WO2003020774A1 - Verfahren zur metallkatalysierten herstellung eines polymeren umsetzungsprodukts - Google Patents
Verfahren zur metallkatalysierten herstellung eines polymeren umsetzungsprodukts Download PDFInfo
- Publication number
- WO2003020774A1 WO2003020774A1 PCT/EP2002/009469 EP0209469W WO03020774A1 WO 2003020774 A1 WO2003020774 A1 WO 2003020774A1 EP 0209469 W EP0209469 W EP 0209469W WO 03020774 A1 WO03020774 A1 WO 03020774A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transition metal
- substituted
- unsubstituted
- alkyl
- polymer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
Definitions
- the invention further relates to a corresponding transition metal complex, a reaction product which can be prepared by the process according to the invention and the use of the transition metal complex according to the invention for the production of reaction products by free-radical polymerization.
- the present invention is in the technical field of radical polymerization, which has features which are typical of a living polymerization system, the process according to the invention being able in principle to provide reaction products or polymers which have a narrow molecular weight distribution (M w / M n ) can have.
- both unbranched and branched homopolymers and copolymers and block copolymers can be prepared by appropriate selection of monomers and, if appropriate, successive addition of different monomers.
- a process concept with which such polymers with a predetermined structure, molecular weight and molecular weight distribution can be obtained is radical atom transfer radical polymerization (ATRP).
- ATRP radical atom transfer radical polymerization
- the ATRP can be catalyzed by suitable metal complexes.
- an initiation takes place by abstraction of a halogen atom from an alkyl halide used as an ATRP initiator through the metal complex, an alkyl radical being formed.
- the alkyl radical then adds to a radically polymerizable monomer in a chain reaction which can be terminated by the (back) addition of the halogen atom abstracted by the metal complex from the metal complex.
- WO 98/01480 relates to the synthesis of homopolymers, block or graft copolymers which contain at least one polar group and have a defined structure and a narrow molecular weight distribution by ATRP.
- At least one free-radically polymerizable monomer is reacted with a system which comprises a macroinitiator which has at least one free-radically transferable group, a transition metal complex and at least one ligand which coordinates to the transition metal via a ⁇ or ⁇ bond.
- the reaction takes place in bulk or in an organic solvent. However, the process takes place at polymerization rates that are unattractive for commercial use.
- WO 00/47634 describes a process for producing an acrylic polymer by ATRP in an organic solvent such as ethyl acetate or o-xylene, in which at least one vinyl monomer is reacted with a suitable transition metal complex and an alkyl halide as initiator. According to WO 00/47634, the reaction rate of the polymerization process is increased by adding a Lewis acid which is soluble in the reaction mixture.
- an ATRP is disclosed, wherein the polymerization of free-radically polymerizable monomers takes place in the presence of an initiator, a transition metal compound and such an amount of the conjugated oxidized form of the transition metal compound that is sufficient to at least a part of that in the polymerization to deactivate initially formed radicals.
- the polymerization can be carried out in the aqueous phase, using monomers which are at least partially soluble in water or using monomers suitable for emulsion polymerization if the polymerization is carried out in the presence of an emulsifier.
- T. Nishikawa et al. Macromolecules 32, 2204 (1999) relates to the living radical suspension polymerization of methyl methacrylate (MMA) in the presence of an initiator PhCOCHCl 2 or CCl 3 Br, a transition metal complex RuCl 2 (PPh 3 ) 3 and optionally Al (O'Pr) 3 in the aqueous phase.
- MMA methyl methacrylate
- an initiator PhCOCHCl 2 or CCl 3 Br a transition metal complex RuCl 2 (PPh 3 ) 3 and optionally Al (O'Pr) 3
- Figure 1 in T. Nishikawa et al. reaction time to be extracted long. After about 5 hours, the Conversion (at a polymerization temperature of 80 ° C) only about 75%. Almost complete sales are only achieved after approx. 18 hours.
- the object of the present invention is to provide a new process for the preparation of a polymeric reaction product which leads in a simple and controlled manner to homopolymers and copolymers which can be prepared by free radicals.
