Copolymer which can be obtained using ATRP methods, and method for producing and using the same

The present invention relates to a copolymer obtained through the ATRP method comprising these copolymers and and a concentrate of the lubricating oil, a method of preparing these copolymers and use them as pour point inhibitor.

Lubricating oil, in particular derived from petroleum by distillation, for example, of mineral oil, long-chain n-alkanes typically comprises, on the one hand to bring about good degree of viscosity/temperature characteristic, but on the other hand the cooling of the crystalline form of the flow of the oil and therefore adversely affect or completely obstructing ("blocked"). Improving the performance of a low temperature flows can be realized by, for example, by dewaxing. However, to obtain complete dewaxing is obviously increase the cost. Therefore, partial dewaxing obtain low to -15 the pour point range of [...] , and the pour point can be through adding the so-called pour point inhibitor or pour point promoter, which is further reduced. These reagent can even 0.01-1% weight concentration of the pour point is effectively reduced.

Mode of action of these compounds, however, have not yet been completely clear. In any case, it is said that stone waxy compound is paraffin wax is introduced into the growth of crystal on the surface and thus stop further crystallization, in particular the formation of the crystal structure extends.

Certain structure with pour point improved activity has been known. In particular, having a sufficient long alkyl side chain of the polymer has a pour point, and the flow promotion effect. In this, it is said that these alkyl is introduced into the positive growth and interrupt the paraffin crystal in the crystal growth (refer to the Ullmann ' s   Encyclopedia   of Industrial   Chemistry, 4th Edition, Vol. 20, Verlag   Chemie, 1981, p.548). Furthermore, the inhibitors can be used for the pour point of the request is, they have good thermal, oxidation and chemical stability, shear strength, and the like. Furthermore, the cost should be produced on the basis of the pour point and flow promoters, because of their large-scale use.

With long-chain alkyl poly (meth) acrylic ester widely used as flow promoter inhibitor or pour point. These compounds are, for example, described in US Patent 2091627, US Patent 2100   993, US Patent 2114233 and EP-A-0   236844. Generally speaking, these pour point inhibitor produced through free-radical polymerization reaction. Therefore, they can be the production on the basis of cost. They are for example in pour point (in accordance with ASTM   D-97), micro-rotary viscosity (according to ASTM   D-4684) testing or scanning Brookfleld (in accordance with ASTM   D-5133) the results of the low-temperature characteristic can be used in many occasions, however, these low-temperature performance is still insufficient in many situations.

In this it should be noted, can be a small amount of more effective additives in order to obtain the required can be of the low-temperature fluidity. The amount of the lubricating oil of an internal combustion engine and used for bio-fuel, even if less there will be a noticeable difference may be saved.

Consider to the prior art, the task of the invention now is to prepare available additive, relative to the traditional additive by the internal combustion engine and internal combustion engine lubricating oil at the low temperature of the biological fuel flow properties. Furthermore, a task of the present invention is prepared in the oxidation and thermal stress with high stability and with high shear strength of the available additive. At the same time, this new kind of additive may be wished to production in a simple and economical manner.

The material can be easily by the introduction of or performance of these and other is not expressly referred to by a has the task of claim 1 all of the features of the solution of the copolymer. According to the present invention is a copolymer of from the belonging to the improvement of claim 1 for those in the claims. As a lubricating oil additive concentrate on, claim 4 provides the following tasks solutions, and claim 6 and 9 containing copolymer of this invention is the protection of the internal combustion engine lubricating oil or biological fuel. 11 and 14 representing a method for preparing the copolymer and use thereof the relevant solutions for the problems.

As pour point improver or flow accelerator obtained in this way efficient copolymer: ethylenically unsaturated monomer with an initiator radical transfer, one or more and comprising at least one transition metal catalyst, in the can with a metal catalyst to form coordination compound ligand of polymerization is carried out in the presence of, wherein the ethylenically unsaturated monomer mixture is as follows:

A) 0-40% by weight of one or more has the formula (I) of an ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R¹ with said 1-5 carbon atoms of the linear or branched alkyl residue of, R² and R³ independently represents hydrogen or has the formula-COOR 'group, wherein R' represents hydrogen or has 1-5 carbon atom alkyl,

B) 10-98% by weight of one or more of the structural formula (II) with an ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R⁴ with said 6-15 carbon atoms of the linear or branched alkyl residue of, R⁵ and R⁶ independently hydrogen or has the formula-COOR "group, wherein R" represents hydrogen or has 6-15 carbon atoms of the alkyl group,

C) 0-80% by weight of one or more of (III) with the structural formula of ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R⁷ with said 16-30 carbon atoms of the linear or branched alkyl residue of, R⁸ and R⁹ independently hydrogen or a group having the formula, -COOR, wherein a represents hydrogen or R  16-30 carbon atom alkyl,

D) 0-50% by weight of copolymerized monomer,

The data are respectively expressed by the % refers to the alkene weight to the total weight of the unsaturated monomer. Pour point for improved results may be, for example, in accordance with ASTM   D97 to determine.

Furthermore, lubricating oil comprising copolymer of this invention has excellent in accordance with ASTM   D4684 the obtained micro-rotary viscosity (MRV) and in accordance with the value ASTM   D5133 scanning Brookfield results obtained.

Internal combustion engine comprising copolymer of this invention the biological fuel in the IP   309 of the cold filter or in accordance with the ASTM measuring jamming spot   D4539 of the low-temperature flow test with abnormal results.

If would like to obtain, at a given temperature, some flow properties, the amount of the additive can be reduced by the present invention.

At the same time, many other advantages obtained through the copolymer of this invention. Including:

The copolymer of this invention is characterized in that a narrow molecular weight distribution. This can be obtained by the effect of high shearing stability.

