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WO2013030261A1 - Production de polymères par polymérisation radicalaire contrôlée - Google Patents

Production de polymères par polymérisation radicalaire contrôlée Download PDF

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Publication number
WO2013030261A1
WO2013030261A1 PCT/EP2012/066838 EP2012066838W WO2013030261A1 WO 2013030261 A1 WO2013030261 A1 WO 2013030261A1 EP 2012066838 W EP2012066838 W EP 2012066838W WO 2013030261 A1 WO2013030261 A1 WO 2013030261A1
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WIPO (PCT)
Prior art keywords
alkyl
addition
monomers
polymers
methyl
Prior art date
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PCT/EP2012/066838
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German (de)
English (en)
Inventor
Pascal Hesse
Sven Fleischmann
Florian Becker
Klaus MÜHLBACH
Klaus-Dieter Hungenberg
Markus Brym
Matthias Kleiner
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority to EP12753968.2A priority Critical patent/EP2751143A1/fr
Priority to IN2321CHN2014 priority patent/IN2014CN02321A/en
Priority to CN201280042447.4A priority patent/CN103764688A/zh
Priority to MX2014002011A priority patent/MX2014002011A/es
Priority to JP2014527650A priority patent/JP2014525486A/ja
Priority to BR112014003922A priority patent/BR112014003922A2/pt
Application filed by BASF SE filed Critical BASF SE
Priority to SG2014014492A priority patent/SG2014014492A/en
Priority to KR1020147007911A priority patent/KR20140069032A/ko
Priority to RU2014111849/04A priority patent/RU2014111849A/ru
Publication of WO2013030261A1 publication Critical patent/WO2013030261A1/fr
Anticipated expiration legal-status Critical
Priority to ZA2014/02272A priority patent/ZA201402272B/en
Ceased legal-status Critical Current

