EP2049576A1 - Procédé de fabrication de produits d'atrp acides - Google Patents

Procédé de fabrication de produits d'atrp acides

Info

Publication number
EP2049576A1
EP2049576A1 EP07729123A EP07729123A EP2049576A1 EP 2049576 A1 EP2049576 A1 EP 2049576A1 EP 07729123 A EP07729123 A EP 07729123A EP 07729123 A EP07729123 A EP 07729123A EP 2049576 A1 EP2049576 A1 EP 2049576A1
Authority
EP
European Patent Office
Prior art keywords
polymers
acid
polymerization
preparation
transition metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07729123A
Other languages
German (de)
English (en)
Inventor
Sven Balk
Gerd LÖHDEN
Christine Miess
Christine TRÖMER
Monika Maerz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2049576A1 publication Critical patent/EP2049576A1/fr
Withdrawn legal-status Critical Current

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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule

Definitions

  • the present invention relates to the synthesis of polymers having acid end groups which have been prepared by means of atom transfer radical polymerization (hereinafter abbreviated to ATRP).
  • ATRP atom transfer radical polymerization
  • a particular aspect is the preparation of acid-dense polymethacrylates, polyacrylates or polystyrenes.
  • a very particular aspect of the present invention is that the addition of the reagent in one process step simultaneously removes the transition metal compounds from the polymerization solution by precipitation and salification of the ligand previously coordinated to the transition metal which in turn allows easy removal of the same.
  • the ATRP represents an important process for the preparation of a variety of polymers such as polyacrylates, polymethacrylates or polystyrenes. With this type of polymerization, the goal of tailor-made polymers has come a good deal closer.
  • the ATRP method was substantially developed in the 1990's by Prof. Matyjaszewski (Matyjaszewski et al., J. Am. Chem. Soo, 1995, 117, p.5614, WO 97/18247, Science, 1996, 272, S.866).
  • a particular advantage here is that both the molecular weight and the molecular weight distribution are controllable.
  • As a living polymerization it also allows the targeted construction of polymer architectures such as random copolymers or block copolymer structures.
  • By appropriate initiators for example, in addition unusual block copolymers and star polymers are accessible.
  • Theoretical fundamentals of the polymerization mechanism are explained inter alia in Hans Georg Elias, Makromolekule, Volume 1, 6th Edition, Weinheim 1999, p.344. State of the art
  • the present invention alone represents a significant improvement over the prior art in both end-group functionalization, halide removal, and transition metal precipitation.
  • a combination of all three functions has not previously been described in the prior art. In the following, this document is therefore limited to the aspects end-group functionalization or hydroxy-functionalized ATRP products.
  • the ATRP process relies on a redox balance between a dormant and an active species.
  • the active species is the low-concentration growing, free radical polymer chain and a transition metal compound in higher oxidation state (eg, copper II).
  • the dormant, preferably present species is the combination of the halogenated or pseudohalogen-terminated polymer chain and the corresponding transition metal compound in a lower oxidation state (eg, copper I). This applies both to the ATRP in the actual form, which is started with correspondingly (pseudo) halogen-substituted initiators, and to the reverse ATRP described below, in which the halogen is bound to the polymer chain only when the equilibrium is established.
  • the halogen atom remains independent of the chosen method after termination of the reaction at the respective chain ends.
  • Terminal halogen atoms can be useful in several ways.
  • the use of such polymers as macroinitiators after purification or by sequential addition of further monomer fractions to form block structures is described in a large number of publications. As a representative example, reference is made to US Pat. No. 5,807,937 with regard to the sequential polymerization and to US Pat. No. 6,512,060 with regard to the synthesis of macroinitiators.
  • a mercaptan such as thioglycolic acid is used for the substitution of the terminal halogen atoms.
  • Snijder et al. J. of Polym., Part: Polym. Chem.
  • Such a substitution reaction is briefly described.
  • the aim of this scientific publication was the functionalization of the chain ends with OH groups.
  • the reaction is described exclusively with mercaptoethanol as reagent.
  • substitution with acid-functionalized mercaptans will not mentioned.
  • a further difference from the present invention is the polymer-analogous implementation.
  • the substitution reaction is carried out only after purification of the ATRP product in a second reaction stage. This directly results in a third, important difference from the present invention.
  • the inventive effect of the precipitation of the transition metal compounds from the ATRP solution by addition of mercaptan reagents is not described in this document.
  • ATRA is the addition of reagents that in-situ decompose into two radicals, one of which in turn irreversibly traps a radical chain end and launches the second, smaller new chain.