The copolymer of this invention on the basis of cost-effective production.

The copolymer has a highly oxidation resistant and chemically very stable.

Copolymer of this invention is basically known; they can by two or more different monomer of the polymer obtained by the polymerization reaction. This term broadly understood as including statistical copolymer, comprises two, three or more kind of block copolymer, graft copolymer and the gradient copolymer.

The copolymer of this invention can be obtained, in particular with different alcohol residue composition comprising the (meth) acrylic ester, maleic acid ester and fumar ester. The term (meth) acrylate comprises a methyl acrylate and acrylic ester and a mixture of the two. These monomer to a large extent is known. In this, alkyl residues can be a linear, cyclic or branched.

Can be obtained a mixture of a copolymer of this invention can include 0-40% weight, in particular 0.5-20% by weight of one or more has the formula (I) of an ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R¹ with said 1-5 carbon atoms of the linear or branched alkyl residue of, R² and R³ independently represents hydrogen or has the formula-COOR 'group, wherein R' represents hydrogen or has 1-5 carbon atoms of the alkyl.

Component (a) is an example of, in addition to the other, of self-saturated alcohols derived from (meth) acrylic ester, fumaric acid ester and maleic acid esters, such as (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, diethyl (meth) acrylic acid, (meth) acrylic acid isopropyl group ester , contact (meth) acrylic acid, (meth)- acrylic acid uncle contact amyl ester and (meth) acrylic acid ; (meth) acrylic acid naphthenic ester, such as (meth) acrylic acid cyclopentyl ester; derived from the unsaturated (meth) acrylic ester such as (meth) acrylic acid 2- propynyl ester , (meth) acrylic acid allylic ester and (meth) acrylic acid vinyl ester.

As an important component, the polymeric composition comprises 10-98% weight, especially 20-95% by weight of one or more of the structural formula (II) with an ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R⁴ with said 6-15 carbon atoms of the linear or branched alkyl residue of, R⁵ and R⁶ independently hydrogen or has the formula-COOR "group, wherein R" represents hydrogen or has 6-15 carbon atoms of the alkyl group.

Including, in addition to the other, of self-saturated alcohols derived from (meth) acrylic ester, fumaric acid ester and maleic acid ester, hexyl ester such as (meth) acrylic acid, (meth) acrylic acid 2-b-based hexyl ester , heptyl ester (meth) acrylic acid, (meth) acrylic acid 2-tert-butyl heptyl ester , (meth) acrylic misery ester, (meth) acrylic acid 3-isopropyl heptyl ester , nonyl ester (meth) acrylic acid, (meth) acrylic acid decyl ester , (meth) acrylic acid, undecane ester, (meth) acrylic acid 5-methyl undecane ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid 2-methyl-dodecyl ester, (meth) acrylic acid tridecane ester, (meth) acrylic acid 5-methyl tridecane ester, alkyl (meth) acrylic acid fourteen, fifteen alkyl (meth) acrylic acid; derived from unsaturated alcohol such as (meth) acrylic acid ester oil base ester (meth) acrylic acid ; (meth) acrylic acid naphthenic base ester like (meth) acrylic acid, 3-vinyl cyclohexyl ester , cyclohexyl ester (meth) acrylic acid, (meth) acrylic acid borneol ester; and the corresponding fumarate and maleate.

Furthermore, the monomer mixture used in the invention can include 0-80% weight, preferably 0.5-60% by weight of one or more of (III) with the structural formula of ethylenically unsaturated ester compound:

Wherein is R hydrogen or methyl , R⁷ with said 16-30 carbon atoms of the linear or branched alkyl residue of, R⁸ and R⁹ independently hydrogen or a group having the formula, -COOR, wherein a represents hydrogen or R  16-30 carbon atoms of the alkyl.

Component (c) is an example of, in addition to the other, of self-saturated alcohols derived from (meth) acrylate, e.g., sixteen alkyl (meth) acrylic acid, (meth) acrylic acid 2-methyl-alkyl ester, seventeen alkyl (meth) acrylic acid, (meth) acrylic acid 5-isopropyl seventeen alkyl ester, (meth) acrylic acid 4-tert-butyl eighteen alkyl ester, (meth) acrylic acid 5-ethyl eighteen alkyl ester, (meth) acrylic acid 3-isopropyl eighteen alkyl ester, alkyl (meth) acrylic acid of eighteen, nineteen alkyl (meth) acrylic acid, (meth) acrylic acid alkyl ester of twenty, twenty whale ceryl (meth) acrylic acid alkyl ester, (meth) acrylic acid stearyl yl twenty alkyl ester, twenty-two (meth) acrylic acid alkyl ester and/or (meth) acrylic acid alkyl ester of the twentieth alkyl octogenarian; naphthenic base ester like (meth) acrylic acid, (meth) acrylic acid 2, 4, 5-tri-tert-butyl-3-vinyl cyclohexyl ester , (meth) acrylic acid 2, 3, 4, 5-tetra-tert-butyl cyclohexyl ester ; methacrylic acid ethylene oxide ester such as methyl acrylic acid 10, 11-epoxy hexadecane ester; and the corresponding fumarate and maleate.

The ester compound with long chain mellow remnant base , especially component (b) and (c) can be for example, the (meth) acrylic ester, fumaric acid esters, maleic acid esters and/or the corresponding acids with long-chain fatty alcohol obtained by a reaction, wherein the generally left with different long chain mellow remnant base (meth) acrylic acid ester of the mixture. These fatty alcohol comprises, in addition to other, Oxo   Alcohol^ 7911 and Oxo   Alcohol^ 7900, Oxo   Alcohol^ 1100 (Monsanto); Alphanol^ 79 (ICI); Nafol^ 1620, Alfol^ 610 and Alfol^ 810 (Condea); Epal^ 610 and Epal^ 810 (Ethyl Corporation); Linevol^ 79, Linevol^ 911 and Dobanol^ 25L (Shell   AG); Lial   125 (Augusta^ Mailis); Dehydad^ and Lorol^ (Henkel   KGaA) and Linopol^ 7-11 and Acropol^ 91 (Ugine   Kuhlmann).