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F4/40—Redox systems
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • 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
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • 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.
  • 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.
  • 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 Kochgangsme- 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • improvements in the catalyst, reactor type and the reaction procedure are objects of the invention.
  • 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 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,
  • 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
  • R 8 , R 9 , R 10 are independently, the same or different, H,
  • 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
  • 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.
  • 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-dimethylbuty
  • 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
  • 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-buten
  • 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,
  • C3-C15-cycloalkyl monocyclic saturated hydrocarbon groups with 3 up to
  • 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 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 preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the catalyst in the catalyst a.
  • Cu (0) is preferably used as a solid, in particular in the form of a wire, grid, mesh, or powder.
  • the catalyst comprises a. Cu (0) zeolites.
  • Cu (II) is also used in the catalyst in the process according to the invention.
  • the catalyst comprises a. Copper alloys such as brass or bronze.
  • the catalysts additionally comprise metals selected from the group Mn, Ni, Pt, Fe, Ru, V.
  • initiators b 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.
  • 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.
  • 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.
  • 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
  • halide salts e. preferably NaCl, NaBr, CaC, additionally CuC, CuBr2, used. Particularly preferred here are NaCl or NaBr.
  • NaCl or NaBr advantageously makes it possible to prepare block copolymers from acrylates and methacrylates.
  • 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.
  • 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.
  • the controlled radical polymerization is carried out in a continuous process.
  • reactors with Rohrreaktorcharektenstik offer.
  • 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.
  • an acrylate as monomer of the general formula (I) using an organic bromide as initiator, is polymerized to a conversion of> 85%.
  • 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.
  • 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.
  • 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.
  • Mn number average
  • 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.
  • 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.
  • 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.
  • PDI polydispersity PDI
  • the catalyst a. added 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.
  • step ii) preferably only a small amount of monomer of the general formula (I) is added.
  • a small amount of monomer of the general formula (I) is added.
  • 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.
  • the polymerization is carried out in a stirred tank, tubular reactor, capillary reactor, belt reactor or another reactor with tube reactor characteristic.
  • 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.
  • selected steel alloys such as X1 CrNiMoCuN20-18-6 (1 .4547), particularly preferably NiCr21 Mo14W (2.4602).
  • materials such as glass, titanium (3.0735) and chemical enamel.
  • catalyst of component a is at all points at which the polymerization reaction is to take place. available.
  • the Cu (0) present in the catalyst is at least partially, preferably for the most part, in powder form.
  • the particle size in the Cu (0) powder is substantially less than or equal to 45 ⁇ m, the proportion of particles. which are greater than 45 ⁇ 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.
  • 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.
  • 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.
  • the polymerization is carried out partly adiabatic, which is positive for the energy consumption, since the heat of reaction is used for heating.
  • 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.
  • 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).
  • sealants or adhesives for example, a well-defined OH telechel is used as the polyol component for the reaction with isocyanates.
  • 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.
  • TPE thermoplastic elastomers
  • 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.
  • Example 1 Continuous operation in a tubular reactor (capillary reactor)
  • 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
  • Thermostats W1 and W2 were tempered. Monomers were
  • Bins B2, B4, B6 and B8 allow solvent switching to purify the reactors.
  • monomer or initiator ligand between the reactors (K1) and (K2) can be metered from the storage vessel B7 if necessary.
  • 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 ⁇ m. 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.
  • 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)
  • 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.
  • 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.
  • Table 1 resulted:
  • Example 3 a. Batch process reaction calorimeter
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • LM solvent
  • MEK methyl ethyl ketone
  • MeOH methanol
  • 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 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.
  • 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:
  • the template was filled and rendered inert 3 times with 8 bar of nitrogen.
  • the reactor was heated to 70 ° C.
  • 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.
  • 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.
  • 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 installed, MeeTREN and methyl-2-bromopropionate were added via a lock and these were rinsed with DMSO.
  • 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.
  • Table 6 The results are summarized in Table 6.
  • Equation (1) 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
  • Feed 1 520.12 g of methyl acrylate 42.021%
  • the template was filled and rendered inert 3 times with 8 bar of nitrogen.
  • the reactor was heated to 30 ° C.
  • 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.
  • 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.
  • Example 7 Block Copolymers and the Influence of Salt Acrylate Block on Methacrylate Block Without salt

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un procédé de production de polymères par polymérisation radicalaire contrôlée, dans lequel un ou plusieurs monomères polymérisables par voie radicalaire de formule générale (I), dans laquelle R1, R2, R3 sont H ou alkyle en C1-C4; R4 est C(=O)OR5, C(=O)NHR15, C(=O)NR5R6, OC(=O)CH3, C(=O)OH, CN, aryle, hétaryle, C(=O)OR5OH, C(=O)OR5Si(OR5)3, halogène, NHC(O)H, P(=O)(OR7)2; R5 est alkyle en C1-C20; R15 est alkyle en C1-C20; R6 est alkyle en C1-C20; R7 est H ou alkyle en C1-C20, sont polymérisés en présence a) d'un ou plusieurs catalyseurs contenant du Cu sous la forme Cu(0), Cu(I), Cu(II) ou des mélanges de ces formes, b) d'un ou plusieurs amorceurs choisis dans le groupe des halogénures ou pseudo-halogénures organiques, c) d'un ou plusieurs ligands, d) facultativement, d'un ou plusieurs solvants, e) facultativement, d'un ou plusieurs sels sous forme d'halogénures inorganiques. Le procédé comprend les étapes suivantes : i) ajout du ou des catalyseur a), ii) facultativement, ajout de monomères de formule générale (I), iii) facultativement, ajout du ou des solvants d), iv) ajout du ou des ligands c), v) ajout du ou des amorceurs b), vi) ajout de monomères de formule générale (I), vii) facultativement, ajout du ou des sels sous forme d'halogénures inorganiques e), à la condition qu'une partie au moins des monomères de formule générale (I) soit ajoutée juste avant ou peu après la dernière des étapes i), iv) et v).
PCT/EP2012/066838 2011-08-30 2012-08-30 Production de polymères par polymérisation radicalaire contrôlée Ceased WO2013030261A1 (fr)

