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    • 专利摘要:
    The present invention relates to a process for the polymerization of ethylenically unsaturated monomers using an initiator having a transitionable atomic group and at least one catalyst containing at least one transition metal, in the presence of a ligand capable of forming a coordination compound with the metallic catalyst (s) (Meth) acrylate of the formula (I) in the presence of 5 to 95% by weight of mineral oil based on the total weight of the composition, based on the total weight of the ethylenically unsaturated monomer, of 50 to 100 wt% % Of an ethylenically unsaturated monomer contained in the composition. Formula I In the above formula (I) R is hydrogen or methyl, R < 1 > is a linear or branched alkyl residue having 6 to 40 carbon atoms, R 2 and R 3 are independently hydrogen or a group of the formula -COOR 'wherein R' is hydrogen or a straight or branched chain alkyl residue having 6 to 40 carbon atoms.
    公开号:KR20020063195A
    申请号:KR1020027006900
    申请日:2000-11-29
    公开日:2002-08-01
    发明作者:루스제바스티안；아이젠베르크보리스；볼링어조셉마틴；쉐러마르쿠스
    申请人:로막스 아디티페스 게엠베하；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method for producing a composition containing an ester polymer compound having a long-chain alkyl group and a use of the composition,
    [1] The present invention relates to a process for preparing an ethylenically unsaturated monomer mixture containing at least 50% by weight of an ethylenically unsaturated ester compound having an alkyl or heteroalkyl chain having 6 or more carbon atoms in the presence of a ligand capable of forming a coordination compound with the metal catalyst (s) To a process for preparing a composition containing a polymeric ester compound having a long-chain alkyl moiety, which is polymerized using at least one catalyst containing an initiator and at least one transition metal containing a transitionable atomic group. The invention also relates to the use of the polymer composition and to a process for separating the polymer from the polymer solution.
    [2] Radical polymerization is an important commercial production process for a number of polymers such as PMMA and polystyrene. A disadvantage of this method is that it is difficult to relatively adjust the composition, molecular weight and molecular weight distribution of the polymer.
    [3] One solution to the problem is provided by the so-called ATRP process (= Atom Transfer Radical Polymerization). It is believed to be a " living " radical polymerization, which is not limited by the description of the mechanism. In this method, a transition metal compound is reacted with a compound having a transitionable atomic group. In this case, the transitionable atomic group is transferred to the transition metal compound to oxidize the metal. In this reaction, a radical is formed and added to the ethylene group. However, the reaction in which an atomic group is transferred to a transition metal compound is reversible, so that the atomic group is transferred again to the growing polymer chain, and a polymer system to be controlled is formed. Thus, the composition, molecular weight and molecular weight distribution of the polymer can be controlled.
    [4] This reaction method is described in the literature (J-S. Wang, et al., J. Am. Chem. Soc., Vol. 117, pp. 5614-5615 (1995); Matyjaszewski, Macromolecules, Vol. 28, pp. 7901-7910 (1995)). In addition, International Patent Publications WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 and WO 99/10387 describe a modification of the ATRP described above, .
    [5] The mechanism described above is not without debate. For example, WO 97/47661 states that polymerization takes place via insertion rather than through a radical mechanism. However, in the case of the present invention, this difference is not important because the compounds are used in the reaction method described in WO 97/47661, which is also used in ATRP.
    [6] The monomer, the transition metal catalyst, the ligand and the initiator are each selected according to the desired polymer solution. The high reaction rate constants for the reaction of the transition metal-ligand complex with the transitionable atomic group and the low concentration of free radicals in the equilibrium state are important for the narrow molecular weight distribution. When the free radical concentration is very high, a typical termination reaction occurs which causes a wide range of molecular weight distributions. The exchange rate depends, for example, on the anion of transitionable atomic groups, transition metals, ligands and transition metal compounds. Experts know, for example, that in the WO 98/40415 important advice has been reported on the selection of these ingredients.
    [7] However, the advantages of the known ATRP polymerization process are limited to monomers which are either polar in nature or have good solubility in the polar medium. Separate applications of non-polar aprotic hydrocarbons such as benzene, toluene, xylene, cyclohexane and hexane are also known in the literature, but the polymers prepared using these solvents are obviously more polydispersities. Such effects are described, for example, in WO 98/40415. Pol. Butyl methacrylate is poorly polymerized, especially when tert-butyl methacrylate is bulk polymerized, is disclosed in Preprint (ACS, Div. Pol. Chem.), 1999, 40 (2), 432, MJ Ziegler et al. . When a polar solvent of about 20 to 25% by weight is used, both molecular weight and polydispersity can be improved. However, an ethylenically unsaturated monomer mixture containing 50% by weight or more of an ethylenically unsaturated ester compound having an alkyl or heteroalkyl chain having 6 or more carbon atoms is preferred because of the limited solubility of the ethylenically unsaturated ester compound having an alkyl or heteroalkyl residue having 6 or more carbon atoms , And in the case of using the known ATRP method, only poor polymerization can be carried out in a polar solvent. In addition, these large amounts of polar solvents must be separated from the composition after preparation of the polymer, depending on the application in each case.
    [8] In view of the prior art, an object of the present invention is to provide a method for producing a poly (meth) acrylate composition, wherein the polymer contained in the composition is formed from at least 50 wt% of a (meth) acrylate having an alkyl or heteroalkyl chain having 6 or more carbon atoms . In addition, the polymers contained in the compositions have a narrow molecular weight distribution. In particular, costly methods, such as anionic polymerization methods, are not used in the preparation of polymer mixtures.
    [9] Another challenge is to provide a viable, economically viable method for large-scale industries. In addition, it should be possible to carry out the method easily and simply using commercially available components.
    [10] These challenges as well as other problems that are not explicitly mentioned but which can be easily derived or developed from the starting materials are solved by a process for the preparation of poly (meth) acrylate compositions having all the features of claim 1. An easy modification method of the process according to the invention is protected by the dependent claims referred to in claim 1. [ With regard to the method of preparing the polymer, the paragraph 11 provides a solution to the basic problem, whereas the paragraph 12 protects the desired use of the polymer solution prepared according to the process.
    [11] Polymerizing an ethylenically unsaturated monomer containing from 50 to 100% by weight of at least one ethylenically unsaturated ester compound of formula I, based on the total weight of the ethylenically unsaturated monomer, in the presence of 5 to 95% by weight of mineral oil relative to the total weight of the composition (Meth) acrylate compositions that can achieve a narrow polymer distribution, which is an unpredictable method.