  • Disadvantage of this procedure in addition to the reduced reaction rate again, is the poor commercial availability of the required reagents and the release of additional radicals, which either have to be absorbed very quickly or lead to undesired oligomeric by-products.
  • This process is described by way of example in the work of Sawamoto (Macromolecules, 31, 6708-11, 1998 and J. Polym., Part A: Polym. Chem., 38, 4735-48, 2000). It should also be noted that also for these two methods no acid-functional reagents are known.
  • the ATRC is based on Fukuda (e-Polymers, no.013, 2002) and is used by Höcker (e-Polymers, No. 049, 2005) or Matyjaszewski (Macromol.Chem. Phys., 205, 154-164, 2004) for polystyrenes.
  • Höcker e-Polymers, No. 049, 2005
  • Matyjaszewski Matyjaszewski
  • the two-sided end group functionalization with simultaneously controlled polymerization conditions using RAFT polymerization is simpler.
  • the radical is transferred to a special RAFT agent, which in the further course of polymerization, for example, alternately acts as a bifunctional radical transfer reagent.
  • RAFT agent which in the further course of polymerization, for example, alternately acts as a bifunctional radical transfer reagent.
  • an acid-functional part of the agent is positioned at the later chain end.
  • RAFT products compared to ATRP products and in particular compared to the polymers according to the invention are the reduced thermal stability of the incorporated in the polymer residues of the RAFT agents, which are mostly trithiocarbonates.
  • Other disadvantages are the possible color of the product and the strong odor of remaining sulfur compounds, which can be released, for example, during thermal degradation.
  • the thioether groups incorporated into the polymer chain according to the invention are significantly more thermally stable. This is revealed to the Skilled very readily from the polymer properties of free radical, with the addition of mercaptan-based regulators produced polymers as a reference substance.
  • the object of the present invention is to prepare polymers by means of atom transfer radical polymerization (ATRP), which have acid groups on more than 90% of the previously polymerization-active chain ends.
  • ATRP atom transfer radical polymerization
  • Transition metal complex compounds of less than 5 ppm to realize.
  • mercaptans to halogen-terminated polymer chains, as present during or at the end of an ATRP process, leads to substitution of the halogen.
  • a thioether group is formed, as already known from free-radical polymerization with sulfur-based regulators.
  • cleavage product a hydrogen halide is formed.
  • a very particular aspect of the present invention is that the addition of a reagent in one step simultaneously removes the terminal halogen atoms from the polymer chains, thereby acid functionalizing the polymer termini, removing the transition metal compounds by precipitation, and salting the ligand previously coordinated to the transition metal , which in turn allows easy removal of ligands from the transition metal occurs.
  • the addition of said sulfur compound is as follows:
  • the initiator used in the ATRP are compounds which have one or more atoms or atomic groups X which are radically transferable under the polymerization conditions of the ATRP process. In the substitution of the active group X on the respective chain ends of the polymers, an acid of the form XH is released.
  • the hydrogen halide which forms can not be hydrolyzed in organic polymerization solutions and thus has a particularly pronounced reactivity, which leads to a protonation of the below-described, mostly basic ligands on the transition metal compound. This quenching of the transition metal complex is extremely rapid and results in direct precipitation of the now unmasked transition metal compounds.
  • the transition metal usually precipitates in the form in which it was used at the beginning of the polymerization: eg in the case of copper as CuBr, CuCI or CU 2 O. Under the condition that the transition metal simultaneously, for example by introducing air or is oxidized by addition of sulfuric acid, the transition metal compound precipitates in addition in the higher oxidation state. In addition to the addition of said sulfur compounds according to the invention, the transition metal precipitation, in contrast to this oxidation-induced precipitation, can moreover be effected almost quantitatively.
  • the ligand L For complexes in which the transition metal and the ligand are present in a ratio of 1: 1, only a very small excess of the sulfur compound is sufficient to achieve complete quenching of the transition metal complex.
  • examples of such ligands are N, N, N ' , N " , N " -pentamethyldiethylenetriamine (PMDETA) and Ths (2-aminoethyl) amine (TREN) described below.
  • this invention is only applicable when the transition metal is used in a significant deficit of eg 1: 2 over the active groups X.
  • An example of such a ligand is 2,2'-bipyridine.
  • the sulfur compounds used are almost completely bound to the polymer chains, and that the residual sulfur constituents can be completely removed completely simply by means of simple modifications in the filtration. In this way, one obtains products that have no unpleasant, sulfur compound-related odor.
  • a major advantage of the present invention is the efficient removal of transition metal complexes from the solution.
  • the reagents added according to the invention after or during the polymerization termination of the polymer solution are preferably compounds which contain sulfur in organically bound form.
  • These sulfur-containing compounds used for precipitation of transition metal ions or transition metal complexes particularly preferably have SH groups and at the same time organic acid groups.
  • Particularly preferred organic compounds are acid-functionalized mercaptans and / or other functionalized or unfunctionalized compounds which have one or more thiol groups and acid groups and / or can form corresponding thiol groups and acid groups under the conditions of the solution. These may be organic compounds such as thioglycolic acid or mercaptopropionic acid.
  • the particularly preferred compounds are commercially readily available compounds used in free-radical polymerization as regulators.
  • the advantage of these compounds is their easy availability, their low price and the wide range of variations that allow optimal adaptation of the precipitating reagents to the respective polymerization system.
  • the present invention can not be restrict to these compounds. Rather, it is decisive that the precipitant used on the one hand has an -SH group or forms an -SH group under the present conditions of the polymer solution in situ.
  • said compound must have an organic acid group or a group which can form an organic acid group under the present conditions.
  • the amount of regulators based on the monomers to be polymerized, usually with 0.05% by weight to 5% by weight specified.
  • the amount of the sulfur compound used is not related to the monomers but to the concentration of the polymerization-active chain ends in the polymer solution.
  • polymerization-active chain ends is meant the sum of dormant and active chain ends.
  • the sulfur-containing precipitating agents according to the invention are used in this sense in 1, 5 molar equivalents, preferably 1, 2 molar equivalents, more preferably below 1, 1 molar equivalents and most preferably below 1.05 molar equivalents. The remaining amounts of residual sulfur can be easily removed by modification of the following filtration step.
  • the mercaptans described may have no further influence on the polymers when added to the polymer solution during or after termination of the polymerization, with the exception of the substitution reaction described. This applies in particular to the breadth of the molecular weight distributions, the molecular weight, additional functionalities, glass transition temperature or melting temperature in semicrystalline polymers and polymer architectures.
  • a further advantage of the present invention is that, by reducing to one or at most two filtration steps, a very fast work-up of the polymer solution compared to many established systems can take place.
  • Adsorbents or adsorbent mixtures can be used to reduce the last traces of sulfur compounds. This can be done in parallel or in successive processing steps.
  • the adsorbents are known in the art, preferably selected from the group consisting of silica and / or alumina, organic polyacids, and activated carbon (e.g., Norit SX plus from Norit).
  • the removal of the activated carbon can also take place in a separate filtration step or in a simultaneous filtration metal removal step.
  • the activated carbon is not added as a solid to the polymer solution, but the filtration is carried out by activated charcoal-loaded filters which are commercially available (for example AKS 5 from PaII Seitz Schenk). Also can be used a combination of the addition of the previously described acidic excipients and activated carbon or the addition of the afore-described auxiliaries and the filtration on charcoal-loaded filter.
  • the present invention relates to end-group functionalization of polymers having acid groups, the removal of the terminal halogen atoms and the transition metal complexes from all polymer solutions prepared by ATRP processes.
  • ATRP the possibilities arising from the ATRP are briefly outlined. However, these lists are not suitable for describing the ATRP and thus the present invention in a limiting manner. Rather, they serve to demonstrate the great importance and versatility of the ATRP and thus also of the present invention for working up corresponding ATRP products:
  • the ATRP polymerizable monomers are well known. The following are a few examples are listed without the present invention in any Restrict shape.
  • the notation (meth) acrylate describes the esters of (meth) acrylic acid and means here both methacrylate, such as methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as methyl acrylate, ethyl acrylate, etc., as well as mixtures of the two.
  • Monomers which are polymerized are selected from the group of (meth) acrylates, for example alkyl (meth) acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 40 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate , n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, l_auryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate;
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate which may each have unsubstitute
  • the monomer selection may also include respective hydroxy-functionalized and / or amino-functionalized and / or mercapto-functionalized and / or olefinically functionalized acrylates or methacrylates such as allyl methacrylate or hydroxyethyl methacrylate.
  • compositions to be polymerized may also consist of or contain other unsaturated monomers.
  • unsaturated monomers include, but are not limited to, 1-alkenes such as 1-hexene, 1-heptene, branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene, acrylonitrile , Vinyl esters such as vinyl acetate, in particular styrene, substituted styrenes having an alkyl substituent on the vinyl group such as ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromosty
  • Vinylpyrimidine 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 2-methyl-1-vinylimidazole, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles, vinyloxazoles and isoprenyl ethers;
  • Maleic acid derivatives such as maleic anhydride, maleimide, methylmaleimide and dienes such as e.g. Divinylbenzene, and the respective hydroxy-functionalized and / or amino-functionalized and / or mercapto-functionalized and / or an olefinically functionalized compounds.
  • these copolymers can also be prepared in such a way that they have a hydroxyl and / or amino and / or mercapto functionality and / or an olefinic functionality in a substituent.
  • monomers are vinylpiperidine, 1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpirrolidone, N-vinylpirrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, hydrogenated vinylthiazoles and hydrogenated vinyl oxazoles.
  • the process can be carried out in any halogen-free solvents.
  • Preference is given to toluene, xylene, acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone; ether; Aliphatic, preferably pentane, hexane; Alcohols, preferably cyclohexanol, butanol, hexanol but also biodiesel.
  • Block copolymers of composition AB can be prepared by sequential polymerization.
  • Block copolymers of composition ABA or ABCBA are prepared by sequential polymerization and initiation with bifunctional initiators.
  • the polymerization can be carried out at atmospheric pressure, underpressure or overpressure.
  • the polymerization temperature is not critical. In general, however, it is in the Range from -20 0 C to 200 0 C, preferably from 0 ° C to 130 0 C and particularly preferably from 50 ° C to 120 ° C.
  • the polymers obtained according to the invention have a number average molecular weight between 5000 g / mol and 120,000 g / mol and more preferably between 7500 g / mol and 50,000 g / mol.
  • the molecular weight distribution is less than 1, 8, preferably less than 1, 6, more preferably less than 1, 4 and ideally less than 1.2.
  • Any compound having one or more atoms or atomic groups X which are radically transferable under the polymerization conditions of the ATRP process can be used as the initiator.
  • the active group X is usually Cl, Br, I, SCN and / or N 3 .
  • Suitable initiators broadly include the following formulas:
  • Particularly preferred initiators include benzyl halides such as p-chloromethylstyrene, hexakis ( ⁇ -bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenylethane and 1-chloro-1-phenylethane.
  • carboxylic acid derivatives which are halogenated at the ⁇ -position, such as, for example, propyl 2-bromopropionate, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate or ethyl 2-bromoisobutyrate.
  • tosyl halides such as p-toluenesulfonyl chloride; Alkyl halides such as tetrachloromethane, tribromoethane, 1-vinylethyl chloride or 1-vinylethyl bromide; and halogen derivatives of phosphoric acid esters such as dimethylphosphonic acid chloride.
  • a particular group of initiators which is suitable for the synthesis of block copolymers are the macroinitiators. These are characterized in that from 1 to 3, preferably from 1 to 2, and very particularly preferably from a group from the group R 1 , R 2 and R 3 is macromolecular radicals.
  • These macro radicals can be selected from the group of polyolefins, such as polyethylene or polypropylene; polysiloxanes; Polyethers, such as polyethylene oxide or polypropylene oxide; Polyester, such as polylactic acid or other known, end phenomenonfunktionalisierbaren macromolecules.
  • the macromolecular radicals may each have a molecular weight between 500 and 100,000, preferably between 1,000 and 50,000, and more preferably between 1,500 and 20000.
  • bi- or multi-functional initiators Another important group of initiators are the bi- or multi-functional initiators.
  • bifunctional initiators R ⁇ 2C CHX-can (CH2) n-CHX-C ⁇ 2R, RO 2 CC (CH 3) X- (CH 2) n C (CH 3) X-CO 2 R, RO 2 C- CX 2 - (CH 2 ) n-CX 2 -CO 2 R, RC (O) -CHX- (CH 2 ) n -CHX-C (O) R, RC (O) -C (CH 3 ) X- (CH 2 ) n - C (CH) 3 XC (O) R, RC (O) -CX 2 - (CH 2) n CX 2 -C (O) R, XCH 2 CO 2 - (CH 2) n -OC (
  • Copper complexes are predominantly described, but also iron, cobalt, chromium, manganese, molybdenum, silver, zinc, palladium, rhodium, platinum, ruthenium, iridium, ytterbium, Samarium, rhenium and / or nickel compounds for use.
  • all transition metal compounds can be used which can form a redox cycle with the initiator, or the polymer chain, which has a transferable atomic group.
  • copper can be supplied to the system starting from Cu 2 O, CuBr, CuCl, CuI, CuN 3 , CuSCN, CuCN, CuNO 2 , CuNO 3 , CuBF 4 , Cu (CH 3 COO) or Cu (CF 3 COO).
  • a variant of the reverse ATRP represents the additional use of metals in the oxidation state zero.
  • an acceleration of the reaction rate is effected. This process is described in more detail in WO 98/40415.
  • the molar ratio of transition metal to monofunctional initiator is generally in the range from 0.01: 1 to 10: 1, preferably in the range from 0.1: 1 to 3: 1 and particularly preferably in the range from 0.5: 1 to 2: 1, without this being a restriction.
