WO2011040881A1 - Systèmes bifonctionnels ligand - initiateur unimoléculaires (umlidfs) et leur utilisation - Google Patents

Systèmes bifonctionnels ligand - initiateur unimoléculaires (umlidfs) et leur utilisation Download PDF

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WO2011040881A1
WO2011040881A1 PCT/SG2010/000362 SG2010000362W WO2011040881A1 WO 2011040881 A1 WO2011040881 A1 WO 2011040881A1 SG 2010000362 W SG2010000362 W SG 2010000362W WO 2011040881 A1 WO2011040881 A1 WO 2011040881A1
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mol
compound
optionally substituted
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composition
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Anbanandam Parthiban
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Agency For Science, Technology And Research
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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
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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

Definitions

  • This invention relates to the polymerization of vinyl monomers including acidic monomers like acrylic acid and methacrylic acid in the free acid form by atom transfer radical polymerization (ATRP) using metal salts in ppm molar quantities. More specifically, this invention relates to the polymerization under ATRP conditions using unimolecular ligand-initiator dual functional systems (UMLIDFS) where the initiator and ligand for complexing the metal are part of the same molecule.
  • ULIDFS unimolecular ligand-initiator dual functional systems
  • ATRP atom transfer radical polymerization
  • ATRP has not become a widely adopted industrial process due to various problems associated with the process.
  • One of the major drawbacks associated with the process is the presence of metal impurities in the final polymer in unacceptably high quantities. This is attributed to the large quantities of metal salt viz. CuBr either alone or in conjunction with CuBr 2 employed during polymerization.
  • the presence of residual metal impurities impacts the performance of polymers in many respects. Due to the presence of residual metal impurities the polymers appear reddish brown to green in colour. This coloration is intensified during the thermal processing of the polymer.
  • the residual metal impurity adversely affects the toxicity of the polymer and also lowers the thermooxidative stability of the polymer. The residual metal could also affect the mechanical properties of injection molded materials.
  • the polymer solutions are passed through a column of alumina (A1 2 0 3 ).
  • the metal impurities are adsorbed on the alumina and the polymer is separated from the resulting solution either by precipitation or by removing the solvent. Since the polymer solutions tend to be highly viscous beyond a molecular weight of 10,000 and above, passing such solutions through alumina column on an industrial scale would be costly and time consuming.
  • Various reports have disclosed processes for removing residual metal impurities from polymers prepared by ATRP catalyzed by copper salts. These processes involve the treatment of polymer solutions with various acidic or basic adsorbents, using oxidizing or reducing agents or an extracting agent.
  • Polar, carboxylic acid groups impart many characteristics to polymers such as pH responsiveness, high adhesion, high oil resistance, high heat resistance, high tensile properties and high resistance to wax removers, improved solvent resistance. As the modern trend in coating industry is to make formulations free of volatile organic components, the ability of these polymers to dissolve in aqueous medium after neutralization is an added advantage of these copolymers.
  • Polar carboxylic acid group bearing homo- and copolymers have many applications in various industry sectors. They are used in the paper industry, in the paint industry, in detergents, in water treatment, in cement industry, in textile industry, in healthcare, in hygienic articles and leather industry. They are also used to aid the grinding of various inorganic minerals like calcium carbonate, precipitated calcium carbonate, titanium dioxide, clay and kaolin.
  • the current ATRP process is energy intensive in that the reaction mixture is subjected to repeated freeze-pump-thaw cycles in order to make it completely free of air, particularly, oxygen. Such freezing and thawing cycles are not viable for an industrial scale process.
  • efforts were concentrated predominantly in the preparation of materials of varying nature well within the limitation of the process. Many attempts were also made to overcome some of the deficiencies of the process. Among the various attempts that were made to improve the process, substantial focus was on ligand modification and on alkyl halide employed as initiator. There were also attempts to carry out the polymerization under high pressure. However, reduction in metal salt employed in the polymerization and broadening the scope of polymerization to include carboxylic acid containing monomers could not be achieved without any additional complications.
  • the present invention provides compounds according to a unimolecular ligand-initiator dual functional system (UMLIDFS) so that an ATRP process could be carried out with low quantities of metal salt(s).