- the aim is to achieve a reaction rate even at low temperatures that makes the process attractive for commercial use, i.e. that complete conversion of the monomers is achieved with comparatively short reaction times.
- Another object of the invention is to provide a method by means of which block copolymers can be produced which cannot be obtained in any other way or can only be obtained in an unsatisfactory manner.
- the process according to the invention is then characterized in that the transition metal is bonded to the hydrophobic part of an amphiphilic polymer which is composed of a hydrophilic part and a hydrophobic part via suitable anchor groups.
- the amphiphilic polymer forms micelles in the aqueous system, the micelles being functionalized with the transition metal complex which serves as an ATRP catalyst. There only the hydrophobic part of the amphiphilic polymer is functionalized with the ATRP catalyst, the controlled radical polymerization takes place exclusively in the micelles.
- This new polymerization process achieves complete monomer conversions at much lower polymerization temperatures and significantly shorter polymerization times than in the prior art processes. Such an increase in the reaction rate enables economical radical polymerization (ATRP) to be carried out economically.
- reaction product is understood to mean both oligomers with an average molecular weight (M n ) of at least 300 g / mol and also polymers.
- the average molecular weight (M n ) is therefore generally 300 to 5,000,000 g / mol, preferably 500 to 2,000,000 g / mol, particularly preferably 500 to 1,000,000 g / mol.
- the molecular weights are determined by GPC in THF based on a polystyrene standard
- the process according to the invention can be used to obtain a reaction product which has a molecular weight distribution M w / M n measured using gel permeation chromatography using polystyrene as the standard of ⁇ 4, preferably ⁇ 3, more preferably ⁇ 2, in particular ⁇ 1.5 and in some cases also ⁇ 1.3.
- the molecular weights of the reaction product (A) can be controlled within wide limits by the choice of the ratio of monomers (a) to radical initiator.
- the process according to the invention it is possible to produce functionalized polymers, homopolymers, block or multiblock and gradient (co) polymers, star-shaped polymers, graft copolymers and branched (co) polymers on the end groups. Furthermore, it is possible to use the reaction product produced by the process according to the invention as a macroinitiator. Macroinitiator is understood to mean an oligomeric or polymeric compound which has one or more active sites, so that it acts as an initiator in further radicals Polymerization can be used. These further radical polymerization processes can be any process for radical polymerisation known to the person skilled in the art and are not limited to the process according to the invention.
- the present invention relates to a process for producing a polymeric reaction product, the polymeric reaction product being a macroinitiator or a block copolymer.
- a “block copolymer” is understood to mean a polymer which has at least two polymer blocks characterized by a different monomer composition.
- a polymer block characterized by a different monomer composition means the finding that at least two areas of the block copolymer It is possible within the scope of the present invention that the transition between two blocks runs continuously, that is to say that between two blocks there is a zone which has a statistical or regular sequence of the monomers constituting the blocks However, it is also provided in the context of the present invention that the transition between two blocks is essentially discontinuous, under an “essentially discontinuous transition g "is understood to mean a transition zone which has a significantly shorter length than at least one of the blocks separated by the transition zone. In a preferred embodiment of the present invention, the chain length of such a transition zone is less than 1/10, preferably less than 1/20, of the block length of at least one of the blocks separated by the transition zone.
- a “different monomer composition” means the finding that the monomers constituting the respective block differ in at least one feature, for example in their interlinking, in their conformation or constitution.
- Block copolymers are preferably used in the context of the present invention prepared, which have at least two blocks, the monomer composition differs at least by the constitution of the monomers.
- an aqueous system is understood to mean a reaction medium which forms a single phase without a macroscopic phase boundary and which comprises 80 to 100% by weight, preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight.
- % Contains water. If the proportion of water is below 100% by weight, the aqueous system is a mixture of water and one or more water-miscible solvents such as tetrahydrofuran, methanol, ethanol, propanol, butanol, acetone, N-methylpyrrolidone or methyl ethyl ketone.
- alkyl is understood to mean both a branched and an unbranched alkyl radical (with the exception of the C 1 and C 2 alkyl groups).