    [12]
    [13] In the above formula (I)
    [14] R is hydrogen or methyl,
    [15] R < 1 > is a linear or branched alkyl residue having 6 to 40 carbon atoms,
    [16] R 2 and R 3 are independently hydrogen or a group of the formula -COOR 'wherein R' is hydrogen or a straight or branched chain alkyl residue having 6 to 40 carbon atoms.
    [17] In the present application, an ethylenically unsaturated monomer is polymerized in the presence of a ligand capable of forming a coordination compound with the metal catalyst (s), using an initiator having a transitionable atomic group and at least one catalyst containing at least one transition metal. Such a manufacturing method can be carried out particularly advantageously in terms of cost and is industrially important to such extent.
    [18] It is surprising that mineral oil can be used as a particularly successful solvent because many compositions used in the ATRP polymerization process contain polar solvents. Polymerization of an ethylenically unsaturated monomer mixture containing at least 50 wt% of an ethylenically unsaturated ester compound having a long chain alkyl or heteroalkyl chain having 6 or more carbon atoms is suppressed because of the limited solubility of these compounds in a polar solvent. It has been found that when a non-polar solvent is used instead of a polar solvent, a polymer mixture having a significantly higher degree of polydispersity is obtained than when a conventional polar solvent is used. In addition, polymer yields in non-polar solvents are lower in most cases. Product properties with these widely distributed polymer properties are insufficient for many industrial applications, such as, for example, additives to lubricant oil, so other methods that cost more should be used multiple times.
    [19] At the same time, a number of additional advantages can be gained through the method according to the invention. Among these, there are the following advantages.
    [20] The distribution of the polymer in the polymer composition produced by this method is narrow.
    [21] The process according to the present invention is excellent in the molecular weight controllability of the polymer contained in the composition.
    [22] - The performance of the polymerization is relatively uncomfortable with respect to pressure, temperature and solvent, and acceptable results are obtained even at mild temperatures under certain conditions.
    [23] - High yields can be achieved using the method according to the invention.
    [24] - The process according to the invention results in less side reactions.
    [25] - The process can be carried out advantageously in terms of cost.
    [26] -Polymers having the desired structure and target structure can be prepared using the method of the present invention.
    [27] The method is characterized in that mineral oil is used as a solvent for polymerizing an ethylenically unsaturated monomer mixture containing at least 50% by weight of an ethylenically unsaturated ester compound having an alkyl or heteroalkyl chain having 6 or more carbon atoms.
    [28] Mineral oil is substantially known and commercially available. In general, mineral oil is obtained from petroleum or crude oil using distillation and / or purification and any further purification and processing methods, and in particular the high boiling fraction of crude oil or petroleum is included in the concept of mineral oil. The boiling point of the mineral oil is generally above 200 ° C, preferably above 300 ° C at 5000 Pa. Cryogenic distillation of shale oil, coking of light carbon, distillation of lignite under air, but also by hydrogenation of hard coal or lignite. In addition, the mineral oil is produced in small amounts but from raw materials of vegetable origin (for example, jojoba oil, cottonseed oil) or animal origin (for example, right oil). Thus, the mineral oil in each case contains different amounts of aromatic hydrocarbons, cyclic hydrocarbons, side chain hydrocarbons and straight chain hydrocarbons, depending on the origin.
    [29] Generally, the paraffinic naphthalene and aromatic fraction are distinguished from crude oil or mineral oil, wherein the paraffinic fraction means a long chain or highly branched isoalkane, and the naphthalene fraction indicates a cycloalkane. In addition, the mineral oil may in each case be selected from the group consisting of n-alkanes, isoalkanes having a low degree of sidechain, so-called monomethyl-branched paraffins, and heteroatoms providing polarity, especially O, N and / or S Are different from each other. However, it is difficult to provide such polarity since each alkane molecule is both long chain branched and has a cycloalkane residue and an aromatic component. For the purposes of the present invention, the classification is carried out in accordance with DIN 51 378. The polar component can also be measured according to ASTM D 2007.
    [30] The fraction of n-alkanes in the preferred mineral oil is less than 3% by weight and the fraction of O, N and / or S containing compounds is less than 6% by weight. In general, the fractions of aromatic compounds and monomethyl-branched paraffins are in each case in the range from 0 to 40% by weight. According to one important embodiment, the mineral oil mainly comprises naphthalene-based and paraffinic alkanes which generally have more than 13 carbon atoms, preferably more than 18, particularly preferably more than 20 carbon atoms. The fraction of the compound is generally at least 60% by weight, preferably at least 80% by weight, and is not limited thereby. Preferred mineral oils are in each case in the range of from 0.5 to 30% by weight of an aromatic component, from 15 to 40% by weight of a naphthalene component, from 35 to 80% by weight of a paraffin component, of up to 3% 5% by weight.
    [31] According to a particularly preferred mineral oil analysis carried out by conventional methods such as urea dewaxing and liquid chromatography on silica gel, for example, the following components appear, wherein the percentages are based on the total weight of the mineral oil concerned will be).
    [32] An n-alkane having about 18 to 31 carbon atoms: 0.7 to 1.0%
    [33] 1.0 to 8.0% of a low-branched alkane having 18 to 31 carbon atoms,
    [34] An aromatic compound having 14 to 32 carbon atoms: 0.4 to 10.7%
    [35] 60 to 82.4% of isoalkane and cycloalkane having 20 to 32 carbon atoms,
    [36] Polar compound: 0.1 to 0.8% and
    [37] Loss rate: 6.9 to 19.4%.
    [38] Important advice on the analysis of mineral oil and on the list of mineral oils with different compositions is described in the literature (Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, under the heading "lubricants and related products").
    [39] The solvent is used in an amount of 5 to 95% by weight, preferably 5 to 80% by weight, particularly preferably 5 to 60% by weight, very particularly preferably 10 to 50% by weight, based on the total weight of the mixture use.
    [40] Additionally, the compositions may contain additional solvents, in which case the type and amount are limited to such an extent that they do not adversely affect the polydispersity or conversion rates. These solvents include, for example, synthetic oils. Synthetic oils are, in particular, organic esters, organic ethers, for example silicone oils, and synthetic hydrocarbons, especially polyolefins.
    [41] According to the process of the present invention, ethylenically unsaturated monomers containing from 50 to 100% by weight, preferably from 60 to 100% by weight, of at least one ethylenically unsaturated ester compound of formula I, based on the total weight of the ethylenically unsaturated monomers, are polymerized .