  • ULIDFS unimolecular ligand-initiator dual functional system
  • These compound have the general formula R-X-Y (I), wherein R is an initiator selected from the group consisting of halogenated alkane, benzylic halide, or-haloester, a-haloketone, a-halonitrile and sulfonyl halides; X is a linker selected from the group consisting of optionally substituted aliphatic, optionally substituted aryl, optionally substituted heteroaryl and optionally substituted aralkyl or is a direct bond connecting R and Y; and Y is a ligand capable of coordinating to a metal centre selected from the group consisting of aliphatic, aryl, heteroaryl and aralky
  • the present invention provides a composition comprising a) at least one compound of the present invention; and b) at least one metal salt.
  • the present invention provides the use of the inventive composition for atom transfer radical polymerization (ATRP) of vinyl monomers.
  • ATRP atom transfer radical polymerization
  • the present invention provides a polymer obtained by the inventive use described in the present application.
  • FIG. 1 depicts a scheme for the typical preparation of copolymers containing polar acidic groups by ATRP.
  • FIG. 2 depicts (a) the general structure of the UMLIDFS of the present invention wherein the ligand and the initiator are connected by the linker group into a single entity and (b) depicts a preferred embodiment of the present inventive technology.
  • FIG. 3 depicts the general mechanism of ATRP.
  • FIG. 4 depicts the homopolymers synthesized using the UMLIDFS of the present invention.
  • FIG. 5 depicts the copolymer of acrylic acid and n-isopropyl acrylamide (AA-b/ran-NIPAAm).
  • FIG. 6 depicts the copolymer of methacrylic acid and n-butyl acrylate (MAA-b/raw-nBA).
  • FIG. 7 depicts (a) the homopolymer of polymethacrylic acid (PMAA) and (b) the copolymer of polymethacrylic acid and polystyrene (PMAA-b/ran-PS).
  • FIG. 8 depicts the aqueous alkali solutions of copolymers, from left to right: (a) polystyrene-methacrylic acid (PS-MAA), (b) acrylic acid-styrene-n-butyl acrylate (AA-Sty-nBA), (c) methacrylic acid-n-butyl acrylate (MAA-nBA), (d) acrylic acid-n- isopropyl acrylamide (AA-NIPAAm), (e) acrylic acid- styrene (AA-Sty), (f) acrylic acid-n- butyl acrylate (AA-nBA), (g) acrylic acid-methacrylic acid-n-butyl acrylate (AA-MMA- nBA).
  • PS-MAA polystyrene-methacrylic acid
  • A-Sty-nBA acrylic acid-styrene-n-butyl acrylate
  • MAA-nBA methacrylic acid-n-butyl
  • FIG. 10 depicts the film developed from 2 wt% aqueous solution of copolymer PAA-b/ran-PS.
  • FIG. 11 depicts a GPC analysis showing the position of molecular weight for PMMA and PMMA-PI
  • FIG. 12 depicts the structures of nBA-MAA copolymer using dispersions ofZnAc.
  • FIG. 13 depicts the structures of PS-MAA copolymer using dispersions of
  • FIG. 14 depicts the structures of AA-NIPAAm copolymer using dispersions of ZnAc.
  • the term “comprising” means including, but not limited to, whatever follows the word “comprising”. Thus, use of the term “comprising” indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present.
  • the term “consisting of means including, and limited to, whatever follows the phrase “consisting of. Thus, the phrase “consisting of ' indicates that the listed elements are required or mandatory, and that no other elements may be present.
  • the term “consisting essentially of means including any elements listed after the phrase, and limited to other elements that do not interfere with or contribute to the activity or action specified in the disclosure for the listed elements. Thus, the phrase “consisting essentially of indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they affect the activity or action of the listed elements.
  • the object of the present invention is the provision of a unimolecular ligand-initiator dual functional system (UMLIDFS), wherein the ligand and initiator are combined into a single molecule.
  • ULIDFS unimolecular ligand-initiator dual functional system
  • ATRP atom transfer radical polymerization
  • the present technology allows the homogenization of the catalyst, i.e. making the metal complex completely soluble in the reaction medium and minimizing the number of components in the reaction medium.
  • the ligand and initiator are connected by a linker group to form a single entity.