- aryl means phenyl, naphthyl, phenanthryl, anthracenyl, triphenylenyl, fluoranthenyl, preferably phenyl and naphthyl, in which each hydrogen atom is denoted by C 1-2 o-alkyl, preferably C 1- 6 -alkyl, particularly preferably methyl, it being possible for each hydrogen atom in the respective alkyl radical to be replaced independently of one another by a halogen atom, preferably fluorine or chlorine; Furthermore, each hydrogen atom in the respective aryl radical can be substituted by C 2-2 o-alkenyl, C 2-2 o-alkynyl, C 1-6 alkoxy, C 1-6 alkylthio, C 3-8 cycloalkyl, phenyl 1-5 halogen atoms and / or 1 to 5 C -4 -alkyl radicals substituted phenyl, halogen, primary or
- aryl is phenyl
- the phenyl radical can be substituted by 1 to 5 of the radicals mentioned
- aryl is naphthyl the naphthyl radical can be substituted by 1 to 7 of the radicals mentioned. Both phenyl and naphthyl, if substituted at all, are preferably substituted 1 to 3 times.
- Aryl is phenyl, phenyl substituted with 1 to 5 fluorine or chlorine atoms, phenyl substituted with 1 to 3 C 1-6 alkyl radicals or 1 to 3 C 1- alkoxy radicals or 1 to 3 phenyl radicals.
- Aryl phenyl or tolyl is particularly preferred.
- amphiphilic polymer Any polymer which has suitable anchor groups for binding the transition metal complex in its hydrophobic part is generally suitable as the amphiphilic polymer (L p ).
- Preferred amphiphilic polymers are selected from lipids, for example phosphoglycerides or glycolipids, polyoxazolines, polyglycols, for example polyethylene glycols or polypropylene glycols, poly (meth) acrylamides and polyurethanes, each of which has suitable anchor groups for binding the transition metal in their hydrophobic parts. Polyoxazolines are particularly preferred.
- amphiphilic polymers are prepared by processes known to those skilled in the art, such as polycondensation, living cationic polymerization, anionic polymerization or controlled radical polymerization or other polymerization techniques using appropriately functionalized monomers.
- Suitable anchor groups for the transition metal complex depend, among other things, on the transition metal M used.
- the transition metal complex repeatedly takes part in a reversible redox cycle with the initiator and / or the dormant halogen-terminated polymer end and the corresponding free radical which grows on one or more growing radicals Polymer end (s) is formed.
- all transition metal compounds are suitable as transition metal compounds which can participate in this redox cycle with the initiator and / or the resting polymer end, but which do not form a direct carbon-metal bond with the polymer chain.
- Preferred transition metals M are selected from Ru, Ru, Cu, Cu, Fe, Fe, Cr 2+ , Cr 3+ , Mo 0 , Mo + , Mo 2+ , Mo 3+ , W 2+ , W 3+ , Rh 3 + , Rh 4+ , Co + , Co 2+ , Re 2+ , Re 3+ , Ni °, Ni + , Mn 3+ , Mn 4+ , V 2+ , V 3+ , Zn + , Zn 2+ , Au + , Au 2+ , Ag + and Ag 2+ .
- Transition metals are particularly preferably selected from Ru 2+ , Ru 3+ , Mn 3+ , Mn 4+ , Cu + , Cu 2+ , Ni °, Ni + , Fe 2+ and Fe 3+ .
- Ru 2+ and Ru 3+ are very particularly preferred.
- suitable anchor groups are those groups which have at least one nitrogen, oxygen, phosphorus and / or sulfur atom attached to the
- Transition metal can coordinate via a ⁇ bond, as well as groups that contain two or more carbon atoms, via a ⁇ bond to the transition metal can coordinate.
- Groups of the following general formulas are preferred, which are generally bonded to the polymer via a single bond, a C 2-8 alkylene group, an ether, ester or amide function or via another group suitable for coupling the anchor group to the polymer: - ⁇ - R 1 (I)
- R 4 and R 5 are independently hydrogen or C 1-2 o-alkyl or R 4 and R 5 together form an alkylene group with 2 to 5 carbon atoms, so that a 3- to 6-membered ring is formed and R is hydrogen, C 1-20 alkyl or aryl; Z 'O, S, NR 7 , PR 7 , where R 7 is selected from the same group as R 1 ;
- R each is a divalent group selected from C 2-4 alkyls and C 2- alkenyls, in which the covalent bonds to the respective Z 'are at vicinal positions or at ⁇ positions, and C 3-8 cycloalkanediyl, C 3 -8 -cycloalkenediyl, aryldiyl and hederocyclic diyl compounds, in which the covalent bonds to the respective Z 'are at vicinal positions; m is 1 to 6.