In in ethylenically unsaturated ester compound, (meth) acrylate are particularly preferred maleic ester, and fumarate, i.e., structural formula (I), (II) and (III) the R², R³, R⁵, R⁶, R⁸, R⁹ in a particularly preferred embodiment said hydrogen.

Component (d) and including, in particular, has the formula (I), (II) and/or (III) the copolymerization of olefinically unsaturated ester compound of an ethylenically unsaturated monomer.

However, corresponding to the copolymerized monomers of the following formula is especially suitable for the polymerization reaction of the present invention:

Wherein R^1* and R^2* independently selected from hydrogen, halogen, CN, can be 1 to (2n + 1) a halogen atom substituted with 1-20, preferably 1-6 and in particular preferably 1-4 carbon atom linear or branched chain alkyl group, the alkyl carbon atom number is n (for example CF₃), can be 1 to (2n-1) a halogen atom, a substituted optimal chlorine 2-10, preferably 2-6 and in particular preferably 2-4 a carbon atoms, β-unsaturated linear or branched chain alkenyl or alkynyl, wherein n is an alkyl such as CH₂ =CCl-carbon atom number, can be 1 to (2n-1) a halogen atom, a substituted optimal chlorine 3-8 carbon atom of the cycloalkyl, wherein the cycloalkyl carbon atoms is n; can be other R^8*, aryl, or heterocyclic group of the quaternized   C (=Y^*) R^5*,

C (=Y^*) NR^6* R^7*, Y^* C (=Y^*) R^5*, SOR^5*,   SO₂ R^5*, OSO₂ R^5*,

NR^8* SO₂ R^5*, PR^5*₂, P (=Y^*) R^5*₂, Y^* PR^5*₂, Y^* P (=Y^*) R^5*₂, NR^e*₂, wherein Y^* can be NR^8*, S or O, preferably O; R^5* has 1-20 carbon atom alkyl, with 1-20 carbon atom alkyl thio group, OR¹⁵ (R¹⁵ is hydrogen or an alkali metal), has 1-20 carbon atoms of the alkoxy, aryloxy or heterocyclic yloxy; R^6* and R^7* is hydrogen or has independently 1-20 carbon atom alkyl, or R^6* and R^7* can be formed together with 2-7, preferably 2-5 carbon atoms of the alkylene, wherein they form 3-8 Yuan, preferably 3-6-membered ring, and R^8* is hydrogen, with 1-20 carbon atoms of the linear or branched chain alkyl or aryl;

R^3* and R^4* independently selected from hydrogen, halogen (preferably fluorine or chlorine), with 1-6 carbon atoms of alkyl and COOR^9*, wherein R^9* is hydrogen, alkali metal or a 1-40 carbon atoms, or R^1* and R^3* can together form a can be 1-2n the [...] halogen atom or C₁-C₄ alkyl substituted with structural formula (CH₂)_n group, or may form a has the formula C (=O)-Y^*-C (=O) group, wherein n ' is 2-6, preferably 3 or 4, and Y^* is as defined above; and wherein at least two of the residues R^1*, R^2*, R^3* and R^4* is hydrogen or halogen.

These include, in addition to the other, (meth) acrylic acid hydroxy alkyl ester such as methyl acrylic acid 3-hydroxy-diethyl, methyl acrylic acid 3, 4-dihydroxy-contact, methyl acrylic acid 2-hydroxy-ethyl ester, methyl acrylic acid 2-hydroxy-diethyl, (meth) acrylic acid 2, 5-dimethyl -1, 6-hexamethylene glycol ester, (meth) acrylic acid, 1, 10- decane diol ester ;

(Meth) acrylic acid amino alkyl group N-(3-dimethyl amino-propyl) methyl acrylamide, methyl acrylic acid 3-diethyl amino amyl ester , (meth) acrylic acid 3-dibutylamino sixteen alkyl ester;

Nitrile of (meth) acrylic acid with other nitrogen-containing methyl acrylate such as N-(methyl acrolyl propoxycyclohexyl ethyl) diisobutylcarbamoylmethyl ketimine, N-(methyl acrolyl propoxycyclohexyl ethyl) II (cetyl) ketimine, methacryloxyl acyl group acid radical amino-acetonitrile, 2-methyl-acryloyl phenoxy ethyl methyl ammonia nitrile , methyl acrylic acid cyano methyl ester;

Aryl (meth) acrylic acid such as methyl acrylate or methyl acrylic acid phenylester activatory termination, wherein the aryl residues may be unsubstituted or substituted, respectively the highest 4 times;

Carbonyl containing methyl acrylate such as methyl acrylic acid 2-carboxyl ethyl ester, methacrylic acid carboxyl methyl ester, methyl acrylic acid oxazole alkyl ethyl ester, N-(methyl acrolyl propoxycyclohexyl) formamide, methyl acrylic acid acetonyl ester , N-methyl-acryloyl morpholine, N-methyl-acryloyl-2-pyrrolidone, N-(2-methyl-acryloyl phenoxy ethyl)-2-pyrrolidone, N-(3-methyl-acryloyl phenoxy-propyl)-2-pyrrolidone, N-(2-methyl-acryloyl propoxycyclohexyl fifteen alkyl)-2-pyrrolidone, N-(3-methyl-acryloyl propoxycyclohexyl seventeen alkyl)-2-pyrrolidone;

