as methyl alcohol or acid acetic. The polymerization reaction is usually carried out at a temperature between 0 ° C and 100 ° C, although higher temperatures can be used. The control of a chosen reaction temperature is desirable since it can influence the effectiveness of the additive polar compound to control the micro-structure of the polymer. The temperature of the reaction can be, for example, from 50 ° C to 80 ° C. The reaction pressure is not critical and varies from atmospheric to 7 kg / cm2. If the polar compounds are used before the polymerization of the first segment (I), the blocks (I) with high content of unit 3.4 are formed. If the polar compounds are added after the initial segment (I) is prepared, the first segment (I) will possess a high percentage of microstructure 1.4 (which is tri-substituted), and the second segment (I) will have a high percentage of micro-structure 3,4. P The production of tri-block polymers having a high content of unit 1,4 in both of the terminal blocks (I) is also possible by using coupling techniques illustrated below for a polyisoprene-block copolymer polybutadiene-polyisoprene: 15 RLi ISOPRENE > 1.4 -POLI-POLAR COMPOSITE SYNERGISM > 1; _ OLI- ISOPRENE-POLYBUTADENE BUTADIENE ^ COUPLING AGENT 1, 4-POLY-ISOPRENE-POLYBUTADIENE-1,4 POLY-ISOPRENE > 25 The substitution of mycerine for isoprene by the polymerization of blocks (I) ensures the incorporation of a high proportion of tri-substituted double bonds, even in the presence of polar compounds since myrcene contains a bond double tri-substituted slope that is not mixed in the polymerization process. In the coupling process, similar to that described above, block polymers containing ^ P end blocks of polyisoprene (or any other polymerized monomer convenient for use in block (I)) having a high micro content - Structure 3.4 can be obtained by adding the polar compound before polymerization of isoprene (or other monomer). The use of coupling technique for the production of tri-block polymers reduces the reaction time necessary for? ß the termination of the polymerization, compared to the sequential addition of isoprene, followed by butadiene, followed by isoprene. These coupling techniques are well known and use coupling agents such as esters, C02, iodine, dihaloalkanes, silicon tetrachloride, divinyl benzene, Alkyl trichlorosilanes and dialkyl dichlorosilanes. The use of tri or tetra-functional coupling agents, such as alkyl trichlorosilanes or silicon tetrachloride, allows the • ^ k formation of macromolecules that have 1 or 2 branches of major chains, respectively. The addition of divinyl benzene as A coupling agent has been documented to produce molecules having up to 20 or more segments joined separately. The use of some of the coupling agents provides a convenient means to produce block and random branched star polymers. The polymers in star branched blocks are made of any combination of blocks (I) and (B), defined above. Star-branched random polymers are made of any combination of at least one diene of formula (1) and at least one diene of formula (3), different from the diene of formula 5 (1), or at least one olefin substituted by aryl, in at least one diene of formula (1) and at least one diene of formula (3), different from the diene of formula (1) . The molecular weight of the star-branched block of the random copolymers will depend on the number of branches in each copolymer, such as fl} apparent to those skilled in the art. Suitable coupling agents and reactions are described in U.S. Patent Nos. 3,949,020; 3,594,452; 3,598,887; 3,465,065; 3,078,254; 3,766,301; 3,632,682; and 3,668,279; and in the patents of Great Britain Nos. 1,014,999; , 1,074,276 and 1,121,978. Selective Hydrogenation After polymerization, hydrogenation Selective ML of the polymer can be carried out using techniques similar to those known in the art. A preferred method and The catalyst is described in U.S. Patent No. 5,187,236. The process and the catalyst are described in more detail below. In general, however, the previously described polymers can be contacted with hydrogen and a hydrogenation catalyst synthesized from of a transition metal compound, typically nickel or cobalt, and an organic metallic reducing agent, for example, triethylaluminum. The hydrogenation is continued at temperature typically not in excess of 40 ° C and at pressures of 2.1 kg / cm2 to 14 kg / cm2. Generally, the polymers are hydrogenated so that substantially all of the unsaturation in the formula (4) is removed, although much of that of the formula (2) is retained. The selective hydrogenation reaction will also be described below using a tri-block of polyisoprene-polybutadiene-polyisoprene as an example. However, it will be apparent to those skilled in the art that any polymer of this invention can be selectively hydrogenated in the same manner. In Example II below, the block copolymer is selectively hydrogenated to saturate the intermediate block (polybutadiene). The method of selectively hydrogenating the polybutadiene block is similar to that of Falk, Coordination Catalysts for the Selective Hydrogenation of Polymeric Unsaturation, Journal of Polymer Science: Part Al, 9: 2617-23 (1971), but is carried out with a catalyst and novel hydrogenation process used herein. Any other known selective hydrogenation method can also be used as will be