- Cyclic or heterocyclic compounds which can be aromatic or aliphatic, are also suitable as anchor groups. These are generally bonded to the polymer via a single bond, a C 2-8 alkylene group, an ether, ester or amide function or via another group suitable for coupling the anchor group to the polymer. Condensed systems such as indenyl derivatives or fluorenyl derivatives are also suitable.
- Preferred carbocyclic anchor groups are aryl or cyclopentadienyl groups, particularly preferably cyclopentadienyl groups, which can optionally be substituted in addition to the bond to the polymer.
- suitable Substituents are C 1-6 alkyl, C 3 .
- the substituent can be a C 1-6 alkyl, C 3-8 cycloalkyl, C 2-6 alkenyl, C 3-8 cycloalkenyl, or an aryl radical which can contain heteroatoms, preferably N or O, in the ring ,
- a very particularly preferred pyridyl derivative is, for example, 2,2'-bipyridyl.
- the further radical is preferably in the 2- or 5-position (depending on the position via which the polymer is linked).
- Suitable substituents are those already mentioned in connection with the pyridyl derivatives. For example, 2,2'-bipyrroles are very particularly preferred.
- the anchor groups are preferably selected from diphenylphosphine residues, where the phenyl groups may be substituted or unsubstituted, pyridyl residues which may be substituted or unsubstituted, in particular bipyridyl residues, such as 2,2′-bipyridyl residues, which are linked to the polymer via one of the pyridyl residues, pyrrole residues which may be substituted or unsubstituted, in particular bipyrrole residues, such as 2,2′-bipyrrole residues, which are linked to the polymer via one of the pyrrole residues and cyclopentadienyl residues which may optionally be substituted in addition to the bond to the polymer.
- the transition metal complex contains additional ligands.
- neutral ligands L are suitable. These are generally selected from the radicals mentioned as anchor groups.
- a hydrogen atom or another substituent is preferred to replace the linkage with the polymer via a single bond, a C 2-8 alkylene group, an ether, ester or amide function or via another group suitable for coupling the anchor group to the polymer selected from C ⁇ -6 - alkyl, C 3-8 cycloalkyl, C 2-6 alkenyl, C 3-8 cycloalkenyl, and aryl radicals, which may contain heteroatoms, preferably N or O, in the ring.
- Other suitable ligands are acetonitrile, carbon monoxide, ethylenediamine, propylenediamine, ethylene glycol, propylene glycol and diethylene dimethyl ether (diglyme).
- the transition metal complex generally contains anionic ligands X, preferably selected from halide, C -5 alkoxy or C 1-5 alkyl radicals.
- halides are particularly preferred. Chloride and bromide are very particularly preferred.
- transition metal complex which has the general formula (III) is preferably used in the process according to the invention.
- M transition metal as defined above, very particularly preferably selected from Ru 2+ , Ru 3+ , Mn 3+ , Mn 4+ , Cu + , Cu 2+ , Ni °, Ni + , Fe 2+ and Fe 3+ ; very particularly 4- "4- are preferred Ru and Ru; L p amphiphilic polymer with suitable anchor groups (as defined above) for binding the transition metal in the hydrophobic part of the polymer as defined above, very particularly preferably a polyoxazoline which has diphenylphosphine residues as anchor groups; L further ligand as defined above, preferably selected from
- Triphenylphosphine in which the phenyl groups can be substituted or unsubstituted, substituted or unsubstituted pyridines, for example 2,2′-bipyridyl, substituted or unsubstituted pyrroles, for example 2,2′-bipyrrole radicals;
- X halide C 1-5 alkoxy or C 1-5 alkyl as defined above; particularly preferably chloride and bromide;
- n is an integer from 0 to 4, preferably from 0 to 2;
- m is a number from 0 to 4, preferably from 0 to 3, depending on the valency of the metal in the first oxidation stage.