    [42] Formula I
    [43]
    [44] In the above formula (I)
    [45] R is hydrogen or methyl,
    [46] R < 1 > is a straight or branched chain alkyl residue having 6 to 40, preferably 6 to 24 carbon atoms,
    [47] R 2 and R 3 are independently hydrogen or a group of the formula -COOR 'wherein R' is hydrogen or a straight or branched chain alkyl residue having 6 to 40 carbon atoms,
    [48] The alkyl residue may be linear, cyclic or branched.
    [49] The compounds of formula (I), in each case, contain (meth) acrylates, maleates and fumarates having at least one alcohol residue having from 6 to 40 carbon atoms.
    [50] In this application, (meth) acrylates of formula (II) are preferred.
    [51]
    [52] In the above formula (II)
    [53] R is hydrogen or methyl,
    [54] R 1 is a straight or branched alkyl residue having 6 to 40 carbon atoms.
    [55] The term (meth) acrylate includes methacrylates, acrylates, and mixtures thereof. These monomers are well known. In particular, they include (meth) acrylates derived from saturated alcohols such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (Meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, (Meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-isopropyl heptadecyl Tert-butyl octadecyl (meth) acrylate, 5- Octadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyl eicosyl (meth) acrylate, ) Acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyl tetratriacontyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as oleyl (meth) acrylate; Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate and boron (meth) acrylate.
    [56] The ester compound having a long-chain alcohol residue can be obtained, for example, by reacting (meth) acrylate, fumarate, maleate and / or the corresponding acid with a long-chain fatty alcohol, For example, (meth) acrylates with different long chain alcohol residues are obtained. Fatty alcohols include Oxo Alcohol R 7911, Oxo Alcohol 7900 and Oxo Alcohol 1100 (manufactured by Monsanto), Alphanol R 79 (manufactured by ICI), Nafol R 1620, Alfol R ) 610 and alpol 810 [Conde O (Condea) manufactured, epal (Epal R) 610 and epal 810 [ethyl Corporation (ethyl Corporation) manufactured, Rhine view (Linevol R) 79, Rhine ball 911 and banol (Dobanol R ) 25L [shell AG (shell AG) manufactured, Rial (Lial) 125 [Augusta email Land (Augusta R Mailand) manufactured], having high Dodd (Dehydad R) and rorol (Lorol R) [Henkel cake ah (Henkel Linopol R 7-11 and Acropol R 91 (manufactured by Ugine Kuhlmann).
    [57] The monomer mixture may contain an ethylenically unsaturated ester compound derived from an alcohol having 6 to 40 carbon atoms [represented as component (a)], as well as other ethylenically unsaturated monomers copolymerizable with the ester compound. These monomers are, in particular, in each case based on the total weight of the ethylenically unsaturated monomers,
    [58] From 0 to 40% by weight, in particular from 0.5 to 20% by weight, of at least one (meth) acrylate of formula (III) (b)
    [59] From 0 to 40% by weight, in particular from 0.5 to 20% by weight, of at least one (meth) acrylate of the formula (IV) (c)
    [60] From 0 to 40% by weight, in particular from 0.5 to 20% by weight, of at least one (meth) acrylate of formula (VI)
    [61] From 0 to 40% by weight, in particular from 0.5 to 20% by weight, of one or more comonomers (e).
    [62]
    [63] In formula (III) above,
    [64] R is hydrogen or methyl,
    [65] R < 4 > is a straight or branched alkyl residue having 1 to 5 carbon atoms.
    [66]
    [67] In the above formula (IV)
    [68] R is hydrogen or methyl,
    [69] R < 5 > is an alkyl residue of 2 to 20, in particular 2 to 6, carbon atoms substituted with an OH group or an alkoxylated residue of formula (V).
    [70]
    [71] In the above formula (V)
    [72] R < 6 > and R < 7 > are independently hydrogen or methyl,
    [73] R 8 is hydrogen or an alkyl residue having 1 to 40 carbon atoms,
    [74] n is an integer of 1 to 60;
    [75]
    [76] In the above formula (VI)
    [77] R is hydrogen or methyl,
    [78] X is oxygen or an amino group of the formula -NH- or -NR 10 - wherein R 10 is an alkyl residue having 1 to 40 carbon atoms,
    [79] R 9 is a straight or branched chain alkyl residue of 2 to 20, preferably 2 to 6, carbon atoms substituted with at least one --NR 11 R 12 - group wherein R 11 and R 12 are independently of each other hydrogen or a C 1-20 , Preferably an alkyl residue of 1 to 6, or together with the nitrogen atom and optionally another nitrogen atom or oxygen atom form a 5 or 6-membered ring (which ring may optionally be substituted by C 1 -C 6 alkyl) .
    [80] Examples of component (b) are, in particular, (meth) acrylates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n- ) Acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as cyclopentyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
    [81] The (meth) acrylates of formula (IV) are known to the expert. These include, in particular, hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2- Methacrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate and 1,2-propanediol (meth) acrylate; Polyoxypropylene derivatives of polyoxyethylene and (meth) acrylic acid, such as triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate and tetrapropylene glycol (meth) acrylate.
    [82] (Meth) acrylate or methacrylamide [component (d)] of formula (VI) is especially an amide of (meth) acrylate such as N- (3- dimethylaminopropyl) methacrylamide, N- Methyl-2-propanol, N- (3-dibutylaminopropyl) methacrylamide, N-tert-butyl- 4-methyl-2-pentanol, N- (methoxymethyl) methane, N-methoxyethyl methacrylate, N-methyl-N-phenylmethacrylamide, N, N-di (trimethylsilyl) amide, N- Ethyl methacrylamide, N-methyl methacrylamide, N, N-dimethyl methacrylamide and N-isopropyl methacrylamide; Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine, N-methylformamidoethyl methacrylate and 2-ureidoethyl methacrylate; (Meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl -Methacryloyloxyethyl) -2-pyrrolidone. ≪ / RTI >
    [83] Component (e) comprises ethylenically unsaturated monomers which can be polymerized, in particular with ethylenically unsaturated ester compounds of the formulas I, II, III, IV and / or VI.
    [84] However, the comonomers for polymerization according to the invention corresponding to the following formulas are particularly suitable for the polymerization according to the invention.