apparent to those skilled in the art, but it is preferred to use the method described herein. In summary, the selective hydrogenation method preferably used herein comprises contacting the previously prepared block copolymer with hydrogen in the presence of a novel hydrogenation catalyst composition. The novel hydrogenation catalyst composition and the hydrogenation process are described in detail in U.S. Patent No. 5,149,895. The hydrogenation catalyst composition is synthesized from at least one transition metal compound and a metallic organ reducing agent. Suitable transition metal compounds are compounds of Group IVb, Vb, VIb or VIII metals, preferably IVb or VIII of the Periodic Table of the Elements, published in Lange's Handbook of Chemistry, 13th Ed., McGraw-Hill Book Company, New York (1985) (John A. Dean, ed.). Non-limiting examples of these compounds are metal halides, for example, titanium tetrachloride, vanadium tetrachloride; vanadium oxytrichloride, titanium and vanadium alkoxides, wherein the alkoxide moiety has a branched or unbranched alkyl radical of 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Preferred transition metal compounds are metal carboxylates or alkoxides of group IVb or VIII of the Periodic Table of the Elements, such as nickel (II) 2-ethylhexanoate, titanium isopropoxide, cobalt (II) octoate, nickel phenoxide (II) and ferric acetylacetonate. The metallic organ reducing agent is any or a combination of any of the materials commonly employed to activate the Ziegler-Natta olefin polymerization catalyst components containing at least one compound of the elements of Groups la, lia, Ilb, Illa, or IVa of Table M ^ Periodic of the Elements. Examples of these reducing agents are metal alkyls, metal hydrides, metal alkyl hydrides, metal alkyl halides, and metal alkyl alkoxides, such as alkyl lithium compounds, dialkyl zinc compounds, trialkyl boron compounds, trialkyl aluminum compounds, alkyl aluminum halides and hydrides, and tetra-alkylgermanium compounds. Mixtures of reducing agents can also be used. Specific examples of useful reducing agents include n-butyllithium, diethylzinc, di-n-propylzinc, triethylboron, diethylaluminumethoxide, triethylaluminum, trimethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, ethylaluminum dichloride, dibromide, and dihydride, dichloride Isobutylaluminum, hydride dibromide, chloride, bromide, and ethyl aluminum hydride, n-propylaluminum chloride, bromide, and hydride, di-isobutyl aluminum chloride, bromide, and hydride, tetramethyl germanium, and tetraethylgermanium. Preferred organ-metal reducing agents are the halides of Metal of alkyls and dialkyls of metals of Group Illa having from 1 to 20 carbon atoms per alkyl radical. More preferably, the reducing agent is a trialkylaluminum compound having from 1 to 6 carbon atoms per alkyl radical. Other reducing agents that can be used herein are described in Stevens et al., United States Patent No. 3,787,384, column 4, line 45 to column 5, lines 12 and in Strobel et al., United States Patent No. 4,148,754, column 4, line 56 to column 5, line 59. Particularly preferred reducing agents are alkyl metal or hydride derivatives of a metal selected from Groups la, lia, and Illa of the Periodic Table of the Elements, such as n-butyl lithium, sec-butyl lithium, n-hexyl lithium, phenyl-lithium, triethyl aluminum, tri-isobutyl aluminum, trimethyl aluminum, diethylaluminum hydride and dibutylmagnesium. - ^ P The molar ratio of the metal derived from the reducing agent against the metal derived from the transition metal compound will vary for the selected combinations of the reducing agent of the transition metal compound, but in general is from 1: 1 to 12: 1, preferably 1.5: 1 to 8: 2, more preferably 2: 1 to 7: 1, and more preferably 2.5: 1 to 6: 1. It will be apparent to those skilled in the art that the optimum proportions will vary depending on the transition metal and the ^ k metallic organ agent used, for example, for the trialkylaluminum / nickel (II) systems, the preferred molar ratio aluminum: nickel is 2.5: 1 to 4: 1, for the trialkylaluminum / cobalt (II) systems, the preferred molar ratio of aluminum: cobalt is 3: 1 to 4: 1, and for trialkyl aluminum alkoxide systems / titanium (IV), the preferred molar ratio of aluminum: titanium is 3: 1 to 6: 1. The mode of addition of the reducing agent ratio to the transition metal compound is important in the production of the novel hydrogenation catalyst having superior selectivity, efficiency and stability, as compared to the prior art catalyst systems. During the synthesis of the catalysts it is preferred to maintain the molar ratio of the reagents used to synthesize the substantially constant catalyst. This can be done either by adding the reducing agent, as quickly as possible, to a solution of the transition metal compound, or by a substantially simultaneous addition of the separate streams of the reducing agent and the transition metal compound to a catalyst synthesis vessel so that the selected molar ratios of the metal of the reducing agent against the metal of the transition metal compound are maintained substantially constant for substantially the entire time of the addition of the two compounds. The time required for the addition must be such that excess pressure and heat buildup are avoided, ie the temperature should not exceed 