- the transition metal complex is an Ru 2+ complex, formed from a polymer which is composed of a hydrophilic and a hydrophobic polyoxazoline block, the hydrophobic polyoxazoline block being functionalized with a diphenylphosphine group that complexes RuCl 3 or di- ⁇ -chlorobis ((p-cymol) chlororuthenium (II).
- the transition metal complexes used according to the invention are prepared by reacting the corresponding transition metal salt, preferably the halide, particularly preferably the chloride or bromide, with the amphiphilic polymer L p ionized by anchor groups and optionally further ligands L.
- the reaction is carried out by methods known to those skilled in the art for the preparation of transition metal complexes.
- the desired polymer and the desired metal salt are combined in methanolic solution, stirred for a reaction time depending on the components used, and then the solvent is removed.
- radical-polymerizable monomers are ethylenically unsaturated monomers.
- At least one ethlyenically unsaturated group having monomers come e.g. considered: olefins such as ethylene or propylene, vinyl aromatic monomers such as
- Styrene divinylbenzene, 2-vinylnaphthalene and 9-vinylanthracene, substituted vinyl-aromatic monomers such as p-methylstyrene, ⁇ -methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl and vinyltoluene, esters of vinyl alcohol and monocarboxylic acids containing 1 to 18 carbon atoms such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, anhydrides or esters of 3 to 6 carbon atoms having ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with in general 1 to 20, preferably 1 to 12, particularly preferably 1 to 8 and very particularly
- Suitable styrene compounds are those of the general formula IV:
- R 'and R "independently of one another are H or C 1 -C 8 -alkyl and n is 0, 1, 2 or 3.
- the monomers styrene, ⁇ -methylstyrene, divinylbenzene, vinyltoluene, N-vinylpyrrolidone and N-vinylformamide, C 1 -C 20 -alkyl acrylates and C 1 -C 20 -alkyl methacrylates, in particular n, are particularly preferred in the process according to the invention -Butyl acrylate, 2-ethylhexyl acrylate or methyl methacrylate and butadiene, also maleic acid and maleic anhydride, acrylonitrile, glycide esters and (poly) alkoxylates of acrylic and methacrylic acid, as well as monomer mixtures, which are at least 85% by weight from the
- the aforementioned monomers or mixtures of the aforementioned monomers are used, very particularly preferably styrene and methyl methacrylate.
- the present invention relates to a process for producing a polymeric reaction product, the radically polymerizable monomer being selected from the group consisting of: styrene compounds of the general formula (IV)
- R 'and R "independently of one another are H or -Cs-alkyl and n is 0, 1, 2 or 3; - acrylic acid or methacrylic acid or their - o-alkyl esters or their Cr oo-alkyloxy esters;
- initiators used in the transition metal-catalyzed ATRP are suitable as initiators.
- Preferred initiators are selected from ethyl 2-bromoisobutyrate, 1-phenylethyl bromide, 1-phenylethyl chloride, p-toluenesulfonyl chloride, benzylhydryl chloride, 1,1,1-trichloroacetone, ⁇ , ⁇ -dichloroacetophenone, bromotrichlorocarbon and carbon tetrachloride.
- the ratio of transition metal complex to initiator is generally 1: 1 to 1: 3, preferably 1: 1.5 to 1: 2.5, particularly preferably 1: 1.75 to 1: 2.25.
- the selected initiator concentration has an influence on the molecular weight.
- the mixture preferably additionally contains a cocatalyst in the form of a Lewis acid.
- Suitable Lewis acids are generally selected from aluminum compounds, preferably aluminum alkoxylates; Metal halides such as ZnHal 2 , LiHal, where shark is a halide, preferably CI " or Br " , FeCl 3 ; BF 3 ; acetylacetonate; conjugated organic acids or other organic acids such as camphorsulfonic acid.
- Aluminum alkoxylates such as Al (O'Pr) 3 are preferred.
