DE102009002730A1 - Preparing copolymer, useful as additive for e.g. mineral oil and ester oil, comprises polymerizing a monomer composition (comprising e.g. ethylenically unsaturated ester compounds and comonomer) in the presence of alkyl(ene) compounds - Google Patents

Abstract

Preparing copolymer, comprises polymerization of a monomer composition (comprising (a) 10 to less than 90 wt.% of at least one ethylenically unsaturated ester compounds (I), (b) more than 10-90 wt.% of at least one ethylenically unsaturated, polar ester compounds (II), and (c) 0-50 wt.% of comonomer) in the presence of (d) 0.1-10 wt.% of one or more alkyl(ene) compounds (III)-(V). Preparing copolymer, comprises polymerization of a monomer composition (comprising (a) 10 to less than 90 wt.% of at least one ethylenically unsaturated ester compounds of formula (C(R3)(R2)=C(R)-C(=O)-OR1) (I), (b) more than 10-90 wt.% of at least one ethylenically unsaturated, polar ester compounds of formula (C(R11)(R12)=C(R)-C(=O)-XR10) (II), and (c) 0-50 wt.% of comonomer) in the presence of (d) 0.1-10 wt.% of one or more alkyl(ene) compounds of formula (R4-Y1-H) (III), (H-Y1-R5-Y2-H) (IV) and/or (R6-(CH 2-CH 2-O-) m(CH(CH 3)-CH 2-O) nH) (V). R : H or CH 3; R1 : 6-40C alkyl; R2, R3 : H or -COOR1a; R1a : H or 1-5C alkyl; X : O, S or amino group of formula -NH- or -NR1b; R1b : 1-40C alkyl; R10 : 2-1000C containing residue with at least hydroxyl group; R11, R12 : H or -COXaR10a; Xa : O, -NH- or -NRa; R10a : 1-100C containing residue; Y1-Y2 : S or O; R4 : 1-3C alkyl; R5 : 2 or 3C alkylene; R6 : 1-32C alkyl; and m, n : 0-100, where both m and n are not 0. An independent claim is included for mineral oil (100 N) comprising the above copolymer in clear solution having a nephlometric turbidity value of = 5.

Description

The Invention relates to the production and use of in mineral oil, Synthetic oil, ester oil and vegetable oils soluble, the performance of motor oils, gear oils, and similar formulations affecting polymeric (VI) improvers with polar groups.

monomers with polar groups, for example hydroxyethyl methacrylate (HEMA), can only be used in combination with long-chain methacrylates Dissolve about 10 mole percent as a copolymer in 100 N mineral oil. Direct polymerization with higher levels of z. Eg HEMA lead to turbidity and precipitation. A Possibility to circumvent these effects would be the polymerization in polar solvents, such as Alcohols and the like. These would have to be, however distilled off costly and the copolymer is converted into mineral oil become.

The polymerization of (VI) improvers directly in mineral oil has also been reported on several occasions. So revealed the

In view of the above-mentioned and discussed prior art, it was an object of the invention to provide a process for the preparation of hydroxyl-containing copolymers having a molar content of the hydroxyl-containing monomer component of more than 10 percent in the copolymer, resulting in mineral oil-soluble and clear concentrates.

• a) 10 bis weniger als 90 Gewichtsprozent mindestens einer ethylenisch ungesättigten Esterverbindung der Formel (I)
  
  worin R Wasserstoff oder Methyl darstellt, R¹ einen linearen oder verzweigten Alkylrest mit sechs bis 40 Kohlenstoffatomen bedeutet, R² und R³ unabhängig Wasserstoff oder eine Gruppe der Formel -COOR' darstellen, worin R' Wasserstoff oder eine Alkylgruppe mit eins bis fünf Kohlenstoffatomen bedeutet,
• b) mehr als 10 bis 90 Gewichtsprozent mindestens einer ethylenisch ungesättigten, polaren Esterverbindung der Formel (II)
  
  worin R Wasserstoff oder Methyl darstellt, X Sauerstoff, Schwefel oder eine Aminogruppe der Formel -NH- oder -NR^a-, worin R^a für einen Alkylrest mit eins bis 40 Kohlenstoffatomen steht, R¹⁰ einen zwei bis 1000 Kohlenstoffatome umfassenden Rest mit mindestens einer Hydroxylgruppe, R¹¹ und R¹² unabhängig Wasserstoff oder eine Gruppe der Formel -COX'R¹⁰' darstellen, worin X' Sauerstoff oder eine Aminogruppe der Formel -NH- oder -NR^a-, worin R^a' für einen Alkylrest mit ein bis 40 Kohlenstoffatomen steht, und R¹⁰' einen eins bis 100 Kohlenstoffatome umfassenden Rest darstellt, und
• c) 0 bis 50 Gewichtsprozent Comonomer, jeweils bezogen auf das Gesamtgewicht (a) + b) + c)) der ethylenisch ungesättigten Monomere, besteht, wobei sich das Verfahren der Erfindung dadurch auszeichnet, dass man die Polymerisation in Gegenwart von
• d) 0,1 bis 10 Gewichtsprozent einer oder einer Mehrzahl von Verbindungen der allgemeinen Formel (III) und/oder der allgemeinen Formel (IV) und/oder der allgemeinen Formel (V) R⁴-Y-H (III) H-Y¹-R⁵-Y²-H (IV)
  
  worin Y, Y1 und Y2 unabhängig voneinander für Schwefel oder Sauerstoff stehen, R4 einen linearen oder verzweigten Alkylrest mit ein bis drei Kohlenstoffatomen bedeutet, R5 einen linearen oder verzweigten Alkylenrest mit zwei oder drei Kohlenstoffatomen bezeichnet, R6 einen linearen oder verzweigten Alkylrest mit ein bis 32 Kohlenstoffatomen bezeichnet und m und n unabhängig voneinander für Null oder natürliche ganze Zahlen im Bereich von eins bis 100 stehen, unter der Bedingung, dass nicht beide von m und n zugleich Null sind; wobei sich die Gewichtsangabe von d) auf die Summe der Gewichte a) + b) + c) + d) bezieht,

durchführt.This problem as well as other objects, which are not explicitly mentioned, but which can be deduced without further ado from the introductory discussion, are solved by a process for the preparation of copolymers by polymerization of a monomer composition consisting of

