WO2013030261A1

WO2013030261A1 - Production of polymers by means of controlled radical polymerisation

Info

Publication number: WO2013030261A1
Application number: PCT/EP2012/066838
Authority: WO
Inventors: Pascal Hesse; Sven Fleischmann; Florian Becker; Klaus MÜHLBACH; Klaus-Dieter Hungenberg; Markus Brym; Matthias Kleiner
Original assignee: Basf Se
Priority date: 2011-08-30
Filing date: 2012-08-30
Publication date: 2013-03-07
Also published as: ZA201402272B; MX2014002011A; BR112014003922A2; CN103764688A; EP2751143A1; KR20140069032A; RU2014111849A; SG2014014492A; JP2014525486A; IN2014CN02321A

Abstract

Method for producing polymers by means of controlled radical polymerisation, wherein the polymerisation of one or several radically polymerisable monomers of general formula (I), where R¹, R², R³ are H, C₁-C₄alkyl, R⁴ is C(=O)OR⁵, C(=O)NHR¹⁵, C(=O)NR⁵R⁶, OC(=O)CH₃, C(=O)OH, CN, aryl, hetaryl, C(=O)OR⁵OH, C(=O)OR⁵Si(OR⁵)₃, halogen, NHC(O)H, P(=O)(OR⁷)₂, R⁵ is C₁-C₂₀alkyl, R¹⁵ is C₁-C₂₀-alkyl, R⁶ is C₁-C₂₀alkyl, and R⁷ is H, C₁-C₂₀alkyl, occurs in the presence of a. one or several catalysts containing Cu in the form of Cu(0), Cu(l), Cu (II) or mixtures thereof, b. one or several initiators selected from the group of organic halogenides or pseudohalogenides, c. one or several ligands, d. optionally one or several solvents, and e. optionally one or several inorganic halogenide salts, said method consisting of the following steps i) addition of the catalyst a., ii) optional addition of monomers of general formula (I), iii) optional addition of solvent d., iv) addition of ligand c., v) addition of initiator b., vi) addition of monomers of general formula (I), and vii) optional addition of inorganic halogenide salts e., on the proviso that the addition of at least some of the monomers of general formula (I) occurs immediately before or shortly after the last of the steps i), iv) and v).

Description

Preparation of Polymers by Controlled Radical Polymerization Description The present invention relates to processes for the preparation of polymers by controlled free radical polymerization. Furthermore, the invention relates to polymers which are prepared by this process and the use of these polymers.

Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. In particular, those embodiments of the present invention in which all features of the article according to the invention have the preferred or very preferred meanings are preferred or very particularly preferred.

WO 96/130421 A1 describes ATRP (Atom Transfer Radical Polymerization) polymerization processes as a special case of "living" or "controlled" free-radical polymerization. ATRP polymerization processes are based on redox reactions between transition metals (for example Cu (I) / Cu (II)) and are used for the living radical polymerization of monomers such as styrene or (meth) acrylates. Organic halogen compounds are used as initiators and transition metal complexes as catalysts for the polymerization reaction. According to WO 96/130421 A1, polymers with a controlled and narrow molar mass distribution thus result.

WO 97/18247 A1 likewise describes ATRP polymerization processes involving a free, radical-deactivating, fraction of a reduced or oxidized transition metal. Other variations of the process include polymerization in homogeneous systems or in the presence of solubilized initiator / catalyst systems.

WO 98/40415 A1 and WO 00/56795 A1 describe further embodiments of ATRP polymerization processes in which, for example, special ligands, counterions or metals are selected for the transition metal complexes.

WO 02/38618 A2 relates to a process for the preparation of polymer compositions by means of continuous process control, in which ethylenically unsaturated monomers by means of initiators which have a transferable atomic group, and catalysts which comprise Übergangsme- metals, in the presence of ligands, with the catalysts can form a coordination compound, polymerized. WO 2008/019100 A2 describes SET-LRP polymerization processes (single electron transfer - living radical polymerization) using Cu (0), Cu2Te, CuSe, CU2S and / or CU2O catalysts. The polymerization reactions also take place using initiators and a component containing solvent and optionally nitrogen-containing ligands. In this case, the interaction of this component with the monomer leads to a disproportionation of Cu (I) halides to Cu (II) halides and metallic Cu (0).

Rosen et al. Review in Chemical Reviews, 109, 5069-51 19 (2009) SET-LRP Polymerization Process.

EP 0 850 957 A1 describes processes for the controlled radical polymerization of (meth) acrylic monomers and / or other monomers wherein at least one of the monomers is polymerized at a temperature which can fall to 0 ° C. in the presence of an initiator system. The initiator system contains a compound that generates radicals and a catalyst containing metal complexes with ligands.

WO 2009/155303 A2 describes methods for the controlled radical polymerization of monomers, in particular using methods of living radical polymerization. Here, a mixture is used, containing at least one monomer, a solvent, a compound capable of coordinating metals and an initiator. This mixture is passed over the surface of a solid catalyst, which is located in a container outside the reaction vessel.

SET-LRP methods make it possible to carry out controlled radical polymerization reactions at elevated reaction rates in comparison with conventional ATRP processes (see Rosen et al.). One of the subtasks of the present invention was to make use of this effect on an industrial scale and to further optimize the reaction rate. A special challenge of the SET-LRP process is given by a high heat output of the reaction, which can be influenced only incompletely with the help of temperature control. A sub-task of the present invention was therefore to provide a method that allows to control the rapid heat release of the reaction. In particular, SET-LRP processes carried out on an industrial scale represent a challenge with regard to the resulting rapid heat release in the case of a larger amount of sales. A sub-task of the invention was therefore to provide a method that allows reactions to be carried out on an industrial scale while maintaining the safety requirements. A further object of the present invention was therefore to provide SET-LRP processes for the preparation of polymers which, even at elevated polymerization temperatures, make it possible to maintain control over the molecular weight distribution of the polymers. Another object of the present invention was to provide SET-LRP processes for the preparation of polymers which make it possible to provide the polymers in a very short time. In general, SET-LRP processes have often been conducted on a laboratory scale, therefore, there is a need to provide processes that allow adaptation of the reaction conditions and feedstocks to industrial scale production. In particular, improvements in the catalyst, reactor type and the reaction procedure are objects of the invention.