  • the molar ratio of transition metal to bifunctional initiator is generally in the range of 0.02: 1 to 20: 1, preferably in the range of 0.2: 1 to 6: 1 and particularly preferably in the range from 1: 1 to 4: 1, without this being intended to limit it.
  • ligands are added to the system.
  • the ligands facilitate the abstraction of the transferable atomic group by the transition metal compound.
  • a list of known ligands can be found, for example, in WO 97/18247, WO 97/47661 or WO 98/40415.
  • the compounds used as ligands usually have one or more nitrogen, oxygen, phosphorus and / or sulfur atoms. Particularly preferred are nitrogen-containing compounds. Very particular preference is given to nitrogen-containing chelate ligands.
  • Examples which may be mentioned are 2,2'-bipyridine, N, N, IST, N “ , N “ -pentamethyldiethylenetriamine (PMDETA), tris (2-aminoethyl) amine (TREN), N, N, IST, IST tetramethylethylenediamine or 1, 1, 4,7,10,10-hexamethyltriethylenetetramine listed. Valuable information on the selection and combination of the individual components will be found by the person skilled in the art in WO 98/40415.
  • ligands can form coordination compounds in situ with the metal compounds, or they can first be prepared as coordination compounds and then added to the reaction mixture.
  • the ratio of ligand (L) to transition metal is dependent on the denticity of the ligand and the coordination number of the transition metal (M).
  • the molar ratio is in the range 100: 1 to 0.1: 1, preferably 6: 1 to 0.1: 1 and more preferably 3: 1 to 1: 1, without this being a restriction.
  • Crucial to the present invention is that the ligands are protonatable.
  • ligands present in the coordination compound in a 1: 1 ratio to the transition metal.
  • ligands such as 2,2'-bipyridine, which are bound in a complex to the transition metal of 2: 1 in the complex
  • a complete protonation can only take place when the transition metal in a significant deficit of eg 1: 2 to the active chain end X is used.
  • Such a polymerization would be much slower than one with equivalent complex X ratios.
  • inventively processed products results in a wide range of applications.
  • the selection of the application examples is not suitable for limiting the use of the polymers according to the invention.
  • the examples are only intended to represent randomly the wide range of possible uses of the described acid-like polymers.
  • polymers synthesized by means of ATRP are used as prepolymers in hotmelts, adhesives, sealants, heat sealants, for polymer-analogous reactions or for the synthesis of block copolymers.
  • the polymers can also find use in formulations for cosmetic use, in coating materials, as dispersants, as polymer additives or in packaging.
  • the present examples were related to the ATRP process.
  • the polymerization parameters were selected such that it was necessary to work with particularly high copper concentrations: low molecular weight, 50% solution and bifunctional initiator.
  • the previously greenish solution turns spontaneously apricot-colored and a red precipitate precipitates.
  • the filtration takes place by means of an overpressure filtration.
  • the average molecular weight and molecular weight distribution are then determined by GPC measurements.
  • From a dried sample of the filtrate is then determined by AAS the copper content and potentiometrically the acid number.
  • Tonsil Optimum 210 FF from Südchemie
  • 4% by weight of water are added to the solution and the mixture is stirred for 60 minutes.
  • the subsequent filtration is carried out under pressure via an activated carbon filter (AKS 5 from PaII Seitz Schenk).
  • the average molecular weight and molecular weight distribution are then determined by GPC measurements. From a dried sample of the filtrate is then determined by AAS the copper content and potentiometrically the acid number.
  • TGS thioglycolic acid
  • n-BA n-butyl acrylate
  • Alox alumina
  • Example 1 From the results of Example 1 it can be seen that corresponding sulfur compounds, based on the transition metal compound, already used in the slightest excess, lead to a very efficient precipitation and a high degree of functionalization. It can also be seen from the examples that thiol-functionalized reagents allow a more efficient removal of the transition metal compounds from the solution than is possible by an already optimized work-up with adsorbents. From the comparison of the molecular weights and molecular weight distributions before and after the work-up, it can be seen that the methods used, with the exception of the substitution of the end groups, have no influence on the polymer characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne la fonctionnalisation in situ par groupements acides de chaînes polymères, obtenues par polymérisation radicalaire par transfert d'atome (ATRP) et l'élimination simultanée des métaux de transition des solutions polymères.
EP07729123A 2006-08-09 2007-05-15 Procédé de fabrication de produits d'atrp acides Withdrawn EP2049576A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006037352A DE102006037352A1 (de) 2006-08-09 2006-08-09 Verfahren zur Herstellung von säureterminierten ATRP-Produkten
PCT/EP2007/054671 WO2008017524A1 (fr) 2006-08-09 2007-05-15 Procédé de fabrication de produits d'atrp acides

Publications (1)

Publication Number Publication Date
EP2049576A1 true EP2049576A1 (fr) 2009-04-22

Family

ID=38617978

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07729123A Withdrawn EP2049576A1 (fr) 2006-08-09 2007-05-15 Procédé de fabrication de produits d'atrp acides

Country Status (11)

Country Link
US (1) US8143354B2 (fr)
EP (1) EP2049576A1 (fr)
JP (1) JP2010500427A (fr)
KR (1) KR20090042783A (fr)
CN (1) CN101490108A (fr)
BR (1) BRPI0715177A2 (fr)
CA (1) CA2660315A1 (fr)
DE (1) DE102006037352A1 (fr)
MX (1) MX2009001259A (fr)
RU (1) RU2454433C2 (fr)
WO (1) WO2008017524A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006037350A1 (de) * 2006-08-09 2008-02-14 Evonik Röhm Gmbh Verfahren zur Herstellung von halogenfreien ATRP-Produkten
DE102007006105A1 (de) * 2007-02-02 2008-08-07 Evonik Röhm Gmbh Verfahren zur Herstellung telecheler Polymere
DE102007039535A1 (de) * 2007-08-21 2009-02-26 Evonik Röhm Gmbh Verfahren zur Herstellung von Pentablockcopolymeren mit OH-funktionalisierten Blöcken auf (Meth)acrylatbasis
DE102008002016A1 (de) * 2008-05-28 2009-12-03 Evonik Röhm Gmbh Verfahren zur Herstellung von silyl-funktionalisierten ABA-Triblockcopolymeren auf (Meth)acrylatbasis
DE102008034106A1 (de) * 2008-07-21 2010-01-28 Evonik Röhm Gmbh Blockcopolymere auf (Meth)acrylatbasis mit A-P-Struktur
DE102008043666A1 (de) * 2008-11-12 2010-05-20 Evonik Röhm Gmbh Verfahren zur Herstellung von AB-Diblockcopolymeren mit einem bimodalen verteilten A-Block
DE102008043669A1 (de) 2008-11-12 2010-05-20 Evonik Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren mit einem breit verteilten B-Block
DE102008043658A1 (de) 2008-11-12 2010-05-20 Evonik Röhm Gmbh Verfahren zur Herstellung von AB-Diblockcopolymeren mit einem breit verteilten A-Block
US20110213091A1 (en) * 2008-11-12 2011-09-01 Evonik Roehm Gmbh Method for producing telechelics having a bimodal molecular weight distribution
DE102008043668A1 (de) * 2008-11-12 2010-05-20 Evonik Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren mit einem bimodalen B-Block
US10316114B2 (en) * 2010-03-30 2019-06-11 Basf Se End-functionalized polymers
RU2566303C1 (ru) * 2014-07-01 2015-10-20 Михаил Юрьевич Заремский Способ получения акриловых и метакриловых полимеров
RU2566302C1 (ru) * 2014-07-01 2015-10-20 Михаил Юрьевич Заремский Способ получения акриловых и метакриловых полимеров
US9587062B2 (en) 2014-12-15 2017-03-07 Henkel IP & Holding GmbH and Henkel AG & Co. KGaA Photocrosslinkable block copolymers for hot-melt adhesives
CN106519154B (zh) * 2016-10-27 2018-08-10 广东工业大学 线形温敏性聚合物及其制备方法

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL30428A (en) * 1967-09-01 1971-05-26 Stauffer Chemical Co Polymercaptan modified vinyl halide polymers
DE19539214A1 (de) * 1995-10-21 1997-04-24 Degussa Brandsicheres, transparentes Scheibenelement und dessen Verwendung
US6143848A (en) * 1997-10-23 2000-11-07 The B.F.Goodrich Company End-functionalized polymers by controlled free-radical polymerization process and polymers made therefrom
US6498209B1 (en) * 1998-03-31 2002-12-24 Roehm Gmbh & Co. Kg Poly(meth)acrylate plastisols
ATE437903T1 (de) * 1999-03-18 2009-08-15 California Inst Of Techn Neue aba triblock und diblock copolymere und verfahren zu deren herstellung
DE19928352A1 (de) * 1999-06-21 2000-12-28 Roehm Gmbh Verbesserte Poly(meth)acrylatptastisole und Verfahren zu ihrer Herstellung
DE10065501A1 (de) * 2000-12-28 2002-07-04 Roehm Gmbh Verfahren zur Herstellung von Perlpolymerisaten mit einer mittleren Teilchengröße im Bereich von 1 bis 40 mum sowie Perlpolymerisat aufweisende Formmassen, Formkörper und PAMA-Plastisole
US6610802B2 (en) * 2001-05-29 2003-08-26 Rohmax Additives Gmbh Process for synthesis of polymer compositions, polymer compositionS obtainable by the process, and use of the same
US6689844B2 (en) * 2001-05-29 2004-02-10 Rohmax Additives Gmbh Process for synthesis of polymer compositions with reduced halogen content, polymer composition with reduced halogen content as well as use of this composition
DE10227898A1 (de) * 2002-06-21 2004-01-15 Röhm GmbH & Co. KG Verfahren zur Herstellung sprühgetrockneter Poly(meth)acrylatpolymere, ihre Verwendung als Polymerkomponente für Plastisole und damit hergestellte Plastisole
JP2004240114A (ja) * 2003-02-05 2004-08-26 Fuji Photo Film Co Ltd 表面機能性部材
DE10350786A1 (de) * 2003-10-29 2005-06-02 Röhm GmbH & Co. KG Mischungen zur Herstellung von Reaktivschmelzklebstoffen sowie daraus erhältliche Reaktivschmelzklebstoffe
FR2870245B1 (fr) * 2004-05-14 2008-08-22 Rhodia Chimie Sa Synthese de copolymeres en forme d'etoile mikto par polymerisation radicalaire controlee
EP1600142B1 (fr) * 2004-05-26 2008-08-06 DENTSPLY DETREY GmbH Composition de ciment dentaire contenant des particules composites avec des chaînes polymères polyacidiques greffées
DE102004030404A1 (de) * 2004-06-23 2006-01-19 Röhm GmbH & Co. KG Plastisole auf Basis eines Methylmethacrylat-Mischpolymerisats
DE102004035937A1 (de) * 2004-07-23 2006-02-16 Röhm GmbH & Co. KG Plastisole mit verringerter Wasseraufnahme
DE102005042389A1 (de) * 2005-06-17 2006-12-28 Röhm Gmbh Heißversiegelungsmasse für Aluminium- und Polyethylenterephthalatfolien gegen Polypropylen-Polyvinylchlorid- und Polystyrolbehälter
DE102005045458A1 (de) * 2005-09-22 2007-03-29 Röhm Gmbh Verfahren zur Herstellung von ABA-Triblockcopolymeren auf (Meth)acrylatbasis
DE102005046681A1 (de) * 2005-09-29 2007-04-05 Construction Research & Technology Gmbh Verwendung von polymeren Mikropartikeln in Baustoffmischungen
DE102005052130A1 (de) * 2005-10-28 2007-05-03 Röhm Gmbh Spritzbare Akustikmassen
DE102006008968A1 (de) * 2006-02-23 2007-08-30 Röhm Gmbh Additive Baustoffmischungen mit Mikropartikeln, deren Schalen porös und/oder hydrophil sind
DE102006008966A1 (de) * 2006-02-23 2007-08-30 Röhm Gmbh Additive Baustoffmischungen mit sprühgetrockneten Mikropartikeln
DE102006008965A1 (de) * 2006-02-23 2007-08-30 Röhm Gmbh Additive Baustoffmischungen mit Mikropartikeln verschiedener Größe
DE102006009511A1 (de) * 2006-02-28 2007-08-30 Röhm Gmbh Synthese von Polyester-pfropf-Poly(meth)acrylat
DE102006009586A1 (de) * 2006-02-28 2007-09-06 Röhm Gmbh Heißversiegelungsmasse für Aluminium- und Polyethylenterephthalatfolien gegen Polypropylen-Polyvinylchlorid- und Polystyrolbehälter
DE102006009842A1 (de) * 2006-03-01 2007-09-06 Röhm Gmbh Additive Baustoffmischungen mit Mikropartikeln die in der Mischung quellen
DE102006009841A1 (de) * 2006-03-01 2007-09-06 Röhm Gmbh Additive Baustoffmischungen mit quellbaren Polymergebilden
DE102006015846A1 (de) * 2006-04-03 2007-10-04 Röhm Gmbh Kupferentfernung aus ATRP-Produkten mittels Zugabe von Schwefelverbindungen
DE102006037350A1 (de) * 2006-08-09 2008-02-14 Evonik Röhm Gmbh Verfahren zur Herstellung von halogenfreien ATRP-Produkten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008017524A1 *