• a) from 10 to less than 90 percent by weight of at least one ethylenically unsaturated ester compound of the formula (I)
  
  wherein R is hydrogen or methyl, R ^{1 is} a linear or branched alkyl group having from six to 40 carbon atoms, R ² and R ^{3 are} independently hydrogen or a group of the formula -COOR ', wherein R' is hydrogen or an alkyl group having one to five carbon atoms means
• b) more than 10 to 90 percent by weight of at least one ethylenically unsaturated, polar ester compound of the formula (II)
  
  wherein R is hydrogen or methyl, X is oxygen, sulfur or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a is} an alkyl radical having one to 40 carbon atoms, R ^{10 is} a radical comprising two to 1000 carbon atoms with at least one Hydroxyl group, R ¹¹ and R ^{12 are} independently hydrogen or a group of the formula -COX'R ¹⁰ ', wherein X' is oxygen or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a 'is} an alkyl radical having a bis 40 carbon atoms, and R ¹⁰ 'represents a radical comprising one to 100 carbon atoms, and
• c) 0 to 50 percent by weight comonomer, in each case based on the total weight of (a) + b) + c)) of the ethylenically unsaturated monomers, wherein the process of the invention is characterized in that the polymerization in the presence of
• d) 0.1 to 10% by weight of one or a plurality of compounds of the general formula (III) and / or the general formula (IV) and / or the general formula (V) R ⁴ -YH (III) HY ¹ -R ⁵ -Y ² -H (IV)
  
  wherein Y, Y1 and Y2 independently of one another represent sulfur or oxygen, R4 denotes a linear or branched alkyl radical having one to three carbon atoms, R5 denotes a linear or branched alkylene radical having two or three carbon atoms, R6 denotes a linear or branched alkyl radical having one to 32 And m and n independently represent zero or natural integers in the range of one to 100, provided that not both of m and n are zero at the same time; where the weight of d) refers to the sum of the weights a) + b) + c) + d),

performs.

It has surprisingly and extremely advantageously been found that small additions of short-chain alcohols, short-chain mercaptans, hydroxyl-terminated ethylene oxide polymers or hydroxyl-terminated propylene oxide polymers lead to the monomer compositions to be polymerized into products which can be dissolved clearly in various lubricating oils in amounts of more than 10% by weight and at the same time act as VI improvers for the various lubricating oil compositions. The viscosity index improving effect is shown by, for example, the kinematic viscosities at 40 ° C and 100 ° C in accordance with ASTM D 2270 , The term "clear solution" in this context is generally understood to mean that the turbidity of a said 100 N mineral oil is comparable to a solution by addition of a copolymer obtainable by the process of the invention in an amount of 1% by weight (w / w) containing an amount of 1 percent by weight (w / w) of a copolymer Viscoplex ^® O-350, available from Evonik RohMax Additives GmbH, DE; contains. In the narrower sense, we understand a clear solution in the context of the invention that the turbidity of a standardized 100 N mineral oil by adding a copolymer obtainable by the process of the invention in an amount of 1 weight percent (w / w) by not more than 5 preferably 3, more preferably 1, very particularly preferably 0.5] nephelometric turbidity units (NTU) increases (measured according to ISO 7027 / DIN EN 27027 ).

With the process according to the invention can be copolymers from a monomer composition which is essential to a Component a), essentially a component and optionally a component c).

As an essential constituent, the monomer compositions to be polymerized contain from 10 to less than 90% by weight, in particular from 20 to 80% by weight, more suitably from 25 to 75% by weight, more suitably from 40 to 70% by weight, based on the total weight of the ethylenically unsaturated monomers ( is equal to the sum of the weights of a) + b) + c)), one or more ethylenically unsaturated ester compounds of the formula (I) wherein R is hydrogen or methyl, R ^{1 is} a linear or branched alkyl radical of one to 40 carbon atoms, especially four R ² and R ³ independently represent hydrogen or a group of the formula -COOR '', wherein R "represents hydrogen or an alkyl group having 6 to 15 carbon atoms.

These compounds include, among others
(Meth) acrylates, fumarates and maleates derived from saturated alcohols, such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl ( meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl ( meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate;
(Meth) acrylates derived from unsaturated alcohols, such as. For example, oleyl (meth) acrylate;
Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate; as well as the corresponding fumarates and maleates.

Of particular interest within the scope of the invention are processes which are characterized in that
as component a) one or a plurality of compounds of formula I, wherein R is methyl, R ^{1 is} a linear or branched alkyl radical having ten to eighteen carbon atoms and R ² and R ^{3 are} each hydrogen.

Even more preferred are processes wherein
as component a) uses an alkyl methacrylate having eleven to 15 carbon atoms in the ester group. It is understood that it is often impossible to give an exact integer for the carbon atoms of the ester chain for corresponding compounds. As a rule, the C-atom number of longer-chain ester radicals are average values, since the corresponding compounds are generally obtained by transesterification of, for example, methyl methacrylate with longer-chain alcohols based on a natural product with a specific chain length distribution.