  • ATRP involves redox cycles of the metal which is directly associated with the active and dormant states of the growing polymer chain as illustrated in FIG. 3, this bifunctional system allows the active and dormant states to proceed intramolecular ly since the ligand would be present in one end of the chain and the halide at the other end of the same polymer chain. This species during active cycle would then combine with the vinyl monomer resulting in chain extension.
  • a four component heterogeneous reaction mixture would be reduced to two component viz. the complex comprising of metal salt and ligand-initiator and the vinyl monomer, homogeneous solution by this modification.
  • the present technology relates to a compound having the following generic structure:
  • R is an initiator selected from the group consisting of halogenated alkane, benzylic halide, ohaloester, ohaloketone, ohalonitrile and sulfonyl halides;
  • X is a linker selected from the group consisting of optionally substituted aliphatic, optionally substituted aryl, optionally substituted heteroaryl and optionally substituted aralkyl or is a direct bond connecting R and Y;
  • Y is a ligand capable of coordinating to a metal centre selected from the group consisting of aliphatic, aryl, heteroaryl and aralkyl.
  • the groups R, X and Y may be independently selected as defined in the following, but are not limited to.
  • aliphatic refers to a straight chain or branched chain hydrocarbon comprising at least one carbon atom.
  • Aliphatics include alkyls, alkenyls, and alkynyls. In certain embodiments, aliphatics are optionally substituted. Aliphatics include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. -butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, ethynyl, butynyl, propynyl, and the like, each of which may be optionally substituted. As used herein, aliphatic is not intended to include cyclic groups.
  • alkyl refers to a fully saturated aliphatic hydrocarbon. In certain embodiments, alkyls are optionally substituted. In certain embodiments, an alkyl may comprises 1 to 20 carbon atoms, for example 1 to 10 carbon atoms or 1 to 6 carbon atoms, wherein (whenever it appears herein in any of the definitions given below) a numerical range, such as “1 to 20" or “C 1 -C 20 ", refers to each integer in the given range, e.g.
  • Ci-C 20 alkyl means that an alkyl group comprises only 1 carbon atom, or 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, up to and including 20 carbon atoms.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
  • alkenyl refers to an aliphatic hydrocarbon having one or more carbon-carbon double-bonds.
  • alkene groups are optionally substituted. Examples of alkene groups may include, but are not limited to, ethenyl, propenyl, butenyl, 1 ,4-butadienyl, pentenyl, hexenyl, 4-methylhex- 1-enyl, 4-ethyl-2-methylhex-l-enyl and the like.
  • alkynyl refers to an aliphatic hydrocarbon having one or more carbon-carbon triple-bonds.
  • alkyne groups are optionally substituted. Examples of alkyne groups may include, but are not limited to, ethynyl, propynyl, butynyl, and the like.
  • aryl refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • aromatic refers to a group comprising a covalently closed planar ring having a delocalized [pi]-electron system comprising 4n+2 [7T] electrons, where n is ah integer.
  • Aryl rings may be formed by five, six, seven, eight, nine, or more than nine carbon atoms.
  • Aryl groups may be optionally substituted.
  • aryl groups may include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, anthracenyl, tetralinyl, fluorenyl, indenyl, and indanyl.
  • an aryl group may be substituted at one or more of the para, meta, and/or ortho positions.
  • aryl groups comprising substitutions may include, but are not limited to, 3-halophenyl, 4-halophenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 3- aminophenyl, 4-aminophenyl, 3-methylphenyl, 4-methylphenyl, 3-methoxyphenyl, 4- methoxyphenyl, 4-trifluoromethoxyphenyl, 3-cyanophenyl, 4-cyanophenyl, dimethylphenyl, naphthyl, hydroxynaphthyl, hydro xymethylphenyl, (trifluoromethyl)phenyl, alkoxyphenyl, 4-morpholin-4-ylphenyl, 4-pyrrolidin-l-ylphenyl, 4-pyrazolylphenyl, 4-triazolylphenyl, and 4-(2-oxopyrrolidin-l-yl)phenyl or any of the groups shown explicitly below.