In the preparation of block copolymers, especially block copolymers of acrylates and methacrylates, the method described in the prior art with the aid of Cu salts slows down the reaction rate and increases the copper input into the resulting polymer. Therefore, it was another object of the present invention to provide processes which do not have these disadvantages in block copolymer formation.

These and other objects, as apparent from the disclosure of the present invention, are achieved by the various embodiments of the process according to the invention for the production of polymers by controlled radical polymerization, wherein the polymerization of one or more free-radically polymerizable monomers of the general formula (I)

With

H, C 1 -C 4 -alkyl, preferably H, C 1 -C 2 -alkyl, particularly preferably H,

R ^{2 is} H, C 1 -C 4 -alkyl, preferably H, C 1 -C 2 -alkyl, particularly preferably H, CH 3,

R ^{3 is} H, C ¹ -C 4 -alkyl, preferably H, C ¹ -C ² -alkyl, particularly preferably H,

C (= O) OR ⁵ , C (= O) NHR ¹⁵ , C (= O) NR ⁵ R ⁶ , OC (= O) CH ₃ , C (= O) OH, CN, aryl, hetaryl,

C (= O) OR ⁵ OH, C (= O) OR ⁵ Si (OR ⁵ ) ₃ , halogen, preferably Cl, NHC (0) H, P (= 0) (OR ⁷ ) ₂ ,

C 1 -C 20 -alkyl, preferably C 1 -C 12 -alkyl, in particular ethyl-hexyl,

_R 15 is C 1 -C 20 -alkyl, preferably isopropyl,

C 1 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 5 -alkyl, in particular C 1 -C 2 -alkyl, very particularly preferably C 1 -alkyl,

H, C 1 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 3 -alkyl, in particular C 2 -alkyl wherein the substituents R ⁵ , R ⁶ , R ⁷ and R ^{15 may} each be interrupted at any position by one or more heteroatoms, wherein the number of these heteroatoms is not more than 10, preferably not more than 8, most preferably not more than 5 and in particular not more than 3, and / or in each case

any position, but not more than five times, preferably not more than

four times and more preferably not more than three times, by NR ⁸ R ⁹ , C (= O) NR ⁸ R ⁹ , C (= O) R ¹⁰ , C (= O) OR ¹ °, SO 3 R ¹⁰ , CN, NO ₂ , C 1 -C ₂₀ -alkyl, C 1 -C ₂₀ -alkoxy, aryl, aryloxy, heterocycles, heteroatoms, heteroatoms or halogen may be substituted, these likewise being able to be substituted at most twice, preferably at most once, with the abovementioned groups,

R ⁸ , R ⁹ , R ^{10 are} independently, the same or different, H,

C ₁ -C ₂₀ -alkyl, C ₂ -C ₂ o-alkenyl, C ₂ -C ₂₀ -alkynyl,

Cs-Cis-cycloalkyl, aryl, in the presence

a. one or more catalysts comprising Cu in the form of Cu (0), Cu (I), Cu (II) or mixtures thereof, b one or more initiators selected from the group of organic halides or pseudohalides, c one or more ligands, d optionally one or more solvents, optionally one or more inorganic halide salts, comprising the steps

i) addition of the catalyst a.,

ii) optionally adding monomers of the general formula (I),

iii) optionally adding solvent d.,

iv) addition of ligand c,

v) addition of initiator b.,

vi) addition of monomers of the general formula (I),

vii) optionally adding inorganic halide salts e., with the proviso that the addition of at least part of the monomers of the general formula (I) takes place immediately before or shortly after the last of the steps i), iv) and v). Before- at least part of the monomers of the general formula (I) is added before the last of the steps i), iv) and v) is carried out. Also preferably, the addition of at least part of the monomers of the general formula (I) takes place simultaneously with the last of the steps i), iv) and v). Also preferably, the addition of at least a portion of the monomers of the general formula (I) takes place within 60 min after the last of steps i), iv) and i, more preferably within 30 min, most preferably within 10 min and especially within 5 min.

Expressions of the form C _a -Cb designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by expressions of the form C _a -Cb-V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.

Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine, bromine or iodine, particularly preferably chlorine or bromine. Pseudohalogens are the groups -CN, -N3, -OCN, -NCO, -CNO, -SCN, -NCS, -SeCN, preferably -CN, -OCN, -NCO, -SCN, -NCS.

In detail, the collective terms given for the various substituents have the following meaning:

C 1 -C 20 -alkyl: straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl, isopropyl , or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl , 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C ₇ -C 10 -alkyl, such as heptyl , Octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers.

C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are attached via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy Ci-Cio-alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.

C 2 -C 20 alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a double bond in any desired position, for example C 2 -C 10 Alkenyl or C 2 -C 20 alkenyl, preferably C 2 -C 10 alkenyl, such as C 2 -C 4 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or C5-C6-alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3 Methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl- 1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,

1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1, 1-dimethyl-3 butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2 butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl 1-Butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2- methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, and C7-Cio-alkenyl, such as the isomers of heptenyl, octenyl, nonenyl or decenyl. C 2 -C 20 -alkynyl: straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, for example C 2 -C 10 -alkynyl or C 1 -C 20 -alkynyl, preferably C 2 -C 10 -alkynyl, such as C 2 -C 4 -alkynyl, as described above Ethynyl, 1-propynyl,

2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, or C 5 -C 7 -alkynyl, such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 - Methyl 2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1 - Hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1 - Ethyl-3-butynyl, 2-ethyl-3-butynyl or 1-ethyl-1-methyl-2-propynyl and Cz-Cio-alkynyl, such as the isomers of hepinyl, octynyl, nonynyl, decynyl.

C3-C15-cycloalkyl: monocyclic saturated hydrocarbon groups with 3 up to

15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as. B. norbornyl or norbenyl.