The ester compounds having a long-chain alcohol radical, in particular the components, can accordingly be obtained, for example, by reacting (meth) acrylates, fumarates, maleates and / or the corresponding acids with long-chain fatty alcohols, in which case a mixture of esters, such as, for example, (meth) acrylates different long-chain alcohol residues arises. These fatty alcohols include Oxo Alcohol ^® 7911 and Oxo Alcohol ^® 7900, Oxo Alcohol ^® 1100; Alfol 610 ^{®, ®} Alfol 810, 125 and Nafol Liai ^{® ®} grades (Sasol Olefins & Surfactant GmbH); Alphanoi ^® 79 (ICI); Epal ^® 610 and Epal ^® 810 (Ethyl Corporation); Linevol ^® 79, Linevol ^® 911 and Neodol ^® 25E (Shell AG); Dehydad® ^®, Hydrenol ^® - and Lorol ^® grades (Cognis); Acropol ^® 35 and Exxal ^® 10 (Exxon Chemicals GmbH); Kalcol ^® 2465 (Kao Chemicals), Dobanol ^® grades from Shell and Dehydag types from Henkel.

Furthermore it is understood for the disclosure of the invention that the component to be polymerized according to the invention a) also from several different compounds of the formula I can recruit.

Also the component b) is for the according to the Invention to be polymerized monomer composition is an essential Component.

As a compulsory constituent, the compositions to be polymerized contain more than 10% by weight up to 90% by weight, in particular more than 10% by weight up to 50% by weight, advantageously from 12.5 to 30% by weight, based on the total weight of the ethylenically unsaturated monomers, one or more ethylenically unsaturated ester compounds of the formula (II)
wherein R is hydrogen or methyl, X is oxygen, sulfur or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a is} an alkyl radical having 1 to 40 carbon atoms, R ^{10 is} a radical comprising 2 to 1000 carbon atoms with at least 1 Hydroxyl group, R ¹¹ and R ^{12 are} independently hydrogen or a group of the formula -COX'R ¹⁰ ', wherein X' is oxygen or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a 'is} an alkyl radical having 1 to 40 Carbon atoms, and R ¹⁰ 'represents a radical comprising 1 to 100 carbon atoms.

In formula (II) X represents oxygen, sulfur or an amino group of the formula -NH- or -NR ^a - in which R ^{a is} an alkyl radical having from 1 to 40, preferably 1 to 4 carbon atoms.

The radicals R ¹¹ and R ¹² in formula (IV) independently represent hydrogen or a group of the formula -COX'R ¹⁰ ', where X' is oxygen, sulfur or an amino group of the formula -NH- or -NR ^a -, where R ^{a 'represents} an alkyl radical having 1 to 40 carbon atoms, preferably 1 to 4 carbon atoms, and R ¹⁰ ' represents a radical comprising 1 to 100, preferably 1 to 30 and particularly preferably 1 to 15 carbon atoms. The term "1 to 100 carbon radical" denotes radicals of organic compounds having 1 to 100 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. The groups mentioned can be branched or unbranched. The radical R ¹⁰ represents a radical comprising 2 to 1000, in particular 2 to 100, preferably 2 to 20, carbon atoms. The term "radical comprising 2 to 1000 carbon" denotes radicals of organic compounds having 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. The groups mentioned can be branched or unbranched. Furthermore, these groups can have customary substituents. Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as, for example, 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.

According to the invention, aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms. Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, where heteroaromatic groups have 3 to 19 carbon atoms atoms.

According to the invention preferred aromatic or heteroaromatic groups are derived from benzene, naphthalene, Biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, Bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, Imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl-1,3,4-triazole, 1,2,5-triphenyl-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, Isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, Benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, Carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, tetrazine, quinoline, Isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, Pyridopyrimidine, purine, pteridine or quinolizine, 4H-quinolizine, Diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole, benzooxadiazole, Benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, Indolizine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, Aciridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridizine, Benzopteridine, phenanthroline and phenanthrene, optionally may also be substituted.

To the preferred alkyl groups include the methyl, ethyl, Propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, Pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, Dodecyl, pentadecyl and the eicosyl group.

To the preferred cycloalkyl groups include the cyclopropyl, Cyclopentyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups, optionally with branched or unbranched alkyl groups are substituted.

To the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and the 2-eicosenyl group. Preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and the 2-decynyl group.

To the preferred alkanoyl groups include the formyl, acetyl, Propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, Hexanoyl, decanoyl and the dodecanoyl group.

To the preferred alkoxycarbonyl groups include the methoxycarbonyl, Ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl group, Hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.

To the preferred alkoxy groups include alkoxy groups whose Hydrocarbon radical is one of the abovementioned preferred Is alkyl groups.

To the preferred cycloalkoxy groups include cycloalkoxy groups, whose hydrocarbon radical is one of the abovementioned preferred Cycloalkyl groups is.

The radical R ¹⁰ has at least one hydroxyl group.

Very particularly preferred compounds of the formula II include, inter alia, hydroxyalkyl (meth) acrylates, such as
3-hydroxypropyl methacrylate,
3,4-dihydroxybutyl,
2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate,
2,5-dimethyl-1,6-hexanediol (meth) acrylate, and
1,10-decanediol (meth) acrylate;

According to a particular aspect of the process of the invention, as component b) one or a plurality of compounds of formula II, wherein R is methyl, X is oxygen, R ^{10 is} a radical comprising two to 18 carbon atoms having at least one hydroxyl group, and R ¹¹ and R ^{12 are} each hydrogen.

Especially preferred process variants are characterized in that it is used as component b) hydroxyethyl methacrylate.

Of the ethylenically unsaturated ester compounds, the (meth) acrylates are particularly preferred over the maleates and fumarates, ie R ¹¹ and R ^{12 of} the formula (II) represent hydrogen in particularly preferred embodiments.

monomers according to component b) may be similar the monomers according to components a) by transesterification of methyl (meth) acrylates with corresponding alcohols, amines and / or Thiols are obtained. Furthermore, some of these monomers commercially available.