80 ° C and the pressure should not exceed the safe pressure limit of the catalyst synthesis vessel . In a preferred embodiment, the reducing agent and the transition metal compound are added substantially simultaneously to the catalyst synthesis vessel so that the selected molar ratio of the reducing agent against the transition metal compound is maintained substantially constant for substantially the entire time of the addition of the two compounds. This preferred embodiment allows control of the exothermic reaction so that the heat buildup is not excessive, and the rate of gas production during the synthesis of the catalyst is not excessive either - in accordance with the above, the accumulation of gas is relatively slow. In this embodiment, carried out with or without a solvent diluent, the rate of addition of the catalyst components is adjusted to maintain the temperature of the synthesis reaction at or below 80 ° C, which promotes the formation of the selective hydrogenation catalyst. In addition, the selected molar ratios of the metal of the reducing agent against the metal of the transition compound are kept substantially constant throughout the entire duration of the catalyst preparation when the technique of simultaneous mixing of this embodiment is employed. In another embodiment, the catalyst is formed by the addition of the reducing agent to the transition metal compound. In this modality, the time and order of addition of the two reagents is important to obtain the hydrogenation catalyst that has superior selectivity, efficiency and superior stability. Thus, in this embodiment, it is important to add the reducing agent to the transition metal compound so that it is in the shortest period of time as practically possible. In this embodiment, the term determined for the addition of the reducing agent to the transition metal compound is critical for the production of the novel catalyst. The term "as short a time period as practically possible" means that the addition time is as fast as possible, so that the reaction temperature is not higher than 80 ° C and the reaction pressure does not exceed the Safe pressure limit for the catalyst synthesis vessel. As will be apparent to those skilled in the art, that time will vary from each synthesis and will depend on factors such as types of reducing agents, transition metal compounds and solvents used in the synthesis, as well as relative amounts thereof, and the type of catalyst synthesis vessel used. For illustration purposes, a solution of 15 milliliters of triethylaluminum in hexane should be added to a solution of nickel (II) octoate in mineral spirits in 10-30 seconds. Generally, the addition of the reducing agent to the transition metal compound should be carried out in 5 seconds (sec) to 5 minutes (min), depending on the amounts of reagents used. If the period of time during which the reducing agent is added to the transition metal compound is prolonged, for example, by more than 15 minutes, the synthesized catalyst is less selective, less stable, and may be heterogeneous. In the embodiment wherein the reducing agent is added as quickly as possible to the transition metal compound, it is also important to add the reducing agent to the transition metal compound in the aforementioned sequence to obtain the novel catalyst. The inverse of the addition sequence, ie, the addition of the transition metal compound to the reducing agent, or the respective solutions thereof, is detrimental to the stability, selectivity, activity and homogeneity of the catalyst and is therefore undesirable . In all embodiments of the hydrogenation catalyst synthesis, it is preferred to use solutions of the reducing agent and the transition metal compound in suitable solvents, such as hydrocarbon solvents, for example, cyclohexane, hexane, pentane, heptane, benzene, toluene , or mineral oils. The solvents used to prepare the solution of the reducing agent and the transition metal compound may be the same or different, but if they are different, they must be compatible with each other so that the solutions of the reducing agent and the transition metal compound are completely soluble one in the other. The hydrogenation process comprises contacting the unsaturated polymer to be hydrogenated with an amount of the catalyst solution containing 0.1 to 0.5, preferably 0.2 to 0.3 mole percent of the transition metal given in moles of polymer unsaturation. The partial pressure of hydrogen is generally 0.35 kg / cm2 at several tens of kg / cm2 but is preferably 0.7 kg / cm2 at 7 kg / cm2. The temperature of the hydrogenation reaction mixture is generally from 0 ° C to 150 ° C, preferably from 25 ° C to 80 ° C, more preferably from 4fc 30 ° C to 60 ° C, since higher temperatures can lead to the deactivation of the catalyst. The duration of the hydrogenation reaction can be as short as 30 minutes and, as will be apparent to those skilled in the art, depends to a large extent on the actual reaction conditions employed. The hydrogenation process can be monitored by any conventional means, for example, infrared, spectroscopy, fl ratio of hydrogen flow, total hydrogen consumption, or any combination thereof. After completing the hydrogenation process, the unreacted hydrogen is vented or consumed by introducing the appropriate amount of an unsaturated material, such as 1-hexene, which