    [85]
    [86] In the above formulas,
    [87] R 1 * and R 2 * are each independently selected from the group consisting of hydrogen, halogen, CN, 1 to 20 carbon atoms which may be substituted by halogen atoms of 1 to (2n + 1) (wherein n is the number of carbon atoms of the alkyl group) (For example, CF 3 ), 1 to (2n-1) (wherein n is the number of carbon atoms of the alkyl group), preferably 1 to 6, particularly preferably 1 to 4, Unsaturated straight chain or branched alkenyl or alkynyl group having 2 to 10, preferably 2 to 6, particularly preferably 2 to 4 carbon atoms which may be substituted by a halogen atom, preferably chlorine, for example, CH 2 = CCl-), 1 to (2n-1) one (where, n is the carbon number of 3 to which may be substituted by a halogen atom, preferably chlorine of the number of carbon atoms in the cycloalkyl group) 8 cycloalkyl group, and the addition of R 8 *, aryl or heterocyclyl C, which can be quaternized by the group reel (= Y * R 5 * , C (= Y * ) NR 6 * R 7 * , Y * C (= Y * ) R 5 * , SOR 5 * , SO 2 R 5 * , OSO 2 R 5 * SO 2 R 5 *, PR 5 * 2, P (= Y *) R 5 * 2, Y * PR 5 * 2, Y * P (= Y *) R 5 * 2, NR 8 * 2 [ wherein, Y * May be NR 8 * , S or O, preferably O, and R 5 * is an alkyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, OR 15 wherein R 15 is hydrogen or an alkali R 6 * and R 7 * are independently hydrogen or an alkyl group of 1 to 20 carbon atoms, or R 6 * and R 7 * together are a hydrogen atom, May form an alkylene group having 2 to 7 carbon atoms, preferably 2 to 5 carbon atoms, in which case they form a 3 to 8 membered ring, preferably a 3 to 6 membered ring, and R 8 * Linear or branched alkyl or aryl group,
    [88] R 3 * and R 4 * are independently hydrogen, halogen (preferably fluorine or chlorine), an alkyl group having 1 to 6 carbon atoms and COOR 9 * , wherein R 9 * is hydrogen, an alkali metal, Alkyl group), or a group selected from
    [89] R 1 * and R 3 * together may form a group of formula (CH 2 ) n , which may be substituted by 1-2n 'halogen atoms or C 1 -C 4 alkyl groups, ) -Y * -C (= O), wherein n 'is 2 to 6, preferably 3 or 4, Y * is as defined above,
    [90] R 1 *, R 2 *, R 3 * and R 4 * two or more of the residue is hydrogen or halogen.
    [91] Component (e) comprises an ethylenically unsaturated monomer which can be polymerized with an ester compound of formula (I). These include, in particular, nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as methacryloylamido acetonitrile, 2-methacryloyloxyethylmethyl cyanamide, cyanomethyl methacrylate; Aryl (meth) acrylates such as benzyl methacrylate or phenyl methacrylate, wherein the aryl moiety is in each case unsubstituted or substituted with up to four substituents; (Meth) acrylate, carboxymethyl (meth) acrylate, oxazolidinylethyl (meth) acrylate, N- (methacryloyloxy) formamide , Acetonyl (meth) acrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone; Glycol dimethacrylate such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, ether alcohol Methoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1-methyl- (2 (meth) acryloyloxyethyl methacrylate, Methoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, Ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, Ethoxymethyl methacrylate; Methacrylates of halogenated alcohols such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2- Methacrylate, 2-iodoethyl methacrylate, chloromethyl methacrylate; Oxiranyl methacrylate such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, glycidyl methacrylate; (Meth) acrylates, such as phosphorus-, boron- and / or silicon-containing methacrylates such as 2- (dimethylphosphato) propyl methacrylate, 2- (ethylene phosphito) propyl methacrylate, dimethylphosphinomethyl methacrylate Dimethylphosphonoethyl methacrylate, diethyl methacryloylphosphonate, dipropyl methacryloyl phosphate; Sulfur-containing methacrylates such as ethylsulfinyl ethyl methacrylate, 4-thiocyanato butyl methacrylate, ethylsulfonyl ethyl methacrylate, thiocyanato methyl methacrylate, methylsulfinyl methyl Methacrylate, bis (methacryloyloxyethyl) sulfide; Trimethacrylate, for example, trimethylolpropane trimethacrylate; Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Vinyl esters such as vinyl acetate; Styrene, substituted styrenes having an alkyl substituent in the side chain such as, for example, -Methylstyrene and -Ethylstyrene, substituted styrenes having an alkyl substituent in the ring, such as vinyltoluene and p-methylstyrene, halogenated styrene , For example, monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene; Examples of the heterocyclic vinyl compound include 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, Vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, N-vinylpyrrolidone, N-vinylcarbazole, Vinyl pyrrolidone, N-vinyl pyrrolidine, 3-vinyl pyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolane, vinyl furan, vinyl thiophene, vinyl thiolane, vinyl Thiazole, halogenated vinyl thiazole, vinyl oxazole and halogenated vinyl oxazole; Vinyl and isophenyl ethers; Maleic acid derivatives such as maleic acid mono- and diesters wherein the alcohol residue has 1 to 5 carbon atoms, maleic anhydride, methyl maleic anhydride, maleic anhydride, methyl maleic anhydride; Fumaric acid and fumaric acid derivatives such as fumaric acid mono- and diesters wherein the alcohol residue has 1 to 5 carbon atoms and dienes such as divinylbenzene.
    [92] In addition to styrene, monomers having a dispersing activity, such as the above-mentioned heterocyclic vinyl compounds, are particularly preferred as comonomers. These comonomers are also referred to as dispersed monomers.
    [93] The ethylenically unsaturated monomers may be used individually or as a mixture. The monomer composition may be varied during the polymerization to obtain a defined structure, for example, a block copolymer.
    [94] In a preferred embodiment of the process according to the invention, the ethylenically unsaturated monomers in an amount of more than 70% by weight, particularly preferably more than 80% by weight, based on the total weight of the ethylenically unsaturated monomers, have an alkyl or heteroalkyl chain having 6 or more carbon atoms Methacrylate, maleate and / or fumarate.
    [95] The monomers are polymerized using an initiator having a transitionable atomic group. Generally these initiators are compounds of the formula Y- (X) m , wherein Y is a core molecule presumed to form radicals, X is a transitionable atom or a group of transposable atoms, and m is a group according to the functionality of the Y group Lt; / RTI > is an integer from 1 to 10). When m > 1, various transitionable atomic groups X can be important in many respects. When the initiator has a functionality of more than 2, a stellate polymer is obtained. Preferred transitionable atoms or groups of atoms are halogens such as Cl, Br and / or I.
    [96] As mentioned above, it is believed that the Y group forms radicals that serve as initiating molecules, wherein the radicals are added to the ethylenically unsaturated monomers. For this reason, preferably the group Y has a substituent capable of stabilizing the radical. These substituents include -CN, -COR, and CO 2 R, wherein R is an alkyl or aryl residue or an aryl and / or heteroaryl group.