Aryl: a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system. Aryloxy: is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system. Hetaryl: Heterocyclic substituents which formally derive from aryl groups by replacing one or more methine (- C =) and / or vinylene groups (-CH = CH-) with tri- or divalent heteroatoms. Preferred heteroatoms are oxygen, nitrogen and / or sulfur. Particularly preferably nitrogen and / or oxygen. Heterocycles: five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, oxygen, nitrogen and / or sulfur atoms, ring rings optionally containing several rings such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl. The heterocycles may be chemically attached in any manner, for example via a bond to a carbon atom of the heterocycle or a bond to one of the heteroatoms. Furthermore, in particular, five- or six-membered saturated nitrogen-containing ring systems, which are attached via a ring nitrogen atom and which may contain one or two further nitrogen atoms or another oxygen or sulfur atom.

Heteroatoms are phosphorus, oxygen, nitrogen or sulfur, preferably oxygen, nitrogen or sulfur whose free valencies are optionally saturated by H or Ci-C2o-alkyl.

As monomers of the general formula (I), alkyl (meth) acrylates, substituted (meth) acrylates, N-substituted (meth) acrylamides or N, N-disubstituted (meth) acrylamides are preferably used in the process according to the invention. The amounts used of the components a. to e. and the monomer of the general formula (I) may vary over a wide range within the scope of the process according to the invention, depending on the desired properties of the polymers. The proportion of catalyst a is preferably. from 0.0001 to 10% by weight, the amount of initiator b. from 0.01 to 10.0 wt .-%, the proportion of ligand c. from 0.0001 to 1, 0 wt .-%, the proportion of solvent d. from 0 to 70% by weight, the proportion of halide salt e. from 0 to 5.0 wt .-% and the proportion of monomer of the general formula (I) of 4 to 99.9898 wt .-%, each based on the total amount of components a. to e. together with monomer of general formula (I). The total amount of monomer of general formula (I) and components a. to e. is 100% by weight. The proportion of catalyst a is particularly preferably. from 0.001 to 5% by weight, the proportion of initiator b. from 0.1 to 5 wt .-%, the proportion of ligand c. from 0.001 to 0.5 wt .-%, the proportion of solvent d. from 0 to 60 wt .-%, the proportion of halide salt e. from 0 to 4% by weight. In particular, the proportion of catalyst a. from 0.002 to 4 wt .-%, the proportion of initiator b. from 0.2 to 4% by weight, the proportion of ligand c. from 0.002 to 0.4 wt .-%, the proportion of solvent d. from 0 to 50 wt .-%, the proportion of halide salt e. from 0 to 3% by weight.

In one embodiment of the process according to the invention, in the catalyst a. Cu (0) is preferably used as a solid, in particular in the form of a wire, grid, mesh, or powder. In a further preferred embodiment, the catalyst comprises a. Cu (0) zeolites. In particular, in addition to metallic Cu (O), Cu (II) is also used in the catalyst in the process according to the invention. An advantage of using Cu (0) and Cu (II) is that the polymerization reaction proceeds in a controlled manner from the beginning.

In a further preferred embodiment, the catalyst comprises a. Copper alloys such as brass or bronze.

In a further preferred embodiment of the process according to the invention, the catalysts additionally comprise metals selected from the group Mn, Ni, Pt, Fe, Ru, V.

As initiators b. In the context of the process according to the invention, preference is given to organic chlorides and bromides, particularly preferably 2,2-dichloroacetophenone, substituted sulfonic acid halides, in particular toluenesulfonyl chloride, methyl 2-bromopropionate, methyl 2-chloropropionate, 2-bromopropionitrile and 2,6-dibromodiethyl heptanedionate and also , 5 dibromadipic acid ethyl ester used.

As ligands c. In the context of the process according to the invention, preference is given to using those which are capable of forming complexes with one or more components of the catalyst; particular preference is given to ligands c. selected from the group of the organic nitrogen compounds, particularly preferably the organic multidentate amines, in particular hexamethylene tris (2-aminoethyl) amine, tris (2-aminoethyl) amine, 2,2-bipyridine and polyimine. Of course, mixtures of ligands c. deploy. In a preferred embodiment of the process according to the invention, one or more solvents d. used, for example, alcohols or polyols, preferably dimethyl sulfoxide, methyl ethyl ketone, ethyl acetate, methanol, ethanol, propanol, isobutanol, n-butanol, tert-butanol, glycol, glycerol, ethylene carbonate, propylene carbonate, acetone, lactates, water and mixtures of These solvents, preferably the water content in the solvent from 0 to 10 wt .-%, particularly preferably from 0 to 7 wt .-%, in particular from 0 to 5

Wt .-%, each based on the total amount of solvent. In particular, mixtures of protic and aprotic solvents can also be used as solvents. In a preferred embodiment of the process according to the invention, one or more halide salts e. preferably NaCl, NaBr, CaC, additionally CuC, CuBr2, used. Particularly preferred here are NaCl or NaBr. The use of NaCl or NaBr advantageously makes it possible to prepare block copolymers from acrylates and methacrylates.

The addition of monomers vi) takes place continuously or discontinuously in the context of the process according to the invention. The monomers of the general formula (I) are added in step vi) in a total amount or in several subsets.

In one embodiment of the process according to the invention, the controlled radical polymerization is carried out in a semibatch process. Semibatch processes are distinguished from batch processes in free radical polymerizations by a higher variability in the addition of the feedstocks, e.g. by feed strategies for monomers in copolymerizations, which minimize the change in the polymer composition over the course of the reaction. Due to the generally lower free monomer concentrations in contrast to the batch process, especially at the beginning of the reaction, the risk potential of the process is minimized in relation to the maximum amount of heat released at any given time.

This means that at least a portion of the monomer after starting the reaction by joining the components i. to v. is added slowly. By suitable feed strategies for monomer and, if appropriate, initiator, the process can be operated continuously at high heat flows to be dissipated (or reaction rates) while avoiding power peaks.

In another embodiment of the method according to the invention, the controlled radical polymerization is carried out in a continuous process. In order to achieve narrowly distributed molecular weights in a controlled radical polymerization, it is necessary to achieve a narrow residence time distribution in the reactor in continuous polymerization processes. Accordingly, reactors with Rohrreaktorcharektenstik offer. In addition to tubular reactors, these can also be strip reactors, stirred tank cascades or certain millireactors. Milli reactors allow good temperature control even in the case of strongly exothermic reactions since they are characterized by high heat exchange surfaces.