- the ratio of the components of the transition metal complex, initiator, Lewis acid and free-radically polymerizable monomer is generally 0.5 to 2: 1 to 3: 2.5 to 5: 100 to 400, preferably 0.75 to 1.5: 1.5 to 2.5: 3.5 to 4.5: 150 to 250, particularly preferably 0.8 to 1.2: 1.8 to 2.2: 3.8 to 4.2: 180 to 220.
- the order of addition of the components used in the method according to the invention can vary.
- the (reaction) mixture can also additionally contain a chain transfer reagent, e.g. a mercaptan or a catalytic chain transfer compound.
- a chain transfer reagent e.g. a mercaptan or a catalytic chain transfer compound.
- Suitable compounds are known to the person skilled in the art.
- Suitable mercaptans are alkyl mercaptans which have at least one -SH group, e.g. Butyl mercaptan, nonyl mercaptan and dodecyl mercaptan.
- reaction mixture may contain other additives which are usually used to modify the properties of the polymers, e.g. Additives to change the impact resistance of the polymers, dyes and processing aids.
- the process according to the invention is carried out under conventional reaction conditions (e.g. stirred reactors) under conventional reaction conditions for free-radical polymerization in an aqueous system.
- the process according to the invention is carried out at temperatures above room temperature and below the decomposition temperature of the monomers used, and below the boiling point of the aqueous phase (depending on the reaction pressure and the monomer content).
- a temperature range from 20 to 140 ° C., particularly preferably from 20 to 120 ° C., very particularly preferably from 20 to 100 ° C. is selected.
- the process according to the invention is characterized in that excellent conversions are achieved even at low temperatures in short reaction times.
- the reaction pressure in the process according to the invention is generally 1 to 300 bar, preferably 1 to 100 bar, particularly preferably 1 to 20 bar.
- reaction times in the process according to the invention for achieving essentially complete conversion are very short in the process according to the invention.
- reaction time depends on the amount of initiator. In general, after 0.5 to 20 hours, preferably after 1 to 15 hours, particularly preferably after 1.5 to 10 hours achieved an essentially complete conversion of the at least one monomer used. An essentially complete conversion is understood to mean that no more monomer is detected by means of NMR spectroscopy.
- the present invention further provides a transition metal complex of the general formula (III)
- M transition metal as defined above, very particularly preferably selected from Ru 2+ , Ru 3+ , Mn 3+ , Mn 4+ , Cu + , Cu 2+ , Ni °, Ni + , Fe 2+ and Fe 3+ ; Ru 2+ and Ru 3+ are very particularly preferred;
- L is particularly preferred triphenylphosphine,
- the average molecular weight (M n ) is generally 300 to 5,000,000 g / mol, preferably 500 to 2,000,000 g / mol, particularly preferably 500 to 1,000,000 g / mol.
- the molecular weights are determined by GPC in THF based on a polystyrene standard.
- reaction products are preferably characterized by a molecular weight distribution M w / M n measured using gel permeation chromatography using polystyrene as the standard of ⁇ 4, preferably ⁇ 3, more preferably ⁇ 2, in particular ⁇ 1.5 and in individual cases also ⁇ 1 , 3 owns.
- the molecular weights of the reaction product can be controlled within wide limits by the choice of the ratio of monomers to free radical initiator.
- the reaction product can for example be a homopolymer, e.g. Polystyrene, poly (styrene-co-maleic anhydride) or a homopolymer composed of (meth) acrylic acid, methyl (meth) acrylates, (meth) acrylates, N-vinylpyrrolidone or olefins, or a copolymer with blocks composed of polystyrene, poly (styrene - Co-maleic anhydride) or polymer units composed of (meth) acrylic acid, methyl (meth) acrylate, (meth) acrylate, N-vinylpyrrolidone or olefins.
- a homopolymer e.g. Polystyrene, poly (styrene-co-maleic anhydride) or a homopolymer composed of (meth) acrylic acid, methyl (meth) acrylates, (meth) acrylates, N-vinylpyr
- the present invention furthermore relates to the use of a reaction product which can be prepared by the process according to the invention or a reaction product according to the invention for the preparation of binder formulations for coatings and other aqueous systems.