Component c) is optional. In particular, ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulas (I) and (II) and which are different from the compounds of the formulas (I) and (II) are included. However, comonomers are particularly suitable for the polymerization according to the present invention, which correspond to the formula: C (R ^{1 *} R ^{3 *} ) = C (R ^{2 *} R ^{4 *} ),
wherein R ^{1 *} and R ^{2 * are} independently selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups having 1 to 20, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms, which are substituted with 1 to (2n + 1) halogen atoms may be substituted, wherein n is the number of carbon atoms of the alkyl group (for example CF ₃ ), α, β-unsaturated linear or branched alkenyl or alkynyl groups having 2 to 10, preferably from 2 to 6 and particularly preferably from 2 to 4 carbon atoms, which may be substituted by 1 to (2n-1) halogen atoms, preferably chlorine, wherein n is the number of carbon atoms of the alkyl group, for example CH ₂ = CCl-, cycloalkyl groups having 3 to 8 carbon atoms, which is 1 to (2n - 1) halogen atoms, preferably chlorine, may be substituted, wherein n is the number of carbon atoms of the cycloalkyl group; C (= Y ^* ) R ^{5 *} , C (= Y *) NR ^{δ *} R ^{7 *} , Y * C (= Y *) R ^{5 *} , SOR ^{5 *} , SO ₂ R ^{5 *} , OSO ₂ R ^{5 *} , NR ^{8 *} 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 which may be quaternized with an additional R ^{8 *} , aryl or heterocyclyl group, where Y * NR ^{8 *} , S or O, preferably O; R ^{5 * is} an alkyl group having 1 to 20 carbon atoms, an alkylthio having 1 to 20 carbon atoms, OR ¹⁵ (R ¹⁵ is hydrogen or an alkali metal), alkoxy of 1 to 20 carbon atoms, aryloxy or heterocyclyloxy; R ^{6 *} and R ^{7 * are} independently hydrogen or an alkyl group having 1 to 20 carbon atoms, or R ^{6 *} and R ^{7 *} may together form an alkylene group having 2 to 7, preferably 2 to 5, carbon atoms, having a 3 to 8 membered one , preferably 3 to 6 membered ring, and R ^{8 * are} hydrogen, linear or branched alkyl or aryl groups of 1 to 20 carbon atoms;
R ^{3 *} and R ^{4 * are} independently selected from the group consisting of hydrogen, halogen (preferably fluoro or chloro), alkyl groups of 1 to 6 carbon atoms and COOR ^{9 *} , where R ^{9 * is} hydrogen, an alkali metal or an alkyl group of 1 to 40 Carbon atoms, or R ^{1 *} and R ^{3 *} may together form a group of formula (CH ₂ ) _n 'which may be substituted with 1 to 2n' halogen atoms or C 1 to C ₄ alkyl groups, or of formula C (= O) -Y * -C (= O) where n 'is from 2 to 6, preferably 3 or 4, and Y * is as previously defined; and wherein at least 2 of the radicals R ^{1 *} , R ^{2 *} , R ^{3 *} and R ^{4 * are} hydrogen or halogen.

These include, but are not limited to, aminoalkyl (meth) acrylates such as N- (3-dimethylaminopropyl) methacrylamide,
3-Diethylaminopentylmethacrylat,
3-Dibutylaminohexadecyl (meth) acrylate;
Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates, such as N- (methacryloyloxyethyl) diisobutylketimine,
N- (methacryloyloxyethyl) dihexadecylketimin,
methacryloylamidoacetonitrile,
2-Methacryloyloxyethylmethylcyanamid,
cyanomethyl;
Aryl (meth) acrylates, such as benzyl methacrylate or
Phenyl methacrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times;
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. Α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as 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, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
Vinyl and isoprenyl ethers;
Maleic acid and maleic acid derivatives such as mono- and diesters of maleic acid, maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide;
Fumaric acid and fumaric acid derivatives such as mono- and diesters of fumaric acid;
Dienes such as divinylbenzene.

Preferred copolymers have a specific viscosity η _{sp / c} measured in chloroform at 25 ° C. in the range from 8 to 74 ml / g, more preferably in the range from 11 to 55 ml / g, measured according to ISO 1628-6 ,

The copolymers resulting from the process according to the invention can generally have a molecular weight in the range from 1000 to 1,000,000 g / mol, preferably in the range from 10 · 10 ³ to 500 · 10 ³ g / mol and more preferably in the range from 20 · 10 ³ to 300 × 10 ³ g / mol, without this being a restriction. These values are based on the weight average molecular weight of the polydisperse polymers in the composition. This size can be determined by GPC.

The preferred copolymers which can be obtained by polymerization of unsaturated ester compounds preferably have a polydispersity M _w / M _n in the range of 1.05 to 4.0. This size can be determined by GPC.

• d) 0,1 bis 10 Gewichtsprozent einer oder einer Mehrzahl von Verbindungen der allgemeinen Formel (III) und/oder der allgemeinen Formel (IV) und/oder der allgemeinen Formel (V) R⁴-Y-H (III) H-Y¹-R⁵-Y²-H (IV)
  

erhalten.The described copolymers are prepared according to the invention by polymerization in the presence of

• d) 0.1 to 10% by weight of one or a plurality of compounds of the general formula (III) and / or the general formula (IV) and / or the general formula (V) R ⁴ -YH (III) HY ¹ -R ⁵ -Y ² -H (IV)
  

receive.

The Formula (III) refers to short chain alcohols or mercaptans. Especially Y is oxygen or sulfur and the radical R4 comprises a linear or branched alkyl radical having one to three carbon atoms. In particular, R4 is methyl, ethyl, n-propyl and isopropyl.

The Formula (IV) refers to short chain diols or dithiols (mercaptodiols). In particular, in the formula (IV), Y1 and Y2 are independently each other for oxygen or sulfur. Y1 and Y2 can be the same or different, so that diols, dithiols or mixed forms possible are. The radical R5 is an alkylene radical with two or three carbon atoms, straight or branched.

preferred Compounds include: ethylene glycol, 1-3-propanediol, ethylenedithiol and 1,3-dimercaptopropanediol.

To with particular success as component d) usable compounds belong in a preferred process variant one or more Compounds selected from the group consisting of n-propanol, isopropanol, Mercaptoethanol, mercaptopropanol and (1,3) -mercaptopropanediol.

Of these, Again, such methods are particularly useful, wherein the polymerization in the presence of isopropanol and / or Mercaptoethanol is performed.

The inventive method can be also succeed if you are in the presence of a connection of the formula (V) polymerized. These include polymers of ethylene and / or propylene oxide. The polymers of formula V have Hydroxylendgrupppen on. These are homopolymers or copolymers.

A special process variant of the invention provides that in Presence of homopolymer of ethylene oxide as compound the formula V polymerized. The index n in this case has the value zero in formula V.

Especially expedient process variants provide that the polymerization in the presence of a compound of formula V, where n is zero and m is in the range of 20 until 50 lies.

Yet a preferred variant relates to methods using compounds of the formula V, wherein n and m are not equal to zero. It is about in this case copolymers of ethylene and propylene oxide, these being statistically or in block form. Especially useful is the use of EO / PO block copolymers with hydroxyl end groups.

R6 in formula V denotes hydrogen or a linear or branched one Alkyl radical having one to 32 carbon atoms.

The Amounts of compounds of the formulas (III), (IV) and / or (V) in whose presence copolymerizes the monomer composition a) to c) can, by the expert with routine tests to the special requirements be adapted to the reaction.

Especially appropriate procedural modifications provide that the polymerization in the presence of 0.5 to 4 weight percent, preferably 1 to 2.5% by weight of a compound of the formulas III and / or IV and / or V, wherein the made Quantity refers to the sum of the weights a) + b) + c) + d) + e).

methods for the polymerization of the compositions described above known in itself. So these polymers can in particular by radical polymerization, as well as related processes, such as for example, ATRP (= atom transfer radical polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer).

The usual Free radical polymerization is u. a. in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition. In general For this purpose, a polymerization initiator and a chain transfer agent used.

To The initiators that can be used include, among others azo initiators well known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, Dilauryl peroxide, tert-butyl per-2-ethylhexanoate (often also referred to as tert-butyl peroctoate tBPO), ketone peroxide, tert-butyl peroctoate, Methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, Dicumyl peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, Cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Mixtures of two or more of the aforementioned compounds with each other and mixtures of the aforementioned compounds with those not mentioned Compounds that can also form radicals.

In A special variant of the process goes in the process of Invention so that you can add the polymerization in the presence of e) from 0.1 to 10% by weight of one of d) Chain controller carries out, where quantity on the Sum of the weights of components a) + b) + c) + d) + e) relates.

When Chain transfer agents are suitable in this context in particular oil-soluble mercaptans such as Dodecyl mercaptan, tert-dodecyl mercaptan or chain transfer agents from the class of terpenes, such as terpinolene.

The ATRP method is known per se. It is believed that it this is a "living" radical polymerization without being limited by the description of the mechanism should be done. In these methods, a transition metal compound implemented with a connection that is a transferable Has atomic group. Here, the transferable atomic group transferred to the transition metal compound, whereby the metal is oxidized. In this reaction, a radical forms, the added ethylenic groups. The transmission of the atomic group however, the transition metal compound is reversible, so that the atomic group is retransmitted to the growing polymer chain is formed, creating a controlled polymerization system becomes. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution are controlled.

This reaction is, for example, of JS. Wang, et al., J. Am. Chem. Soc, Vol. 117, p. 5614-5615 (1995) , from Matyjaszewski, Macromolecules, Vol. 28, p. 7901-7910 (1995) described. In addition, the patent applications disclose WO 96/30421 . WO 97/47661 . WO 97/18247 . WO 98/40415 and WO 99/10387 Variants of the previously discussed ATRP.

Furthermore, the polymers according to the invention can also be obtained, for example, by RAFT methods. This method is for example in WO 98/01478 and WO 2004/083169 which is expressly referred to for purposes of the disclosure.

The Polymerization can be at normal pressure, under or over pressure be performed. Also the polymerization temperature is not critical. In general, however, it is 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 become. The term of the solvent is hereby far to understand. Preferably, the polymerization is in a nonpolar Solvent carried out. These include Hydrocarbon solvents, such as aromatic Solvents, such as toluene, benzene and xylenes, saturated Hydrocarbons, such as cyclohexane, heptane, octane, nonane, Decane, dodecane, which can also be branched. These Solvents can be used individually or as a mixture be used. Particularly preferred solvents are mineral oils, natural oils and synthetic oils as well Mixtures thereof. Of these, mineral oils are very special prefers.

Of the Structure of the copolymers of the invention is for many applications and features are not critical. Accordingly can the copolymers of the invention represent random copolymers.

According to one Another aspect of the present invention, the inventive Copolymers represent block copolymers. These polymers can be, for example obtained by allowing the monomer composition during the chain growth changed discontinuously. Prefers have the ester compounds of the formulas (I), (II) and optionally (III) derived blocks at least 30 monomer units on.

block copolymers denote copolymers having at least two blocks. Blocks are here segments of the copolymer, which is a constant Have composition of one or more monomer building blocks. The individual blocks can be different Be constructed monomers. Furthermore, the Blocks only by the concentration of different Distinguish monomer units, where within a block a statistical distribution of the various monomer units are present can.

According to one interesting aspect of the present invention are the different blocks by a concentration difference at least one monomer building block of 5% or more, preferably at least 10% and more preferably at least 20%, without thereby affecting a restriction should be made.

Of the Term "concentration of monomeric building blocks" based on the number of these units used by the Monomers are derived, based on the total number of recurring Units within a block. The difference in concentration results from the difference between the concentrations at least a monomer module of two blocks.

the One skilled in the art is aware of the polydispersity of polymers. Accordingly, the information relating to of the concentration difference over to a static agent all polymer chains of the corresponding segments.

The Length of the blocks can vary within wide ranges. According to the invention, the blocks preferably at least 30, preferably at least 50, more preferably at least 100 and most preferably at least 150 monomer units exhibit.

Next Diblock copolymers are also multiblock copolymers which are at least three, preferably at least four blocks, subject of the present invention. These block copolymers can have alternating blocks. Furthermore For example, the block copolymers may also be used as comb polymers or as star polymers available.

Preferred block copolymers may comprise hydrophobic segments formed by polymerization of Monomer compositions are obtained which may in particular (meth) acrylates, maleates and / or fumarates. The hydrophobic segments are in particular derived from ethylenically unsaturated compounds of the formulas (I), (II) and, where appropriate, (III).

Preferably For example, the copolymer of the present invention may be used in a lubricating oil composition be used. A lubricating oil composition comprises at least one lubricating oil. Belong to the lubricating oils especially mineral oils, synthetic oils and natural oils.

to Accordingly, the invention involves the use of one after the polymerizate described herein as a clearly soluble additive to mineral oil, synthetic oil, Ester oil or vegetable oil.

mineral oils are known per se and commercially available. you will be generally from petroleum or crude oil by distillation and / or refining and optionally further cleaning and Obtained by refining process, taking the term mineral oil in particular the higher boiling fractions of the raw or Petroleum fall. In general, the boiling point of Mineral oil higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering shale oil, coking coal, Distillation under exclusion of air from lignite and hydrogenation from coal or brown coal is also possible. To a mineral oils are also made from vegetable raw materials (eg from jojoba, rapeseed) or animal (eg claw oil) Made of origin. Accordingly, mineral oils, depending on the origin different proportions of aromatic, cyclic, branched and linear hydrocarbons.

In general, a distinction is made between paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes. In addition, mineral oils, depending on their origin and refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are attributed to polar properties , The assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties. For the purposes of the present invention, the association may be, for example, according to DIN 51 378 respectively. Polar components may also be used according to ASTM D 2007 be determined. The proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of ON and / or S-containing compounds less than 6 wt .-%. The proportion of aromatics and monomethyl branched paraffins is generally in the range of 0 to 40 wt .-%.

According to one interesting aspect includes mineral oil mainly naphthenic and paraffinic alkanes, which are generally more as 13, preferably more than 18, and most preferably more have 20 carbon atoms. The proportion of these compounds is generally> 60 Wt .-%, preferably> 80 Wt .-%, without this being a limitation should. A preferred mineral oil contains 0.5 to 30% by weight of aromatic components, 15 to 40% by weight of naphthenic components, From 35 to 80% by weight of paraffin-based fractions, up to 3% by weight of n-alkanes and 0.05 to 5 wt .-% polar compounds, each based on the total weight of mineral oil.

An analysis of particularly preferred mineral oils, which was carried out by conventional methods, such as urea separation and liquid chromatography on silica gel, shows, for example, the following constituents, the percentages being based on the total weight of the particular mineral oil used: n-alkanes having about 18 to 31 C atoms:
0.7-1.0%, slightly branched alkanes having 18 to 31 C atoms:
1.0-8.0%
Aromatics with 14 to 32 C atoms:
0.4 to 10.7%
Iso- and cycloalkanes with 20 to 32 carbon atoms:
60.7-82.4%, polar compounds:
0.1-0.8%
Loss:
6.9 to 19.4%.

Valuable information regarding the analysis of mineral oils as well as an enumeration of mineral oils, which have a different composition, can be found for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997 , Keyword "lubricants and related products".

Synthetic oils include organic esters, for example, diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, in particular polyolefins, of which polyalphaolefins (PAO) are preferred are silicone oils and perfluoroalkyl ethers. They are mostly a little more expensive than the mineral oils, but have advantages in terms of their performance.

Natural oils are animal or vegetable oils, such as Claw oils or jojoba oils.

These Lubricating oils can also be used as mixtures are and are often commercially available.

The Concentration of the polyalkyl ester in the lubricating oil composition is preferably in the range of 2 to 40 wt .-%, more preferably in the range of 4 to 20 wt .-%, based on the total weight of Composition.

Next The above-mentioned components may be a lubricating oil composition contain further additives and additives. To these additives include antioxidants, corrosion inhibitors, anti-foaming agents, Anti-wear components, dyes, color stabilizers, detergents, Pour point depressants and / or DI additives.

Preferred lubricating oil compositions have one according to ASTM D 445 at 40 ° C measured viscosity in the range of 10 to 120 mm ² / s, more preferably in the range of 22 to 100 mm ² / s.

According to a particular aspect of the present invention, preferred lubricating oil compositions are one according to ASTM D 2270 certain viscosity index in the range of 120 to 350, especially from 140 to 200 on.

A preferred use provides in the context of the invention to the addition Mineral oil in an amount of up to 17.5 weight percent (w / w) before, using a mineral oil with a nephelometric Turbidity value (NTU) of less than 5 results.

object The invention is also a 100 N mineral oil having in clear solution with a nephelometric turbidity value (NTU) of less than 5, having one according to the method of Invention obtained copolymer.

One contains appropriate 100 N mineral oil to 17.5 wt .-% of a copolymer.

Yet a preferred embodiment of the 100 N mineral oil contains one to 15 percent by weight of a copolymer.

Especially preferred is a 100N mineral oil comprising a C11-C15 alkyl methacrylate hydroxyethyl methacrylate Copolymer with a content of hydroxyethyl methacrylate of more as ten percent by weight based on the sum of C11-C15 alkyl methacrylate and hydroxyethyl methacrylate.

The The following examples and comparative examples are used in detail Explanation of the invention:

Example 1:

Preparation of a C11-C15-alkyl methacrylate (Component a) - Hydroxyethyl methacrylate (component b) - Copolymerisats in the presence of i-propanol (component d) and dodecylmercaptan (Component e) after a batch process.

Mix:
160 g C11-C15 alkyl methacrylate
40 g of hydroxyethyl methacrylate
4 g of i-propanol
4 g of dodecylmercaptan
2 g of tert-butyl perpivalate

The components (except for the initiator tert-butyl pivalate) were in a 500 ml three-necked flask, with Saber stirrer, thermometer, coolable stirrer sleeve and condenser under N2 gas cushion at 80 ° C polymerized by batch process for 20 hours. The addition of the initiator was carried out at 80 ° C. 2 and 4 hours after the first addition of initiator 0.4 g of initiator were added again. After the end of the polymerization, 200 g of KPE 100 SN oil were added and the oil solution was filtered through a 125 μm filter.

KPE 100 SN oil is a 100 N mineral oil available from Kuwait Petroleum Europoort (KPE). KPE 100 SN oil has the following specifications: Feature / unit method specification limits Appearance visually bright colour ASTM D 1500 1.0 max. Density 15 ° C, g · cm ^-3 ASTM D 4052 0.860 ± 0.005 n _D20 DIN 51423/2 1,473 typ. Flash point, ° C ASTM D92 190 min. Noack,% by weight DIN 51581 28 typ. Pour Point, ° C DIN ISO 3016 -12 max. KV 100 ° C, mm ² · s ^-1 ASTM D 445 4.00 typ. KV 40 ° C mm ² · s ^-1 ASTM D 445 18.8 to 21 VI ASTM D 2270 100 ± 5 Sulfur,% by weight DIN 51400/6 0.20 max. CA,% by weight IR-fire 6.0 max. Oxidative Stability IOT / ° C KPI 64-0797 (DSC method) 165 min. Demulsibility to 40/40/0 / min. ASTM D 1401 10 max. Filterability Cetop FF> 104 / min. G6.015.01D 25 max.

The with the copolymer of the invention obtainable oil concentrate had a clear appearance.

Comparative Example 1

As Example 1, but in the absence of i-propanol (component d)

• 160 g of C11-C15-alkymethacrylate
• 40 g of hydroxyethyl methacrylate
• 4 g of dodecylmercaptan
• 2 g of tert-butyl perpivalate

The components (except for the initiator tert-butyl perpivalate were in a 500 ml three-necked flask with
Saber stirrer, thermometer, coolable stirrer sleeve and condenser under N2 gas cushion at 80 ° C polymerized by batch process for 20 hours. The addition of the initiator was carried out at
80 ° C. 2 and 4 hours after the first addition of initiator 0.4 g of initiator were added again. The polymer was again dissolved in the same oil as in Example 1.

The oil concentrate had a milky appearance.

Comparative Example 2:

Preparation of a copolymer of C 12 -C 15 -methacrylate / hydroxyethyl methacrylate = 80/20% after a feed process

• 22.88 grams of C12-C15 methacrylate;
• 5.72 g of hydroxyethyl methacrylate;
• 0.57 g of dodecylmercaptan;
• 0.29 g of dodecanol;
• 0.29 g of tert-butyl perpivalate was dissolved in a 1 L 3-neck round bottom flask submitted.

At 80 ° C was allowed
under inert gas and stirring, a mixture of 456.8 g of C12-C15 methacrylate; 114.2 g of hydroxyethyl methacrylate; 11.43 g of dodecylmercaptan; 5.71 g of dodecanol; Run 5.71 g of tert-butyl perpivalate in 3.5 hours. 2 hours after the end of the feed, a further 1.2 g of tert-butyl perpivalate were added and the mixture was heated at 80 ° C. for a further 16 hours.

After that was diluted to 70% with 258.1 g of 100N mineral oil. Subsequently, 250 g of the dilution at 100 ° C. with 2 bar over a Seitz T-1000 - depth filter pressure filtered.

25 g of the 70% solution were dissolved in 75 g of 150 N oil and the kinematic viscosity was determined in the Herzog HVM 472; The prepared formulation was used for characterization; a clear solution was obtained with the following values:
KV100 = 11.56 mm ² / s; KV40 = 70.4 mm ² / s; VI = 159

Example 2:

Preparation of a copolymer of C 12 -C 15 methacrylate / hydroxyethyl methacrylate = 60/40% after a feed process

12 g n-Propanol was placed in the 1 L three-necked round bottom flask. At 80 ° C ° C was allowed under inert gas and stirring a mixture from 360 g C12-C15 methacrylate; 240 g of hydroxyethyl methacrylate; 11.25 g dodecylmercaptan; 11.43 g of n-propanol; 5.71 g of tert-butyl perpivalate) run in 3.5 hours. 30 min. After the end of the feed was the Stir off and stir at 95 ° C for 16 hrs. annealed.

15.00 g of the resulting polymer were dissolved in 6.43 g of 100 N oil and 64.29 g of 150 N oil and determined from the solution, the kinematic viscosity in the Duke HVM 472; the prepared formulation was used for characterization and a clear solution was obtained with the following values: KV100 = 20.32 mm ² / s; KV40 = 217.4 mm ² / s; VI = 109

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 96/30421 [0056]
• WO 97/47661 [0056]
• WO 97/18247 [0056]
• WO 98/40415 [0056]
• WO 99/10387 [0056]
• WO 98/01478 [0057]
• WO 2004/083169 [0057]

Cited non-patent literature

• ASTM D 2270 [0005]
• - ISO 7027 [0005]
• - DIN EN 27027 [0005]
• - ISO 1628-6 [0034]
• - JS. Wang, et al., J. Am. Chem. Soc, Vol. 117, p. 5614-5615 (1995) [0056]
• - Matyjaszewski, Macromolecules, Vol. 28, p. 7901-7910 (1995) [0056]
• - DIN 51 378 [0072]
• - ASTM D 2007 [0072]
• Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition to CD-ROM, 1997 [0075]
• ASTM D 445 [0081]
• ASTM D 2270 [0082]
• ASTM D 1500 [0091]
• ASTM D 4052 [0091]
• - DIN 51423/2 [0091]
• ASTM D 92 [0091]
• - DIN 51581 [0091]
• - DIN ISO 3016 [0091]
• ASTM D 445 [0091]
• ASTM D 445 [0091]
• ASTM D 2270 [0091]
• - DIN 51400/6 [0091]
• ASTM D 1401 [0091]

Claims (15)

Process for the preparation of copolymers by polymerization of a monomer composition consisting of a) from 10% to less than 90% by weight of at least one ethylenically unsaturated ester compound of the formula (I)

wherein R is hydrogen or methyl, R ^{1 is} a linear or branched alkyl group having from six to 40 carbon atoms, R ² and R ^{3 are} independently hydrogen or a group of the formula -COOR ', wherein R' is hydrogen or an alkyl group having one to five carbon atoms b) more than 10 to 90 percent by weight of at least one ethylenically unsaturated, polar ester compound of the formula (II)

wherein R is hydrogen or methyl, X is oxygen, sulfur or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a is} an alkyl radical having one to 40 carbon atoms, R ^{10 is} a radical comprising two to 1000 carbon atoms with at least one Hydroxyl group, R ¹¹ and R ^{12 are} independently hydrogen or a group of the formula -COX'R ¹⁰ ', wherein X' is oxygen or an amino group of the formula -NH- or -NR ^a -, wherein R ^{a 'is} an alkyl radical having a bis 40 carbon atoms, and R ¹⁰ 'is a radical comprising one to 100 carbon atoms, and c) 0 to 50 percent by weight comonomer, based in each case on the total weight of (a) + b) + c)) of the ethylenically unsaturated monomers, characterized in that the polymerization is carried out in the presence of d) 0.1 to 10% by weight of one or a plurality of compounds of the general formula (III) and / or the general formula (IV) and / or the general formula (V) R ⁴ -YH (III) HY ¹ -R ⁵ -Y ² -H (IV)

wherein Y, Y1 and Y2 independently of one another represent sulfur or oxygen, R4 denotes a linear or branched alkyl radical having one to three carbon atoms, R5 denotes a linear or branched alkylene radical having two or three carbon atoms, R6 denotes a linear or branched alkyl radical having one to 32 And m and n independently represent zero or natural integers in the range of one to 100, provided that not both of m and n are zero at the same time; wherein the weight of d) refers to the sum of the weights a) + b) + c) + d). Method according to claim 1, characterized, that he the polymerization additionally in the presence from e) from 0.1 to 10% by weight of one of d) Chain controller performs, with the amount of information on the sum of the weights of components a) + b) + c) + d) + e) relates. Method according to one of claims 1 or 2, characterized in that one carries out the polymerization in the presence of one or a plurality of compounds of formula III and / or IV, selected from the group consisting of n-propanol, iso-propanol, mercaptoethanol, mercaptopropanol and (1,3) -Mercap topropandiol. Method according to one of the preceding claims, characterized in that the polymerization in the presence of isopropanol and mercaptoethanol or in the presence of n-propanol and dodecylmercaptan. Method according to one of claims 1 to 3, characterized in that the polymerization in the presence a compound of formula V wherein n is zero and m is in the range of 20 to 50. Method according to one of the preceding claims, characterized in that the polymerization in the presence from 0.5 to 4% by weight, preferably 1 to 2.5% by weight, a compound of formulas III and / or IV and / or V, where the quantity is based on the sum of the weights a) + b) + c) + d) + e). Method according to one of the preceding claims, characterized in that as component a) one or a plurality of compounds of the formula I, wherein R is methyl, R ^{1 is} a linear or branched alkyl radical having ten to eighteen carbon atoms and R ² and R ³ each hydrogen. Method according to one of the preceding claims, characterized in that as component a) an alkyl methacrylate with from 11 to 15 carbon atoms in the ester group. Method according to one of the preceding claims, characterized in that one or a plurality of compounds of formula II, wherein R is methyl, X is oxygen, R ^{10 is} a radical comprising two to 18 carbon atoms having at least one hydroxyl group as component b) and R ¹¹ and R ^{12 are} each hydrogen. Method according to one of the preceding claims, characterized in that as component b) hydroxyethyl methacrylate starts. Use of a method according to the Claims 1 to 10 available polymer as a clearly soluble additive to mineral oil, synthetic oil, Ester oil or vegetable oil. Use according to claim 11 as an additive to mineral oil in an amount of up to 17.5% by weight with a nephelometric Turbidity value (NTU) of less than or equal to 5. 100 N mineral oil containing in clear solution with a Nephelometric Haze Value (NTU) of smaller or equal to 5 a by the method according to the Claims 1 to 10 obtained copolymer. 100 N mineral oil according to claim 13 containing one to 17.5 percent by weight of a copolymer obtained after the claims 1 to 10. 100 N mineral oil according to claim 13 or 14 containing C11-C15-alkyl methacrylate-hydroxyethyl methacrylate copolymer with a proportion of hydroxyethyl methacrylate of more than ten percent by weight based on the sum of C11-C15-alkyl methacrylate and hydroxyethyl methacrylate.