In a preferred embodiment of the process according to the invention, first of all an acrylate as monomer of the general formula (I), using an organic bromide as initiator, is polymerized to a conversion of> 85%. Before the addition of a methacrylate as further monomer of the general formula (I), for example for the introduction of a second polymer block, an inorganic chloride is preferably added, particularly preferably an alkali metal or alkaline earth metal chloride, in particular NaCl. Telecheles with methacrylate groups at the end of the acrylate polymer chain can be produced with particular preference using this process.

In general, as known to those skilled in the art, the rate of radical polymerization depends, for example, on the temperature, the monomers used, the Solvents or the initiator concentration. The speed of the reaction can therefore vary over a wide range. The process according to the invention is preferably carried out in such a way that the controlled radical polymerization takes place within a short time, preferably within less than 10 h, more preferably within less than 6 h, in particular within less than 1 h, to a conversion of greater than 80%, preferably greater than 85%, particularly preferably greater than 90% is performed.

In the context of the process according to the invention, the polymers obtained usually have, after conversion of the monomers from 80 to 100%, a mean molar mass Mn (number average) of from 1 000 to 1 000 000 g / mol, preferably from 2 000 to 200 000 g / mol, in particular from 3,000 to 150,000 g / mol. The average molecular weights generally depend on the concentration of initiator, as known to those skilled in the art. Mn can be adjusted over a wide range depending on the desired application of the polymer. For sealants values of 2,000 to 4,000 g / mol are desired. For resins and thermoplastics values of 100,000 to 150,000 g / mol are common.

In the context of the process according to the invention, the polymers obtained generally have, after a conversion of the monomers from 80 to 100%, an average molar mass Mw (weight average) of from 1 to 100 to 2,000,000 g / mol, preferably from 2,200 to 300,000 g / mol , in particular from 3,300 to 200,000 g / mol.

In the context of the process according to the invention, the polymers obtained generally have a polydispersity PDI (quotient of weight average and number average molecular weight distribution) of from 80 to 100% of the monomers of from .0 to 2.5, preferably from 1.05 to 1 .5, in particular from 1.1 to 1 .3 on.

In a preferred embodiment of the process according to the invention, first the catalyst a. added, then optionally takes place the addition of monomers of the general formula (I) and / or solvent d. and thereafter ligand c, initiator b. and optionally inorganic halide salt e. added. Particularly preferred is the addition of ligand c. and initiator b. simultaneously.

In a further preferred embodiment of the process according to the invention, in step ii), preferably only a small amount of monomer of the general formula (I) is added. In this case, from 5 to 15% by weight of monomer, based on the total amount of components a. to e. and monomer of the general formula (I) used, preferably from 10 to 15 wt .-%.

The process according to the invention can be carried out in the apparatus known to the skilled person from the prior art. Preferably, the polymerization is carried out in a stirred tank, tubular reactor, capillary reactor, belt reactor or another reactor with tube reactor characteristic. Preferably, in the apparatuses a permanent mixing or an optimized mixing of components such as ligand and initiator instead, which is ensured by mixing apparatus known in the art.

The reaction mixture often shows corrosion phenomena in the apparatuses used, and therefore selected materials for the apparatuses are preferably selected steel alloys, such as X1 CrNiMoCuN20-18-6 (1 .4547), particularly preferably NiCr21 Mo14W (2.4602). Also preferred are materials such as glass, titanium (3.0735) and chemical enamel.

In a preferred embodiment, catalyst of component a is at all points at which the polymerization reaction is to take place. available. For reactions on an industrial scale, the Cu (0) present in the catalyst is at least partially, preferably for the most part, in powder form. Preferably, the particle size in the Cu (0) powder is substantially less than or equal to 45 μm, the proportion of particles. which are greater than 45 μηη is preferably at most 2 wt .-%. Copper wire, copper mesh, grid, or copper wool have the advantage that the polymer is easily separated from the catalyst after the reaction. Particularly preferred are combinations of copper wire, copper mesh, grating, or copper wool with copper powder as constituents of the catalyst a. used.

In a further preferred embodiment of the process according to the invention, a purification of the resulting polymers by reducing the residual content of copper or copper ions by filtration, precipitation, ion exchange or electrochemical processes is additionally carried out after step vii).

The process according to the invention can be carried out at temperatures which vary over a wide range. The choice of temperature depends, for example, on the desired properties of the resulting polymers. Advantageously, the method according to the invention can also be used at relatively high temperatures. In general, the inventive method at temperatures from -70 to 180 ° C, preferably from 0 to 150 ° C, more preferably from 20 to 120 ° C, in particular from 30 to 120 ° C.

In a preferred embodiment, the polymerization is carried out partly adiabatic, which is positive for the energy consumption, since the heat of reaction is used for heating.

For the rate of the reaction and the molecular weight control, it is advantageous to start the polymerization at low temperatures, ie for example in the range from 20 ° C. to 50 ° C., preferably in the range from 30 to 40 ° C., in order not to generate additional cooling requirements. The molecular weight control, which leads to a narrow molecular weight distribution, while remaining over the entire temperature range (eg from 30 to 90 ° C). The process according to the invention can be carried out at pressures which vary over a wide range. For example, the polymerization can be carried out at a slight negative pressure or at elevated pressures. The pressure is preferably from 1 to 50 bar, in particular especially from 1 to 5 bar. The pressure conditions are usually also dependent on the temperature and composition of the system.

Another object of the invention are polymers which are obtainable according to the embodiments of the method according to the invention. These polymers preferably have average molecular weights Mn and Mw and polydispersities (Mw / Mn) in the abovementioned ranges.

The polymers according to the invention are preferably homopolymers, random copolymers, block copolymers, gradient copolymers, graft copolymers, star copolymers or Telechele polymers. Particularly preferred are acrylate-methacrylate diblock copolymers and acrylate-methacrylate multiblock copolymers, particularly preferably acrylate-methacrylate triblock copolymers and block copolymers of acrylates and methacrylates, preferably pBA-b-pMMA or triblock copolymers of pMMA-b-pBA-b-pMMA.