- Another object of the present invention is the use of transition metal complexes, composed of an amphiphilic polymer, which is composed of a hydrophilic part and a hydrophobic part, on the hydrophobic part of which transition metals via suitable anchor groups, which optionally contain further ligands. exhibit, are bound in a process for the preparation of a reaction product under radical conditions in the presence of at least one radical-polymerizable monomer in the aqueous phase.
- Suitable amphiphilic polymers, transition metals, any other ligands present, as well as monomers and initiators have already been mentioned above.
- the functionalized polyoxazolines are synthesized using the known methods of Witte and Seeliger.
- a 25-50 mM solution of methyl triflate in acetonitrile is introduced in a protective gas countercurrent.
- the 2-methyl-2-oxazoline is added and the mixture is stirred at a bath temperature of 80 ° C. for 14 h.
- the monomer (s) of the second block is / are added and dry chlorobenzene is added if necessary.
- the mixture is stirred for a further 14 h at a bath temperature of 90 ° C.
- the residue is mixed with 3 g of ground and heated potassium carbonate and the amount of chloroform acetonitrile used above.
- the suspension is stirred overnight.
- the insoluble constituents are separated off and the chloroform solution is precipitated in diethyl ether.
- the precipitated polymer is separated from the liquid phase by filtration and dried in the.
- composition of the polymer obtained (number of repeat units, from 1H-NMR):
- the polymer precursor (about 2-3 g, 1 equivalent of iodoaromatic), potassium acetate (1.44 equivalents based on the iodoaromatic) and the palladium catalyst (tr ⁇ -Di- ( ⁇ -acetato) -bis [o- (di-o -tolylphosphino) benzyl] dipalladium (II), in a ratio of 1: 500 in relation to the iodoaromatic). 10 ml of dry acetonitrile are added per lg of polymer. Diphenylphosphine (1.2 equivalents based on the iodoaromatic) is added and the mixture is stirred at 110 ° C. for at least 36 h.
- the molecular weight of the macroligand is 6143 g / mol. Each molecule has an average of 4.93 triphenylphosphine functions.
- reaction temperature 80 ° C.
- reaction temperature 80 ° C.
- the reaction was terminated by sudden cooling using a cooling bath. All volatiles are removed and a black solid is obtained. This was examined by GPC (gel permeation chromatography).
- the mixture is then heated to 80 ° C.
- the reaction is terminated by cooling the solution in a cooling bath. All volatile constituents are removed and the solid obtained is examined by GPC.
- the following table gives the time until a complete conversion of the monomer (in hours (h)) at 80 ° C and various conditions (tests A, B, C and D), as well the molecular weight averages (M n and M w (each in g / mol)) and the polydispersity index (PDI; M w / M n ) of the polymers obtained.
- the average molecular weights were determined by means of gel permeation chromatography (GPC).
- the ruthenium complex was prepared according to 2a); AI and A3 differ in that the polymerization was carried out at different concentrations of MMA;
- the ruthenium complex was prepared according to 2b); AI and A3 differ in that the polymerization was carried out at different MMA concentrations.