    [97] The alkyl moiety is a saturated or unsaturated straight or branched chain hydrocarbon moiety having from 1 to 40 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl, Heptadecyl, octadecyl, nonadecyl, octadecyl, heptadecyl, octadecyl, heptadecyl, octadecyl, heptadecyl, octadecyl, heptadecyl, octadecyl, Eicosyl, cetyl eicosyl, docosyl and / or eicosyl tetratriacontyl.
    [98] The aryl moiety is a cyclic aromatic moiety having from 6 to 14 carbon atoms in the aromatic ring. The residue may be substituted. The substituent may be, for example, a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; Aromatic groups such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
    [99] Aromatic residues include, for example, phenyl, xylyl, tolyl, naphthyl or biphenylyl.
    [100] The term " heteroaryl " means a heteroaromatic ring system in which one or more CH groups are replaced by N or two adjacent CH groups are replaced by S, O or NH, for example thiophene, furan, pyrrole, Thiazole, oxazole, pyridine, pyrimidine and benzo [a] furan, which may likewise have the above-mentioned substituents.
    [101] Initiators that may be used in accordance with the present invention may be any compound having at least one atom or group of atoms capable of being transited by a radical under polymerization conditions.
    [102] Suitable initiators include compounds of the formula:
    [103] R 11 R 12 R 13 CX
    [104] R < 11 > C (= O) -X
    [105] R 11 R 12 R 13 Si-X
    [106] R 11 R 12 NX
    [107] R 11 NX 2
    [108] (R 11 ) n P (O) m -X 3-n
    [109] (R 11 O) n P ( O) m -X 3-n and
    [110] (R 11 ) (R 12 O) P (O) m -X
    [111] In the above formulas,
    [112] X is selected from the group consisting of Cl, Br, I, OR 10 wherein R 10 is an alkyl group having 1 to 20 carbon atoms in which each hydrogen atom may independently be replaced by a halide, preferably a chloride or fluoride, Preferably 2 to 20 carbon atoms, preferably vinyl, an alkynyl having 2 to 10 carbon atoms, which may be substituted by 1 to 5 halogen atoms or an alkyl group having 1 to 4 carbon atoms, preferably acetylenyl or phenyl, Alkyl (aryl-substituted alkyl wherein the aryl group is phenyl or substituted phenyl and the alkyl group is alkyl of 1 to 6 carbon atoms, such as benzyl), SR 14 , SeR 14 , OC (= O) R 14 , OP (= O) R 14, OP (= O) (OR 14) 2, OP (= O) OR 14, ON (R 14) 2, SC (= S) N (R 14) 2, CN, NC, SCN, CNS, OCN, CNO and N 3 (wherein, R 14 is the alkyl group or the presence of 1 to 20 carbon atoms, preferably 1, and straight or branched chain alkyl group of 1 to 10, the two R 14 groups Occurrence, is selected from the group consisting of 5, 6 or 7 can form a membered heterocyclic ring) with,
    [113] R 11 , R 12 and R 13 are independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, particularly preferably 1 to 6, a cycloalkyl group having 3 to 8 carbon atoms, R 8 * 3, Si, C (= Y * ) R5 * , C (= Y * ) NR6 * R7 * , wherein Y * , R5 * , R6 * and R7 * , OH (preferably one of the residues R 11 , R 12 and R 13 is OH), CN, an alkenyl or alkynyl group having 2 to 20, preferably 2 to 6, carbon atoms, particularly preferably allyl or An alkylene or alkenylene group having 2 to 6 carbon atoms substituted by vinyl, oxiranyl, glycidyl, oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl (wherein aryl is as defined above alkenyl is one or two C 1 -C 6 alkyl groups and / or halogen atom, preferably a vinyl-substituted by chlorine aryl-substituted alkenyl), 1 (Preferably fluorine, chlorine or bromine when one or more hydrogen atoms are substituted, preferably fluorine or chlorine when one or more hydrogen atoms are substituted, and preferably fluorine, chlorine or bromine when one hydrogen atom is substituted) of 1 to 6 alkyl groups, C 1 -C 4 alkoxy, aryl, heterocyclyl, C (= Y *) R 5 * ( wherein, R * 5 are the same as defined above), C (= Y *) NR 6 * R 7 * (wherein R * 6 and R 7 * are as defined above), oxiranyl and glycidyl, each of which is substituted by 1 to 3 (preferably 1) substituents selected from the group consisting of to be selected from the group consisting of a 6-alkyl group (preferably R 11, R 12 and R 13 is not more than two of the moieties are hydrogen, most preferably R 11, R 12 and R 13 residues up to one of the Hydrogen),
    [114] m is 0 or 1,
    [115] n is 0, 1 or 2;
    [116] Particularly preferred initiators include benzyl halides such as p-chloromethylstyrene, alpha -dichlorooxylene, alpha, alpha -dichlorooxylene, alpha, alpha -dibromooxylene and hexakis (alpha -bromomethyl) Benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenylethane and 1-chloro-1-phenylethane; halogenated carboxylic acid derivatives such as propyl-2-bromopropionate, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2- Bromoisobutyrate; Tosyl halides such as p-toluenesulfonyl chloride; Alkyl halides such as tetrachloromethane, tribromomethane, 1-vinylethyl chloride, 1-vinylethyl bromide; And halogen derivatives of phosphoric esters, such as dimethylphosphoric chloride.
    [117] The initiator is generally used in a concentration of from 10 -4 to 3 mol / l, preferably from 10 -3 to 10 -1 mol / l, particularly preferably from 5 × 10 -2 to 5 × 10 -1 mol / l, But is not limited thereto. The molecular weight of the polymer is obtained from the ratio of initiator to monomer when all the monomers are converted. Preferably, the ratio is in the range of 10 -4 : 1 to 0.5: 1, particularly preferably 1 10 -3 : 1 to 5 10 -2 : 1.
    [118] The polymerization is carried out using a catalyst comprising at least one transition metal. In the present application, any transition metal compound capable of forming an oxidation-reduction cycle together with a polymer chain or an initiator having a transitionable atomic group can be used. In this cycle, the transitionable atomic groups and the catalyst reversibly form the compound, wherein the degree of oxidation of the transition metal increases or decreases. Here, it can be inferred that the radicals are released or trapped and the radical concentration remains very low. However, also inserting into the YX or Y (M) z -X bond of the ethylenically unsaturated monomer (where Y and X are as defined above and M is a monomer and z is a degree of polymerization) It can be said that it is possible or easy to add to a possible atomic group.