is converted to an inert hydrocarbon, for example, hexane. Subsequently, the catalyst is removed from the resulting polymer solution by any convenient means, selected depending on the particular process and polymer. For a low molecular weight material, for example, the removal of the catalyst residue may consist of a treatment of the solution with an oxidant, such as air, and subsequent treatment with ammonia and optionally methanol in amounts equal to the molar amount of the metals (i.e., the sum of the transition metal and the metal of the reducing agent) present in the hydrogenation catalyst to produce the catalyst residues as a filterable precipitate, which is filtered. The solvent can then ^ P to be removed by any conventional method, such as vacuum division, to produce the product polymer as a transparent, colorless fluid. Alternatively, and in a preferred embodiment, after completion of the hydrogenation reaction, the mixture is treated with ammonia in the molar amount approximately equal to the metals (i.e., the sum of the transition metal and the metal of the agent ^ P reductant) and an aqueous hydrogen peroxide, in a molar amount equal to one half to one, preferably one half, of the amount of the metals. Other levels of ammonia and peroxide are also operative, but those specified above are particularly preferred. In this method, a precipitate is formed, which can be filtered as described above. In still another alternative method, the catalyst can be removed by extraction with aqueous mineral acid, such as sulfuric, phosphoric, or hydrochloric acid, followed by washing with distilled water. A small amount of a The material commonly used as an aid to remove transition metal-based catalysts, such as a commercially available high molecular weight diamine, for example, Huntsman's Jeffamina D-2000, can be added to aid in phase separation and removal. of catalyst during extractions. The resulting polymer solution is then dried over a drying agent, such as magnesium sulfate, separated from the drying agent and the solvent is then separated by any conventional method, such as vacuum partitioning, to produce a polymer as a clear fluid . Other methods of polymer isolation such as steam or alcohol flocculation can be employed depending on the properties of the hydrogenated polymer. After the hydrogenation and purification is complete, the polymer can be functionalized and used in the lubricant compositions of the invention: liquids will serve as dispersants and solids as viscosity index improvers of the dispersant. Functionalization of the Polymers The unsaturated terminal blocks of the block polymers of this invention can be chemically modified or functionalized to provide benefits that increase dispersion and viscosity improvement qualities of the materials of the invention. These benefits can be obtained through methods similar to those used for modifying existing commercial materials, such as poly-isobutylene or EPDM. After the selective hydrogenation step, the remaining sites of unsaturation can be chemically modified. These methods include reacting the unsaturated groups in the polymer with any of several reagents to produce functional groups, such as halogen, hydroxyl, epoxy, sulfonic acid, mercapto, acrylate or carboxyl groups. Functionalization methods are well known in the art. A preferred chemical modification method involves the reaction of polymer with an unsaturated carboxylic acid and / or derivatives, such as acrylic acid, maleic acid, fumaric acid, maleic anhydride, methacrylic acid, esters of these acids, and the like. More preferably, maleic anhydride is used for the chemical modification of unsaturation. Numerous methods are known for the chemical modification of polyisobutylene and EPDM via the ene reaction. Methods for the reaction of maleic anhydride with EPDM via a radical reaction in the presence of a radical initiator are also known. These methods can be adapted to incorporate the carboxylic acid derivatives unsaturated in the polymeric dispersants of the invention. After the acylation reaction (or other suitable chemical modifications as noted above), the chemically modified polymers can be reacted with a Lewis base, such as monoamine, a polyamine, a Polyhydroxy compound, a reactive polyether, or a combination thereof. Amines that are useful for this modification reaction are characterized by the presence of at least one primary (i.e., H2N-) or secondary (ie, HN =) amino group. The monoamines and polyamines can be aliphatic amines, cycloaliphatic amines, heterocyclic amines, aromatic amines, or hydroxylamines. Preferably, the polyamines contain only one primary or secondary amine, with the remaining amines being tertiary (i.e., -N =) or aromatic amines. The amination can be carried out by heating the maleic anhydride-modified diene polymer to 150 ° C in the presence of the amine, followed by the division of water. A useful monoamine is ethanol amine. Useful polyamines include aminopropylmorpholine and tetraethylenepentamine. Useful polyhydroxy compounds include ethylene glycol and pentaerythritol. Useful reactive polyethers f) include polyethers containing hydroxide or amino groups which will react with the modified polymer, such as polyethylene glycol monoalcohol. Further, when the modified polymers react with an aromatic polyamine, the resulting dispersant has improved anti-oxidant properties. In a preferred functionalization of diene copolymers, the selectively hydrogenated copolymer is functionalized with functional groups selected from halogen IV, ML epoxides, sulfonic acids, mercapto acid and / or derivatives and carboxylic acid derivatives, and subsequently modified further by reacting with a monoamine, a polyamine, a polyhydroxy compound, a reactive polyether, or a combination thereof. The reaction of the maleic anhydride with materials of the invention can be carried out on clean polymers or solutions of polymers in light mineral oil or polyalphaolefin at temperatures of 150 ° C to 250 ° C, typically under an inert atmosphere. This modification of the polymers of ML any modality of our invention is easily presented, since the unsaturation of the residual isoprene, mainly of the type 3,4, illustrated above, is known to be more reactive with maleic anhydride than with the internal bonds found in EPDM. In addition, the selectively hydrogenated polymer can be functionalized by other methods that increase dispersion, ^ P including but not limited to: grafting olefins containing heteroatoms; formation of Mannich base condensates at unsaturation sites; hydroformylation / reductive amination; addition of nitrosamines or nitrosophenols; lithiation followed by reaction with electrophilic compounds capable of Displacement or addition reactions to provide carboxy, nitrile, or amino groups; 1,3-dipolar addition of nitrile oxides, nitrones, and the like; catalyzed cycle-addition ML light of activated olefins; and light catalyst insertion reactions. The grafting of olefins containing heteroatoms can be carried out by reacting the polymer with a vinyl monomer in the presence of a free radical inhibitor, such as t-butylperoxybenzoate, to directly form a dispersing molecule. Vinyl monomers containing Nitrogen and / or oxygen, such as vinyl imidazole and maleic anhydride, can be used. The number of vinyl monomers attached to the polymer in this manner can be from 1 to 20 or more ^ P by molecular weight of 10,000. Suitable vinyl monomers are described in U.S. Patent Nos. 5,663,126; 5,140,075; 5,128,086; 4,146,489; 4,092,255 and 4,810,754. Free radical initiators are described in the patents of the States United Nos. 5,663,126 and 4,146,489. Any conventional graft method can be used. flP For example, grafts can be made by dissolving the polymer in a solvent, preferably a hydrocarbon solvent, adding a free radical initiator and a vinyl monomer containing nitrogen and / or oxygen. The mixture is heated to obtain a grafted polymer. The grafted polymer can be isolated by conventional methods. For example, the graft copolymer can be converted into a concentrate by the evaporative distillation of the solvent, unreacted vinyl monomer, and the by-products of the reaction. For ease of handling, an oil or mineral diluent can be added before or after the evaporative process. The grafted polymer can be further reacted with an amine, preferably containing at least one group -NH Suitable amines include monoamines, polyamines, amino alcohols, amino acids or derivatives thereof, and 5 amino-terminated polyethers.

The selectively hydrogenated polymer can also be functionalized by Mannich base condensation reaction or chemical modification followed by Mannich base condensation reaction. The polymer is reacted with a phenol to provide a hydroxy aromatic functionalized polymer which is subsequently reacted with an aldehyde or an aldehyde precursor and at least one amino or polyamino compound having at least one -NH group to form a molecule dispersant. The number of phenolic groups (Mannich condensates B) per molecule can be from 1 to 20 or more per molecular weight of 10,000. The amines useful in the preparation of the Mannich condensed dispersants of this invention include monoamines, polyamines, amino alcohols, amino acids or derivatives thereof, and amino-terminated polyethers with the proviso that the amine has at least one -NH group. Suitable aldehydes include branched or linear cyclic aldehydes with from 1 to 10 carbon atoms. Mannich base condensation reactions are described in U.S. Patent Nos. 3,413,347; 3,697,574; 3,634,515; 3,649,229; 3,442,808; 3,798,165; 3,539,633; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 5,102,566 and 5,663,130. Alternatively, the selectively hydrogenated polymer can be functionalized by aminoethylation or hydroformylation followed by reductive amination. The polymer is reacted with carbon monoxide and hydrogen, in the presence of a transition metal catalyst to provide carbonyl derivatives of the polymer. The functionalized polymer is subsequently modified by reductive amination. Useful amines include, but are not limited to, monoamines, polyamines, amino alcohols, amino acids or derivatives thereof, and amino-terminated polyethers with the proviso that the amine has at least one NH group. The number of convenient reaction sites per molecule can be from 1 to 20 or more per molecular weight of 10,000. Aminomethylation and hydroformylation followed by reductive amination are described in U.S. Patent Nos. 3,311,598; 3,438,757; 4,832,702 and 5,691,422. The above description illustrates only some of the potentially valuable chemical modifications of the polymers of this invention. The polymers of this invention provide a means for a wide variety of chemical modifications at selected sites in the polymer, for example, at selected ends, in medium, or randomly, thereby presenting the opportunity to prepare previously impossible materials due to lack of availability of these polymers. Some examples of well-known chemical reactions that can be performed on polymers of this invention are found in E.M. Fettes, "Chemical Reactions of Polymers," High Polvmers, Vol. 19, John Wiley, NY, (1964). Post-Treatment of the Polymers The post-treatment compositions of this invention include those formed by contacting the dispersants of this invention with one or more post-treatment agents to give improved properties to the finished lubricants. These improved properties include improved performance in high-temperature oxidation tests and in large-scale related tank and wear machinery testing. Suitable post-treatment agents include boronating agents; phosphorylating agents; sulfonating oxidizing agents and alkaline earth metal carbons; and oxidizing, sulfating and sulfonating agents of metals IB and IIB. Suitable boronating agents or compounds that contain boron include boron acids, particularly boric acid or metaboric acid, boron oxide, boron oxide hydrate, boron esters, boron salts, particularly a borate _ ^ ammonium and boron halides. Suitable phosphorylating agents include a Organic phosphorus acid, such as phosphorous acid and phosphoric acid, an anhydride thereof, a partial or complete sulfur analogue thereof and an organic acid phosphate, such as 2-ethylhexyl acid phosphate. The alkaline earth oxidizing, sulfonating and carbonating agents include calcium oxide, calcium sulfonate, calcium carbonate, barium oxide, barium sulfonate and barium carbonate. Suitable oxidizing, sulfating and sulfonating agents of metals IB and IIB include zinc sulfate, zinc oxide, zinc sulphonate and coprosed oxide. Post-treatment agents and the methods by which they can be used to effect post-treatment of ash dispersants are described in U.S. Patent Nos. 5,464,549 and 4,234,435. Applications of Dispersants and Viscosity Index Meters The polymers of the invention, whether block copolymers, reduced block copolymers, branched and branched star polymers, or random copolymers, have been found to have an unexpected ability to modify properties. of dispersion and / or viscometric of the fluids, such as lubricants of mineral and synthetic oil and liquid fuels normally. Accordingly, it is within the scope of the invention that the dispersing polymers of the invention are employed in dispersing substances that can be added in fluids to modify the dispersion and / or the viscometric properties of the fluids. The invention, thus, also includes a method for modifying and improving the dispersion and / or the viscometric properties of a fluid by mixing with the fluid a sufficient amount of a dispersing substance of the invention to obtain or provide a modified or improved fluid that has a modified or improved dispersion and / or viscometric properties. Moreover, the invention also includes modified dispersant or improved dispersant fluids to which a dispersing substance of the invention has been added to modify the dispersion and / or the viscometric properties of the fluid. The improvement of the viscometric properties includes any one or more of the properties of fluids that are related to the viscosity. The viscosity index improvers of the invention specifically improve the viscosity index of these fluids. The viscosity index is a property that characterizes the relationship between fluid viscosity and temperature. The improvement in the viscosity index is characterized by a decrease in the speed of change of the viscosity per unit of temperature change. Typical properties that are modified or improved by the viscosity index improvers of dispersants of the invention include relative thickening power (RTP) boundary line pumpability, permanent shear stability (DIN) temporary shear stability at low temperatures (CCS), and temporary high temperature shear stability (HTHS).

Each of these properties can be determined or characterized by conventional methods. The polymers of the invention can be employed as dispersants and / or viscosity index improvers of dispersant in a variety of lubricating fluids. Typically, this fluid is a mineral oil such as a mineral oil lubrication system, for example, engine oils, automatic transmission fluids, tractor hydraulic fluids, gear oils, aviation oils, and the like. Other convenient applications include liquid fuels normally. The lubricant or fuel can occur naturally or be synthetic, or a combination thereof. Natural oils include mineral oils obtained from petroleum, including distilled and residual lubricating oils and the like. Synthetic oils may include synthetic hydrocarbon fluids eg, PAO, liquid esters, fluorocarbons, polyethers, polysilicones, and the like. The dispersants can be added to a lubricant or fuel formulation of any convenient and effective amount to modify the dispersion and / or the viscometric properties of the formulation. An exemplary broad range is from 0.001 weight percent to 20 weight percent, preferably from 0.1 weight percent to 10 weight percent, most preferably from 0. 5 weight percent to 7 weight percent of the formulation. The polymers of the invention can be supplied clean or as an oil concentrate for ease of handling.

