Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/63—Halogen-containing esters of saturated acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

• the present invention relates to ⁇ -halocarboxylic acid esters with polyhydric alcohols which can be used as initiators for ATRP, processes for the preparation of these initiators, polymers or copolymers which can be prepared with the initiators, compositions with these polymers or copolymers, processes for their preparation and their use for the preparation of polymers or block copolymers, in which the end group • X is replaced by an open-chain or cyclic group R'R "NO".
• Radical atom transfer polymerization is a long-known, particularly suitable polymerization process for the preparation of "living" polymers, block copolymers, graft copolymers etc. with a low polydispersity and largely predictable molecular weights.
• the present invention is based, for the synthesis of branched polymer structures, for. B. star polymers, dendrimers, comb polymers, etc., to produce suitable polymerization initiators.
• This object is achieved by the present invention, which relates to ⁇ -halocarboxylic acid esters with polyhydric alcohols which can be prepared by simple acylation processes.
• the invention relates to ⁇ -halocarboxylic acid esters of the formula
• R hydrogen, CC ⁇ alkyl, cyano, phenyl or CC 4 alkylphenyl;
• X is chlorine, bromine or iodine
• R 2 is the residue of an acylated, branched, trihydric alcohol, the residue of a fully or partially acylated, linear or branched, tetravalent alcohol, the rest of a fully or partially acylated, linear, pentavalent or hexavalent alcohol, the rest represent a fully or partially acylated, linear or cyclic C 4 -C 6 aldose or C 4 -C 6 ketose or the rest of a fully or partially acylated disaccharide, and isomers of these compounds.
• dC 4 -alkyl is methyl, ethyl, n- or isopropyl or n-, sec- or tert-butyl.
• C 1 -C 4 -alkylphenyl is preferably p-methylphenyl.
• X is preferably chlorine or bromine.
• Ri preferably forms a 2-haloacyl group with the ⁇ -C atom, for example 2-halo-C 3 -C 4 -alkanoyl, for example 2-halopropionyl, 2-halo-n-butyryl or 2-halo-isobutyryl, for example 2-chloro or 2-bromopropionyl or ⁇ -chloro or ⁇ -bromoisobutyryl, or an ⁇ -halophenylacetyl group, for example ⁇ -chloro or ⁇ -bromophenylacetate.
• the radical R 2 of an acylated, branched, trihydric alcohol is preferably derived from 1,3,5-trihydroxybenzene or trimethylolethane and is, for example, a group of the partial formula
• R a means ⁇ -haloacyl.
• R a with the meaning ⁇ -haloacyl preferably represents identically
• groups of the partial formula for example ⁇ -halo-C 3 -C 4 -alkanoyl or ⁇ -halophenylacetyl, for example ⁇ -chloropropionyl, ⁇ -bromopropionyl or ⁇ -chloro-henyl acetyl.
• the radical R 2 of a fully or partially acylated, linear tetravalent alcohol is derived, for example, from erythritol and its 3 isomeric forms, e.g. B. D-, L- and mesoerythritol.
• the radical R 2 is preferably derived from a fully or partially acylated, branched tetravalent alcohol, for example from pentaerythritol, and is, for example, a group of the partial formula wherein R a represents ⁇ -haloacyl with the meanings mentioned.
• linear pentites such as D (+) - and L (-) - arabitol, adonite or xylitol
• C 4 aldoses such as D (-) - and L (+) - erythrosis or D ( -) - and L (+) - threose
• C 5 aldoses such as D (-) - and L (+) - arabinose, D (-) - ribose or D (+) - xylose
• C 6 aldoses such as D (+) - glucose, D (+) - mannose or D (+) - galactose
• isomeric forms encompasses the isomeric forms known in the chemistry of sugar alcohols and carbohydrates, e.g. the optically pure stereoisomers (antipodes), diastereomers or epimers or racemic mixtures.
• a preferred embodiment of the invention relates to ⁇ -halocarboxylic acid ester (I), in which
• R 2 is the residue of an acylated, branched, trihydric alcohol, for example the residue of 1, 3,5-trihydroxybenzene or trimethylolethane which is acylated by R a , the residue of a fully or partially acylated, linear or branched, tetravalent alcohol, for example the one by R a represent fully acylated residue of pentaerythritol, or the residue of a fully or partially acylated, linear, pentavalent or hexavalent alcohol, and isomers of these compounds.
• R a with the meaning ⁇ -haloacyl has in particular the meaning ⁇ -chloropropionyl and ⁇ -bromopropionyl.
• a particularly preferred embodiment relates to ⁇ -halocarboxylic acid esters of the formula
• the invention also relates to the process for the preparation of the .alpha.-halocarboxylic acid ester (I), in which RR 2 and X have the meanings mentioned above, which is characterized in that an .alpha.-halocarboxylic acid of the formula
• R 2 'with the OH group is a branched, trihydric alcohol, a linear or branched, tetravalent alcohol, a linear, pentavalent or hexavalent alcohol, a linear or cyclic C 4 -C 6 aldose or C -C 6 ketose or a disaccharide, and isomers of these compounds.
• the usual esterification methods are used to prepare the ⁇ -halocarboxylic acid ester (I), e.g. the equivalents of a reactive, functional acid derivative of ⁇ -halocarboxylic acid (II), e.g. an acid halide, e.g. the acid chloride, which corresponds to the valence of the alcohol (III), with this alcohol, or the ⁇ -halocarboxylic acid (II) with the equivalents of a reactive, functional derivative of the alcohol (III), e.g. an ester of this alcohol, e.g. a halide, e.g. Chloride, or a sulfonic acid ester of the alcohol, e.g. the p-toluenesulfonic acid ester.
• a reactive, functional acid derivative of ⁇ -halocarboxylic acid (II) e.g. an acid halide, e.g. the acid chloride, which corresponds to the valence of the alcohol
• the invention further relates to a polymer or block copolymer of the formula:
• Ri is hydrogen, CC 4 alkyl, cyano, phenyl or C r C 4 alkylphenyl;
• R 2 is the residue of an acylated, branched, trihydric alcohol, the residue of a fully or partially acylated, linear or branched, tetravalent alcohol, the residue of a completely or partially acylated, linear, pentavalent or hexavalent alcohol, the rest of a fully or partially acylated , linear or cyclic C 4 -C 6 aldose or C 4 -C 6 ketose or the rest of a fully or partially acylated disaccharide;
• a and B polymer blocks from ethylenically unsaturated monomer units; x and y the number of monomer units in blocks A and B, one value of x and y being zero and the other value being integers greater than zero or both values x and y being integers greater than zero;
• X is chlorine, bromine or iodine; and m are integers from three to six.
• the invention also relates to the process for the preparation of the polymer or block copolymer (V), in which R 1, R 2 , A, B, X, x, y and m have the meanings mentioned above, which is characterized in that radicals Atom- transfer polymerization (ATRP) in the presence of the ⁇ -halocarboxylic acid ester (I) as the polymerization initiator, in which R 1 f R 2 and X have the meanings mentioned above, and an oxidizable, transition metal complex catalyst which is based on the polymer blocks A and B and which are based on polymer blocks A and B, undergo a polymerization reaction with ethylene groups.
• ATRP radicals Atom- transfer polymerization
• I ⁇ -halocarboxylic acid ester
• R 1 f R 2 and X have the meanings mentioned above
• an oxidizable, transition metal complex catalyst which is based on the polymer blocks A and B and which are based on polymer blocks A and B, undergo a polymer
• polymer encompasses oligomers, cooligomers, polymers or copolymers, for example block copolymers, multiblock copolymers, star-shaped, gradient, random, branched and dendritic copolymers and graft copolymers.
• the copolymer blocks A and B contain at least two recurring structural units made of polymerizable, aliphatic monomers with at least one or more olefinic double bonds.
• Such polymerizable, aliphatic monomers with an olefinic double bond are selected, for example, from the group comprising styrenes, acrolein, acrylic acid or methacrylic acid or salts thereof, acrylic or methacrylic anhydrides, acrylic or methacrylic acid-CrC 24 alkyl esters, acrylic or methacrylic acid mono- or -di-C C alkylamino-C 2 -C -alkyl esters, acrylic or methacrylic acid-hydro- xy-C 2 -C -alkyl esters, acrylic or methacrylic acid (C 1 -C 4 alkyl) 3 silyloxy-C 2 -C 4 alkyl esters, acrylic acid or methacrylic acid (C 1 -C 4 alkyl) 3 silyl-C 2 -C 4 alkyl esters, acrylic acid or methacrylic acid heterocyclyl-C 2 -C 4 alkyl esters, acrylic or methacrylic acid
• Suitable styrenes can be substituted on the phenyl group by one to three substituents from the group containing hydroxy, CrC alkoxy, for example methoxy or ethoxy, halogen, for example chlorine, amino and CC 4 alkyl, for example methyl or ethyl.
• Suitable salts of acrylic acid or methacrylic acid are, for example, (C 1 -C 4 alkyl) 4 ammonium or (CrC t -alkyl sNH salts, for example the tetramethyl, tetraethyl, trimethylammonium or triethylammonium salt, the trimethyl-2-hydroxyethylammonium or triethyl-2-hydroxyethylammonium salt, the dimethyl-2-hydroxyethylammonium or diethyl-2-hydroxyethylammonium salt.
• Suitable acrylic or methacrylic acid-CrC 24 alkyl esters are esterified, for example, by methyl, ethyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, isobomyl, isodecyl, lauryl, myristyl, stearyl or behenyl.
• acrylic acid and methacrylic acid mono- or -di-dC ⁇ alkylamino- C 2 -C 4 alkyl esters are acrylic acid or methacrylic acid-2-monomethylaminoethyl ester, acrylic acid or methacrylic acid-2-dimethylaminoethyl ester or the corresponding 2-monoethylaminoethyl or 2-diethylaminoethyl ester and the acrylic acid or methacrylic acid 2-tert-butylaminoethyl ester.
• acrylic acid and methacrylic acid hydroxy-C 2 -C 4 alkyl esters are acrylic acid or methacrylic acid 2-hydroxyethyl ester (HEA, HEMA) or acrylic acid or methacrylic acid 2-hydroxypropyl ester (HPA, HPMA).
• acrylic acid and methacrylic acid-silyloxy-C 2 -C 4 -alkyl esters are acrylic acid or methacrylic acid-2-trimethylsilyloxyethyl ester (TMS-HEA, TMS-HEMA).
• acrylic acid or methacrylic acid (C r C 4 alkyl) 3 silyl-C 2 -C 4 alkyl esters are acrylic acid or methacrylic acid-2-trimethylsilylethyl ester or acrylic acid or methacrylic acid-3-trimethylsilyl-n-propyl ester.
• Acrylic or methacrylic acid esters with poly-C 2 -C 4 alkylene glycol ester groups which in turn can be esterified by substituted CC 2 alkoxy groups, correspond to the formula:
• R 1 and R 2 independently of one another are hydrogen or methyl and R 3 is CrC ⁇ alkyl, for example methyl, ethyl, n- or isopropyl, n-, iso- or tert-butyl, n- or neopentyl, lauryl, myristyl or Stearyl or aryl-CrC 24 -alkyl, for example benzyl or phenyl-n-nonyl, and also CrC 24 -alkylaryl or C 1 -C 24 -alkylaryl-C 1 -C 24 -alkyl.
• acrylic and methacrylic acid heterocyclyl-C 2 -C -alkyl esters are acrylic acid or methacrylic acid 2- (N-morpholinyl, 2-pyridyl, 1-imidazolyl, 2-oxo-1-pyrrolidinyl, 4-methyl-piperidine- 1-yl or 2-oxoimidazolidin-1-yl) ethyl ester.
• acrylic acid or methacrylic acid mono- or di-CrC 4 -alkyl amides acrylic acid or methacrylic di-CrC 4 -alkylamino-C 2 -C 4 -alkylamides or acrylic acid or methacrylic acid amino-C 2 - C 4 alkylamides are N, N-dimethylacrylamide, N, N-dimethyl- (meth) acrylamide, 2- (N, N-dimethylaminoethyl) acrylamide, 2- (N, N-dimethylaminoethyl) methacrylamide, 2-aminoethylacrylamide and 2 -Aminoethyl methacrylamide.
• the indices x and y define the number of monomer units in blocks A and B, one value of x and y being zero and the other value being an integer greater than zero or both values x and y are integers greater than zero.
• the preferred molecular weight range of blocks A and B is approximately 1,000 to 100,000, in particular approximately 1,000 to 50,000.
• a very particularly preferred molecular weight range is approximately 2,000 to 15,000.
• a particularly preferred embodiment of the invention relates to a block copolymer (V), in which
• R 2 is the residue of an acylated, branched, trihydric alcohol, the residue of an acylated, linear or branched, tetravalent alcohol or the residue of a fully or partially acylated, linear, pentavalent or hexavalent alcohol;
• a and B polymer blocks from ethylenically unsaturated monomer units; x and y represent integers greater than zero and represent the number of monomer units in blocks A and B; and m is three or four.
• the invention also relates to all polymers or block copolymers which can be prepared using ⁇ -halocarboxylic esters (I) and the ATRP method.
• the subject of the invention is all process products ("products-by-process"), even if they do not fall under the definitions of the formula V given above or formula V should not correctly define the structure of the process products.
• X represents terminal chlorine, bromine or iodine in the polymer chain.
• These terminal groups are obtained using initiators using the ATRP method.
• Halogen as a terminal group of a polymer chain can be disadvantageous.
• R and R 2 are CC 7 alkyl and the other is CC 4 alkyl or dC 4 alkyl substituted by CC 4 alkoxycarbonyl or dC alkoxy; or
• R T and R 2 together with the neighboring C atom are C 3 -C 7 cycloalkyl
• R 3 and R 4 have the meanings of Ri and R 2 ;
• R b has the meanings of R a ;
• R a and R b together form a divalent group and an aliphatic or aromatic heterocyclic group with 5, 6, 7 or 8-ring members, which can contain 1-3 additional hetero atoms from the group nitrogen, oxygen and sulfur.
• R 5 , R ⁇ . 7 and R 8 are hydrogen; and one of the radicals R 9 and R 10 independently of one another are hydrogen or further substituents.
• the groups are representative examples of groups of partial formula A.
• R a is hydrogen, -CC 18 alkyl, which can be interrupted by one or more oxygen atoms, 2-cyanoethyl, benzoyl, glycidyl, or the acyl group of an aliphatic C 2 -C 2 carboxylic acid, a cycloaliphatic C 7 -C 5 - Carboxylic acid, an a, b-unsaturated C 3 -C 5 carboxylic acid or an aromatic C 7 -C 15 carboxylic acid; m 2;
• R a is the divalent acyl group of an aliphatic d-Cae dicarboxylic acid; n 1;
• R b C r C 12 alkyl, C 5 -C 7 cycloalkyl, dC 8 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenoyl or benzoyl;
• R c Ci-Ci ⁇ -alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl, which can be substituted by cyano, carbonyl or a carbamide group, glycidyl, or a group of the sub-formulas -CH 2 CH (OH) -Z, -CO-Z or -CONH-Z, where Z is hydrogen, methyl or phenyl.
• Another preferred embodiment relates to a group of partial formula A 1; wherein one of the groups R 9 and R 0 is hydrogen and the other CrC 4 alkanoyl or dd alkanoylamino.
• Another object of the invention relates to an N ⁇ O substituted polymer or block copolymer of the formula:
• R hydrogen, C 1 -C 4 -alkyl, cyano, phenyl or C r C -alkylphenyl;
• R 2 is the residue of an acylated, branched trihydric alcohol, the residue of a fully or partially acylated, linear or branched, tetravalent alcohol, the residue of a fully or partially acylated, linear, branched or cyclic, pentavalent or hexavalent alcohol, the rest of a complete or partially acylated, linear or cyclic C 4 -C 6 aldose or C 4 -C 6 ketose or the rest of a fully or partially acylated disaccharide;
• a and B polymer blocks from ethylenically unsaturated monomer units; x and y the number of monomer units in blocks A and B, one value of x and y being zero and the other value being integers greater than zero or both values x and y being integers greater than zero;
• X is chlorine, bromine or iodine; m are integers from three to six; one of t and R 2 is dC 7 alkyl and the other is dC 4 alkyl or dd alkyl substituted by CC 4 alkoxycarbonyl or dC alkoxy; or
• R T and R 2 together with the neighboring C atom are C 3 -C 7 cycloalkyl
• R 3 and R 4 have the meanings of R ⁇ and R 2 ;
• R b has the meanings of R a ;
• R a and R b together form a divalent group and an aliphatic or aromatic heterocyclic group with 5, 6, 7 or 8-ring members, which can contain 1-3 additional hetero atoms from the group nitrogen, oxygen and sulfur.
• the polymerization process can be carried out in the presence of water or an organic solvent or mixtures thereof. Additional cosolvents or surfactants, for example glycols or ammonium salts of carboxylic acids, can be added to the reaction mixture. The amount of solvent should be kept as low as possible.
• the reaction mixture can contain the above-mentioned monomers or oligomers in a concentration of 1.0 to 99.9 percent by weight, preferably 5.0 to 99.9 percent by weight, particularly preferably 50.0 to 99.9 percent by weight, based on the monomer content in the polymer.
• Suitable organic solvents are alkanes (hexane, heptane, octane, isooctane), hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), esters (ethyl acetate) or ether ( Diethyl, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran) or mixtures thereof.
• a water-miscible or hydrophilic solvent can be added to the reaction mixture. It is important to ensure that the reaction mixture remains in a single homogeneous phase during the polymerization reaction and that no precipitation or phase separation takes place.
• Suitable co-solvents are from the group of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and their salts, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxy ether dehydates, e.g.
• Butyl carbitol or cellosolve amino alcohols, ketones, derivatives and mixtures thereof selected, e.g. Methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerin, dipropylene glycol, tetrahydrofuran or other water-soluble or water-miscible solvents or mixtures thereof.
• Hydrophilic monomers, polymers and copolymers can be separated from the reaction mixture using customary methods, for example by distillation, precipitation, extraction, changing the pH range or other customary separation methods.
• the temperature range for the polymerization reaction is about 50 ° C to about 180 ° C, preferably about 80 ° C to 150 ° C.
• the oxidizable transition metal complex catalyst which can be used in the ATRP process is in the form of an oxidizable complex ion in the lower stage of a redox system.
• Preferred examples of such redox systems are formed by elements from groups V (B), VI (B), VII (B), VIII, IB and MB of the periodic table, for example redox systems of Cu7Cu 2+ , Cu ° / Cu + , Fe ° / Fe 2+ , Fe'VFe 3 * , Cr ⁇ Cr 3 * , Co7Co 2+ , Co ⁇ / Co 3 * , Ni ° / Ni + , Ni7Ni 2+ , Ni 2 7Ni 3+ , Mn ° / Mn 2+ , Mn ⁇ / Mn 3 * , Mn ⁇ / Mn 4 "or Zn7Zn 2+ .
• the transition metal or transition metal cation in the oxidizable transition metal complex catalyst is converted from the lower oxidation stage to a higher one.
• a Cu (l) complex catalyst salt is converted into the corresponding Cu (II) oxidation stage is transferred.
• the oxidizable transition metal complex catalyst which can be used in the ATRP process can be prepared in a separate precursor or preferably in situ from the ligands and a metal salt, for example Cu (I) CI, which is then added to the complex compound by adding the ligand former, for example ethylenediamine, EDTA, Me 6 TREN or PMDETA.
• anionic ligands which are known from the complex chemistry of transition metals, for example hydride ions (H) or anions of inorganic or organic acids, for example F, Cl “ , B or I " , fluorine complexes of the type BF 4 " , PF 6 “ , SbF 6 “ or AsF 6 " , anions of oxygen acids, alcoholates or acetylides or anions of the cyclopentadiene anion type.
• Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, anions of dC 8 -carboxylic acids, for example format, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloroacetate or -fluoroacetate, sulfonates, for example mesylate, ethane, propane or n-butane sulfonate, trifluoromethane sulfonate (triflate) or benzene or benzyl sulfonate, which can be substituted by CrdAlkyl, CC 4 alkoxy or halogen, especially fluorine, chlorine or bromine , for example tosylate, brosylate, p-methoxy or p-ethoxybenzenesulfonate, pentafluor
• Neutral and anionic ligands can be present up to the preferred coordination number, in particular four, five and six.
• Total negative charges are from cations, e.g. B. monovalent cations, such as Na + , K + , NH 4 + or (-C-C 4 alkyl) 4 N + balanced.
• Suitable neutral ligands are known from the complex chemistry of transition metals. They are coordinated with the coordination center with the formation of various types of bonds, for example ⁇ , ⁇ , ⁇ , ⁇ bonds or combinations thereof up to the preferred coordination number of the complex cation.
• Suitable ligands are selected from the group comprising aquo (H 2 O), amino, nitrogen, carbon monoxide, nitrosyl, phosphines, for example (C 6 H 5 ) 3 P, (iC 3 H 7 ) 3 P, (C 5 H 9 ) 3 P or (CeHn ⁇ P, amines, e.g.
• EDTA ethylenediaminetetraacetate
• M ⁇ eTREN 2-di
• Heterocyclic e ⁇ donor ligands are derived, for example, from unsubstituted or substituted heteroarenes from the group comprising furan, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine, ⁇ -pyran, ⁇ -thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine , Indole, coumarin, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, phenothiazine, phenidine, chromanine, phenoman , Triazines, thianthrene, purine, bis-imidazole and bisoxazo
• the polymer (V) can be isolated or this with an N ⁇ O compound of the formula
• the polymer can be isolated, for example, by known methods, for example distilling and filtering off unreacted monomers.
• the transition metal complex catalyst is separated off, the solvent is evaporated off or the polymer (VII) substituted by the N ⁇ O group precipitates out of a suitable liquid phase, the polymer is filtered off and then washes and dries.
• the elimination of the leaving group -X, e.g. Halogen, and the substitution of the polymer with the N ⁇ O compound (VIII) takes place e.g. by dissolving the polymer (V) in a solvent and adding the N ⁇ O compound (VIII).
• the reaction can be carried out in a temperature range from room temperature to the boiling temperature of the reaction mixture, preferably from room temperature to 100 ° C.
• the block copolymers (V) and (VII) obtainable according to the process have a low polydispersity.
• N ⁇ O compounds (VIII) are known. They are commercially available or as described in U.S. Pat. Patents 5,204,473 or 4,581, 429 and the processes mentioned therein can be produced.
• the ATRP process and its various advantages are e.g. in the publication by K. Matyjaszewski in ACS Symp. Ser. Vol. 685 (1998), pg. 2-30.
• the polymers and copolymers can be processed further by customary processes and can in most cases be used without further purification steps. This is advantageous if the intention is to scale up approaches ("scale-up") with a view to industrial use.
• the invention also relates to all N ⁇ O substituted polymers or block copolymers which can be prepared using ⁇ -halocarboxylic acid esters (I), an N ⁇ O compound of the formula VIII and the ATRP method.
• the invention relates to all process products ("products-by-process"), even if they do not fall under the definitions of the formula VII given above or formula VII does not correctly define the structure of the process products.
• Another object of the invention relates to a polymer composition containing a polymer or block copolymer (V), in which R 1, R 2 , A, B, x, y and m have the meanings mentioned, and to conventional additives contained in polymer compositions.
• V polymer or block copolymer
• the invention also relates to polymer compositions comprising a polymer or block copolymer (V) in a mixture with an N ⁇ O-substituted polymer or block copolymer (VII) and conventional additives contained in polymer compositions.
• Such additives can be added in small amounts, e.g. UV absorbers or light stabilizers, e.g. from the series of hydroxyphenylbenzotriazoles, hydroxyphenylbenzophenones, oxalamides or hydroxyphenyl-s-triazines.
• Light stabilizers from the group of so-called sterically hindered amines (HALS), e.g. 2- (2-hydroxyphenyl) -1, 3,5-triazine or 2-hydroxyphenyl-2H-benzotriazole type. Examples of light stabilizers of the 2- (2-hydroxyphenyl) -1, 3,5-triazine type are known from the patent literature, e.g.
• compositions may also contain other conventional additives, for example fillers, for example calcium carbonate, silicates, glass or glass fiber material, talc, kaolin, mica, Barium sulfate, metal oxides and hydroxides, carbon black, graphite, powdered wood and powdered or fibrous material from other natural products, synthetic fibers, plasticizers, lubricants, emulsifiers, pigments, flow agents, catalysts, optical brighteners, flame retardants, antistatic agents or blowing agents.
• fillers for example calcium carbonate, silicates, glass or glass fiber material, talc, kaolin, mica, Barium sulfate, metal oxides and hydroxides, carbon black, graphite, powdered wood and powdered or fibrous material from other natural products, synthetic fibers, plasticizers, lubricants, emulsifiers, pigments, flow agents, catalysts, optical brighteners, flame retardants, antistatic agents or blowing agents.
• the composition can the mentioned polymers in concentrations of about 0.01 to 99.0 percent by weight, preferably 0.1 to 95 percent by weight, in particular 1.0 to 90.0 percent by weight, especially 5.0 to 80.0 percent by weight on the monomer content of the composition.
• Another object of the invention is a polymer composition
• a polymer composition comprising a) a polymer or block copolymer (V), wherein R ⁇ R 2 , A, B, x, y and m have the meanings given above; and b) another polymer or oligomer of the formula wherein
• a and B are polymer blocks of ethylenically unsaturated monomer units and x and y are the number of monomer units in blocks A and B, where one value of x and y is zero and the other value is an integer greater than zero or both values x and y are greater than be zero.
• the invention also relates to a polymer composition
• a polymer composition comprising a ') an N ⁇ O substituted polymer or block copolymer (VII) and b') a further polymer or oligomer (IX).
• compositions can contain the customary additives mentioned and the polymer or oligomer components a) and b), or a ') and b'), in concentrations of about 0.01 to 99.0 percent by weight, preferably 0.1 to 95 percent by weight, in particular 1.0 to 90.0 percent by weight, especially 5.0 to 80.0 percent by weight, based on the monomer content of the composition.
• the polymers and the compositions according to the present invention can be used for a wide variety of technical applications, for example as adhesives, detergent auxiliaries, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, flow improvers, thickeners, crosslinking agents, as additives for water treatment , electronic materials, paints and varnishes, coatings, inks, photo developers, "Superab- sorbants ", cosmetics, preservatives, or as biocides or modifiers and auxiliaries for asphalt, textiles, ceramics and wood.
• Example 5 a) Preparation of a "3-star" polymer with a low molecular weight
• the temperature is kept at 95-100 ° C. by cooling with an ice bath. After a polymerization time of 20 minutes, a conversion of 100% is achieved ( 1 H-NMR control), the reaction mixture is cooled and diluted with 50 ml of dioxane. 30 g of Al 2 O 3 (Alox®) are added, the mixture is stirred for 1 h and filtered. The polymer solution is completely concentrated in a rotary evaporator in vacuo at 80 ° C. Yield: 39.5 g (95%).
• Example 5 a Analogously to Example 5 a), the reaction is carried out at 90 ° C., a conversion of about 100% ( 1 H-NMR control) being obtained after a polymerization time of 90 minutes. 19.9 g (90%) of the pure product are isolated.
• MMA methyl methacrylate
• Fluka puriss methyl methacrylate
• the respective amounts of Cu (l) Br catalyst are added (Fluka, purum), the initiator 1, 3,5-tris (2-bromo-2-methylpropanoyloxy) benzene, Example 7, the solvent (if necessary) and MMA in the flask, which is tightly sealed with a rubber septum.
• the vessel is evacuated with stirring and flushed three times with nitrogen.
• the ligand former PMDETA (N, N, N ', N ", N” -pentamethyldiethylenetriamine, Fluka, purum) is then added using a syringe.
• the vessel is heated to 90 ° C. in an oil bath and the progress of the reaction is monitored by regular sampling and NMR control in CDCI 3 .
• the reaction conditions are described in Table 1: Table 1
• the PDI values are low and the higher M w value of the LS relative to that of the GPC indicates a compact molecular structure of these star-shaped macromolecules.
• n-butyl acrylate (n-BA, Fluka puriss) are polymerized in a 25 ml round-bottom flask equipped with a septum and magnetic stirrer under a nitrogen atmosphere as follows: The respective amounts of Cu (l) are added Br catalyst (Fluka, purum), initiator 1, 2,3,4,5,6-hexakis (2-chloro-propanoyloxy) -n-hexane, example 8, the solvent (if necessary) and n-BA in the flask, which is tightly closed with a rubber septum. The vessel is evacuated with stirring and flushed three times with nitrogen.
• Br catalyst Fluka puriss
• the ligand former PMDETA (N, N, N ', N ", N” -pentamethyldiethylenetriamine, Fluka, purum) is then added using a syringe.
• the vessel is heated in an oil bath to 90 ° C and observes the progress of the reaction through regular sampling and NMR control in CDCI 3 .
• the reaction conditions are described in Table 3:
• the PDI values are low and the higher M w value of the LS relative to that of the GPC indicates a compact molecular structure of these star-shaped macromolecules.
• the initiator 1, 2,2,3-tetrakis (2-bromopropionyloxymethyl) propane is prepared analogously to Example 3.

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