A further subject of the invention is the use of polymers or polymers according to the invention as teleches for sealants, adhesives (adhesives), polymeric additives or reactive components (for example silane-functionalized). When used as sealants or adhesives, for example, a well-defined OH telechel is used as the polyol component for the reaction with isocyanates.

The use according to the invention of polymers as triblock copolymer is preferably carried out in TPE (thermoplastic elastomers) applications, as impact modifier for styrene-acrylonitrile copolymers or polybutylene terephthalate or as plasticizer / impact modifier for PVC.

With further preference the use according to the invention of polymers is carried out as dispersing aids, usually in the form of block copolymers. The present invention provides methods that allow radical polymerization reactions to be carried out which allow even at elevated polymerization temperatures to maintain control over the molecular weight distribution of the polymers. These processes provide polymers within a very short time. The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.

Examples: Example 1: Continuous operation in a tubular reactor (capillary reactor)

Monomer: methyl acrylate (methyl acrylate) Solvent: dimethyl sulfoxide

Initiator: methyl 2-bromopropionate

Ligand: Hexamethylene tris- (2-aminoethyl) amine (MeeTREN) Several experiments were carried out for continuous operation in the tubular reactor. The experimental setup is shown schematically in FIG.

It shows: FIG. 1 The experimental structure of the capillary reactor is shown in FIG.

The reactor comprised two capillaries (K1, K2) each 10 m in length (4 mm inner diameter), through each of which a copper wire of 1 .6 mm

Diameter and 10 m in length was pulled and which over the

Thermostats W1 and W2 were tempered. Monomers were

continuously from a storage vessel (B3) via an HPLC pump (P3) and the solvent from (B5) via an HPLC pump (P4) metered and mixed in a static mixer (M1). The initiator ligand feed was metered from storage vessel (B1) with the HPLC pump (P2) and then mixed with the monomer-solvent feed with another static mixer (M2). The flow rates of the pumps P1 to P4 were controlled by the scales A1 to A4.

Bins B2, B4, B6 and B8 allow solvent switching to purify the reactors. With the pump P1, monomer or initiator ligand between the reactors (K1) and (K2) can be metered from the storage vessel B7 if necessary.

Monomer is effectively given just before or shortly after the addition of ligand or initiator. With a residence time (corresponding to the reaction time) of about 38 minutes and a bath temperature of the thermostats (W1) and (W2) of 70 ° C., a monomer conversion of over 90% was obtained (molar ratio of monomer to initiator to ligand of 100 to 1) to 0.1, solvent content: 73% by weight). A significant acceleration of the reaction in a continuous mode of operation compared to the semi-batch experiments was possible. The continuous mode of operation offered good control over the reaction because of the large heat exchange area of the tubular reactor. The experimental molecular weight Mn was about 38% higher than the theoretical molecular weight at a polydispersity (Mw / Mn) of 1.36. The residence time profile of the tube reactor led to a widening of the molecular weight distribution. Example 2: Semibatch Process

Experimental setup:

Reaction Calorimeter METTLER Toledo RC1 with ReactIR 4000, software IC-Control 4.0, IC-IR 4.0.

2 m of Cu wire with a diameter of 1 mm were wound around a baffle and introduced into the reactor via a flange. The contact area with the Cu wire increases as the fill level increases, resulting in a comparable Cu exchange area per volume of solution in the course of monomer addition.

The samples taken from the reactor at regular intervals were analyzed as follows:

1) The solids content was determined on a Mettler Toledo HR73 IR dryer. The monomer conversion can be calculated from the recipe parameters.

2) The molecular weight distribution of the polymer was determined by means of a GPC system (gel permeation chromatography, Agilent Technologies). This contained four columns of the company MZ-analytics from Mainz. The columns have the dimension 300 x 8 mm and are filled with cross-linked divinylbenzene-styrene polymer of a particle size of 5 μm. The porosities are 100, 1000, 10000 and 100000 angstroms, respectively. The eluent used was tetrahydrofuran at 35 ° C. The calibration was carried out against narrowly distributed polystyrene standards of the company PSS (Type Ready Kai.) With a peak molecular weight Mp of 2,180,000, 1,000,000, 659,000, 246,000, 128,000, 67,500, 32,500, 18,100, 9,130, 3,420, 1, 620 resp 374 g / mol.

From the measured molecular weight distributions Mn, Mw and PDI were determined. The theoretically expected number-average molecular weight Mn (theor) is calculated from the assumption of the uniform distribution of all reacted monomer molecules via the chains whereby in the case of monofunctional initiators such as methyl 2-bromopropionate (MBP) each initiator molecule starts a chain. It follows:

/ Wn (theor) = / 77monomer * initiator * - ^ monomer / initiator (1) mMonomer: total mass of the submitted and until the time of sampling

Accumulated monomer

minitiator: mass of the initiator (has been submitted)

Monomer: fractional conversion of monomer to polymer (only that presented and bis at the time of sampling, accumulated monomer is considered again)

itiator molar mass of the initiator (167 g ^» mo ¹ in MBP)

Test Description:

Template: 13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO) 46.929% addition: 0.75 g Me ₆ TREN 0.062%

1.69 g of methyl 2-bromopropionate 0.141%

40.00 g of dimethylsulfoxide (DMSO) 3.303%

Feed 1: 594.41 g of methyl acrylate 49.535%

Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 70 ° C. The copper wire with holder was then added, the MeeTREN and methyl 2-bromopropionate added via a lock and rinsed with DMSO. Directly afterwards, feed 1 was started and metered in 240 minutes. After the end of the feed was postpolymerized for 10 hours. During dosing, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The reaction sequence shown in Table 1 resulted:

Table 1 :

/ W _n ^theor /

f / min conversion /% M _n 1 (g / mol) (g / mol) PDI

0 0.0

45 5,3 5033 581 1, 94

90 9,0 5652 1989 1, 76

172 6.3 5312 2661 1, 85

200 5.9 5741 2894 1, 80

240 5,4 5781 3178 1, 82

300 9.1 10446 5360 1, 33

420 564 54301 331 19 1, 26

480 72.1 65085 42369 1, 30

540 78.1 70006 45902 1, 31

1090 87.4 88225 51357 1, 1 1 Alternative modes of operation have, in part, resulted in a significant slowing of the polymerization. A preliminary preparation of ligand and initiator already prior to the actual reaction (ie, well before the addition of the monomer) resulted in slower polymerization reactions. The farther the time of introduction of ligand and initiator before the time of addition of the monomer, the slower was the subsequent polymerization reaction. Presumably, when the ligand and initiator are initially introduced, activation of the initiator occurs, ie presumably short-lived initiator radicals are formed, which terminate rapidly in the absence of the monomer. In the subsequent addition of the monomer, these initiators are then probably no longer available for a reaction and the polymerization reaction slows down significantly or there is hardly any reaction. In a preliminary template of ligand and initiator already in the run-up to the actual implementation was also shown that also the molecular weight control deteriorates, since the experimental number average molecular weights are significantly higher than the theoretically determined molecular weights. This is probably due to the fact that premature bimolecular termination reactions cause fewer initiator radicals to start chain growth.

The observations on the different modes of slowing the reaction and the molecular weight control were more pronounced at 70 ° C reaction temperature than at 50 ° C.

Example 3: a. Batch process reaction calorimeter

Template:

13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO) 46.929%

addition:

0.75 g M _e 6TREN 0.062%

1.69 g of methyl 2-bromopropionate 0.141%

40.00 g dimethyl sulfoxide (DMSO) 3.333%

594.41 g of methyl acrylate 49.535%

Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 70 ° C. Subsequently, the copper wire with holder were incorporated, the methyl acrylate added, immediately afterwards MeeTREN and methyl 2-bromopropionate added via a lock and rinsed with DMSO. During the reaction, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The results are summarized in Table 2.

Table 2:

/ W _n ^theo /

f / min conversion /% M _n 1 (g / mol) (g / mol) PDI

0 0.0

15 40.3 321 12 23683 1, 25

45 70.7 49891 41504 1, 18

138 91.2 59818 53539 1, 14

190 93.5 61257 54902 1, 18

260 95.8 67978 56241 1, 18

320 97.0 69533 56964 1, 14

410 97.9 70221 57498 1, 15

500 100.0 68237 58738 1, 25

b. Batch process in the laboratory

A reaction apparatus consisting of round bottom flask, reflux condenser, internal thermometer and gas inlet for nitrogen was briefly purged with inert gas. The copper catalyst was wound around the blade stirrer of the apparatus as a wire of 2 m length or added as copper powder (300 mg). Successively, 1072.8 g (8.37 mol) of butyl acrylate, 250 ml of methanol and 750 ml of methyl ethyl ketone and 30.1 g (83.7 mmol) of diethyl dibromoadipate and 1.93 mg (8.37 mmol) of MeeTREN were added. Thereafter, the heating was carried out with the heating bath, which was heated to 60 ° C. Within 5 minutes, the internal temperature rose to reflux temperature (70 ° C). The heating bath was removed. To control the degree of conversion, the solids content was determined. About 45 min. after heating, the temperature dropped back to 58 ° C and the degree of conversion was 91%. The average molecular weight was M _n = 13,700 g / mol of PDI was M _w / M _n = 1, 17.

General procedure of the SET-LRP in the laboratory experiment for the further examples:

In the laboratory, the polymerizations were basically carried out by means of SET-LRP as follows: The glass apparatus consisted of a reflux condenser, gas inlet for nitrogen, stirring device (paddle stirrer or magnetic stirrer), internal thermometer. The Cu wire was wound around the blade stirrer or around the magnetic stirrer. In some cases, Cu powder or Cu zeolites were used as a solid. The apparatus was purged with nitrogen before the reaction. The charging of the flask was carried out successively with monomer, immediately followed by solvent, initiator and ligand. Thereafter, the heating to desired outside temperature, usually 60 ° C. The onset of the reaction was characterized by an increase in internal temperature and onset of green coloration of the reaction solution. After reaching the highest possible degree of conversion, determined by the solids content which was determined by IR-T rocker company Sartorius, the reaction was stopped by removing the heating bath and removal of the Cu catalyst. Typically, sales levels of 80-100% were targeted, depending on the application. The workup of the product was finally carried out by removing residual monomer and solvent by means of a rotary evaporator. The characterization of the polymer was carried out by GPC under the conditions described above. The product was additionally analyzed by means of 1 H-NMR with CDC as solvent using a Bruker 500 MHz spectrometer.

Example 4 Polymerization of Butyl Acrylate Results of the experiments are summarized in Table 3:

Table 3:

Mn (theor) Mn (exp) turnover

No X LM [g / mol] [g / mol] Mw / Mn [%]

1 25 MeOH 3800 3200 1 .19 95

2 500 DMSO 48000 59800 1 .25 75

3 200 - 23400 20000 1 .15 78

4 200 MEK 25600 23000 1 .25 95

5,200 MEK / MeOH 25600 22100 1 .29 95

6 200 MeOH 25600 26200 1 .14 95

7 1500 MeOH 150000 1 16000 1 .4 81

8 10000 DMSO 680000 480000 1 .4 79

LM: solvent, MEK: methyl ethyl ketone, MeOH: methanol, # 5: MEK / MeOH = 50/50 (volume);

Outside temperature: T = 60 ° C

[BA] / [I] / [L] = x / 1 / 0.1 (molar ratios).