- the metal complex-catalyzed ATRP polymerization in toluene is not disturbed by the amphiphilic polymer (C).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02776942A EP1440095A1 (de) | 2001-09-03 | 2002-08-23 | Verfahren zur metallkatalysierten herstellung eines polymeren umsetzungsprodukts |
US10/488,190 US20040242816A1 (en) | 2001-09-03 | 2002-08-23 | Method for the production of a polymer conversion product by means of metal catalysis |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10142908.8 | 2001-09-03 | ||
DE10142908A DE10142908A1 (de) | 2001-09-03 | 2001-09-03 | Verfahren zur metallkatalysierten Herstellung eines polymeren Umsetzungsprodukts |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003020774A1 true WO2003020774A1 (de) | 2003-03-13 |
Family
ID=7697401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/009469 WO2003020774A1 (de) | 2001-09-03 | 2002-08-23 | Verfahren zur metallkatalysierten herstellung eines polymeren umsetzungsprodukts |
Country Status (4)
Country | Link |
---|---|
US (1) | US20040242816A1 (de) |
EP (1) | EP1440095A1 (de) |
DE (1) | DE10142908A1 (de) |
WO (1) | WO2003020774A1 (de) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000047634A1 (en) * | 1999-02-08 | 2000-08-17 | Ineos Acrylics Uk Ltd. | Production of vinylic polymers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU735085B2 (en) * | 1996-06-12 | 2001-06-28 | Warwick Effect Polymers Limited | Polymerisation catalyst and process |
-
2001
- 2001-09-03 DE DE10142908A patent/DE10142908A1/de not_active Withdrawn
-
2002
- 2002-08-23 EP EP02776942A patent/EP1440095A1/de not_active Withdrawn
- 2002-08-23 US US10/488,190 patent/US20040242816A1/en not_active Abandoned
- 2002-08-23 WO PCT/EP2002/009469 patent/WO2003020774A1/de not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000047634A1 (en) * | 1999-02-08 | 2000-08-17 | Ineos Acrylics Uk Ltd. | Production of vinylic polymers |
Also Published As
Publication number | Publication date |
---|---|
DE10142908A1 (de) | 2003-03-20 |
US20040242816A1 (en) | 2004-12-02 |
EP1440095A1 (de) | 2004-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69636326T2 (de) | Verbesserte verfahren basierend auf atom (oder gruppen) übertragungs-radikalpolymerisation und neue (co)polymere mit nützlichen strukturen und eigenschaften | |
DE69917311T2 (de) | Mikrogele und verfahren zu deren herstellung | |
DE60024605T2 (de) | Katalytische prozesse für die kontrollierte polymerisation von freiradikalischen, copolymerisierbaren monomeren und funktionellpolymersysteme hergestellt davon | |
DE69635802T2 (de) | Polymerisationsverfahren basierend auf atom (oder gruppen) übertragungsradikalpolymerisation | |
DE60125409T2 (de) | Polymerisationsverfahren für ionische monomere | |
DE60019419T2 (de) | Verfahren zur herstellung von polymeren durch eine kontrollierte radikalischpolymerisation mit halogenierten xanthaten | |
DE60305978T2 (de) | Kontrollierte polymerisation | |
DE3783158T2 (de) | Blockpfropfcopolymere und ihr herstellungsverfahren. | |
Debuigne et al. | Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects | |
Debuigne et al. | Organometallic-mediated radical polymerization of ‘less activated monomers’: Fundamentals, challenges and opportunities | |
DE60124747T2 (de) | Kontrollmittel für polymerisationen von lebenden freien radikal typen, verfahren zur polymerisation, emulsionen und polymere durch diese | |
DE69836501T3 (de) | Polymerisationsverfahren mit lebenden eigenschaften und daraus hergestellte polymere | |
DE60310521T2 (de) | Metallkomplexe für die metathese | |
DE3685583T3 (de) | Verfahren zur oligomerisation. | |
DE1520119A1 (de) | Verfahren zur Herstellung von Polymerdispersionen | |
DE112006000410T5 (de) | Pfropf-Copolymer und Verfahren zum Herstellen desselben | |
WO2003020774A1 (de) | Verfahren zur metallkatalysierten herstellung eines polymeren umsetzungsprodukts | |
EP2269995B1 (de) | Verfahren zur herstellung von polymeren mit eisenkomplexkatalysator | |
EP1171476A1 (de) | Verfahren der radikalisch initiierten wässrigen emulsionspolymerisation | |
EP0945469B1 (de) | Verfahren zur Herstellung von Telechelen, so hergestellte Telechele und ihre Verwendung | |
DE19806853A1 (de) | Verfahren zur Herstellung von Polymeren aus N-Vinylverbindungen | |
DE19959252A1 (de) | Verfahren zur (Co)polymerisation von polaren und unpolaren Monomeren | |
JP4344779B2 (ja) | 鉄錯体及び該鉄錯体を触媒とする重合体の製造方法 | |
EP0944654B1 (de) | Anionische polymerisation von acrylaten und methacrylaten | |
DE60307980T2 (de) | Koordinationskomplex |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): JP US Kind code of ref document: A1 Designated state(s): JP |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FR GB GR IE IT LU MC NL PT SE SK TR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 10488190 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002776942 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2002776942 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2002776942 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |