MXPA06010963A - Polymers with h-bridge forming functionalities - Google Patents

Abstract

The invention relates to graft copolymers produced by radically polymerising polymerisable monomers and, in addition comprising long-chain ethylenically unsaturated compounds which contain alkyl substitutes, in particular acrylates or methacrylates and monomers with hydrogen bridge donator functions. According to said invention, said hydrogen bridge donator monomer is introduced into a polymer backbone and into graft side branches. The inventive polymers are particularly usable for lubricating oil formulations.

Description

Polymers with functionalities forming the bridge H Field of the invention The present application deals with grafted copolymers which are formed from radically free polymerizable monomers and which, in addition to ethylenically unsaturated compounds substituted by long alkyl chains, especially acrylates or methacrylates, also they also comprise monomers with hydrogen bond donor functions. According to the invention, the monomer with the hydrogen bond donor property is present in both the marrow of the polymer and the grafted side branches. In addition to the monomer-containing polymers with hydrogen bond donor function, those containing monomers which simultaneously carry hydrogen bond donor functions and the hydrogen bond acceptor function are also disclosed. The polymers are particularly suitable as additives for lubricating oil formulations. It has been found that the hydrogen bond donor functions in the polymer, but in particular the simultaneous presence of the hydrogen bond donor and acceptor functions, have positive effects on protection against wear, detergency and dispersancy. State-of-the-art technology Polyalkyl acrylates are common polymeric additives for lubricating oil formulations. Long alkyl chains (typical chain length: C8-C18) in the ester functionalities of acrylate monomers impart good solubility in apolar solvents, for example mineral oil, to polyalkyl acrylates. Common fields of use of additives are hydraulic oils, for transmission or for engines. An optimizing action of the viscosity index (VI) is attributed to the polymers, from which the name VI improvers originates. A high viscosity index means that an oil has a relatively high viscosity at high temperatures (for example in a typical range of 70-140 ° C) and a relatively low viscosity at low temperatures (for example in a typical range of -60 to 20 ° C). The improved lubricity of an oil at high temperatures compared to an oil which does not contain polyacrylates having otherwise an identical kinematic viscosity, for example at 40 ° C is caused by a higher viscosity in the increased temperature range. At the same time, in the case of the use of a VI improver at relatively low temperature, when it is present, for example, during the cold start phase of an engine, a lower viscosity is recorded compared to an oil which another mode has a kinematic viscosity identical to 100 ° C. As a result of the lower viscosity of the oil during the starting phase of an engine, a cold start is thereby substantially improved. In recent times, polyacrylate systems that, like VI optimization, provide additional properties, for example dispersancy, have been established in the lubricant industry. Either alone or together with dispersant inhibitor additives (DI) used specifically for dispersancy purposes, such polymers have the effect, among other things, that the oxidation products that occur as a result of stress in the oil contribute less to a Damaging viscosity increase. By means of the improved dispersion capacity, the service life of a lubricating oil can be increased. By virtue of their detergent action, said additives likewise have the effect that cleaning the motor, for example expressed by cleaning the pistons or seizing rings, is positively influenced. The products of oxidation are, for example, soot or sediments. In order to impart dispersancy to the polyacrylates, the nitrogen-containing functionalities can be incorporated into the side chains of the polymers. Common systems are polymers that carry ester side chains partially functionalized with amine. Frequently, dialkylamine substituted methacrylates, their methacrylamide analogues or N-heterocyclic vinyl compounds are used as comonomers to improve dispersibility. Another class of monomer types that must be mentioned due to their dispersibility in lubricants is that of acrylates with ethoxylate or propoxylate-containing functions in the ester substituents. The dispersible monomers may be present in the polymer in a casual manner, ie they are incorporated into the polymer in a conventional copolymerization or otherwise grafted onto a polyacrylate, which results in systems with a non-random structure. To date, research has not been carried out for polyacrylates which, in addition to the known advantages in relation to detergency dispersancy, also offer advantages in relation to the reduction of wear. EP 164 807 (Agip Petroli S.p.A.) describes a multifunctional VI improver with dispersancy, detergency and low temperature action. The composition of VI improvers corresponds to VP grafted polyacrylates which additionally contain acrylates difficult to prepare with ethoxylated radicals containing amines. DE-A 1 594 612 (Shell Int. Research Maatschappij N.V.) discloses lubricating oil blends comprising oil soluble polymers with carboxyl groups, hydroxyl groups and / or nitrogen containing groups and a dispersed salt or hydroxide of an alkaline earth metal. As a result of the synergistic mode of action of these components, a wear reducing action is observed. United States Patent 3153640 (Shell Oil Comp.) Includes copolymers consisting of long chain esters of methacrylic acid and N-vinylactams, which show a beneficial influence on wear in lubricating applications. The polymers described are random copolymers. Monomers that function as hydrogen bond donors and graft copolymers are not mentioned. In the operations of ASLE (1961, 4, 97-108), E.H. Okrent states that the polyisobutylenes or polyacrylates used as VI improvers have had an influence on the wear behavior of the engine. No interference is made in the chemistry used and the specific composition of the polymers. The wear reducing action is formulated only with the viscoelastic effects of the oils with polymer content. For example, no difference is detected between oils with polyacrylate content as those with a GDP content in the influence on wear. Literature publications by Neudorf and Schdel (Schmierungstechnik 1976, 7, 240-243, SAE Paper 760269, SAE Paper 700054, Die Angewandte Makromolekulare Chemie 1970, 2, 175-188) emphasize in particular the influence of concentration polymer in the wear of the engine. HEY. Okrent refers to the aforementioned article and in analogy with Okrent, no connection of a wear-enhancing action with the polymer chemistry is performed. In general, it is concluded that the best ones of the low molecular weight viscosity index bring improved wear results. Like Neudórfl and Schódel, K. Yoshida (Tribology Transactions 1990, 33, 229-237) attributes effects of polymers on wear behavior only for viscometric aspects. The beneficial effects are explained by giving preference to the formation of the elastohydrodynamic film. Almost without exception, the polymers known in the prior art are formed from monomers whose dispersing functionalities comprise groups which are hydrogen bond acceptors (hereinafter referred to as H-bond acceptors), or, like dimethylaminopropylmethacrylamide, both have a functionality with the hydrogen bond acceptor and a functionality with the hydrogen bond donor (hereinafter referred to as the donor of the H bond). It is another feature of such polymers useful for motor oil applications that the N-heterocycle-bearing monomers have preferably been grafted into the marrow of the polymer. The polymers containing dimethylaminopropylmethallylamide are, in contrast, random copolymers and non-copolymers grafted. It was therefore an object of the present invention to provide novel graft copolymers containing monomers with H-bond donor functions, to provide multifunctional VI improvers which, in lubricating oil formulations, are remarkably not only for their action in VI but also for its dispersancy and / or detergency, provide multifunctional VI improvers which, in lubricating oil formulations, are remarkable not only for their action in VI but also for their positive influence on wear behavior, to provide a universally applicable process for preparing grafted copolymers containing grafted monomers with binding donor functions H. provide lubricants comprising the graft copolymers of the invention with improved properties in relation to protection against wear, dispersancy and detergency, corrosion behavior and stability in oxidation.

These objectives, and also other objectives that are not explicitly stated but can be obtained or discerned directly from the connections discussed by means of introduction in the present are achieved through a graft copolymer that contains, in the marrow, polymerized units. radically free from a) from 0.01 to 15% by weight of a compound of the formula (I) wherein Ri, R2 and R3 can each independently be hydrogen or an alkyl group having from 1 to 5 carbon atoms and R4 is a group having one or more structural units capable of forming hydrogen bonds and is a donor of hydrogen, and b) from 0 to 40% by weight of one or more methacrylates of the formula (II) wherein R is hydrogen or methyl and R5 is a linear or branched alkyl radical having from 1 to 5 carbon atoms. c) from 35 to 99.99% by weight of one or more ethylenically unsaturated ester compounds of the formula (III) wherein R is hydrogen or methyl, R8 is a linear, cyclic or branched alkyl radical having from 6 to 40 carbon atoms, R6 and R7 each are independently hydrogen or a group of the formula -COOR8 wherein R8 is hydrogen or a linear, cyclic or branched alkyl radical having from 6 to 40 carbon atoms, and d) from 0 to 40% by weight of one or more comonomers, wherein the percentage by weight of the above components is based on the total weight of the ethylenically unsaturated monomers of the marrow and where a ') from 0.01 to 25% by weight based on the total weight of the copolymer, of a compound of the formula (I) wherein R1, R2 and R3 can each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms and R4 is a group having one or more structural units capable of forming hydrogen bonds and is a donor of hydrogen, and b ') from 0 to 20%, based on the total weight of the copolymer, of one or more compounds of the formula (IV) wherein R9, R10 and R11, each independently can be hydrogen or an alkyl group having from 1 to 5 carbon atoms and R12 is a group of C (O) OR13 and R13 is a linear or branched alkyl radical which is substituted by at least one group -NR14R15 and has from 2 to 20, preferably from 2 to 6 carbon atoms, where R14 and R15 are each independently hydrogen, an alkyl radical has from 1 to 20, preferably from 1 to 6 and where R14 and R15, including the nitrogen atoms and, if another nitrogen or oxygen atom is present, form a ring of 5 or 6 elements which optionally can be substituted by alkyl of 1 to 6 carbon atoms, or R12 is a group NR1SC (= 0) R17 where R16 and R17 together form an alkylene group having from 2 to 6, preferably from 2 to 4 carbon atoms, where these form a ring of 4 to 8 elements, preferably 4 to 6 elements, saturated or unsaturated, if appropriate include another nitrogen atom or oxygen no, where this ring also optionally be substituted by alkyl of 1 to 6 carbon atoms, are grafted into the marrow of the copolymer. Appropriate modifications of the graft copolymers of the invention are protected in the secondary claims depending on claim 1. With respect to the process for preparing the grafted copolymers, claims 10 to 14 establish solutions for the underlying problems while the claims 15 a 17 protect a lubricating oil formulation using the graft copolymers prepared according to the present invention and also the preferred uses thereof. Benefits of the invention The polymers of the invention with functions of donor of the bond of hydrogen in the polymer, especially the polymers with simultaneous presence of the functions of donor and acceptor of the hydrogen bond, have positive effects on the protection against wear, the detergency and dispersancy of the lubricating oil formulations produced therewith. Thus, the polymers constitute an alternative or supplement for reduction of wear to the phosphorus and sulfur additives customary in the industry and help to avoid their known disadvantages. In particular, the benefits obtained in the wear behavior have a positive effect on energy consumption, for example of a diesel or gasoline engine. The formulations produced using the graft copolymers of the invention exhibit good anti-corrosion behavior and also good resistance to oxidation. The kinematic viscosity of the polymer solutions comprising grafted methacrylic acid according to the invention has been substantially reduced as compared to the comparable polymer which exclusively contains methacrylic acid in the medulla of the polymer. The disclosed process for preparing grafted copolymers leads to homogeneous polymer solutions of transparent appearance and demonstrates that the principle of synthesis presented in this document is universal in nature, ie it can be applied not only for the introduction of carboxylic acids but also, for example , with carboxamides. At the same time, the process according to the invention allows a number of other benefits to be obtained. These include: >; = > With respect to pressure, temperature and solvent, the result of the polymerization to a certain extent presents no problems; Even at moderate temperatures, acceptable results are achieved under certain conditions. < X > The process according to the invention has few side reactions. > = > The process can be carried out inexpensively. "=! > With the help of the process according to the invention, large productions can be achieved." = > With the aid of the process of the present invention, it is possible to prepare polymers with a predefined constitution and controlled structure. Polymers having VI and dispersing action and which to date have been used in motor oils, as discussed above, preferably comprise monomer types with H-bond acceptor functionalities, which are especially N-heterocycles. Therefore, it can not be predicted directly that the use of monomers with H-bond donor properties leads to polymers possessing the improved properties described. As it is known from the prior art that the grafting of monomers with H-bond donor functions into polyalkyl acrylates is generally difficult, it is not immediately foreseen that the grafting of this type of monomers to polyacrylates can be achieved without any problem and with a wide variety of applications when, before grafting, a small portion of one of these monomers has been incorporated into the marrow of the polyacrylate by polymerization. It is especially amazing that the grafting performed more than once in succession was even possible, without the formation of unusable products. This in particular is contrary to the background that corresponding synthesis attempts according to the prior art allow inhomogeneous products that have a cloudy appearance. DETAILED DESCRIPTION OF THE INVENTION The grafted copolymers contain, as components, one or more compounds of the formula I wherein R1, R2 and R3 can each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms and R4 is a group having one or more structural units capable of forming hydrogen bonds and is a donor of hydrogen. The definition of a functionality as a group with hydrogen bond acceptor or hydrogen bond donor action can be taken from current literature or known chemical reference works, for example "Ropp Lexikon Chemie, lOth edition, 1999 , Verlag Thieme Stuttgart New York ". According to the present, a hydrogen bond (H bond) is an important form of secondary valence bond that is formed between a hydrogen atom covalently attached to an atom of an electronegative element (hydrogen bond donor, proton donor , X) and the pair of solitary electrons from another electronegative atom (proton acceptor, Y). In general, said system is formulated as RX-H ... YR ', where the dotted line symbolizes hydrogen bonding. X and Y possible are mainly O, N, S and halogens. In some cases (for example HCN), C can also function as a proton donor. The polarity of the covalent bond of the donor causes a partial positive charge, d +, of the hydrogen (proton), while the acceptor atom carries a corresponding negative partial charge, d "The characteristic, structural and spectroscopic properties of a complex linked through a hydrogen bond are: a) The distance rH? is distinctly less than the sum of the van der aals radii of the H and Y atoms. b) The separation of the equilibrium number XH is lengthened in comparison to the free molecule RX -H. c) XH elongation vibration (donor elongation vibration) undergoes a change to longer wavelengths ("redshift") .In addition, its intensity increases distinctly (in the case of relatively H bonds). strong, in more than one order of magnitude) d) Due to mutual polarization, the dipole moment of the complex linked with H bond is greater than corresponds to the sum of the vectors of the moments dipoles of the constituents. e) The density of the electrons in the hydrogen bonding atom is reduced in the case of formation of a hydrogen bond. This effect is expressed experimentally in the form of reduced NMR changes (reduced proton protection). At relatively short intermolecular distances, the envelopes of the electrons of the monomers overlap. In this case, a chemical bond associated with some charge transfer of the bond type of 3 centers, 4 electrons can be formed. Additionally, repulsion of the exchange is present, because the Pauli principle keeps the electrons separated with identical turns and prevents two monomers from getting too close. The dissociation energies D0 =? H0 (molar enthalpies of the reaction RX-H ... YR '? RX-H + YR' at the absolute zero point) are generally between 1 and 50 kJ mol "1. experimental, thermochemical measurements (2 virial coefficients, thermal conductivities) or spectroscopic analyzes are used (more on this topic can be seen in "Chem. Rev. 88, Chem. Phys. 92, 6017-6029 (1990)). For hydrogen atoms of structural units that are capable of forming H bonds and are an H donor, it is characteristic that they bind to relatively electronegative atoms, for example oxygen, nitrogen, phosphorus or sulfur. The terms "electronegative" or "electropositive" are familiar to those skilled in the art as a designation for the tendency of an atom in a covalent bond to attract the pair or pairs of valence electrons towards it in the sense of an asymmetric distribution of the electrons, which forms a dipole moment. A more detailed discussion of the terms "electronegativity" and "hydrogen bonds" can be found for example in "Advanced Organic Chemistry", J. March, th edition, J. Wiley & amp;; Sons, 1992. In some dimers, more than one hydrogen bond is formed, for example in dimers of carboxylic acids that form cyclic structures. Cyclic structures are often energetically favored in higher oligomers, for example in methanol oligomers above trimers. The dissociation energy of the trimer in 3 monomers at 52 kJ mol "1 is almost four times as great as that of the dimer.Non-adhesion at the dissociation energies per monomer is a typical property of hydrogen-bonded complexes. In the case of H-bonding functionalities, the present invention deals in particular with groups containing heteroatoms, where the heteroatom is preferably O, N, P or S. Even when a carbon-hydrogen bond theoretically may also work as an H-bond donor, such functions will not fall within the scope of the claims formulated herein, for functionalities with link donor function. Monomers with H-bond donor fusions are, for example, ethylenically unsaturated carboxylic acids and all its derivatives which continue to have at least one free carboxyl group, examples of which are: acrylic acid, metracrylic acid lico, 1- [2- (isopropenylcarbonyloxy) ethyl] maleate (monoester of 2-hydroxyethyl methacrylate (HEMA) and maleic acid), l- [2- (vinylcarbonyloxy) ethyl] aleate (monoester of 2-hydroxyethyl acrylate (HEA) and maleic acid), 1- [2- (isopropenylcarbonyloxy) ethyl] succinate (monoester of HEMA and succinic acid), 1- [2- (vinylcarbonyloxy) ethyl] succinate (monoester of HEA and succinic acid), 1- [2- ( isopropenylcarbonyloxy) ethyl] phthalate (monoester of HEMA and phthalic acid), 1- [2- (vinylcarbonyloxy) ethyl] phthalate (monoester of HEA and phthalic acid), 1- [2- (isopropenylcarbonyloxy) ethyl] hexahydrophthalate (monoester of HEMA and hexahydrophthalic acid) 1- [2- (vinylcarbonyloxy) ethyl] hexahydrophthalate (monoester of HEA and hexahydrophthalic acid), 1- [2- (isopropenylcarbonyloxy) butyl] maleate (monoester of 2-hydroxybutyl methacrylate (HBMA) and maleic acid), - [2- (vinylcarbonyloxy) butyl] maleate (2-hydroxybutyl acrylate monoester (HBA) and maleic acid), 1- [2- (isoprope nylcarbonyloxy) butyl] succinate (monoester of HBMA and succinic acid), 1- [2- (vinylcarbonyloxy) butyl] succinate (monoester of HBA and succinic acid), 1- [2- (isopropenylcarboxyloxy) butyl] phthalate (monoester of HBMA and phthalic acid), 1- [2- (vinylcarbonyloxy) butyl] phthalate (monoester of HBA and phthalic acid), 1- (2- (isopropenylcarbonyloxy) butyl] hexahydrophthalate (monoester of HBMA and hexahydrophthalic acid), 1- [2-vinylcarbonyloxy] butyl] hexahydrophthalate (monoester of HBA and hexahydrophthalic acid), fumaric acid, methyl-fumaric acid, mono-esters of fumaric acids and other derivatives, maleic acid, methylmaleic acid, monoesters of maleic acid or its derivatives, crotonic acid, itaconic acid, acrylamidoglycolic acid, methacrylamidobenzoic acid, cinnamic acid, vinylacetic acid, trichloroacrylic acid, 10-hydroxy-2-decenoic acid, 4-methacryloyloxyethyltrimethyl acid, styrenecarboxylic acid. Particular preference is given to acrylic acid and methacrylic acid. Other suitable monomers with H-bond donor function are acetoacetate-functionalized compounds (for example, LONZAMON® AAEMA from Lonza) ethylenically unsaturated, for example 2-acetoacetoxymethyl methacrylate or 2-acetoacetoxyethyl acrylate. These compounds may be present at least partially in the tautomeric enol form. Also suitable as monomers with H-bond donor function are all ethylenically unsaturated monomers having at least one sulfonic acid group and / or at least one phosphonic acid group. All of these are organic compounds having at least one ethylenic double bond and at least one sulfonic acid group and / or at least one phosphonic acid group. They include, For example: 2- (isopropenilcarboniloxi) ethanesulfonic acid, 2- (vinilcarboniloxi) ethanesulfonic acid, 2- (isopropenilcarboniloxi) propylsulfonic acid, 2- (vinilcarboniloxi) propylsulfonic, acrylamido-2-methylpropanesulfonic 2-, acrilamidododecanosulfónico acid, 2 -propen-1-sulfonic acid, methallyl sulfonic acid, styrenesulfonic acid, estirenodisulfónico acid, metacrilamidoetanofosfónico acid, vinylphosphonic acid, 2- fosfatoetil methacrylate, 2-sulfoethyl methacrylate, acids O-alquenocarboxílieos as 2-hydroxy-4-pentenoic acid, 2-methyl -4-pentenoic, 2-n-propyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 4-pentenoic acid, 5-hexenoic acid, acid. 6-heptenoic, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, acid 16-heptadecenoic, 17-octadecenoic acid, 22-tricosenoic acid, 3-butene-1, 1-dicarboxylic acid. It is also suitable that the monomers are the acid amides, which are known, as well as the carboxylic acids, because they can act at the same time as both H-bond donors and H-bond acceptors. The unsaturated carboxamides can carry either one amide moiety unsubstituted or an optionally monosubstituted carboxamide group. Suitable compounds are, for example: methacrylic acid amides and N-alkyl-substituted methacrylamides such as N- (3-dimethylaminopropyl) methacrylamide, N- (diethylphosphono) methacrylamide, l-methacryloylamido-2-methyl-2-propanol, N- ( 3-dibutylaminopropyl) methacrylamide, Nt-butyl-N- (diethylphosphono) methacrylamide, N, N-bis (2-diethylaminoethyl) methacrylamide, 4-methacryloylamido-4-methyl-2-pentanol, N- (butoxymethyl) methacrylamide, N- (methoxymethyl) methacrylamide, N- (2-hydroxyethyl) methacrylamide, N-acetilmetacrilamida, N- (dimethylaminoethyl) methacrylamide, N-methyl methacrylamide, N-methacrylamide, methacrylamide, acrylamide, N-isopropylmethacrylamide, aminoalkyl methacrylates such as tris (2 -metacriloxietil) amine, N-metilformamidoetil methacrylate, N-phenyl-N '-metacriloilurea, N-metacriloilurea, 2-ureidoethyl methacrylate, N- (2-methacryloyloxyethyl) etilenourea methacrylates heterocyclic groups such as 2- (1-imidazolyl) -ethyl methacrylate, 2- (4-morpholinyl) ethyl methacrylate, 1- (2-methacrylate) loyloxyethyl) -2-pyrrolidone, furfuryl methacrylate. Carboxylic esters also suitable as donors will link H are: 2-tert-butylaminoethyl methacrylate, N-metilformadioetil methacrylate, 2-ureidoethyl methacrylate, methacrylates heterocyclic groups such as 2- (1-imidazolyl) ethyl methacrylate, 1- (2-methacryloyloxyethyl) -2-pyrrolidone. Hydroxyalkyl methacrylates such as 3-hydroxypropyl methacrylate, 3-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol methacrylate, 1, 10-decanediol methacrylate, 1, 2 methacrylate propanediol; polyoxyethylene and polyoxypropylene derivatives of methacrylic acid such as triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate and tetrapropylene glycol monomethacrylate. Methacryloylhydroxamic acid, acryloylhydroxamic acid, N-alkylmethacryloylhydroxamic acid, N-alkylacryloylhydroxamic acid, reaction product of methacrylic or acrylic acid with lactams, for example with caprolactam, reaction product of methacrylic or acrylic acid with lactoses, for example with caprolactone; reaction product of methacrylic or acrylic acid with acid anhydrides; reaction products of matracrilamide or acrylamide with lactam for example with caprolactam, reaction product of matacrilamide or acrylamide with lactones for example with caprolactane; reaction product of methacrylamide or acrylamide with acid anhydrides. The content of the compounds having one or more structural units capable of forming H bonds and giving H's has 0.01 to 15% by weight, preferably 0.1 to 10% by weight and more preferably 0.5 to 8% by weight , based on the total weight of the ethylenically unsaturated monomers of the marrow of the graft copolymer. The grafted copolymers of the invention contain, as another component of the marrow, compounds of the formula II where R is hydrogen or methyl and R5 is a linear or branched alkyl radical having from 1 to 5 carbon atoms. Examples of the components of formula II include methacrylates originating from unsaturated alcohols, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate and pentyl methacrylate; Cycloalkyl methacrylates such as cyclopentyl methacrylate; Methacrylates which are produced from unsaturated alcohols, such as 2-propynyl methacrylate and allyl methacrylate, vinyl methacrylate. The content of the methacrylates of the formula (II) is from 0 to 40% by weight from 0.1 to 30% by weight or from 1 to 20% by weight, based on the total weight of ethylenically unsaturated monomers of the copolymer marrow grafted. The grafted copolymers of the invention comprise, as another component of the marrow, one or more of the ethylenically unsaturated ester compounds of the formula III where R is hydrogen or methyl, R8 is a linear, cyclic or branched alkyl radical having from 6 to 40 carbon atoms, R6 and R7 are each independently hydrogen or a group of the formula -COOR8 where R8 is hydrogen or a linear, cyclic or branched alkyl radical having from 6 to 40% carbon atoms. These compounds of the formula (III) include methacrylates, maleates and fumarates, each of which has at least one alcohol radical having from 6 to 40 carbon atoms. Preference is given in the present to the methacrylates of the formula (Illa) where R is hydrogen or methyl and R1 is a linear or branched alkyl radical having from 6 to 40 carbon atoms. When the term "methacrylates" is used in the context of the present application, this term in each case encompasses methacrylates or acrylates alone or otherwise in mixtures of the two. These monomers are widely known. These include. methacrylates derived from saturated alcohols, such as hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, 2-tert-butylheptyl methacrylate, octyl methacrylate, 3-isopropylheptyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate , dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, 2-methylhexadecyl methacrylate, heptadecyl methacrylate, 5-isopropylheptadecyl methacrylate, 4-tert-butyloctadecyl methacrylate, 3-ethylctadecyl methacrylate, 3-isopropyloctadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, cetyleicosyl methacrylate, stearylene methacrylate, docosyl methacrylate and / or eicosyltetratriacontyl methacrylate; methacrylates derived from unsaturated alcohols, for example oleyl methacrylate; cycloalkyl methacrylates such as 3-vinylcyclohexyl methacrylate, diclohexyl methacrylate, bornyl methacrylate. The ester compounds with long-chain alcohol radical can be obtained, for example, by reacting the methacrylates, fumarates, maleates and / or the corresponding acids with long-chain fatty alcohols which generally form a mixture of esters, for example methacrylates with various long chain alcohol radicals. These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanol® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 Sasol; Epal® 610 and Epal® 810 from Ethyl Corporation; and Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell Ag; Lial 125® by Sasol; Dehydad® and Lorol® by Henkel KGaA and Linopol® 7-11 and Acropol® 91. The long-chain alkyl radicals of the methacrylates of the formula (III) generally have from 6 to 40 carbon atoms, preferably from 6 to 24 carbon atoms and more preferably from 8 to 18 carbon atoms and they can be linear, ramified, linear / branched mixed fractions or cyclic fractions. The preferred embodiment is to use a mixture of methyl methacrylate and alkyl methacrylates of 8 to 18 carbon atoms such as methacrylates. Alcohols with long chain alkyl radicals, which are used to prepare the methacrylic esters are commercially available and generally consist of more or less broad mixtures of various chain lengths. In these cases, the specification of the number of carbon atoms is related to the general with the average carbon number. When a long chain methacrylic ester or alcohol prepared using alcohol is referred to in the context of the present application as "C-12" alcohol or "C-12" ester, the alkyl radical of these compounds will generally contain not only alkyl radicals having 12 carbon atoms but possibly those having 8, 10, 14 or 16 carbon atoms in smaller fractions, the average carbon number being 12. When in the context of the present application, for example, a compound is termed as C12-C18 alkyl acrylate, this means a mixture of acrylic acid esters which is characterized in that linear and / or branched alkyl substituents are present and that the alkyl substituents contain between 12 and 18 carbon atoms. The content of the methacrylates of the formula (III) or (Illa) is from 35 to 99.99% by weight, from 40 to 99% by weight or from 50 to 80% by weight, based on the total weight of the monomers ethylenically unsaturated of the main chain of the grafted copolymer. To form the marrow of the copolymer, it is also possible that from 0 to 40% by weight, in particular from 0.5 to 20% by weight, based on the total weight of eitlenically unsaturated monomers of the marrow of the graft copolymer, of one or more additional radically polymerizable monomers are included. Examples thereof are: nitriles of metracrylic acids and other methacrylates with nitrogen content, such as methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl methacrylate; aryl methacrylate such as benzyl methacrylate or phenyl methacrylate, wherein the aryl radicals can each be substituted or up to four times substituted; methacrylates with carbonyl content such as orazolidinylethyl methacrylate, N- (methacryloyloxy) -formamide, acetonyl methacrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone; glycol dimethacrylates such as 1,4-butanediol methacrylate, 2-butoxyhethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, methacrylates of ether alcohols such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1- methyl- (2-vinyloxy) ethyl m methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate; methacrylates of halogenated alcohols, such as 2, 3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, 2-iodoethyl methacrylate, chloromethyl methacrylate; oxiranyl methacrylates such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, glycidyl methacrylate, methacrylates containing phosphorus, boron and / or silicone, such as 2- (dimethylphosphate) propyl methacrylate, 2- (ethylene-phosphite) propyl methacrylate, dimethylphosphinomethyl methacrylate, dimethylphosphonoethyl methacrylate, diethylmethacryloyl phosphonate, dipropylmethacryloyl phosphate; sulfur-containing methacrylates such as ethylsufinethyl ethyl methacrylate, 4-thiocyanatotobutyl methacrylate, ethylsulfinyl methacrylate, thiocyanatomethyl methacrylate, methylsufinylmethyl methacrylate, bis (methacryloyloxyethyl) sulfide; trimethacrylates such as trimethylolprapane trimethacrylate; vinyl halides, for example vinyl chloride; vinyl fluoride, vinylidene chloride and vinylidene fluoride; a, vinyl esters such as vinyl acetate, styrene, substituted styrene having an alkyl substituent on the secondary chain, for example α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, for example monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyridine, vinylpiperidine, 9-vinylcarbazole, 3- vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinyl-pyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-pyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N- vinylcaprolactam, N-vinylbutyrolactam, vinylxodane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles; vinyl and isoprenyl ethers; maleic acid derivatives, for example, maleic acid diesters, wherein the alcohol radicals of 1 to 9 carbon atoms, maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; fumaric acid derivatives, such as, for example, fumaric acid diesters, wherein the alcohol radicals have from 1 to 9 carbon atoms; dienes, for example divinylbenzene, radically free polymerizable α-olefins having 4 to 40 carbon atoms. Representative examples include: butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene- 1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1, heneicosene-1, docoseno-1, trocoseno-1, tetracoseno-1, pentacoseno-1, hexacoseno-1, heptacoseno-1, octacoseno-1, nonacoseno-1, triacontene-1, hentriacontene-1, dotriacontene-1, or the like. Also suitable are branched-chain alkenes, for example, vinylcyclohexane, 3,3-dimethylbutene-1,3-methylbutene-1, diisobutylene-4-methylpentene-1 or the like. Also convenient are the alkenes-1 that have to 32 carbon atoms, which are obtained in the polymerization of ethylene, propylene or mixtures thereof, that these materials in turn are obtained from hydro-disintegrated materials. 0.01 to 25% by weight, based on the weight of the copolymer, are grafted into the marrow of the copolymer wherein R1, R2 and R3 can independently be hydrogen or an alkyl group having from 1 to 5 carbon atoms, and R4 is a group having one or more units capable of forming H bonds and is a donor of H.

In particular embodiments, the fraction of grafted compounds of formula I can also be from 0.1 to 20% by weight, from 1 to 15% by weight or from 1 to 10% by weight, based in each case on the total weight of the copolymer. The maximum possible amount of monomer that can be used for grafting depends on the chemical nature of the monomer in a form that one skilled in the art can understand. For example, it will be easily possible to incorporate an amount corresponding to the upper limiting added in the graft copolymer amount range when an alkyl- dialkylamino used, although the amount added of more highly polar monomers such as methacrylic acid or acrylic acid will vary suitable within the region of less than 10% by weight or less than 5% by weight. The structure of the compounds of the formula (I) and specific examples thereof have already been described in detail for the components of the marrow and are explicitly referred to herein. Optionally, bone marrow grafting can be carried out with from 0 to 20% by weight or from 0 to 10% by weight, based on the total weight of the copolymer, of one or more compounds of the formula (IV) wherein R9 and R10 and R11 and R12 are each as defined above. Examples of the compounds of the formula (IV) include N, N-dimethylacrylamide and N, N-dimethylmethacrylamide, N, N-diethyl acrylamide and N, N-diethylmethacrylamide, aminoalkyl methacrylates such as tris (2-methacryloyloxyethyl) amine, N-metilformamidoetil methacrylate, 2-ureidoethyl methacrylate; Heterocyclic methacrylates such as 2- (l-imidazolyl) ethyl methacrylate, 2- (4-morpholinyl) ethyl methacrylate and 1- (2-methacryloylethyl) -2-pyrrolidone, heterocyclic compounds such as 2-vinylpyridine, 3-vinylpyridine, 2 methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l -vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinyl thiazoles and hydrogenated vinylthiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles. Preparation of the polymers. The aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is also possible to vary the monomer composition during the polymerization. The basic polymerization techniques for the preparation of the polymers are known per se. For example, these polymers can be carried out especially by free radical polymerization and also related processes, for example ATRP (= radical atom transfer polymerization) or RAFT (= chain transfer by reversible addition fragmentation). The typical polymerization of free radicals is explained, among others, in the Encyclopedia of Ullmanns of Chemical Industry in the Sixth Edition. In general, a polymerization initiator is used for this purpose. These include azo initiators well known in the art such as AIBN and 1,1-azo-bisciclohexanecarbonitrilo and also peroxy compounds such field as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethyl- hexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis- (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl-peroxy-2-ethylhexanoate, tert-butyl- peroxy-3, 5, 5-trimethylhexanoate, dicumyl peroxide, 1,1- bis (tert-butylperoxy) cilcohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, hydroperoxide dicumyl, tert. butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of two or more of the aforementioned compounds, and also mixtures of the aforementioned compounds with compounds which have not been mentioned and which can also form free radicals. The ATRP process is known per se. It is assumed to be a polymerization of "active" free radicals, without any intention that this should restrict the description of the mechanism. In these processes, a transition metal compound is reacted with a compound having a group of transferable atoms. This transfers the group of transferable atoms to the transition metal compound that oxidizes the metal. This reaction forms a radical that is added to the ethylenic groups. However, the transfer of the group of atoms to the transition metal compound is reversible, so that the group of atoms is transferred back to the growing polymer chain, which forms a controlled polymerization system. The structure of the polymer, the molecular weight and the molecular weight distribution can be controlled to the same extent. This reaction is described, for example, by J-S. Wang, et al., J. Am. Chem. Soc., Volume 117, page 5614-5615 (1995), by Matyjaszewski, Macromolecules vol. 28, p. 7901-7910 (1995). In addition, patent applications WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 and WO 99/10387, disclose variants of the ATRP explained above. In addition, the polymers of the invention can be obtained, for example, also via the RAFT methods. This process is presented in detail, for example, in WO 98/01478, for which explicit reference is made to the purposes for the purposes of disclosure. The polymerization can be carried out at normal pressure, reduced pressure or elevated pressure. The polymerization temperature is also not important, however, it is generally in the range of -20 ° -200 ° C, preferably 0 ° -130 ° C and more preferably 60 ° -120 ° C. The polymerization can be carried out with or without solvent. The term solvent must be understood in the present in a broad sense. The polymerization is preferably carried out in a non-polar solvent. These include hydrocarbon solvents, for example aromatic solvents such as toluene, benzene, xylene, saturated hydrocarbons, for example cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be present in branched form. These solvents can be used individually as a mixture. Particularly preferred solvents are mineral oils, natural oils and synthetic oils and also mixtures thereof. Among these, particular preference is given to mineral oils. Mineral oils are known per se and can be obtained commercially. Generally obtained from mineral oil or crude oil by distillation and / or refining and optionally other purification and finishing processes, the term mineral oil includes in particular the boiling fractions at high temperatures of petroleum or mineral oil. In general, the boiling temperature of the mineral oil is above 200 ° C, preferably above 300 ° C, at 5000 Pa. The production through low temperature carbonization of the botanical shale oil, bituminous coal cooking, distillation of lignite, excluding air and also hydrogenation of bituminous coal or lignite, is also possible. Mineral oils are also produced in smaller proportion from raw materials of vegetable origin (for example from hump and rapeseed). In consecuense, mineral oils, depending on their origin, have different proportions of aromatic, cyclic, branched and linear hydrocarbons. In general, a distinction is made between paraffin-based, naphthenic and aromatic fractions of crude petroleum or mineral oil, in which the term paraffin-based fraction represents longer-chain isoalkanes or of very many branches and naphthenic fraction represents cycloalkanes . In addition, mineral oils, depending on their origin and finish, have different fractions of N-alkanes, isoalkanes have a lower degree of branching, known as mono-methyl-branched paraffins and compounds having heteroatoms, in particular O, N and / or S, for which a degree of polar properties are attributed. The fraction of N-alkanes in the preferred mineral oils is less than 3% by weight, the proportion of compounds containing O, N and / or S, less than 6% by weight. The proportion of the aromatic and mono-methyl branched paraffins generally in each case is in the range of 0 to 30% by weight. In an interesting aspect, the mineral oil comprises mainly naphthenic and paraffin-based alkanes having generally more than 13, preferably more than 18 and more preferably more than 20 carbon atoms. The fraction of these compounds is usually >; 60% by weight, preferably _ > 80% by weight, without any intention that they should impose a restriction. A particularly preferred analysis of mineral oils, which was carried out by means of conventional processes such as separation of urea and liquid chromatography on silica gel shows, for example, the following constituents, the percentages related to the total weight of the particular mineral oil used: n-alkanes having from about 18 to 31 carbon atoms: 0.7-1.0% slightly branched alkanes having from 18 to 31 carbon atoms: 1.0-8.0% Aromatics having 14 to 32 carbon atoms: 0.4-10.7 % iso- and cycloalkanes having from 20 to 32 carbon atoms: 60.7-82.4% polar compounds: 0.1-0.8% losses: 6.9-19.4% Valuable information regarding the analysis of mineral oils and a list of mineral oils that have A different composition can be found, for example, in the Ullmann Encyclopedia of Chemical Industry in the Fifth Edition on CD-ROM, 1997, under "Lubricants and related products. ions. " Synthetic oils include organic esters, organic ethers such as silicone oils, and synthetic hydrocarbons, especially polyolefins. These are normally somehow more expensive than mineral oils, but have benefits with respect to their performance. Natural oils are animal or vegetable oils, for example cow paw oils or jojoba oils. These oils are also used as mixtures and in many cases can be obtained commercially. These solvents are preferably used in an amount of 1 to 99% by weight, more preferably 5 to 95% by weight and more preferably 10 to 60% by weight, based on the total weight of the mixture. The composition may also have polar solvents, although its amount is restricted by the fact that these solvents must not exert any unacceptable disadvantage in the solubility of the polymers. The molecular weights Mw of the polymers are from 5,000 to 4,000,000 g / mol in particular 10,000-2,000,000 g / mol and more preferably 20,000-5,000,000 g / mol. Polydispersions (Mw / Mn) are preferably in a range of 1.2-7.0. The molecular weights can be determined by known methods. For example, gel permeation chromatography, also known as "size exclusion chromatography" (SEC), can be used. Equally useful for determining molecular weights in an osmometric process, for example, vapor phase osmometry. The mentioned processes are described, for example in: P.J. Flory, "Principles of Polymer Chemistry" Cornell University Press (1953), Chapter VII, 266-316 and "Macromolecules, an Introduction to the Science of Polymers", F.A. Bovey and F.H. Winslow, Editors Academic Press (1979), 296-312 and W.W. Yau, J.J. Kirkiand and D.D. Bly, "Modern Liquid Size Exclusion Chromatography", John Wiley and Sons, New York, 1979. To determine the molecular weights of the polymers that occur in the present, preference is given to using gel permeation chromatography. It is preferable to measure against polymethyl acrylate or polyacrylate standards. The residual monomeric content (for example alkyl acrylate of 8 to 18 carbon atoms), methacrylic acid MMA, NVP) were determined by typical HPLC analytical processes. These are advertised in either ppm or% by weight relative to the total weight of the polymer solutions prepared. Mention should be made as an example for the acrylates having long chain alkyl substitution that the residual monomer content declared for the C8-C18 alkyl acrylates for example includes all the acrylate monomers used having alkyl substitutions on the ester side chains , which are characterized in that they contain between 8 and 18 carbon atoms. The syntheses described in the present invention comprise the preparation of polymer solutions, prescribing that the described syntheses can not be prepared without a solvent. The specified kinematic viscosities are therefore related to the polymer solutions and not the pure isolated polymers. The term "thickener action" refers to the kinematic viscosity of a polymer solution, which is measured by diluting a certain amount of the polymer solution with another solvent at a certain temperature. Typically, 10-15% by weight of the polymer solution prepared in each case are diluted in 150N of oil and the kinematic viscosities of the resulting solution are determined at 40 ° C- and 100 ° C. The kinematic viscosities are determined by traditional processes, for example in an Ubbelohde discometer or in the Herzog automatic test apparatus. The kinematic viscosity is always specified in mm2 / s. The process for preparing the grafted polymers of the present invention is characterized in that the marrow is prepared in a first step by polymerization of free radicals of the monomers a), c) and optionally b) and d) and in that an additional amount of one or more monomers of the formula (I) is then grafted into the marrow in the second step. The copolymers thus grafted are prepared using the monomers which have one or more structural units capable of forming H bonds and which are H-donors, not only in the grafting process but also, in a small fraction, to form the marrow of the graft. grafted copolymer, which is often referred to as the core of the polymer. A beneficial process may consist, for example, of incorporating 1, 2, 3 or 5% by weight, based on the total weight of the ethylenically unsaturated monomers of the marrow, of a monomer having a group having one or more units structural elements capable of forming H and which is an H donor through free radical polymerization in an acrylate copolymer and then being followed by a graft with, for example, incorporating 1, 2, 3 or 5% by weight thereof monomer or another compound of the formula (I). A monomer particularly suitable for use according to the process described above is methacrylic acid. The monomers with H-bond donor functionalities that are used for grafting, and also the monomers with H-bond donor functionality already used to form the polymer backbone do not necessarily correspond. Thus, according to the present invention, it is possible to obtain polymers in which it is optionally also possible to use different monomers with H-bond donor functionalities to form the marrow of the polymer and / or for the grafting step.

In a beneficial embodiment of the process for preparing grafted copolymers, after performing the grafting on one or more monomers of the formula (I), another grafting process is carried out with one or more monomers of the formula (IV) which they do not have structural units capable of forming H bo Likewise it is possible to reverse the aforementioned sequence of the grafting steps. In this embodiment of the process for preparing grafted copolymers, after the polymerization of the marrow, a grafting process is carried out with one or more monomers of the formula (IV), followed by another grafting process with one or more monomers of the formula (I). The present process for preparing the grafted copolymers can also be carried out in a beneficial manner by carrying out a grafting process using a mixture in each case one or more monomers of the formulas (I) and (IV).

In another beneficial embodiment of the present process for preparing grafted copolymers, the grafting process is carried out up to 5 times in succession. In this case, a plurality of grafts in each case with a small amount of monomer, for example in each case 1% by weight of a monomer that can act as an H-bond donor, are made successively. When, for example, a total of 2% by weight of said monomer is used for grafting, preference is given to carrying out two successive grafting steps with, for example, in each case 1% by weight of the monomer in question. It is clear to those skilled in the art that, depending on the individual case, it is also possible in the present to use a number of other values for the amounts of monomer used and for the number of grafting steps, so that they do not have to be listed. individually in the present. It is self-evident that multiple repetition up to 5 times of the grafting step can also be carried out with mixtures of the monomers of formulas (I) and (IV). The monomer in formula (IV) can be an N-functionalized monomer, preferably a N-vinyl-substituted monomer, for example N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyltriazole, N-vinylbenzotriazole or N-vinylimidazole. In another embodiment, it can also be a vinylpyridine, for example 2-vinylpyridine. It can also be a methacrylate or acrylate containing an N-heterocycle in its ester function. In addition, the N-containing monomer can be an N-dialkylamino acrylate or its analogue methacrylate, wherein the aminoalkyl groups contain 1 to 8 carbon atoms. With respect to the other possible compou reference is made here to the large list of the definition of the monomers of the formula (IV). It is possible to use the grafted copolymers of the invention to produce a concentrate as a lubricating oil additive. The concentrate contains from 15 to 85% by weight of one or more of the graft copolymers. In addition, it is also possible that organic solvents, especially a mineral oil and / or a synthetic oil, are present in the concentrate. The grafted copolymers of the invention are particularly suitable for producing lubricating oil compositions. In this case, the grafted copolymers are generally used in an amount ranging from 0.2 to 30% by weight. The lubricating oil compositions may also comprise from 5 to 90% by weight of mineral and / or synthetic base oil and, all together, from 0.2 to 20% by weight of other customary additives, for example pour point surfactants, improvers VI, aging stabilizers, detergents, dispersion assistants or wear reducing components. In practice, acid-functionalized polymers are often neutralized in polymer-like reactions with amine, polyamines or alcohols; methods for this purpose are disclosed for example by DE-A 2519197 (ExxonMobil) and US 3,994,958 (Rohm &Haas Company). As in these two applications, the polymers of the invention of the present application can be subsequently neutralized or esterified in a polymer-like reaction with primary and secondary amine compounds or alcohols. In this case a partial or total neutralization of the polymers can be carried out. In addition to VI, the dispersion capacity and the properties not discussed here, for example oxidation stability, the influence of a lubricating oil on the wear behavior of a machine element is also of particular interest. The wear reducing additives specifically used for this purpose are usually added lubricating oils. Said additives usually have phosphorus and / or sulfur content. In the lubricant industry, there is an impulse to reduce the phosphorus and sulfur content in modern lubricating oil formulas. This has both technical reasons (prevention of catalytic converter exhaust gas poisoning) and environmental policies. The search for phosphorus and sulfur-free lubricant additives has thus become, specifically in the recent past, an intensive research activity of many additive manufacturers. The advantages in the wear behavior can have a positive effect on the energy consumption, for example of a diesel or gasoline engine. The polymers of the present invention to date have not yet been connected with the positive effect on the wear behavior.

The polymers of the present invention are superior to known commercial polymers with N functionalities with respect to wear protection. According to the current state of the art, the crankshaft transmission, the piston group, the cylinder inner diameter and the valve control system of an internal combustion engine are lubricated with an engine oil. This is done by transferring the engine oil that is collected in the engine sump to the individual lubrication points by means of a transmission pump through an oil filter (pressurized circulation lubrication together with injection and mist lubrication). oil). In this system, the engine oil has the functions of: transferring forces, reducing friction, reducing wear, cooling the components and sealing the piston gas. The oil is fed under pressure to other bearing points (crankshaft, connecting rod and camshaft bearings).

The lubrication points of the valve drive the group of pistons, the flywheels and chains receive injected oil, by-product oil or oil vapor. At the individual lubrication points, the forces to be transferred, the contact geometry, the lubrication speed and the temperature vary within wide ranges of operation.

The increase in the potential density of the motors (kW / capacity, torque / capacity) leads to higher component temperatures and surface pressures of the lubrication points. To ensure that the engine oil works under these conditions, the performance of a motor oil is tested in standardized test methods and motor tests (for example API classification in the United States of America or ACEA test sequences in Europe). In addition, test methods self-defined by individual manufacturers are used before a motor oil is tested for use. Among the aforementioned lubricating oil properties, wear protection of motor oil is of particular importance. As an example, the list of requirements of the 2002 ACEA test sequences shows that, in each category (A for petrol engines for passenger vehicles, B for diesel engines for passenger vehicles and E for engines for heavy-duty vehicles) ) with a separate motor test, confirmation of sufficient wear protection for the valve drive must be conducted. The oil is exposed to the following stresses in the operation: • Contact with hot components (up to 300 ° C). • Presence of air (oxidation), nitrogen oxides (nitration), fuel and its combustion residues (condensation of walls, introduction in liquid form) and particles of soot from combustion (introduction of solid foreign substances). • At the time of combustion, the oil film in the cylinder is exposed to high radioactive heat. • The turbulence generated by the crankshaft impulse of the engine creates a large active surface of the oil in the form of droplets in the gaseous space of the crankshaft impeller and the gas bubbles in the sump. The indicated voltages of evaporation, oxidation, nitration, dilution with fuel and introduction of particles that are due to the operation of the engine, change to the engine oil itself and to the engine components that are moistened with the engine oil in operation. As a consequence, the following undesired effects for the tro-free operation of the motor arise: • Change in viscosity (determined in the low temperature range and at 40 ° and 100 ° C). • The pump capacity of the oil at low outside temperatures.

• Formation of reservoirs in hot and cold engine components: this is understood to mean the formation of lacquer-like layers (brown to black) to include the formation of carbon. These deposits impair the function of individual components such as: free passage of the piston rings and narrowing of turbocharger air-conducting components (diffuser and spirals). The result can cause serious engine damage or loss of power and increase in exhaust gas emissions. further, a sediment type deposit layer. It is preferably formed on the horizontal surfaces of the oil space and in the extreme case can even block the oil filters and the oil channels of the engine which can likewise cause engine damage. The reduction in the formation of deposits and the provision of high detergency and dispersion capacity and also anti-wear action during a long time of use of central importance in the current purification procedures as can be seen by the following example of the test sequences ACEA 1998: • Category A (gasoline engines): in 6 engine test methods, the oil deposition is determined 10 times, the wear 4 times and the viscosity 2 times. In determining the deposition behavior, piston cleaning is evaluated 3 times, piston ring seizure 3 times and sediment formation three times. • Category B (light diesel engines): in 5 test methods in engines, the deposition of oils is determined 7 times, the wear 3 times and the viscosity 2 times. In the determination of the deposition behavior, piston cleaning is evaluated 4 times, piston ring seizure 2 times and sediment formation once.

• Category E (heavy duty diesel engines = heavy duty diesel): In 5 engine test methods, the oil deposition is determined 7 times, the wear 6 times and the viscosity one. In the determination of the deposition behavior, the cleaning of the piston is evaluated 3 times, the sediment formation 2 times and the deposition of a tube. For the present invention, the influence of the lubricant used in the wear was measured by the test method CEC-L-51-A-98. This test method is suitable both for the investigation of the wear behavior in a diesel engine for passenger vehicles (category B of ACEA) and in diesel engine of vehicle for heavy work (category E of ACEA). In these test methods the circumference profile of each cam is determined in first steps on a 2 or 3 D test machine before and after the test and compared. The profile deviation formed in the test corresponds to the wear on the cam. To evaluate the engine oil examined, the wear results of the individual cams are averaged and compared with the limiting value of the corresponding ACEA categories. In a deviation from the CEC test method, the test time was cut from 200 hours to 100 hours. The investigations carried out showed that clear differentiations can be made between used oils even after 100 hours, since important differences in wear were detected after this time. Oil A (see Tables 1 and 2) of the present invention served as the first comparative example for the attrition experiment. It was a heavy-duty diesel engine oil formulation of the SAE 5W-30 category. As is usual in practice, this oil was mixed from a commercial base oil. In the present case Nexbase 3043 of Fortum and also other typical additives. The first of these additives is Oloa 4549 from Oronite. The second component is a typical DI additive for motor oils. In addition to ashless dispersants, the product also comprises components to improve the wear behavior. The second components in Oloa 4549 are zinc and phosphorus compounds. The compounds of zinc and phosphorus can be considered as the additives most commonly used today to improve the wear behavior. As another additive, for the purpose of the thickener or VI improver, an ethylene propylene copolymer (Paratone 8002 from Oronite) was used. As usual practice, for Paratone 8002 it was used as a solution in a mineral oil. Even though their VI action is limited, ethylene-propylene copolymers are currently the most common VI improvers in motor oils for heavy-duty vehicles and passenger vehicles due to their very good thickener action. A remarkable action that improves the wear has not yet been described to date by such systems. A polyacrylate was not used as an additive component for oil A. In summary, oil A was composed of 75.3% by weight of Nexbase 3043, 13.2% by weight of Oloa 4594 and 11.5% by weight of a Paratone solution. 8002. Table 1. Wear results for CEC-L-51-A-98, obtained with AG oils Oil content of Paratone 8002 Polyacrylate in each case 3% by weight CEC-L-51-A-98, average wear of cam after 100 hours [μm] To 11.5% by weight 47.4 B 8.5% by weight Example 1 23.9 C 8.5% by weight Example 3 3.9 Table 2. The rheological data and the TBN values of the formulations used for the wear tests. Oil Content of Paratone 8002 polyacrylate in each case KV40 ° C KV100 ° C VI TBN CCS HTHS [% by weight] 3% by weight A 11.5 - 11.38 B 8.5 Example 1 67.07 11.91 176 9.1 4621 3.41 C 8.5 Example 3 62.88 11.46 180 9.3 4406 3.35 As is evident from Table 2, all the formulations used for the wear experiments did not differ in essence with respect to their kinematic viscosity data. This can be seen with reference to the kinematic viscosities measured at 40 and 100 ° C (indicated in Table 2 as KV40 ° C and KV100 ° C, respectively). Similarly, Table 2 shows that the formulations used are not markedly different from the viscosity index (VI), the total base number (TBN), the cold start behavior expressed by the crankcase simulator data (CCS) and the temporary shear losses at high temperatures expressed by the high temperature high shear data (HTHS) ). Data of KV40 ° C, KV100 ° C, VI, TBN, CCS and HTHS were determined through ASTM data known to those skilled in the art. With respect to the corrosion behavior and resistance to oxidation, no observable difference of the formulations of the invention compared to the comparative examples were recognizable. Through examples, the formulations of the invention B and C were examined for their corrosion behavior in direct comparison with oil A (see Table 3). These exams were performed for ASTM D 5968 for lead, copper and brass and for ASTM D 130 for copper.

Table 3. Corrosion behavior of the formulations used for wear tests Polyacrylate Oil Corrosion ASTM D ASTM D 5968 130 Pb Cu Sn Cu A - 109.5 4 0 Ib B Example 1 130.0 4 0 Ib C Example 3 77.0 4.5 0 Ib Oxidation behavior was determined using the PDSC method known to those skilled in the art (CEC L-85-T-99). It was common for oils B and C 3% by weight of the Paratone 8002 solution in each case to be replaced by 3% by weight of the particular polyacrylate solution. The oils B and C are formulations of the invention with respect to wear behavior. It is clear that, in particular, a formulation comprising a polymer of Example 3 should be considered particularly beneficial with respect to protection against wear (see Table 1). The average cam wear at 3.9 μm was particularly low in the present compared to the comparative formulations. It was concluded that the polymer of example 1 which is simple to prepare, improved above the prior art, as indicated by a comparison in the wear of the cams against the values determined for oil A. The base oils suitable for the Preparation of a lubricating oil formulation of the invention are in principle in any compound that ensures a sufficient lubricating film that does not decompose even at elevated temperatures. To determine this property, it is possible, for example, to use the viscosities as explained, for example, in the SAE specifications. Particularly suitable compounds include those having a viscosity that are in the range of 15 seconds of Saybolt (SUS, Saybolt Universal Seconds) to 250 SUS, preferably in the range of 15 to 100 SUS in each case determined at 100 ° C. Suitable compounds for this purpose include natural oils, mineral oils and synthetic oils and further mixtures thereof.

Natural oils are animal or vegetable oils, for example cow paw or jojoba oils. Mineral oils are obtained mainly by distillation of crude oil. They are beneficial in especially with respect to its favorable cost. Synthetic oils include organic esters, synthetic hydrocarbons, especially polyolefins, which satisfy the aforementioned requirements. Normally somehow these are more expensive than mineral oils, but they have advantages with respect to their performance. These base oils can also be used in the form of mixtures and in many cases are commercially available. In addition to the base oil and the polymers mentioned herein, which already make contributions to dispersion behavior and protection against wear, lubricating oils generally comprise other additives. This is the case especially for motor oils, transmission oils and hydraulic oils. The additives suspend the solids (detergency behavior - dispersion), neutralize the acid reaction products and form a protective film on the surface of the cylinder (EP additive), of "extreme pressure"). In addition, the friction reducing additives such as friction modifiers, aging protectants, surfactants, corrosion protectors, dyes, demulsifiers and odorants are used. Those skilled in the art can find other valuable information in the Ullmanns Encyclopedia of Industrial Chemistry, Fifth Edition on CD-ROM, 1998 Edition. The polymers of the invention can, due to their contribution to wear protection, ensure sufficient protection against wear even in the absence of a friction modifier or an EP additive. The wear-improving action is then contributed through the polymer of the invention to which the action of the friction modifier could therefore be attributed. The amounts in which the aforementioned additives are used depend on the field of use of the lubricant. In general, the proportion of the base oil is between 25 to 90% by weight, preferably 50 to 75% by weight. The additives can also be used in the form of DI packages (detergent inhibitor) which are widely known and commercially available. Particularly preferred motor oils comprise, in addition to the base oil, for example, 0.1-1% by weight of pour point surfactants 0.5-15% by weight of VI improvers 0.4-2% by weight of anti-aging protectors 2-10% by weight of detergents 1-10% by weight of lubricity improvers 0.0002-0.07% by weight antifoams 0.1-1% by weight of corrosion protectants The lubricating oil of the invention is also preferably in a concentration of 0.05- 10.0 percent by weight, can comprise an alkyl alkoxylate of the formula (V) The alkyl alkoxylate can be added to the lubricating oil composition directly as a constituent of the VI improver, as a constituent of the DI package, as a constituent of the lubricant concentrate or subsequently to the oil. The oil used in the present may also be processed waste oils. wherein R1, R2 and R3 are each independently hydrogen or a hydrocarbon radical having up to 40 carbon atoms, R4 is hydrogen, a methyl or ethyl radical, L is a linking group n is an integer in the limits from 4 to 40, A is an alkoxy group having from 2 to 25 repeating units which are derived from ethylene oxide, propylene oxide and butylene oxide, where A includes homopolymers and also random copolymers of at least two of the compounds above, and z is 1 or 2 where the non-polar part of the compound (V) of the formula (VI) R'-f- (CR2! ^ -J ^ -L- (vi, contains at least 9 carbon atoms These compounds are mentioned in the context of the invention as alkyl alkoxylates.These compounds can be used, either individually or as a mixture.The hydrocarbon radicals having up to 40 carbon atoms must be understood to mean, example, radicals can be linear, branching two or cyclic, and also aryl radicals which may also comprise heteroatoms and alkyl substituents, which may optionally be provided with substituents, for example halogens. Among these radicals, preference is given to alkyl (1 to 20 carbon atoms), in particular alkyl (1 to 8 carbon atoms) and very particularly to alkyl radicals (1 to 4 carbon atoms). The term "(C 1 -C 4) alkyl" is understood to mean an unbranched or branched hydrocarbon radical having from 1 to 4 carbon atoms, for example, the methyl, ethyl, propyl, isopropyl radical, 1 -butyl, 2-butyl, 2-methylpropyl or tert-butyl; the term "alkyl (1 to 8 carbon atoms)" the aforementioned alkyl radicals, and also, for example, the pentyl radical, 2-methylbutyl, hexyl, heptyl, octyl or the 1, 1, 3 radical , 3-tetramethylbutyl; the term "alkyl (1 to 20 carbon atoms)" the radicals mentioned above, and also, for example, the nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical. In addition, cycloalkyl radicals (3 to 8 carbon atoms) are preferred as the hydrocarbon radical. These include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group. In addition, the radicals can also be unsaturated. Among these radicals, preference is given to "alkenyl (2 to 20 carbon atoms)", "alkynyl (2 to 20 carbon atoms)" and in particular to "alkenyl (2 to 4 carbon atoms)" and "alkynyl ( 2 to 4 carbon atoms) ". The term "alkenyl (2 to 4 carbon atoms)" is understood to mean, for example, the group of vinyl, allyl, 2-methyl-2-propenyl or 2-butenyl; the term "alkenyl of (2 to 20 carbon atoms)" the radicals mentioned above, and also, for example, the group of 2-pentenyl, 2-decenyl or 2-eicosenyl. the term "alkenyl (2 to 4 carbon atoms)", the aforementioned radicals and also for example, the 2-pentynyl or 2-decinyl group. In addition, preference is given to aromatic radicals such as "aryl" or "heteroaromatic ring systems". The term "aryl" is understood to mean an isocitric aromatic radical preferably having from 6 to 14, in particular from 6 to 12 carbon atoms, for example phenyl, naphthyl or biphenylyl, preferably phenyl. The term "heteroaromatic ring system" is understood to mean an aryl radical in which at least one group of CH has been replaced by N and / or at least two adjacent CH groups have been substituted by S, NH or O , for example a radical of theophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2,4-oxadiazole, 1 , 2,4-thiadiazole, 1, 2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c ] thiophene, benzo [c] furan, isoindol, benzoxazole, benzothiazole, benzomidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1, 3, 5-triazine, quinoxaline , cinoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine or 4H-quinolicine. The radicals R2 or R3 that can occur repeatedly in the hydrophobic half of the molecule can each be the same or different.

The linking group L serves to join the polar alkoxide moiety to the non-polar alkyl radical. Suitable groups include, for example, aromatic radicals such as phenoxy (L = C6H4-0-), acid-derived radicals for example ester groups (L = -C0-0-), carbamate groups (L = NH-C0-0-) and amide groups (L = -C0-? H-), ether group (L = -0-) and keto groups (L = -C0-). Preference is given in the present to particularly stable groups, for example the ether, keto and aromatic groups. As mentioned above, n is an integer in the range of 4 to 40, in particular in the limits of 10 to 30. If n is greater than 40, the viscosity that is generated by the additive of the invention generally becomes too much. . If n is less than 4, the lipophilicity of the molecular moiety is generally insufficient to maintain the compound of the formula (V) in solution. Accordingly, the non-polar moiety of the compound (V) of the formula (VI) preferably contains a total of 10 to 100 carbon atoms and more preferably a total of 10 to 35 carbon atoms. The polar moiety of the alkyl alkoxylate is illustrated by A in the formula (V). It is assumed that this alkyl alkoxylate moiety can be illustrated by the formula (VII) (VII) in which the radical R5 is hydrogen, a methyl radical and / or an ethyl radical and m is an integer between the limits of 2 to 40, preferably 2 to 25, in particular between 2 and 15 and more preferably between 2 to 5. In the context of the present invention, the aforementioned numerical values are to be understood as meaning values, since this alkyl alkoxylate moiety is generally obtained by polymerization. If m is greater than 40, the solubility of the compound in the hydrophobic environment is too low so that there is opacity in the oil, in some cases, precipitation. When the number is less than 2, the desired effect can not be assured. The polar half can have units that are derived from ethylene oxide, propylene oxide and / or butylene oxide, preference being given to ethylene oxide. In this context, the polar half can have only one of these units. These units can also occur together in a random way in the polar radical. The number z is a result of the selection of the connection group and from the starting compounds used. It is 1 or 2. The number of carbon atoms of a non-polar moiety of alkyl alkoxylate of the formula (VI) is preferably greater than the number of carbon atoms of the polar moiety A, probably of the formula (VII) , of this molecule. The non-polar half preferably comprises at least twice as many carbon atoms as the polar half, more preferably three times the number or more. The alkyl alkoxylates can be obtained commercially. These include, for example, ®Marlipal and ®Marlophen types of Sasol and types ®Lutensol of BASF. These include, for example, ® Marlophen NP 3 (nonylphenol polyethylene glycol ether (3E0)), ®Marlophen NP4 (nonylphenol polyethylene glycol ether (4E0)), ®Marlophen NP 5 (nonylphenol polyethylene glycol ether (5E0)), ®Marlophen NP 6 (nonylphenyl, polyethylene glycol ether (6EO)); ®Marlipal 1012/6 (polyethylene glycol ether (6EO) of fatty alcohol of 10 to 12 carbon atoms), ®Marlipal MG (polyethylene glycol ether of 12 carbon atoms), ®Marlipal 013/30 (polyethylene glycol ether) (3EO) of oxo alcohol of 13 carbon atoms), ®Marlipal 013/40 (polyethylene glycol ether (4EO) of alcohol oxo of 13 carbon atoms); ®Lutensol TO 3 (fatty alcohol i-C13 with 3 EO units), ®Lutensol TO 5 (fatty alcohol i-C13 with 5 EO units) ®Lutensol TO 7 (fatty alcohol iC? 3 with 7 EO units) ®Lutensol TO 8 (fatty alcohol i-C13 with 8 EO units) ®Lutensol TO 12 (fatty alcohol i-C13 with 12 EO units) Examples Comparative examples 1-3 of the present invention, which are intended to be representative of those attempts at synthesis that failed, which lead to reaction products characterized in that a portion of the polymers formed precipitates from the polymer solution in solid form in reality. The preparation of agreements with Example 1), provides a homogeneous polymer solution with transparent appearance. When the grafting process is carried out analogously, ie with 2% by weight of methacrylic acid under the same process conditions but without having used a small amount of methacrylic acid before to form the marrow of the polymer, a polymeric solution Inhomogeneous, with cloudy appearance is obtained (see Comparative Example 3). Even in the case of grafting with only 1% by weight of methacrylic acid, an inhomogeneous reaction product is obtained (see Comparative Example 1). It is therefore not surprising that grafting with 3% by weight of methacrylic acid without having incorporated a certain fraction of this species into the marrow of the polymer in the same way in the same way leads to a very turbid product, characterized in that the constituents solids are actually precipitated from the solution (see Comparative Example 2). This is also the case when attempts are made to react 3% by weight of methacrylic acid in a grafting process in a rather gradual manner than at one time, for example in 1% by weight portions each. Interestingly, it is conveniently possible to prepare a copolymer with 3% by weight of methacrylic acid that has been incidentally polymerized in the polymer and not by means of a grafting step. Like the carboxylic acids, the acid amides are known for their possible simultaneous action both as H-bond donors and as H-bond acceptors. In analogy with Example 1, in which the methacrylic acid was selected as the type of monomer with function of linker H, Example 4, of the present invention describes a polymer in which dimethylaminopropyomethacrylamide (DMAPMAM) is present in both the marrow of the polymer and the grafted fraction. The process detailed in Example 4 leads to a homogeneous polymer solution of transparent appearance and demonstrates that the principle of synthesis presented herein is of a universal nature, that is, it can be applied not only to the carboxylic acid derivatives but also for example , to the acid amides. The monomers with H-bond donor functionalities used for grafting and the monomers with H-bond donor functionalities already used to form the polymer backbone need not necessarily correspond. Therefore, the present invention includes polymers in which mixtures of different monomers with H-bond donor functionalities are used to form the marrow of the polymer and / or for the grafting step. Example 2 describes a polymer synthesis in which 1% by weight of methacrylic acid is incorporated into the marrow of the polymer and another 2% by weight of the same species, followed by 3% by weight of DMAPMAM, is present in the fraction grafted. In addition to a graft with a monomer having the function of an H-bond donor, it is possible to carry out other grafts with other types of monomer. For this purpose, the monomer types with N content or O content, with dispersing action mentioned from the beginning, are preferably used. The second monomers are characterized in that their functionality of content N or O, is generally a function of H-bond acceptor. An additional graft with such a monomer can follow either the grafting process with the monomer having the function of binding donor H or antecede it. It is also possible to make grafts with monomer mixtures which, like the monomers with H-bond donor functionalities, also contain the aforementioned monomers through the polymerization process of the invention. Example 3 of the present invention encompasses the synthesis of polymers in which 1% by weight of methacrylic acid was used to form the marrow by the process according to the invention, then two times grafted with another 1% by weight of methacrylic acid in each case through the process according to the invention and then finally followed by a grafting step with 3% by weight of N-vinylpyrrolidone. In this case too, a homogeneous reaction product, which is characterized by a clear solution, is contained. Each clear that, in particular, a formulation comprising a polymer of Example 3 should be considered as particularly beneficial with respect to the protection against wear. The average cam wear at 3.9 μm was particularly low in the present compared to the comparative formulations. The copolymers of Example 1 which are simple to prepare were found to be better than those of the prior art, indicated by a comparison in cam wear compared with values determined with oil A. Products and raw materials used Raw materials such as the initiators or chain transfer agents used for the polymer syntheses described herein were fully commercial products, and obtainable, for example from Aldrich or Akzo Nobel. Monomers, for example MMA (Degussa), NVP (BASF), DMAPMAM (Degussa), 10-undecenoic acid (Atofina) or methacrylic acid (Degussa) could also be obtained from commercial sources. Plex 6844-0 was a methacrylate containing urea in the Degussa ester radical. For other monomers used herein, for example ethoxylated alkyl methacrylates methacrylates of 8 to 18 carbon atoms, reference is made to the description of the present application. This is equally true for the most accurate description of the solvents used, for example oils, alkyl alkoxylates. Explanations of the terms, test methods When an acrylate or, for example, an acrylate or polyacrylate polymer is discussed in the present invention, it is understood that it means not only acrylates, ie acrylic acid derivatives but also methacrylates, i.e. methacrylic acid derivatives or otherwise mixtures of systems based on acrylate and methacrylate. When a polymer is referred to as a casual polymer in the present application, this means a copolymer wherein the types of monomers used are randomly distributed in the polymer chain. The graft copolymers, the block copolymers or the systems with a concentration gradient of the types of monomers used along the polymer chain are referred to in this context as non-random polymers or non-randomly structured polymers. The term "grafted fraction" refers to the fraction of the polymer that is subsequently bound, ie after the conclusion of the polymerization of the polymer marrow. It should be noted that this does not give any information about the structure of the final products, expressed in the number, size and precise covalent attachment points of the grafted fractions. However, the statement that all polymers described herein with the grafted fractions have a non-random structure, does apply. Polymer Synthesis Comparative Example 1 (Failed graft of 1% by weight of methacrylic acid in a polyacrylate) A 2-liter four-necked flask equipped with saber agitator (operated at 150 revolutions per minute), thermometer and rising coolant is initially charged with 430 g of a 150N oil and 47.8 g of a monomer mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0. The temperature is adjusted to 100 CC. After 100 ° C was obtained, 0.38 g of tert-butyl peroctoate is added, and at the same time, a load of 522.2 g of a mixture comprising alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0 together with 2.09 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours and the feeding speed is uniform. Two hours after the feeding ended, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 4.3 g of 150 N oil, 5.7 g of methacrylic acid and 1.45 g of tert-butyl peroctoate are added at 100 ° C. One hour after this addition, 0.72 g of tert-butyl peroctoate are added again three times with a separation of one hour each time. The total reaction time is 8 hours. A turbid reaction product of inhomogeneous appearance, characterized in that the polymer fractions have already precipitated out of the liquid phase in solid form, is obtained. Comparative Example 2 (2% by weight unsuccessful graft of methacrylic acid in a polyacrylate) A 2-liter four-necked flask equipped with saber stirrer (operated at 150 revolutions per minute), thermometer and rising coolant is initially charged with 430 g of a 150N oil and 47.8 g of a monomer mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0. The temperature is adjusted to 100 ° C. After 100 ° C was obtained, 0.38 g of tert-butyl peroctoate is added, and at the same time, a load of 522.2 g of a mixture comprising alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0 together with 2.09 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours and the feeding speed is uniform. Two hours after the feeding is finished, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 13.17 g of 150 N oil, 17.45 g of methacrylic acid and 1.45 g of tert-butyl peroctoate are added at 100 ° C. One hour after this addition, 0.73 g of tert-butyl peroctoate is added again three times with a separation of one hour each time. The total reaction time is 8 hours. A turbid reaction product of inhomogeneous appearance, characterized in that the polymer fractions have already precipitated out of the liquid phase in solid form, is obtained. Comparative Example 3 (2% by weight unsuccessful grafting of methacrylic acid in a polyacrylate) A 2-liter four-necked flask equipped with saber agitator (operated at 150 revolutions per minute), thermometer and rising coolant is initially charged with 430 g of a 150N oil and 47.8 g of a monomer mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0. The temperature is adjusted to 100 ° C. After 100 ° C was obtained, 0.38 g of tert-butyl peroctoate is added, and at the same time, a load of 522.2 g of a mixture comprising alkyl methacrylate of 12 to 18 carbon atoms and methyl methacrylate in a weight ratio of 85.0 / 15.0 together with 2.09 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours. The feeding speed is uniform. Two hours after the feeding is finished, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 8.68 g of 150N of oil ,. 11.52 g of methacrylic acid and 1.45 g of tert-butyl peroctoate are added at 100 ° C. One hour after this addition, 0.72 g of tert-butyl peroctoate is added again three times with a separation of one hour each time. The total reaction time after the addition of methacrylic acid is 8 hours. An opaque reaction product of inhomogeneous appearance, characterized in that the polymeric fractions have already precipitated out of the liquid phase in solid form, is obtained. Example 1 (Casual polyacrylate with 1% by weight of methacrylic acid in the marrow of the polymer and 2% by weight of methacrylic acid in the grafted fraction) A four-neck flask of two liters equipped with saber stirrer (operated at 150 revolutions per minute ), thermometer and upward coolant was initially charged with 430 g of a 150 N oil and 47.8 g of a monomer mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms, methyl methacrylate and methacrylic acid in a weight ratio of 84.0 /15.0/1.0 The temperature is adjusted to 100 ° C. After 100 ° C was obtained, 0.80 g of tert-butyl peroctoate are added and at the same time, a load of 522.2 g of a monomer mixture consisting of alkyl methacrylates of 12 to 18 carbon atoms, methyl methacrylate and Methacrylic acid in a weight ratio of 84.0 / 15.0 / 1.0, together with 4.44 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours and the feeding speed is uniform. Two hours after the feeding was completed, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 8.69 g of 150 N oil, 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate were added at 100 ° C. One hour later, another 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate were added. The total reaction time is 8 hours. A homogeneous appearance reaction product is obtained. Kinematic viscosity at 100 ° C: 3764 mm / s Thickening action at 100 ° C (10% in 150N oil): 11.14 mm2 / s Thickening action at 40 ° C (10% in 150N oil): 59.60 mm2 / Residual monomeric content of alkyl methacrylate of 12 to 18 carbon atoms: 0.51% Residual monomeric content of MMA: 0.036% Residual monomeric content of methacrylic acid: 0.072% Example 2 (Polyacrylate with 1% by weight of methacrylic acid in the marrow of the polymer and 2% by weight of methacrylic acid and 3% by weight of DMAPMAM in the grafted fraction) A four-neck flask of two liters equipped with saber stirrer ( operated at 150 revolutions per minute), thermometer and rising coolant was initially charged with 430 g of a 150 N oil and 47.8 g of a monomer mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms, methyl methacrylate and methacrylic acid in a weight ratio of 84.0 / 15.0 / 1.0. The temperature is adjusted to 100 ° C. After 100 ° C was obtained, 0.75 g of tert-butyl peroctoate are added and at the same time, a load of 522.2 g of a monomer mixture consisting of alkyl methacrylates of 12 to 18 carbon atoms, methyl methacrylate and Methacrylic acid in a weight ratio of 84.0 / 15.0 / 1.0, together with 4.17 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours and the feeding speed is uniform. Two hours after the feeding was completed, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 8.69 g of 15% oil, 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate were added at 100 ° C. One hour later, 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate are added. After another hour, 13.43 g of 150 N oil, 17.81 g of dimethylaminopropyl methacrylamide (DMAPMAM) and 1.48 g of tert-butyl peroctoate are added. One hour and two hours later, another 0.74 g of tert-butyl peroctoate is added each time. The total reaction time is 8 hours. A homogeneous appearance reaction product is obtained. Kinematic viscosity of the polymer solution at 100 ° C: 3634 mm2 / s Thickening action at 100 ° C (10% in 150N oil): 11.21 mm2 / s Residual monomeric content of alkyl methacrylate of 12 to 18 carbon atoms: 4.44% Residual monomeric content of MMA: 0.035% Residual monomeric content of methacrylic acid: 98 ppm Example 3 (Polyacrylate with 1% by weight of methacrylic acid in the polymer marrow and 2% by weight of methacrylic acid in and 3% by weight of NVP in the grafted part) A 2-liter four-necked flask equipped with saber agitator (operated at 150 revolutions per minute), thermometer and rising coolant are initially charged with 430 g of a 15ON oil and 47.8 g of a monomer mixture of alkyl methacrylate of 12 to 18 carbon atoms, methyl methacrylate and methacrylic acid, in a weight ratio of 84.0 / 15.0 / 1.0. The temperature is adjusted to 100 ° C. After 100 ° C was obtained, 0.94 g of tert-butyl peroctoate are added and at the same time, a load of 522.2 g of a mixture consisting of alkyl methacrylate of 12 to 18 carbon atoms, methyl methacrylate and acid methacrylic in a weight ratio of 84.0 / 15.0 // 1.0 together with 5.22 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours. The feeding speed is uniform. Two hours after the feeding was completed, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 8.69 g of 150 N oil, 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate were added at 100 ° C. One hour later, another 5.76 g of methacrylic acid and 0.72 g of tert-butyl peroctoate are added. After another hour, the mixture is heated to 130 ° C. Once 130 ° C was obtained, 13.43 g of 150 N of oil, 17.81 g of N-vinylpyrrolidone (NVP) and 1.48 g of tert-butyl peroctoate are added. One hour and two hours later, another 0.74 g of tert-butyl peroctoate is added each time. The total reaction time of the 3 grafting steps in general is 8 hours. A clear reaction product of homogeneous appearance is obtained. Specific viscosity (20 ° C chloroform): 36.5 ml / g Kinematic viscosity at 100 ° C: 3584 mm2 / s Thickening action at 100 ° C (10% in a 150N oil): 11.02 mm2 / s Thickening action at 40 ° C (10% in a 150N oil): 59.60 mm2 / s Residual monomeric content of alkyl methacrylate of 12 to 18 carbon atoms: 0.064% Residual monomeric content of MMA: 45 ppm Residual monomer content of methacrylic acid: 9.5 ppm Residual monomer content of N-vinylpyrrolidone: 0.045% Example 4 (Polyacrylate with 1% by weight of DMAPMAM in the marrow of the polymer and 2% by weight of DMAPMAM in the grafted fraction) A two-neck flask of 2 liters equipped with saber agitator (operated at 150 revolutions per minute), thermometer and rising coolant are charged initially with 430 g of a 150 N oil and 47.8 g of a monomeric mixture of alkyl methacrylate of 12 to 18 carbon atoms, methyl methacrylate and DMAPMAM in a weight ratio of 84.0 / 15.0 / 1.0. The temperature is adjusted to 100 ° C.

After 100 ° C was obtained, 0.80 g of tert-butyl peroctoate are added and at the same time, a load of 522.2 g of a mixture consisting of alkyl methacrylates of 12 to 18 carbon atoms, methyl methacrylate and DMAPMAM in a weight ratio of 84.0 / 15.0 / 1.0 together with 4.44 g of tert-butyl peroctoate is initiated. The feeding time is 3.5 hours and the feeding speed is uniform. Two hours after the feeding was completed, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, 8.69 g of 150 N oil, 5.76 g DMAPMAM and 0.72 g of tert-butyl peroctoate were added at 100 ° C. One hour later, another 5.76 g of DMAPMAM and 0.72 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. A homogeneous appearance reaction product is obtained.

Claims (22)

1. CLAIMS 1. A graft copolymer containing, in the marrow, free radically polymerized units of a) from 0.01 to 15% by weight of a compound of the formula (I) wherein R x, R 2 and R 3 can each independently be hydrogen or an alkyl group having from 1 to 5 carbon atoms and R 4 is a group having one or more structural units capable of forming hydrogen bonds and is a donor of hydrogen, and b) from 0 to 40% by weight of one or more methacrylates of the formula (II) wherein R is hydrogen or methyl and R5 is a linear or branched alkyl radical having from 1 to 5 carbon atoms. c) from 35 to 99.99% by weight of one or more ethylenically unsaturated ester compounds of the formula (III) wherein R is hydrogen or methyl, R8 is a linear, cyclic or branched alkyl radical having from 6 to 40 carbon atoms, R6 and R7 each are independently hydrogen or a group of the formula -COOR8 wherein R8 is hydrogen or a linear, cyclic or branched alkyl radical having from 6 to 40 carbon atoms, and e) from 0 to 40% by weight of one or more comonomers, wherein the percentage by weight of the above components is based on the total weight of the ethylenically unsaturated monomers of the marrow and where a ') from 0.01 to 25% by weight based on the total weight of the copolymer, of a compound of the formula (I) wherein R1, R2 and R3 can each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms and R4 is a group having one or more structural units capable of forming hydrogen bonds and is a donor of hydrogen, and b ') from 0 to 20%, based on the total weight of the copolymer, of one or more compounds of the formula (IV) wherein R9, R10 and R11, each independently can be hydrogen is an alkyl group having from 1 to 5 carbon atoms a group of C (0) OR13 and R13 is a linear or branched alkyl radical that is substituted by at least one group - NR14R15 and has from 2 to 20, preferably from 2 to 6 carbon atoms, where R14 and R15 are each independently hydrogen, an alkyl radical has from 1 to 20, preferably from 1 to 6 and where R14 and R1S, including the nitrogen atom and, if another nitrogen or oxygen atom is present, form a ring of 5 or 6 elements that can optionally be substituted by alkyl of 1 to 6 carbon atoms, or R12 is a group NR16C (= 0) R17 where R16 and R17 together form an alkylene group having from 2 to 6, preferably from 2 to 4 carbon atoms, where these form a ring of 4 to 8 elements, preferably 4 to 6 elements, saturated or unsaturated, if appropriate include another nitrogen or oxygen atom, where this ring also optionally be substituted by alkyl of 1 to 6 carbon atoms, they are grafted into the marrow of the copolymer.
2. 2. The graft copolymer according to claim 1, characterized in that the structural unit R4 capable of forming hydrogen bonds is a carboxyl group, an optionally substituted carboxamide group or a carboxamide substituted by an alkylamino group.
3. The graft copolymer according to claim 1 or 2, characterized in that the compound of the formula (I) capable of forming hydrogen bonds is methacrylic acid, acrylic acid, dimethylaminopropyl methacrylamide, or dimethylaminoethyl methacrylamide.
4. The graft copolymer according to one of the preceding claims, characterized in that the weight-average molecular weight is 5000-4,000,000 g / mol.
5. The graft copolymer according to one of the preceding claims, characterized in that from 10 to 80% by weight of the monomer of the formula (I) used in general is incorporated into the medulla of the polymer.
6. The graft copolymer according to one of the preceding claims, characterized in that the proportion of the monomer of the formula (III) is from 70 to 99.5% by weight based on the total weight of the ethylenically unsaturated monomers of the marrow .
7. 7. The graft copolymer according to one of the preceding claims, in which it is characterized in that the monomer of the formula (II) is methyl methacrylate or n-butyl methacrylate or a mixture of the two.
8. 8. The graft copolymer according to one of the preceding claims, characterized in that the monomer of formula (III) is one or more compounds selected from the group of 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate , pentadecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate.
9. The graft copolymer according to one of the preceding claims, characterized in that another comonomer d) is either an α-olefin or styrene or a mixture of the two.
10. 10. The graft copolymer according to one of the preceding claims, characterized in that the monomer of formula (IV) is dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, morpholinoethyl methacrylate or n-heterocyclic vinyl compound such as 2-vinylpyridine, 3-vinylpyridine , 2-methyl-5-vinylpyridine, 3-ethylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyridine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole , 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, n-vinilturiolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles, or a mixture of said compounds.
11. 11. A process for preparing graft copolymers according to one of the preceding claims characterized in that in the first step the bone is prepared by free radical polymerization of the monomers a), c) and optionally b) and / or d ), and in which another quantity of one or more of the monomers of the formula (I) is then grafted into the cord in the second step.
12. 12. The process for preparing graft copolymers according to claim 11, characterized in that, after grafting one or more monomers of the formula (I), another grafting process is carried out with one or more monomers of the formula (IV).
13. The process for preparing grafted copolymers according to one of claims 1 to 10, characterized in that a grafting process is first carried out with one or more monomers of the formula (IV), followed by another grafting process with one or more monomers of the formula (I) •
14. 14. The process for preparing graft copolymers according to one of claims 1 to 10, characterized in that a grafting process is carried out using a mixture in each case one or more monomers of the formulas (I) and (IV).
15. 15. The process for preparing grafted copolymers according to claim 11 or 14, characterized in that the grafting process is carried out up to five times in succession.
16. 16. A concentrate as a lubricating oil additive, characterized in that the concentrate contains from 15 to 85% by weight of one or more graft copolymers according to one or more of claims 1 to 10.
17. 17. The concentrate according to claim 16 , characterized in that the concentrate additionally comprises organic solvents, in particular a mineral oil and / or a synthetic oil.
18. 18. A lubricating oil composition comprising grafted polymers according to one of claims 1 to 10.
19. 19. The lubricating oil composition according to claim 18, characterized in that the graft copolymers according to one of claims 1 to 10 are present in an amount in the range 0.2 to 30% by weight.
20. 20. The lubricating oil composition according to claim 18 or 19, characterized in that the lubricating oil composition further comprises: from 25 to 90% by weight of mineral and / or synthetic base oil, all together from 0.2 to 20% by weight of other traditional additives, for example surfactants with pour point, VI improvers, aging stabilizers, detergents, dispersing assistants or wear reducing components.
21. 21. The lubricating oil composition according to one of claims 18 to 20, characterized in that it additionally contains 0.05 to 10.0 percent by weight of an alkyl alkoxylate of the formula (V) wherein Ri, R2 and R3 are each independently hydrogen or a hydrocarbon radical having up to 40 carbon atoms, R4 is hydrogen, a methyl or ethyl radical, L is a linking group, n is a complete number in the range from 4 to 40, A is an alkoxy group having from 2 to 25 repeating units which are produced from ethylene oxide, propylene oxide and / or butylene oxide, where A includes homopolymers and random copolymers of at least two of the aforementioned compounds and z is 1 or 2, wherein the non-polar half of the compound of the formula (V) of the formula (VI) contains at least 9 carbon atoms. The use of grafted polymers according to one of claims 1 to 9, in the lubricating oil compositions as a dispersant or non-dispersing viscosity index improver, as a detergent or non-detergent component, as a pour point improver, as a wear reducing component or a component that reduces energy consumption by reducing wear.