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SG2014014492A SG2014014492A (en) 2011-08-30 2012-08-30 Production of polymers by means of controlled radical polymerisation
IN2321CHN2014 IN2014CN02321A (fr) 2011-08-30 2012-08-30
CN201280042447.4A CN103764688A (zh) 2011-08-30 2012-08-30 借助受控自由基聚合生产聚合物
MX2014002011A MX2014002011A (es) 2011-08-30 2012-08-30 Produccion de polimeros por medio de polimerizacion controlada por radicales.
JP2014527650A JP2014525486A (ja) 2011-08-30 2012-08-30 制御されたラジカル重合によるポリマーの製造
EP12753968.2A EP2751143A1 (fr) 2011-08-30 2012-08-30 Production de polymères par polymérisation radicalaire contrôlée
RU2014111849/04A RU2014111849A (ru) 2011-08-30 2012-08-30 Получение полимеров контролируемой радикальной полимеризацией
BR112014003922A BR112014003922A2 (pt) 2011-08-30 2012-08-30 processo para preparar polímeros por polimerização controlada via radical livre, polímero, e, uso de polímero
KR1020147007911A KR20140069032A (ko) 2011-08-30 2012-08-30 제어 라디칼 중합에 의한 중합체 제조
ZA2014/02272A ZA201402272B (en) 2011-08-30 2014-03-27 Production of polymers by means of controlled radical polymerisation

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Publication number Priority date Publication date Assignee Title
EP2899215A1 (fr) 2014-01-24 2015-07-29 Basf Se Procédé de préparation d'un mélange (G), contenant un composant organique (A), qui présente au moins une liaison halogène carbone, et un composant métallique de transition (B)
JP2016516854A (ja) * 2013-03-18 2016-06-09 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 制御された単一電子移動リビングラジカル重合のための方法および装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016005214A1 (fr) * 2014-07-09 2016-01-14 Basf Se Monomères réactifs servant de co-monomères pour la production de polymères
WO2025079623A1 (fr) * 2023-10-10 2025-04-17 株式会社ダイセル Procédé de production de polymère
WO2025079624A1 (fr) * 2023-10-10 2025-04-17 株式会社ダイセル Procédé de production de polymère

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030421A1 (fr) 1995-03-31 1996-10-03 Krzysztof Matyjaszewski Nouveaux copolymeres et un nouveau procede de polymerisation base sur une polymerisation radicalaire par transfert d'atome (ou de groupe)
WO1997018247A1 (fr) 1995-11-15 1997-05-22 Carnegie Mellon University Procedes ameliores, fondes sur la polymerisation de radicaux par transfert d'atomes (ou de groupements) et (co)polymeres nouveaux ayant des structures et des proprietes utiles
EP0850957A1 (fr) 1996-12-26 1998-07-01 Elf Atochem S.A. Procédé de polymérisation ou copolymérisation radicalaire contrÔlée de monomères (méth)acryliques, vinyliques, vinylidéniques et diéniques et (co)polymères obtenus
WO1998040415A1 (fr) 1997-03-11 1998-09-17 Carnegie Mellon University Perfectionnements applicable a la polymerisation par transfert d'atomes ou de groupes
WO2000056795A1 (fr) 1999-03-23 2000-09-28 Carnegie Mellon University Procedes catalytiques de polymerisation controlee de monomeres (co)polymerisables par des radicaux libres et systemes de polymeres fonctionnels prepares de la sorte
WO2002038618A2 (fr) 2000-11-13 2002-05-16 Rohmax Additives Gmbh Procede de production continue de compositions polymeres et utilisation associee
JP2004210858A (ja) * 2002-12-27 2004-07-29 Kanegafuchi Chem Ind Co Ltd ビニル系重合体の製造方法
WO2008019100A2 (fr) 2006-08-04 2008-02-14 The Trustees Of The University Of Pennsylvania Polymérisation du radical vivant de monomères activés et non activés contenant des groupes latéraux à extraction d'électrons
WO2009155303A2 (fr) 2008-06-18 2009-12-23 Henkel Corporation Appareil et procédé pour polymérisation radicalaire commandée
JP2010241907A (ja) * 2009-04-02 2010-10-28 Kaneka Corp （メタ）アクリル系ブロック共重合体の製造方法
EP2248835A1 (fr) * 2008-02-29 2010-11-10 Kaneka Corporation Composition durcissable

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030421A1 (fr) 1995-03-31 1996-10-03 Krzysztof Matyjaszewski Nouveaux copolymeres et un nouveau procede de polymerisation base sur une polymerisation radicalaire par transfert d'atome (ou de groupe)
WO1997018247A1 (fr) 1995-11-15 1997-05-22 Carnegie Mellon University Procedes ameliores, fondes sur la polymerisation de radicaux par transfert d'atomes (ou de groupements) et (co)polymeres nouveaux ayant des structures et des proprietes utiles
EP0850957A1 (fr) 1996-12-26 1998-07-01 Elf Atochem S.A. Procédé de polymérisation ou copolymérisation radicalaire contrÔlée de monomères (méth)acryliques, vinyliques, vinylidéniques et diéniques et (co)polymères obtenus
WO1998040415A1 (fr) 1997-03-11 1998-09-17 Carnegie Mellon University Perfectionnements applicable a la polymerisation par transfert d'atomes ou de groupes
WO2000056795A1 (fr) 1999-03-23 2000-09-28 Carnegie Mellon University Procedes catalytiques de polymerisation controlee de monomeres (co)polymerisables par des radicaux libres et systemes de polymeres fonctionnels prepares de la sorte
WO2002038618A2 (fr) 2000-11-13 2002-05-16 Rohmax Additives Gmbh Procede de production continue de compositions polymeres et utilisation associee
JP2004210858A (ja) * 2002-12-27 2004-07-29 Kanegafuchi Chem Ind Co Ltd ビニル系重合体の製造方法
WO2008019100A2 (fr) 2006-08-04 2008-02-14 The Trustees Of The University Of Pennsylvania Polymérisation du radical vivant de monomères activés et non activés contenant des groupes latéraux à extraction d'électrons
EP2248835A1 (fr) * 2008-02-29 2010-11-10 Kaneka Corporation Composition durcissable
WO2009155303A2 (fr) 2008-06-18 2009-12-23 Henkel Corporation Appareil et procédé pour polymérisation radicalaire commandée
JP2010241907A (ja) * 2009-04-02 2010-10-28 Kaneka Corp （メタ）アクリル系ブロック共重合体の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200454, Derwent World Patents Index; AN 2004-557436, XP002684825 *
ROSEN ET AL., CHEMICAL REVIEWS, vol. 109, 2009, pages 5069 - 5119

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016516854A (ja) * 2013-03-18 2016-06-09 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 制御された単一電子移動リビングラジカル重合のための方法および装置
EP2899215A1 (fr) 2014-01-24 2015-07-29 Basf Se Procédé de préparation d'un mélange (G), contenant un composant organique (A), qui présente au moins une liaison halogène carbone, et un composant métallique de transition (B)

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EP2751143A1 (fr) 2014-07-09
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MX2014002011A (es) 2014-03-27
IN2014CN02321A (fr) 2015-06-19
RU2014111849A (ru) 2015-10-10
ZA201402272B (en) 2015-12-23
CN103764688A (zh) 2014-04-30
KR20140069032A (ko) 2014-06-09
JP2014525486A (ja) 2014-09-29

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