Also Published As

Publication number Publication date
US20090326163A1 (en) 2009-12-31
KR20090042783A (ko) 2009-04-30
WO2008017524A1 (fr) 2008-02-14
US8143354B2 (en) 2012-03-27
RU2009107869A (ru) 2010-09-20
CN101490108A (zh) 2009-07-22
MX2009001259A (es) 2009-02-11
RU2454433C2 (ru) 2012-06-27
BRPI0715177A2 (pt) 2012-12-25
JP2010500427A (ja) 2010-01-07
CA2660315A1 (fr) 2008-02-14
DE102006037352A1 (de) 2008-02-14

Similar Documents

Publication Publication Date Title
EP2049574B1 (fr) Utilisation d'un compose de soufre pour la fabrication de produits d'atrp sans halogène
EP2001914B1 (fr) Extraction des metaux de transition des produits obtenus par atrp par ajout de mercaptans
EP2049576A1 (fr) Procédé de fabrication de produits d'atrp acides
EP2049575B1 (fr) Procédé de fabrication de produits hydroxytéléchéliques d'atrp
EP2079764B1 (fr) Procédé de production de polymères silyl téléchéliques
EP2285849B1 (fr) Copolymères triblocs aba à base de (méth)acrylate à fonctionnalisation silyle et procédé pour leurs production
EP2346915B1 (fr) Procédé de fabrication de copolymères diblocs ab avec un bloc a à distribution large
EP2344559B1 (fr) Procédé de fabrication de copolymères triblocs aba avec un bloc b bimodal
WO2010054894A1 (fr) Procédé de production de substances téléchéliques à une distribution bimodale des masses moléculaires
EP2350151B1 (fr) Procédé de fabrication de téléchéliques avec une distribution large des masses moléculaires
WO2008092515A1 (fr) Procédé de production de polymères téléchéliques
EP2350152B1 (fr) Procédé de fabrication de copolymères diblocs ab avec un bloc a à distribution bimodale
WO2010054893A1 (fr) Procédé de fabrication d'un copolymère tribloc aba avec un bloc b à distribution large

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081202

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20131203