Turnover: Reaction butyl lactylate monomer

Experiment No. 1 was stopped after 4 hours, the remaining experiments after 6 hours

Example 5: Reaction procedure depending on the time of addition of the monomer a. Monomer is (partially) submitted

Template:

13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO) 46.929%

addition:

0.75 g MeeTREN 0.062%

1.69 g of methyl 2-bromopropionate 0.141%

40.00 g dimethyl sulfoxide (DMSO) 3.333%

74.30 g of methyl acrylate 6.192%

Feed 1:

520.12 g of methyl acrylate 43.343% Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 70 ° C. Then the copper wire with holder was installed, MeeTREN and methyl-2-bromopropionate were added via a lock and these were rinsed with DMSO. Thereafter, 12.5% of the monomer was added within 5 minutes. Subsequently, the feed 1 was added in 210 minutes. After the end of the feed was postpolymerized for 20 hours. During dosing, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The results are summarized in Table 4. Table 4:

M / W _n ^theo /

f / min U /% (g / mol) (g / mol) PDI

0 0.0

30 43.9 10060 2441 1 6.40

93 42.2 15732 23509 2.80

162 35.1 19585 19536 1, 70

210 29.2 20288 16249 1, 39

275 31, 1 22918 17319 1, 28

300 45.2 34078 25144 1, 21

345 64.0 45591 35628 1, 27

390 76.9 51519 42786 1, 27

450 82.8 55269 46089 1, 31

510 85.2 68523 47389 1, 42

1 140 92.5 64599 51486 1, 46 b. Monomer addition together with initiator and catalyst addition

Compare Example 2.

Template: 13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO)

Addition: 0.75 g Me6TREN 0.062%

1.69 g of methyl 2-bromopropionate 0.141%

40.00 g of dimethylsulfoxide (DMSO) 3.303%

Feed 1: 594.41 g of methyl acrylate 49.535%

Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 70 ° C. Then the copper wire with holder was installed, MeeTREN and methyl-2-bromopropionate were added via a lock and these were rinsed with DMSO. 5 minutes after the feed 1 was started and dosed in 240 minutes. After the end of the feed was postpolymerized for 10 hours. During dosing, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The results are summarized in Table 5.

Table 5:

M / W _n ^theo /

f / min U /% (g / mol) (g / mol) PDI

0 0.0

45 2.7

90 5.0 5028 2941 2.05

135 6.0 4297 3542 2.03

195 3,2 4254 1853 2,16

240 3.4 4046 2004 2.1 1

300 4,4 4868 2597 1, 80

360 26,3 28282 15427 1, 38

420 60.1 65105 35313 1, 1 1

480 73.7 85683 43305 1, 13

857 92.6 105670 54404 1, 21

c. Monomer addition after initiator and catalyst addition Template: 13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO) 46.929%

Addition: 0.75 g Me ₆ TREN 0.062%

1.69 g of methyl 2-bromopropionate 0.141%

40.00 g of dimethylsulfoxide (DMSO) 3.303%

Feed 1: 594.41 g of methyl acrylate 49.535% Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 70 ° C. Then the copper wire with holder was installed, MeeTREN and methyl-2-bromopropionate were added via a lock and these were rinsed with DMSO. Before the start of feed 1, the original was stirred for 60 minutes and then metered in the methacrylate in 240 minutes. After the end of the feed was postpolymerized for 10 hours. During dosing, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The results are summarized in Table 6.

Table 6:

M / W _n ^theo /

f / min U /% (g / mol) (g / mol) PDI

0 0.0

45 0.0

90 0.0

1 16 0.0

176 0.0

240 0.0

300 0.0

360 0.0

420 7.7 1551 1 4542 1 .67

480 33.6 62374 19744 1 .16

1200 89.7 154460 52709 1 .36

By fitting Equation (1) to the experimental molecular weights in Tables 1 and 4 to 6, the effective initiator concentration can be estimated relative to the ideal reference. This is 33% for example 5c, 51% for example 5b, 61% for example 2 and 80% for example 5a.

The GPC was calibrated against narrow polystyrene standards as described above.

Example 6: Reaction procedure depending on temperature control a) increase in temperature from 30 ° C to 70 ° C

Template: 13.1 1 g of copper wire

563.15 g dimethyl sulfoxide (DMSO) 48.024%

Addition: 0.75 g Me ₆ TREN 0.064%

1.69 g of methyl 2-bromopropionate 0.144%

40.00 g dimethylsulfoxide (DMSO) 3.41 1%

74.30 g of methyl acrylate 6.336%

Feed 1: 520.12 g of methyl acrylate 42.021%

Procedure:

The template was filled and rendered inert 3 times with 8 bar of nitrogen. The reactor was heated to 30 ° C. Then the copper wire with holder was installed, 15% of the monomer was metered in within 5 minutes, MeeTREN and methyl 2-bromopropionate were added via a lock and these were rinsed with DMSO. Subsequently, feed 1 was metered in over 210 minutes and the outside temperature was increased to 70 ° C. within 40 minutes during the metering. After the end of the feed was postpolymerized for 16 hours. During dosing, samples were taken and stabilized with 0.01 g of hydroquinone. Thereafter, the batch was cooled and drained. The results are summarized in Table 7.

Table 7:

M / W _n ^theo /

f / min U /% (g / mol) (g / mol) PDI

0 0.0

30 13.6 9206 7969 3.21

60 28.9 8081 16949 2.31

105 62.2 18146 36554 1, 30

150 53.8 24748 31574 1, 18

210 39.9 27078 23420 1, 18

270 36.8 26288 21617 1, 16

330 49.5 35079 29076 1, 15

390 69.2 47722 40649 1, 18

450 77.8 54632 45689 1, 19

510 82.8 58236 48653 1, 19

1 123 92.9 64353 54594 1, 27

Isothermal at 70 ° C Compare Example 5a.