    [119] Preferred transition metals are Cu, Fe, Co, Cr, Ne, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, Yb and / do. These metals may be used individually or as a mixture. These metals are presumed to act as catalysts, for example, in the redox cycle of the polymerization process in which the redox pair Cu + / Cu 2+ or Fe 2+ / Fe 3+ is active. Thus, the metal compound is added to the reaction mixture as a halide, such as a chloride or bromide, an alkoxide, a hydroxide, an oxide, a sulfate, a phosphate, a hexafluorophosphate or trifluoromethane sulfate. Preferred metal compounds include Cu 2 O, CuBr, CuCl, CuI, CuN 3 , CuSCN, CuCN, CuNO 2 , CuNO 3 , CuBF 4 , Cu (CH 3 COO), Cu (CF 3 COO), FeBr 2 , RuBr 2 , CrCl 2 and NiBr 2 .
    [120] However, compounds of high oxidation state such as CuO, CuBr 2 , CuCl 2 , CrCl 3 , Fe 2 O 3 and FeBr 3 can also be used. In this case, the reaction may be initiated using a conventional radical former such as AIBN. Here, the transition metal compound is reduced first because it reacts with a radical generated from a conventional radical former. This is the reverse ATRP (Wang and Matyjaszewski, Macromolecules (1995) Vol. 28, pp. 7572-7573].
    [121] The amount of active catalyst present in the polymer composition can vary widely. The amount of active transition metal catalyst used within the scope of the present invention is reduced by any proportion of the source substantially releasing the active portion of the catalyst that may be present in the polymer composition, and if it exceeds 200 ppm based on the total weight of the polymer composition, Particularly advantageous polymerization proceeds. For example, if the polymerization takes place in the presence of copper with an oxidation step of 0 as the source of the active part of the catalyst, it is possible to carry out the oxidation steps (I) and (II) during the polymerization, preferably as oxidized copper The amount of copper present in the polymer composition is important (active). Due to the measurement method used, the amount of copper in the oxidation step (II) is said to be in equilibrium with the copper in the oxidation step (I).
    [122] In order to determine the amount (concentration) of the relevant transition metal according to the invention, for example, the following method may be used as a function of the nature of the source which is introduced into the transition metal.
    [123] When proceeding from a metal, for example copper, as a source, the metal source may be removed from the composition, for example, by removing the metal source from the batch or by filtration after completion of the polymerization. The amount of the metal in the residual polymer composition can be measured, for example, by atomic absorption spectroscopy (AAS) or atomic emission spectroscopy (AES), after performing the known decomposition method, as the case may be. According to these methods, the amount of the metal of the oxidation step released (oxidized) from the metal source is measured and its concentration is measured.
    [124] When proceeding from a transition metal compound (eg, a copper salt or an iron salt) as a source, it is sufficient to measure the amount of metered addition and to derive the maximum amount of transition metal of the relevant oxidation step present in the system from this information Do.
    [125] As mentioned, the transition metal can be used for catalysis as a metal in oxidation step 0, in particular as a mixture with the above-mentioned compounds as described, for example, in WO 98/40415. In this case, the conversion reaction rate can be increased. In this way, it is believed that the concentration of the catalytically active transition metal compound increases as the transition metal in the higher oxidation step is balanced with the metallic transition metal.
    [126] The molar ratio of transition metal to initiator is generally in the range of from 0.0001: 1 to 10: 1, preferably from 0.001: 1 to 5: 1, particularly preferably from 0.01: 1 to 2: 1, .
    [127] The polymerization is carried out in the presence of a ligand capable of forming a coordination compound with the metal catalyst (s). The ligand in particular acts to increase the solubility of the transition metal compound. Another important function of the ligand is to prevent the formation of stable organometallic compounds. This is particularly important because stable compounds are not polymerized under the selected reaction conditions. In addition, it is assumed that the ligand facilitates the separation of the transitionable atomic groups.
    [128] Such ligands are known in the art and are described, for example, in WO 97/18247 and WO 98/40415. Generally, the compound has at least one nitrogen atom, oxygen atom, phosphorus atom and / or sulfur atom to which a metal atom can be bonded. Most of the ligands are compounds of the formula R 16 -Z- (R 18 -Z) m -R 17 wherein R 16 and R 17 are independently H, C 1 -C 20 alkyl, aryl or heterocyclyl, R 16 and R 17 may optionally form a saturated, unsaturated or heterocyclic ring; Z is O, S, NH, NR < RTI ID = 0.0 > 19 or PR 19 , wherein R 19 is as defined for R 16 , and R 18 is independently a straight, branched or cyclic divalent group of 1 to 40 carbon atoms, preferably 2 to 4 carbon atoms, methylene, ethylene, and propane or butylene group, an alkyl and aryl are as defined above, a heterocyclyl moiety is a cyclic residue having 4 to 12 carbon atoms, in which rings one or more of the CH 2 groups can be, for heteroatom groups such , O, S, NH and / or NR (wherein, R is for R 16 Is replaced by the same as defined) can be.
    [129] Another group of suitable ligands is compounds of formula VII.
    [130]
    [131] In the above formula (VII)
    [132] R 1, R 2, R 3 and R 4 are independently saturated with H, C 1 -C 20 alkyl, aryl, heterocyclyl and / or heteroaryl residue, R 1 and R 2 or R 3 and R 4 Or an unsaturated ring.
    [133] Preferred ligands herein are chelating ligands containing N atoms.
    [134] Preferred ligands include triphenylphosphine, 2,2-bipyridine, alkyl-2,2-bipyridine such as 4,4-di- (5-nonyl) N, N ', N', N''-pentamethyldiethylenetriamine, 1, 2 ', 3'-di- (5-heptyl) -2,2-bipyridine, , 1,4,7,10,10-hexamethyltriethylenetetramine and / or tetramethylethylenediamine. Other preferred ligands are described, for example, in WO 97/47661. Can be used individually or as a mixture.
    [135] The ligand is formed together with a metal compound in the in situ coordinate system, or the ligand is first prepared as a coordination compound and then added to the reaction mixture.
    [136] The ratio of ligand to transition metal depends on the dentation of the ligand and the coordination number of the transition metal. The molar ratio is generally in the range of 100: 1 to 0.1: 1, preferably 6: 1 to 0.1: 1, particularly preferably 3: 1 to 0.5: 1, and is not limited thereto.