Dimethyl acrylic acid glycol ester, such as methyl acrylic acid 1, 4-butane diol ester, methyl acrylic acid 2-butoxy ethyl ester, methyl acrylic acid 2- ethoxy group second grade propoxycyclohexyl methyl ester, methyl acrylic acid 2-ethoxy ethyl ester;

Ether alcohols of methacrylic acid ester such as methyl acrylic acid four tetrahydrofurfuryl ester , methyl acrylic vinyl oxygen radical second grade propoxycyclohexyl ethyl ester, methyl acrylic acid methoxyethoxy ethyl ester, methyl acrylic acid 1-butoxypolyethylene diethyl, methyl acrylic acid 1-methyl-(2-vinyl oxy) ethyl ester, methyl acrylic cyclohexyl propoxycyclohexyl methyl ester, ethyl ester methoxy methoxy methacrylate, methyl acrylic acid methyl ester phenmethyl oxygen radical , furfuryl ester methacrylate, methyl acrylic acid 2-butoxy ethyl ester, methyl acrylic acid 2- ethoxy group second grade propoxycyclohexyl methyl ester, methyl acrylic acid 2-ethoxy ethyl ester, methyl acrylic acid allyl propoxycyclohexyl methyl ester, methyl acrylic acid 1-ethoxy contact, methyl acrylic acid methoxy methyl ester, methyl acrylic acid 1-ethoxy ethyl ester, methyl acrylic acid ethoxy methyl ester;

Methyl acrylate of halogenated alcohols, such as methyl acrylic acid 2, 3-dibromo-diethyl, methyl acrylic acid 4-bromophenylacetic ester, methyl acrylic acid 1, 3-dichloro-2-diethyl, methyl acrylic acid 2-bromo ethyl ester, methyl acrylic acid 2-iodo ethyl ester, methyl acrylic acid chlorine methyl ester ;

Methacrylic acid ethylene oxide ester such as methyl acrylic acid 2, 3-epoxy contact, methyl acrylic acid 3, 4-epoxy contact, methyl acrylic acid 10, 11-epoxy undecane ester, methyl acrylic acid 2, 3-epoxy cyclohexyl ester ; glyceryl ester glycidyl methacrylate;

Phosphorus-, boron-and/or silicon of methacrylic acid ester such as methyl acrylic acid 2-(dimethyl-phosphoryl) diethyl, methyl acrylic acid 2-(jaya ethyl Asia phosphoryl) diethyl, methyl acrylic acid dimethyl phosphino methyl ester, methyl acrylic acid dimethyl cinnamenyl acyl ethyl ester, diethyl methacryloxyl acylphosphanes ester, dipropyl methacryloxyl acyl phosphate ester, 2-(b-butyl phosphono) ethyl ester, boric acid 2, 3- butylidene methacryloxyl acyl ethyl ester, methyl diethoxy methacryloxyl acyl ethoxy silane, methyl acrylic acid diethyl phosphoryl ethyl ester;

Sulfur-containing methyl acrylate such as methyl acrylic acid ethyl sulfinyl ethyl ester, methyl acrylic acid 4- cyanogen sulfur base contact, methyl acrylic acid ethyl sulfonyl ethyl ester, methyl acrylic acid cyanogen sulfur yl methyl ester, methyl acrylic methyl thionyl yl methyl ester, b (methyl acrolyl propoxycyclohexyl ethyl) sulfur;

Trimethylacetophenone acrylate such as trimethylolpropane trimethylacetophenone acrylate;

Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;

Heterocyclic (meth) acrylate such as (meth) acrylic acid 2-(1-imidazolyl) ethyl ester, (meth) acrylic acid 2-(4-morpholinyl) ethyl ester and 1-(2-methyl-acryloyl phenoxy ethyl)-2-pyrrolidone;

Vinyl group vinyl acetate;

Styrene, an alkyl substituent group in the side chains substituted styrene, such as α-methyl styrene and α-ethyl styrene, an alkyl substituent on the ring substituted styrene such as vinyl toluene and p-methyl styrene, halogenated styrene such as a paradichlorbenzene ethylene, dichloro ethylene, tribromostyrene and four bromophenylacetic ethylene;

Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinyl pyridine, 2, 3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, vinyl piperidine, 9-vinyl carbazole, 3-vinyl carbazole, 4-vinyl carbazole, 1-vinyl imidazole, 2-methyl-1-vinyl imidazole, N-vinylpyrrolidone, 2-vinyl pyrrolidone, N-vinyl pyrrolidine, 3-vinyl pyrrolidine, N-vinyl caprolactam, vinyl BUTYROLACTAMS-N, vinyl oxygen mixed fifth heavenly stem link , vinyl furan, vinyl thiophene, vinyl sulfur generation of fifth heavenly stem link , vinyl thiazole and hydrogenated vinyl thiazole, vinyl oxazole and halogenovinyl oxazole;

Vinyl and Prenyl ether;

Maleic acid and maleic acid derivatives such as maleic acid-and diesters, maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide;

if fumaric acid fumaric acid and fumaric acid derivatives of mono-and diesters;

two alkene like divinyl benzene.

Actual particularly preferred mixture containing methyl acrylic acid methyl ester, contact methacrylate, methyl acrylic acid lauryl ester , methyl acrylic acid stearyl ester and/or styrene.

Each component can be used alone or mixed for use. However, requires at least two different monomer to conduct polymerization.

These components can be added to a reaction mixture at the same time or in sequence, in accordance with the obtained copolymer of the present invention. According to the feeding of the types, statistical copolymers obtained respectively, gradient copolymers, graft copolymers and block copolymers.