Example 7: Block Copolymers and the Influence of Salt Acrylate Block on Methacrylate Block Without salt

17.9 g (0.14 mmol) of butyl acrylate, followed immediately by 15 ml of methyl ethyl ketone and 5 ml of methanol, and 16 mg (0.7 mmol) of 2-MMethylbromopropionate and 32 mg (0.14 mmol) were added successively to the reaction apparatus under a nitrogen atmosphere ) Given Me6-TREN. The heating of the reaction solution to 60 ° C by means of heating bath. After reaching a degree of conversion of 91%, 14.0 g (0.14 mmol) of methyl methacrylate and again 32.1 mg (0.14 mmol) of Me6-TREN were added in the second stage. After a reaction time of 6 hours, the degree of conversion in the second stage was 78%. The product was obtained by precipitation from methanol and the molecular weights were determined by means of GPC. Mn = 40,000 g / mol, PDI = 1, 85. (Bimodal)

With CuCl ₂

17.9 g (0.14 mmol) of butyl acrylate, followed immediately by 15 ml of methyl ethyl ketone and 5 ml of methanol, and 1 16 mg (0.7 mmol) of 2-methylbromopropionate and 32 mg (0.14 mmol) were added successively to the reaction apparatus under a nitrogen atmosphere ) Given Me6-TREN. The heating of the reaction solution to 60 ° C by means of heating bath. After reaching a conversion of 95% in the second stage 14.0 g (0.14 mmol) of methyl methacrylate and again 32.1 mg (0.14 mmol) of Me6-TREN and 3 mg (0.014 mmol) of copper (II) chloride added. After a reaction time of 6 hours, the degree of conversion in the second stage was 33%. The product was recovered by precipitation from methanol and the molecular weights were determined by GPC. Mn = 26,000 g / mol, Mw / Mn = 1, 37. (Monomodal)

With NaCI

17.9 g (0.14 mmol) of butyl acrylate, followed immediately by 15 ml of methyl ethyl ketone and 5 ml of methanol, and 1 16 mg (0.7 mmol) of 2-methylbromopropionate and 32 mg (0.14 mmol) were added successively to the reaction apparatus under a nitrogen atmosphere ) Given Me6-TREN. The heating of the reaction solution to 60 ° C by means of heating bath. After reaching a degree of conversion of 93%, in the second stage, 14.0 g (0.14 mmol) of methyl methacrylate and again 32.1 mg (0.14 mmol) of Me6-TREN and 80 mg (2 mmol) of sodium chloride were added. After a reaction time of 6 hours, the degree of conversion in the second stage was 80%. The product was recovered by precipitation from methanol and the molecular weights were determined by GPC. Mn = 42,600 g / mol, Mw / Mn = 1.30.

Claims

claims

1 . Process for the preparation of polymers by controlled radical polymerization, characterized in that the polymerization of one or more free-radically polymerizable monomers of the general formula (I)

H, C 1 -C ₄ -alkyl,

C (= O) OR ⁵ , C (= O) NHR ¹⁵ , C (= O) NR ⁵ R ⁶ , OC (= O) CH ₃ , C (= O) OH, CN, aryl, hetaryl, C (= 0) OR ⁵ OH, C (= O) OR ⁵ Si (OR ⁵ ) ₃ , halogen, NHC (0) H, P (= 0) (OR ⁷ ) ₂ ,

R ^{5 is} C 1 -C ₂₀ -alkyl,

R ^{15 is} C 1 -C ₂₀ -alkyl,

R ^{6 is} C 1 -C ₂₀ -alkyl,

R ^{7 is} H, C 1 -C ₂₀ -alkyl, where the substituents R ⁵ , R ⁶ , R ⁷ and R ^{15 may} each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, and / or respectively

any position, but not more than five times by NR ⁸ R ⁹ , C (= O) NR ⁸ R ⁹ , C (= 0) R ¹⁰ , C (= 0) OR ¹ °, SO 3 R ¹⁰ , CN, N0 ₂ , Ci -C ₂₀ alkyl, C ₂₀ alkoxy, aryl, aryloxy, heterocycles, heteroatoms or halogen may be substituted, which may also be substituted with a maximum of twice the above-mentioned groups,

R ⁸ , R ⁹ , R ^{10 are} independently, the same or different, H,

Ci-C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl,

Cs-Cis-cycloalkyl, aryl,

in present

a. one or more catalysts comprising Cu in the form of Cu (0), Cu (I), Cu (II) or mixtures thereof, b. one or more initiators selected from the group of organic halides or pseudohalides, c. one or more ligands, d. optionally one or more solvents, e. optionally one or more inorganic halide salts, comprising the steps

i) addition of the catalyst a.,

ii) optionally adding monomers of the general formula (I),

iii) optionally adding solvent d.,

iv) addition of ligand c,

v) addition of initiator b.,

vi) addition of monomers of the general formula (I),

vii) optionally adding inorganic halide salts e., with the proviso that the addition of at least part of the monomers of the general formula (I) takes place immediately before or shortly after the last of the steps i), iv) and v).

A method according to claim 1, characterized in that the addition of monomers vi) takes place continuously or discontinuously.

A method according to claim 1 or 2, characterized in that the monomers vi) are added in a total amount or in several subsets.

Process according to claims 1 to 3, characterized in that first the catalyst a. is added, then optionally the addition of monomers of general formula (I) and / or solvent d. followed by ligand c, initiator b. and optionally inorganic halide salt e. be added.

Process according to claims 1 to 4, characterized in that the addition of ligand c. and initiator b. takes place simultaneously.

Process according to claims 1 to 5, characterized in that solvent d. is added. Process according to claims 1 to 6, characterized in that after the polymerization as a further step, a purification of the polymer by reducing the residual held on copper or copper ions by filtration, precipitation, ion exchange or electrochemical processes.

8. Process according to claims 1 to 7, wherein the catalyst used is a transition metal-ligand complex.

9. The method according to claims 1 to 8, wherein as monomers alkyl (meth) acrylates, substituted (meth) acrylates, N-substituted (meth) acrylamides or N, N-disubstituted

(Meth) acrylamides are used.

10. The method according to claims 1 to 9, wherein as ligand an organic multi-toothed amine is used.

1 1. Polymers obtainable by the process according to claims 1 to 10.

12. Polymers according to claim 1 1, wherein the polymers are homopolymers, random copolymers, block copolymers, gradient copolymers, graft copolymers, star copolymers or Telechele polymers. 13. Use of polymers according to claims 1 1 and 12 as telechels for sealants, adhesives, modifiers or reactive component.

14. Use of polymers according to claims 11 and 12 as triblock copolymer in TPE applications, toughening modifiers for styrene-acrylate copolymers or polybutylene terephthalate or plasticizer / impact modifier for PVC.

15. Use of polymers according to claims 1 1 and 12 as a dispersing aid.