    [137] The monomer, transition metal catalyst, ligand and initiator are, in each case, chosen according to the desired polymer solution. The high reaction constant for the reaction of a transition metal-ligand complex with a transitionable atomic group is believed to be important for a narrow molecular weight distribution. When the rate constant is too low, the concentration of the radicals is too high, resulting in a typical termination reaction that causes a broad molecular weight distribution. The exchange rate depends, for example, on the anion of transitionable atomic groups, transition metals, ligands and transition metal compounds. As an expert, WO 98/40415 knows that important advice is given in selecting these ingredients.
    [138] The polymerization can be carried out at normal pressure, reduced pressure or elevated pressure. The polymerization temperature is also not critical. However, the polymerization temperature is generally in the range of -20 to 200 占 폚, preferably 0 to 130 占 폚, particularly preferably 60 to 120 占 폚, and is not limited thereto.
    [139] A polymer having a predetermined structure can be obtained simply by using this method. This possibility is due to the " active " nature of the polymerization process. Such structures include in particular block copolymers, gradient copolymers, stellate copolymers, highly branched polymers, polymers with reactive end groups and graft copolymers. The molecular weight of the polymer produced by this method is not limited to 1,000 to 1,000,000 g / mol, preferably 10,000 to 500,000 g / mol, particularly preferably 20,000 to 300,000 g / mol. These values represent the weight average molecular weight of the polydispersed polymer in the composition.
    [140] A particular advantage of ATRP over conventional radical polymerization processes lies in the fact that polymers with narrow molecular weight distributions can be produced. This not to be limited by, prepared by the process according to the invention polymers M w / M n shown polydispersity of from 1 to 12, preferably 1 to 4.5, particularly preferably from 1 to 3, very particularly preferably with Lt; / RTI >
    [141] According to an interesting aspect of the process according to the invention, the catalyst can be separated by a solid-liquid separation process after polymerization. This includes, for example, chromatography, centrifugation and filtration.
    [142] Preferably the catalyst is removed by filtration. In this case, the degree of oxidation in the transition metal is increased after polymerization. In the presence of a solvent, especially a mineral oil having a dielectric constant of 4 or less, preferably 3 or less, particularly preferably 2.5 or less, by oxidizing the transition metal, in each case the solubility of the catalyst The transition metal can be separated by filtration.
    [143] Oxidation of the transition metal can be carried out using known oxidizing agents, for example oxygen, H 2 O 2 or ozone. Preferably, the catalyst is oxidized using atmospheric oxygen. It is not necessary to completely oxidize the transition metal or the transition metal compound. In many cases, contacting the composition with atmospheric air for several minutes is sufficient to ensure sufficient precipitation of the transition metal compound.
    [144] Filtration is practically known and is described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, under the "filtration". Preferably, the composition is applied in the presence of a filter having a sieve size of 0.01 to 1 mm, preferably 1 to 100 m, particularly preferably 10 to 100 m, in the range of 0.1 to 50 bar, preferably 1 to 10 bar, It is purified at a pressure difference in the range of 1.5 to 2.5 bar. These data are intended as starting points since the purification depends on both the viscosity of the solvent and the particle size of the precipitate.
    [145] The filtration is carried out in a temperature range similar to the polymerization, the upper limit being dependent on the stability of the polymer. The lower limit depends on the viscosity of the solution.
    [146] The poly (meth) acrylate compositions prepared by this method can be readily used as additives in lubricating oils without further purification. In addition, the polymer can be separated from the composition.
    [147] In this case, the polymer can be separated from the composition by filtration.
    [148] The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited by these Examples.
    [149] Examples 1 to 4
    [150] The ATRP polymerization test is carried out in mineral oil according to the following general procedure.
    [151] The ATRP polymerization test is carried out in a four-neck round bottom flask equipped with a saber stirrer, heating mantle, nitrogen inlet and quench system. 258.2 g of an alkyl methacrylate mixture of C 12 -C 18 alcohol, 29 g of methyl methacrylate, and a mineral oil (SM 920, manufactured by Shell Co.) Composition: 0.84% n-alkane having about 18 to 31 carbon atoms, 5.16% low-chain-branched alkane having 18 to 31 carbon atoms, 8.8% aromatic compound having 14-32 carbon atoms, 71.4% iso- and cycloalkane having 20-32 carbon atoms, Polar compound: 0.6% and loss rate: 13.2%] was placed in a reaction flask, and dry ice was added thereto, and nitrogen was introduced to inactivate the reaction mixture. Then, a corresponding amount of catalyst, in each case CuBr, and a ligand (pentamethyldiethylenetriamine (PMDETA) or bipylyl) is added.
    [152] After heating to 90 캜, an appropriate amount of initiator (ethyl 2-bromoisobutyrate (EBiB) or para-toluenesulfonyl chloride (pTSCl)) is added. The temperature in the reaction flask is raised to 100 캜 or 105 캜. After reacting for about 20 hours at the temperatures listed in the table, the mixture is cooled to room temperature and the product is diluted with mineral oil and filtered to separate the transition metal catalyst. The mixture is analyzed by GPC.
    [153] In Table 1, the amounts of the components used and the reaction temperature in each case are described. Table 2 summarizes the results obtained, such as the polymerization conversion, the number average molecular weight M n of the obtained polymer, and the polydispersity PDI.
    [154] Comparative Examples 1 to 4
    [155] A comparative test is carried out analogously to the example using 72.5 g of n-decane instead of mineral oil.
    [156] In Table 1, the amounts of the components used and the reaction temperature in each case are described. Table 2 summarizes the results obtained, such as the polymerization conversion, the number average molecular weight M n of the obtained polymer, and the polydispersity PDI (M w / M n ).
    [157] The catalyst (g)The ligand (g)Initiator (g)Temperature (℃) Example 10.540.65PMDETA1.42 pTSCl100 Comparative Example 10.540.65PMDETA1.42 pTSCl100 Example 20.642.1bipy1.42 pTSCl105 Comparative Example 20.642.1bipy1.42 pTSCl105 Example 30.540.65PMDETA1.45EBiB100 Comparative Example 30.540.65PMDETA1.45EBiB100 Example 41.342.92 bipy1.46EBiB105 Comparative Example 41.342.92 bipy1.46EBiB105
    [158] Conversion Rate (%)M n (g / mol)PDI Example 197.941,8501.16 Comparative Example 186.332,3101.38 Example 252.020,2701.82 Comparative Example 275.853,3603.91 Example 398.937,5001.17 Comparative Example 393.035,8601.29 Example 450.248,9401.46 Comparative Example 48.628,8101.77
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] (Meth) acrylate polymer that polymerizes an ethylenically unsaturated monomer using an initiator having a transitionable atomic group and at least one catalyst containing at least one transition metal, in the presence of a ligand capable of forming a coordination compound with the metal catalyst (s) A process for the preparation of an acrylate composition comprising, in the presence of from 5 to 95% by weight of mineral oil, based on the total weight of the composition, of at least one ethylenically unsaturated ester compound of formula I in an amount of from 50 to 100% ≪ / RTI > wherein the ethylenically unsaturated monomer is polymerized.