Respectively comprise the large amount of polymerization of the monomer mixture can be used to obtain a statistical copolymer. Furthermore, one can imagine that the monomer mixture of the continuous or intermittent feeding, wherein their composition generally in a charging process is kept constant in order to guarantee that each structural unit of the statistical distribution in the copolymer.

In addition to the statistical copolymer, gradient copolymers and block copolymer can make use of the method of the invention, the change in the course of the polymerization monomer composition, and hence the relative concentration of different monomer obtained between.

The block copolymer can be intermittent to the reaction mixture to get monomer or mixture of monomers. At this time it should be noted that the active nature of ATRP process, therefore the addition of different monomers or monomer mixtures can be used in the reaction between the interrupted for a longer time. Similar effect can also be through the in the course of continuous feeding thereof in certain point in time a sudden change to realize the composition of the monomers.

Gradient copolymer is, for example, two kinds of monomer A and B copolymer, in in its single chain , monomer structural unit of the chain are distributed along the gradient. In other words, a chain structure unit A-rich, and the other rich in B a unit structure. These polymer is easy to pass through the ATRP process for preparing, because of their active nature. In other words, by continuously changing the gradient copolymer can be added in the process of the polymerization of the monomer mixture. In this preferably, the change in a single chain of the monomer added in the reaction mixture through a different inlet.

The aforesaid monomers by has a can transfer a radical initiator for polymerization. Generally speaking, these initiator can be described as formula Y-(X)_m, wherein Y said that the nuclear molecule (assume that it can form the free radical), X represents a transferable atom or an atomic group and m is transfer 1-10 integer, depending on the functionality of the Y group. If m> 1, various transfer atomic group X can have different meaning. If the functionality of the initiator> 2, the star-shaped polymer. The preferred transferring atom or atomic group is a halogen such as Cl, Br and/or I.

As mentioned above, assume that group Y can be formed and used as the starting molecule radical, in this free-radical addition to the ethylenically unsaturated monomer. To this end, the group Y preferably has a substituent of the free-base stabilized. These substituents are as, in addition to the other, -CN, -COR and CO₂ R, wherein R is alkyl or aryl residues, respectively, aryl and/or heteroaryl.

Alkyl residues are with 1-40 carbon atoms of the saturated or unsaturated, branched or linear hydrocarbon remnant base , such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl , 2-methyl heptenyl , 3-methyl heptyl , octyl, nonyl, 3-ethyl-nonyl, decyl, eleven alkyl, 4-propenyl eleven alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, seventeen alkyl, octadecyl, enndecyl, twenty alkyl, twenty whale ceryl alkyl, twenty-two alkyl and/or twenty alkyl thirtyfour alkyl.

Aryl residues are in aromatic ring has 6-40 carbon atom of the cyclic aromatic residue. These residues can be substituted. Substituents are as, for example, has 1-6 carbon atom linear and branched alkyl such as methyl, ethyl, propyl, butyl, pentyl, 2-methyl butyl or hexyl; cycloalkyl such as cyclopentyl and cyclohexyl; aromatic group such as phenyl or naphthyl; amino group, with an ether group, ester groups and halide.

Aromatic residues are, for example, phenyl, xylyl, tolyl, naphthyl or biphenyl.

The term "heteroaryl" refers to heteroaromatic ring system, wherein at least one group is CH N alternative or two adjacent CH group is S, O or NH alternative, such as thiophene, furan, pyrrole, thiazole, oxazole, pyridine, pyrimidine and benzo furan residues, can also be provided with the substituent.

Can be used for the initiator can be of this invention having one or more free radicals under the conditions of the polymerization reaction of an atom or the transfer of a plurality of atomic of any compound.

Suitable initiators include those having the following structural formula:

R¹¹ R¹² R¹³ C-X

R¹¹ C (=O)-X

R¹¹ R¹² R¹³ Si-X

R¹¹ R¹² N-X

R¹¹ N-X₂

(R¹¹)_n P (O)_m-X_3-n

(R¹¹ O)_n P (O)_m-X_3-n and

(R¹¹) (R¹² O) P (O)_m-X,

Wherein X is selected from Cl, Br, I, or OR¹⁰, [wherein R¹⁰ has 1-20 carbon atoms of the alkyl group, wherein each hydrogen atom can be independently is halide, preferably chloride or fluoride substituted, with 2-20 carbon atom alkenyl, preferably vinyl, with 2-10 carbon atoms of the alkynyl, preferably ethynyl, can be 1-5 a halogen atom or with 1-4 carbon atoms of the alkyl group substituted phenyl, or aralkyl (aryl-substituted alkyl, wherein the aryl group is phenyl or substituted phenyl and the alkyl group has 1-6 carbon atom alkyl, such as benzyl)], SR¹⁴, SeR¹⁴, OC (=O) R¹⁴, OP (=O) R¹⁴, OP (=O) (OR¹⁴)₂, OP (=O) OR¹⁴, O-N (R¹⁴)₂, S-C (=S) N (R¹⁴)₂, CN, NC, SCN, CNS, OCN, CNO and N₃, wherein R¹⁴ say with 1-20, preferably 1-10 carbon atoms of the aryl group or a linear or branched alkyl group, wherein two R¹⁴ group (if it exists) may together form a 5, 6 or 7-membered heterocyclic; and R¹¹, R¹² and R¹³ is independently selected from hydrogen, halogen, with 1-20, preferably 1-10 and in particular preferably 1-6 carbon atoms of the alkyl group, with 3-8 carbon atoms of the cycloalkyl group, R^8*₃ Si, C (=Y^*) R^5*, C (=Y^*) NR^6* R^7*, wherein Y^*, R^5*, R^6* and R^7* is as defined above, COCl, OH, (residues R¹¹, R¹² and R¹³ one is preferably OH), CN, has 2-20 carbon atom, preferably 2-6 carbon atom alkenyl or alkynyl group, and especially optimizes allylic propyl or vinyl, epoxy ethyl, glycidyl, with 2-6 carbon atoms of an alkylene or alkenylene group, can be epoxy ethyl alkyl or glycidyl group, aryl, heterocyclyl, aralkyl, fragrant alkene base (aryl-substituted alkenyl, wherein aryl is defined as above and alkene base is a vinyl, by one or two C₁-C₆ alkyl group and/or a halogen atom, is preferably chlorine substitution) substituted, with 1-6 carbon atom alkyl, wherein one straight to all of the hydrogen atom, preferably a hydrogen atom is a halogen-substituted (preferably fluorine or chlorine, if one or more of the hydrogen atoms are alternative, and optimal fluorine , chlorine or bromine, if a hydrogen atom is replaced), with 1-6 carbon atom alkyl, it is 1-3 a (preferably 1) is selected from C₁-C₄ alkoxy, aryl, heterocyclic base, C (=Y^*) R^5*, (wherein R^5* is as defined above), C (=Y^*) NR^6* R^7* (wherein R⁶ and R⁷ is as defined above), epoxy ethyl and substituting group substituted glycidyl group ; (preferably not more than two residues R¹¹, R¹² and R¹³ is hydrogen, especially preferably at most, one residue R¹¹, R¹² and R¹³ is hydrogen);