Typically, these dispersant concentrates include a polymer of the invention in an amount of from 5 weight percent to 90 weight percent, preferably 10 weight percent to 70 weight percent, of the concentrate. In addition to the polymers described in this invention, the dispersant formulations and fluid formulations may also include one or more additional additives known to those skilled in the art. These additives include, for example, anti-oxidants, pour point depressants, detergents, dispersants, friction modifiers, anti-wear agents, viscosity index improvers, anti-foaming agents, corrosion and rust inhibitors, and so on. Undoubtedly, it is among the advantages of the compositions of the invention that they are unusually efficient modifiers of dispersion and / or viscometric properties, such as in many cases significantly less of these additives need to be added to achieve a desired combination of fluid properties. Emploses The following examples are intended to help further understand the invention. The particular materials and conditions employed are intended to be more illustrative of the invention but not limiting after the reasonable scope thereof. In the following examples, the polymerization and functionalization work was carried out with dry reactors and equipment under strictly anaerobic conditions. Extreme care must be used to exclude air, moisture and other impurities capable of interfering with the delicate chemical balance involved in the synthesis of the polymers of this invention, such as • apparent to those skilled in the art. Example I: Preparation of Core Structures B-I-B Using a process according to U.S. Patent No. 5,633,415, Example V, a tri-block butadiene-isoprene-butadiene polymer having a molecular weight of 15,000 is prepared. Eight thousand seven hundred millimeters (8700) of purified pentane are introduced under a nitrogen atmosphere into a nineteen liter stainless steel reaction vessel. The reactor is equipped with a belt-driven stirrer, a pressure gauge, thermocouple, heat exchange reactor jacket, inlet valve on the upper surface, addition facilities in the sub-surface, and a disk of ^ L pressure (7.75 kg / cm2). Ten milliliters of 0.1 M dipyridyl in cyclohexane solution was added to the reactor together with 150 milliliters of anhydrous tetrahydrofuran. The solution was heated to 50 ° C and titrated with 1.6M n-butyl lithium until an orange / red color persisted. Then 228 milliliters of n-butyl lithium were added, followed by butadiene (4.370 grams, 7.030 milliliters, 80.7 moles), which was added over 1.2 hours.

When the butadiene addition was complete, and after a 15 minute wait, isoprene (1090 grams, 1600 milliliters, 16.0 moles) was added over 20 minutes. After the addition of isoprene was complete, the reaction mixture was maintained for another 15 minutes, and another block of butadiene was polymerized (4370 grams, 7030 milliliters, 80.7 moles). After this addition, the mixture was maintained for another 15 minutes and the living polymer anions were buffered with acetic acid. This gave a polymer of 15,000 molecular weight and polydispersity (Mw / Mn) of 1.01 (Polymer A). The process was also used to produce a polymer of molecular weight 30,000 and 1.18 Mw / Mn (Polymer B) by a 50 percent reduction in polymerization initiator concentration of n-butyl lithium. Example II Selective Hydrogenation of the Polymers of Example I The polymer solutions of Example I were subjected to a selective hydrogenation process using a ^ fc catalyst prepared by triethylaluminum and cobalt octoate (3.5 to 1 molar ratio and 0.35 M in cobalt) according to the Example VI of U.S. Patent No. 5,633,415. The reactor nitrogen was removed under reduced pressure and hydrogen was introduced at a pressure of 2.1 kg / cm2. The mixture was heated to 68 ° C and stirred at 500 rpm. Twenty-eight (28) milliliters of catalyst were added followed by hydrogen at a maximum speed of 0.5 scfm. The temperature of the reaction was maintained between 68 ° C and 82 ° C. The degree of hydrogenation was followed by infrared Fourier transfer (FTIR) k and continued until the spectrum showed minimal transbutadiene unsaturation (968 cm "1) and complete disappearance of vinyl absorptions (910, 990 cm" 1). The catalyst was removed by precipitation with acetic acid (49 milliliters) and 30 percent hydrogen peroxide (2 milliliters). The temperature was maintained at 67 ° C for 60 minutes with agitation 250 rpm. The stirring was stopped, the solution was filtered, and the polymer was isolated by removing the solvent under reduced pressure. Gel permeation chromatography (GPC) was used to determine the molecular weight of the final polymer after selective hydrogenation. Polymer Mn Mw / Mn A 15000 1.01 B 30000 1.18 Thus, although what was presently believed to be the preferred embodiments of the present invention was described, those skilled in the art will realize that other modalities can be made without departing from the spirit of the invention, and it is intended to include all these modifications and changes within the true scope of the claims presented herein.

Claims (10)

1. CLAIMS 1. A block copolymer, comprising at least ML three (3) alternating blocks of a first conjugated diene and a second conjugated diene, wherein: said first conjugated diene comprises at least one relatively less substituted conjugated diene different from the first diene conjugate and having at least four carbon atoms and the formula: R7-C-C-C-C-R12 (3) f R8 R9 R10 R11 where R7-R12 each is hydrogen or a hydrocarbyl group, with the proviso that after polymerization, the unsaturation of the polymerized conjugated diene of formula (3) has the formula: RVI Rv-C = C-RVI11 (4) 20 RVII where Rv, RVI, RVI1 and RVI11 are each hydrogen (H) or a hydrocarbyl group, with the proviso that one of Rv or RVI is hydrogen, one of RVI1 or RVI11 is hydrogen, and at least one of Rv, RVI, RVI1 and RVIXI is a hydrocarbyl group; and said second conjugated diene comprises at least one relatively more substituted conjugated diene having at least five carbon atoms and the formula: R 1 C C - R 6 (1) R 3 R 4 R 4 • where Rx-R6 each is hydrogen or a hydrocarbyl group, with the proviso that at least one of R1-R6 is a hydrocarbyl group, and also with the proviso that, after polyaerization, the unsaturation of the polymerized conjugated diene of formula (1) has the formula: R11 R1 - C = C - R111 (2) R? v 15 where RI # R11, R111 and RIV each is hydrogen or a hydrocarbyl group, with the proviso that either R1 and R11 are hydrocarbyl groups or both R111 and RIV are hydrocarbyl groups; and wherein said first and second conjugated dienes are polymerized as a block copolymer comprising at least three (3) alternating blocks: Mk (B) and- (I) X- (B) Z where: the block (s) (B) ) comprise at least one polymerized conjugated diene 25 of the formula (3); the block (I) comprises at least one polymerized conjugated diene of the formula (1); x is the number of monomeric units polymerized in block (I) and is at least 1; and is the number of monomeric units polymerized in block (B) and is at least 25; and z is the number of monomeric units polymerized in block (B) and is the same or different as selectively hydrogel primary block (B) of said copolymer to provide a selectively hydrogenated copolymer, where said blocks (B) are the blocks terminals of said copolymer.
2. 2. The composition of claim 1, wherein the copolymer has a molecular weight in the range of 2,000 to 1,000,000.
3. The composition of claim 1, wherein the first conjugated diene is included in the polymer in an amount of 75 to 99% by weight; and the second conjugated diene is included in the polymer in an amount of 1 to 25% by weight.
4. 4. The composition of claim 1, wherein after the step of selective hydrogenation, the Iodine Number for the residual unsaturation of the block (s) (I) is 50 to 100% of the Iodine Number before the step of selective hydrogenation.
5. The composition of claim 1, wherein after the step of selective hydrogenation, the Iodine Number for the residual unsaturation of the block (s) (I) is from 0 to 10% of the Iodine Number before the step of selective hydrogenation.
6. 6. The composition of claim 1, wherein the conjugated diene of the formula (1) comprises 1,3-butadiene.
7. 7. The composition of claim 6, wherein the conjugated diene of the formula (3) comprises isoprene.
8. The composition of claim 7, wherein each of the blocks (B) has from 25 to 90% of 1,2 subunits.
9. 9. The composition of claim 7, wherein each of the blocks (I) has from 10 to 90% of 3.4 subunits.
10. 10. The composition of claim 9, wherein each of the blocks (I) has from 50 to 90% of 3.4 subunits. Summary The invention provides dispersants and enhancers of the ^^ viscosity index of dispersants, including polymers of conjugated dienes that have been hydrogenated, functionalized, optionally modified and post-treated. Dispersant substances include a copolymer of two different conjugated dienes, such as butadiene-isoprene-butadiene. The polymers are selectively hydrogenated to produce polymers that have highly controlled amounts of unsaturation, '^ P allowing highly selective functionalization. Lubricating fluids are also provided, such as mineral and synthetic oils, which have been modified in their dispersancy and / or viscometric properties by means of the dispersing substances of the invention. Methods of modifying the 15 dispersancy and / or viscometric properties of lubricating fluids such as mineral and synthetic lubricating oils. Dispersing substances can also include a carrier fluid MLt to provide dispersant concentrates.