    Formula I

    In the above formula (I)
    R is hydrogen or methyl,
    R < 1 > is a linear or branched alkyl residue having 6 to 40 carbon atoms,
    R 2 and R 3 are independently hydrogen or a group of the formula -COOR 'wherein R' is hydrogen or a straight or branched chain alkyl residue having 6 to 40 carbon atoms.
    [2" claim-type="Currently amended] The method according to claim 1, wherein, in each case, the proportion of the aromatic component is from 0.5 to 30 wt%, the naphthalene component is from 15 to 40 wt%, the paraffin component is from 35 to 80 wt%, the n-alkane is less than 3 wt% 0.0 > 5% < / RTI > by weight of the compound.
    [3" claim-type="Currently amended] The method according to any one of claims 1 to 5, wherein the mineral oil is used in an amount of 10 to 60% by weight, based on the total weight of the composition.
    [4" claim-type="Currently amended] 4. A process according to any one of claims 1 to 3, characterized in that a monomer composition comprising at least 50% by weight of at least one (meth) acrylate of formula (II) is polymerized.
    (II)

    In the above formula (II)
    R is hydrogen or methyl,
    R 1 is a straight or branched alkyl residue having 6 to 40 carbon atoms.
    [5" claim-type="Currently amended] 5. The composition according to any one of claims 1 to 4, wherein the monomer composition comprises, in each case, in an amount, based on the total weight of the ethylenically unsaturated monomer,
    At least one ethylenically unsaturated ester compound of formula (I) (a) 60 to 100% by weight,
    From 0 to 40% by weight of one or more (meth) acrylates of formula (III) (b)
    From 0 to 40% by weight of one or more (meth) acrylates of formula (IV) (c)
    From 0 to 40% by weight of one or more (meth) acrylates of formula (VI) (d) and
    And 0 to 40% by weight of at least one comonomer (e).
    Formula I

    In the above formula (I)
    R is hydrogen or methyl,
    R < 1 > is a linear or branched alkyl residue having 6 to 40 carbon atoms,
    R 2 and R 3 are independently hydrogen or a group of the formula -COOR 'wherein R' is hydrogen or a straight or branched chain alkyl residue having 6 to 40 carbon atoms.
    (III)

    In formula (III) above,
    R is hydrogen or methyl,
    R < 4 > is a straight or branched alkyl residue having 1 to 5 carbon atoms.
    Formula IV

    In the above formula (IV)
    R is hydrogen or methyl,
    R < 5 > is an alkyl residue of 2 to 20 carbon atoms substituted with an OH group or an alkoxylated residue of formula (V).
    Formula V

    In the above formula (V)
    R < 6 > and R < 7 > are independently hydrogen or methyl,
    R 8 is hydrogen or an alkyl residue having 1 to 40 carbon atoms,
    n is an integer of 1 to 60;
    VI

    In the above formula (VI)
    R is hydrogen or methyl,
    X is oxygen or an amino group of the formula -NH- or -NR 10 - wherein R 10 is an alkyl residue having 1 to 40 carbon atoms,
    R 9 is a straight or branched chain alkyl residue of 2 to 20, preferably 2 to 6, carbon atoms substituted with at least one --NR 11 R 12 - group wherein R 11 and R 12 are independently of each other hydrogen or a C 1-20 , Preferably an alkyl residue of 1 to 6, or together with the nitrogen atom and optionally another nitrogen atom or oxygen atom form a 5 or 6-membered ring (which ring may optionally be substituted by C 1 -C 6 alkyl) .
    [6" claim-type="Currently amended] The method according to claim 5, wherein styrene, (meth) acrylate derivative and / or dispersed monomer are used as comonomers.
    [7" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6, further comprising the steps of: preparing an aqueous solution containing at least one of Cu 2 O, CuBr, CuCl, CuI, CuN 3 , CuSCN, CuCN, CuNO 2 , CuNO 3 , CuBF 4 , Cu (CH 3 COO) 3 COO) is used as the catalyst.
    [8" claim-type="Currently amended] 8. The method according to any one of claims 1 to 7, wherein at least one chelating ligand containing N atoms is used.
    [9" claim-type="Currently amended] Claim 1 to claim according to any one of 8, wherein the Cl, Br, I, characterized by the SCN and / or initiator is used which contains N 3.
    [10" claim-type="Currently amended] 10. A process according to any one of claims 1 to 9, characterized in that the catalyst is separated by a solid-liquid separation process.
    [11" claim-type="Currently amended] Characterized in that the polymer is separated from the polymer solution obtained according to the process of any one of claims 1 to 10.
    [12" claim-type="Currently amended] Use of a polymer composition obtained according to the process of any one of claims 1 to 11 as an additive in a lubricant.
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    同族专利:
    公开号 | 公开日
    CN1187379C|2005-02-02|
    US6403746B1|2002-06-11|
    MXPA02005216A|2002-11-07|
    BR0015941B1|2011-12-13|
    CN1399653A|2003-02-26|
    KR100663660B1|2007-01-03|
    AT288931T|2005-02-15|
    JP2003515630A|2003-05-07|
    WO2001040328A1|2001-06-07|
    CA2392018C|2010-08-31|
    EP1244716B1|2005-02-09|
    AU2669401A|2001-06-12|
    CA2392018A1|2001-06-07|
    DE50009516D1|2005-03-17|
    JP4681187B2|2011-05-11|
    BR0015941A|2002-09-17|
    EP1244716A1|2002-10-02|
    DE10015537A1|2001-06-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-11-30|Priority to US09/450,746
    1999-11-30|Priority to US09/450,746
    2000-11-29|Application filed by 로막스 아디티페스 게엠베하
    2002-08-01|Publication of KR20020063195A
    2007-01-03|Application granted
    2007-01-03|Publication of KR100663660B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/450,746|US6403746B1|1999-11-30|1999-11-30|Method for preparation of a composition that contains polymer ester compounds with long-chain alkyl residues and use of this composition|
    US09/450,746|1999-11-30|
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