M is 0 or 1 ; and m=0, 1 or 2.

Particularly preferred is the initiator phenmethyl halogen like p-chloro methyl styrene, α- two chloroxylene , α, α- two chloroxylene , α, α- two xylyls and six (α-bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-l-phenyl ethane and l-chloro-l-phenyl ethane; is halogenated α is the carboxylic acid derivatives, such as 2- bromo-propionic acid diethyl, 2-chloropropionic acid methyl ester, 2-chloropropionic acid ethyl ester, 2- bromo-propionic acid methyl ester, 2- bromine different butyric acid ethyl ester; toluene sulfonyl halogen like p-toluene sulfonyl chloride; alkyl halogen liketetrachloromethane , bromoform, l-vinyl ethyl chloride, l-vinyl bromoethane; and a phosphoric ester of the halogen derivatives such as dimethyl chloride.

Initiator general to 10^-4 mol/L-3mol/L, preferably 10^-3 mol/L-10^-1 mol/L, and in particular preferably 5 × 10^-2 mol/L-5 × 10^-1 mol/L using a concentration of, by the limited but do not wish to. If all of the monomer conversion, from the molecular weight of the polymers the ratio of the initiator and the monomer. The ratio is preferably 10^-4: 1 until the 0.5 [...] 1, the special preferably 5 × 10^-3: 1 until 5 × 10^-2: 1.

Comprises at least one kind of transition metal catalyst can be used in the polymerization reaction to proceed. In this, any of the initiator can be used or has a can transfer atomic oxidation-reduction cycle to produce the polymer of the transition metal compound. In these cycle, can transfer the atomic groups and catalyst can be reversibly forming a compound, the oxidation state of the transition metal at the same time increased or decreased. In this assumption, free radical released or binding, therefore, keep the concentration of free radicals is very low. But it may also by the transition metal compound with the addition of the atomic transfer or promoting ethylenically unsaturated monomer into the Y-X or Y (M)_z-X in, wherein the Y and X has the meanings given above and M said monomer, and degree z.

In the preferred transition metal is cu, Fe, Co, Cr, Ne, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, yd and/or Ru, the oxidation state may be appropriate. These metal can be used alone or mixed for use. Assumptions, these metal can catalyze oxidation-reduction cycle of the polymerization reaction, wherein the oxidation-reduction pair of cu⁺/Cu²⁺ or Fe²⁺/Fe³⁺, is, for example, active. Therefore, these metallized compound as a halide such as chloride or bromide, alkoxide, hydroxide, oxide, sulfate, phosphate or hexafluoro-phosphate or trifluoromethane in sulphate are added to a reaction mixture. A preferred metal compound is cu₂ O, CuBr, CuCl, CuI, CuN₃, CuSCN, CuCN, CuNO₂, CuNO₃, CuBF₄, cu (CH₃ COO) Cu (CF₃ COO), FeBr₂, RuBr₂, CrCl₂ and NiBr₂.

But can also use relatively high oxidation state compound, such as CuO, CuBr₂, CuC1₂, CrCl₃, Fe₂ O₃, and FeBr₃. In these circumstances, the reaction can utilize the traditional free radical forming agent such as AIBN caused. In this, the transition metal compound is first reduction, because of their self-produced and these traditional free radical formers the free radical reaction. This is reverse ATRP, such as described of Matyjaszewski Macromolecules and Wang (1995) Vol. 28, pp.7572-7573.

Furthermore, the transition metal can be used as a zero oxidation state of the metal, in particular to a mixture of the aforementioned compounds for catalytic, for example, described in WO98/40415. In these circumstances, the reaction rate is increased. It is said that, catalytic activity of the concentration of the transition metal compounds of the oxidation state of the transition metal and the increase is proportional to the reductive supplies transition metal.

Transition metal and is generally the molar ratio of the initiator, the 0.0001 [...] the 1-10 [...] 1, preferably 0.001 the [...] the 1-5 [...] 1 and especially preferably 0.01 the [...] the 1-2 [...] 1, but this is not limited to any form.

Polymerization reaction, in the can with a metal catalyst to form coordination compounds carried out in the presence of the ligand. In addition to the other, these ligands used for increasing the solubility of transition metal compounds. Ligand another important function is to avoid the formation of stable organic metal compound. This is particularly important, because these stable compounds will not be under the selected reaction conditions for polymerization. Furthermore, it is said that biligand contribute to seize can transfer atomic group.

Basically these ligands is known and described in, for example, WO97/18247 and WO98/40415. These compounds generally have one or more in order to key joint metal atom of nitrogen, oxygen, phosphorus and/or sulfur atom. Many of these ligands general can be expressed as formula R¹⁶-Z-(R¹⁸-Z)_m-R¹⁷, wherein R¹⁶ and R¹⁷ independently represent H, C₁-C₂₀ alkyl, aryl, heterocyclyl, visual need to be substituted. These substituents include, in addition to other, alkoxy residues and alkyl amino residues. R¹⁶ and R¹⁷ visual need to form a saturated, unsaturated or heterocyclic ring. Z expresses O, S, NH, NR¹⁹, or PR¹⁹, wherein R¹⁹ with R¹⁶ same meaning. R¹⁸ independently represent a linear, branched, or cyclic with 1-40 carbon atoms, preferably 2-4 bivalent group of carbon atoms, such as methylene, ethylidene, propylidene or butylidene. Alkyl and aryl have a meaning as given above. Is a heterocyclic residue 4-12 cyclic residue carbon atoms, wherein the ring of one or more CH₂ group has the hetero atom group such as O, S, NH and/or alternative NR, wherein the residues with the R R¹⁶ same meaning.

Another kind of appropriate ligand can be represented by the following structural formula:

Wherein R¹, R², R³ and R⁴ independently represent H, C₁-C₂₀ alkyl, aryl, heterocyclic radical and/or heteroaryl residue, wherein the residues R¹ and R² or R³ and R⁴ can together form a saturated or unsaturated ring.

In this, the preferred ligands that contains atomic N the chelating ligand.

The preferred ligands is, in addition to other, triphenyl phosphorane (phosphane), 2, 2-bipyridine, alkyl -2, 2-bipyridine such as 4, 4-bis-(5-nonyl)-2, 2-bipyridine, 4, 4-bis-(5-kyoung yl)-2, 2-bipyridine, three (2-amino ethyl) amine (TREN), N, N, N ', N' , N "-pentamethyl-diethylene-triamine, 1, 1, 4, 7, 10, 10-six methyl Sanya ethyl tetramine and/or tetramethyl Asia ethyl diamine. Other preferred ligands, for example, described in W097/47661. Ligand can be used alone or mixed for use.

These ligands can be and a metal compound on-site to form coordination compounds or they can be first produced into a complex compound and subsequently joined reaction mixture.

Ligand depends on the ratio of the transition metal of the ligand and tooth condition coordination number of a transition metal. In general, the molar ratio of the 100 [...] 1-0.1: 1, preferably the 6 [...] 1-0.1: 1 and especially preferably the 3 [...] 1-0.5: 1, for it has no intention of any limitation.

Monomer, transition metal catalyst, a ligand and an initiator according to the required selection, as appropriate, of the polymer solution. It is said that, transition metal-ligand complex and can transfer atomic reaction between the high-rate constant to the narrow molecular weight distribution are important. If the reaction rate constant is too low, too high concentration of free radical, therefore generating common termination reaction, cause wide molecular weight distribution. The exchange rate depends on the atomic transfer, for example, transition metal, ligand and the transition metal compound anion. It can be in for example the professional technical personnel WO98/40415 for selecting found in the value of these components of the recommendations.

At normal pressure polymerization reaction, carried out under high pressure or under reduced pressure. Polymerization reaction temperature is not important. However, the value is generally -20-200 the [...] , preferably the 0-130 [...] and particularly preferred the 60-120 [...] , but has no intention to limit to this.

Polymerization with or without the reaction can be carried out under solvent. Terminology in this solvent should be broadly understood.

Preferably, the polymerization is carried out in a nonpolar solvent. These solvent is a hydrocarbon solvent such as aromatic solvent such as toluene, benzene and xylene, saturated as cyclohexane, heptane, octane, nonane, decane, dodecane, can also be a branched form. These solvents can be used alone or mixed for use. The particularly preferred solvent is mineral oil and synthetic oil, and mixtures thereof. Wherein the actual mineral oil is particularly preferred.

Mineral oil is basically known and can be purchased. They generally by distillation and/or refining, as required, other purification and processing method derived from petroleum or crude oil , wherein the mineral oil or the petroleum crude oil concept including in particular the higher boiling point fraction. Generally, mineral oil in the 5000 Pa higher than the boiling point of the the 200 [...] , is preferably higher than the 300 [...]. Shale oil can also be through low-temperature distillation, coking hard coal, under the exclusion of air distillation lignite and hard coal or lignite is prepared by hydrogenation. In a few cases, plant sources can also be composed of mineral oil (such as simoneaux be wood oil , rapeseed oil) or animal source (such as hoof oil) of the raw materials. Therefore, the content of mineral oil have different aromatic, cyclic, branched and linear hydrocarbon , depends on the source, respectively.

Generally speaking, in or crude oil the paraffin-base mineral oil, naphthene and aromatic fraction of the difference, that the gelled network terminology paraffin groundlevel hours or highly branched isoalkane, and naphthenic groundlevel sub-expressed cyclanes. Furthermore, according to the source and the processing method, respectively, having different content of mineral oil n-alkane, a low degree of branching of an isoalkane, so-called a a-base-branched paraffin, and a polarity performance can lead to the hetero-atom, in particular O, S N and/or compound. N-alkane in the preferred mineral oil is lower than the content of 3% weight, containing O, S N and/or content of the compound of less than 6% weight. Aromatic compound and a a base-branched paraffin content of the respective normal 0-30% weight. In accordance with a significant aspect, cycloalkyl and paraffin-base mineral oil mainly containing alkane, generally have more than 13, is preferably greater than 18, in fact, particularly preferred more than 20 carbon atoms each. The content of these compounds generally ≥ 60% weight, preferably ≥ 80% weight, has no intention of any limitation to this.

The use of traditional method such as escapes the urea and the particularly preferred silica gel liquid chromatography analysis of mineral oil provides, for example, the following components, wherein the percentage of the gross weight of the corresponding mineral oil is:

Has about 18-31 carbon atoms n-alkanes of:

0.7-1.0%,

Has about 18-31 low branching alkane carbon atoms:

1.0-8.0%,

With 14-32 carbon atoms of the aromatic compound:

0.4-10.7%,

With 20-32 carbon atom heterobasidion-and cyclanes:

60.7-82.4%,

Polar compounds:

0.1-0.8%,

Loss:

6.9-19.4%.

The analysis of the recommendations of the valuable mineral oil and mineral oil to a list of other composition can refer to, for example, Ullmanns   Encyclopedia   of   Chemistry   Industrial, paragraph 5 Edition CD-ROM, 1997, the entry "lubricant and related products" the lower.

Synthetic oil is, in addition to other, organic ester, machine ether such as silicone oil and a synthetic hydrocarbon, in particular polyolefin. Most of them than mineral oil slightly expensive , but has advantages in their performance. In order to explain, it should be mentioned that 5 the base oil of a grade API (API: American petroleum Institute), and particularly preferred of these base oil is used as the solvent.

These the dosage of the solvent is, in addition to the other, of the total weight of the mixture-based 1-99% weight, preferably 5-95% weight, in particular preferably 5-60% weight and in fact especially preferably 10-50% weight, but do not intend to be limited to this.

The molecular weight of the polymer thus prepared is generally 1,000-1,000, 000g/mol, preferably 10 × 10³ -500 × 10³ g/mol and in particular preferably 20 × 10³ -300 × 10³ g/mol, for limited to this but do not wish to. These values refer to the more in the composition has a weight average molecular weight of the dispersed polymer.

The ATRP compared with traditional free radical polymerization reaction of the particular advantage of the method lies in that, to obtain the polymer with a narrow molecular weight distribution. Not limited to this, is made by the method of the invention the polymer is the polydispersity expressed Mw/Mn 1-12, preferably 1-4.5, in particular preferably 1-3, and in fact especially preferably 1.05-2.

In addition to the other, can be used as copolymer of this invention the biological internal combustion engine and internal combustion engine lubricating oil additive in order to reduce the pour point of the fuel. In other words, other meaningful of the present invention the copolymer of this invention is a lubricating oil of the internal combustion engine and internal combustion engine the biological fuel.

Copolymer of this invention can be used alone or mixed for use, the broad understanding terminology to the mixture. Which comprises a mixture of different copolymers of the present invention and the traditional copolymer of this invention both a mixture of polymers.

Biological fuel internal combustion engine is basically known and designated as natural, renewable, in particular oil, is suitable for the special adaptation of the operation of the internal combustion engine. These internal combustion engine fuel including, for example, vegetable oil such as rapeseed oil.

Examples of the lubricating oil is, in addition to other, vehicle engine oil, engine oil, turbine oil, pressure-transmitting fluid, oil pumping, heat transfer oil , breakage, the cutting fluid and the cylinder oil.

These lubricating oil generally includes base oil and one or more additives, to a very great extent this known to the professional technical personnel.

Usually, any sufficient to provide even under the high temperature of the lubricant film will not collapse the compounds are suitable as a base oil. Viscosity can be for example used for determining this kind of performance, as they for example are established in SAE specifications of the engine.

In addition to the other, is suitable for this natural compounds, mineral oil and synthetic oil, and mixtures thereof.

Natural hoof oil is an animal or vegetable oil such as wood or oil. Mineral oil has been used as a solvent for the above described in-depth. They are particularly useful because favourable prices. In addition to the other, the synthetic oil is organic ester meet the above mentioned requirements, synthetic hydrocarbon, in particular polyolefin. Most of them more expensive than mineral oil, but they are more advantageous in performance.

Mixtures of these base oils can be also acquired and can be widely used.

Copolymer of this invention can also be used as the adding lubricating oil and most of the so-called known DI packet (detergent inhibitor) or other concentrate use of the component. These concentrate comprising 15-85% by weight of one or more copolymer of this invention. Furthermore, the concentrate can also comprise organic solvent, in particular mineral oil and/or synthetic oil.

Lubricating oil or the concentrate generally includes additives and base oil. These additive is viscosity index improver, antioxidant, anti-aging agent, corrosion inhibitors, detergents, dispersing agent, EP additive, foam inhibitors, friction reducing agent, pour point inhibitor, dye, flavoring agent and/or de-emulsifier.

Additive bring favorable the low and high temperature of the flowing nature of the (improve the viscosity index), they make the solid material suspension (detergent-dispersant nature), and an acidic reaction product in them and form a protective film on the cylinder surface (EP additive, EP to "extreme pressure"). In Ullmann professional technical personnel can '   Chemistry   Industrial   of s Encyclopedia, paragraph 5 Edition CD-ROM, 1998 found in the recommendations of other valuable.

The dosage of these additives will depend on the use of the lubricant. However, in general, the amount of base oil 25-90% weight, preferably 50-75% weight. In the copolymer of this invention the amount of lubricating oil is preferably 0.01-10% weight, especially preferably 0.01-2% weight. Biological internal combustion engine fuel comprises preferably 0.01-10% weight, in particular 0.01-2% by weight of the copolymer of this invention.