  • heteroaryl refers to an aromatic heterocycle. Heteroaryl rings may be formed by three, four, five, six, seven, eight, nine, or more than nine atoms. Heteroaryls may be optionally substituted. Examples of heteroaryl groups may include, but are not limited to, aromatic C 3 - 8 heterocyclic groups comprising one oxygen or sulfur atom or up to four nitrogen atoms, or a combination of one oxygen or sulfur atom and up to two nitrogen atoms, and the like. In certain embodiments, heteroaryl groups may be optionally substituted.
  • heteroaryl groups may include, but are not limited to, unsubstituted and mono- or di-substituted derivatives of furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, imidazole, benzimidazole, pyrazole, indazole, tetrazole, quinoline, isoquinoline, pyridazine, pyrimidine, purine and pyrazine, furazan, 1,2,3-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, triazole, benzotriazole, pteridine, phenoxazole, oxadiazole, benzopyrazole, quinolizine, cinnoline, phthala
  • aralkyl refers to a group comprising an aryl group bound to an alkyl group.
  • linker refers to an atom or group of atoms that link (or separate) two or more groups to (or from) one another by a desired number of atoms. For example, in certain embodiments, it may be desirable to link or separate the initiator and the ligand by one, two, three, four, five, six, or more than six atoms. In such embodiments, any atom or group of atoms may be used to link or separate those groups by the desired number of atoms.
  • the linker of the present invention may also be a direct bond connecting R and Y.
  • the term "optionally substituted” refers to a group in which none, one, or more than one of the hydrogen atoms has been replaced with one or more group(s) independently selected from: alkyl, heteroalkyl, haloalkyl, heterohaloalkyl, cycloalkyl, aryl, arylalkyl, heteroaryl, nori-aromatic heterocycle, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O- thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C- carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl,
  • R may have the following general formula (II): (R'XR ⁇ CCZHR 3 )-, wherein in formula (II) R 1 and R 2 may be independently selected from hydrogen, optionally substituted alkyl, such as methyl, ethyl, /-propyl, «-butyl, /-butyl and tert.
  • R 3 may be a group which can activate the cleavage of the C-Z bond, such as, but not limited to, C(O), CN, phenyl, -CONH 2 , lactone, ketone and the like.
  • R may be, but is not limited to, (H) 2 C(Br)-C(0)-, (H) 2 C(C1)-C(0)-, (CH 3 )(H)C(Br)-C(0)-, (CH 3 )(H)C(C1)-C(0)-, (CH 3 ) 2 C(Br)-C(0)-, (CH 3 ) 2 C(C1)-C(0)-, (C 2 H 5 )(H)C(Br)-C(0)-, (C 2 H 5 )(H)C(C1)-C(0)-, (C 2 H 5 ) 2 C(Br)-C(0)-, (C 2 H 5 ) 2 C(C1)-C(0)- and the like.
  • X is a linking atom or group which preferably covalently connects the initiating moiety R and the ligating species Y.
  • X may be, but is not limited to, optionally substituted -CH 2 -, optionally substituted i C 2 H 5 -, optionally substituted -C 6 H 4 -, optionally substituted -C 5 H N- and the like.
  • X may also be a Si-group, for example a Si chain provided that it is stable under the conditions of the present invention.
  • Y is the ligating species of the UMLIDFS of the present invention.
  • Y may comprise at least one heteroatom.
  • the ligand Y is capable to coordinate to the metal centre via the at least one heteroatom so that a complex between the compound of the invention and the metal centre can be formed.
  • Y may comprise at least two heteroatoms, such as at least three heteroatoms or at least four heteroatoms.
  • the heteroatom(s) may be independently selected from nitrogen, oxygen and sulphur.
  • the heteroatom is nitrogen.
  • the ligating nitrogen atoms may be tertiary in nature. In one embodiment of
  • the invention Y may be, but is not limited to,
  • the at least one heteroatom may be part of the aliphatic, alicyclic, aromatic or hetero aromatic units and positioned in such a way that complexation occurs when treated with a metal salt.
  • the compounds may be, but are not limited, as illustrated in FIG. 2(b) or as follows:
  • the present invention also encompasses a polymerization composition
  • a polymerization composition comprising a) at least one compound as described above, and b) at least one metal salt.
  • a composition may be used in polymerization reaction of one or more independently selected vinyl monomers, such as atom transfer radical polymerization (ATRP).
  • ATRP atom transfer radical polymerization
  • the composition may comprise at least one kind of vinyl monomer. Suitable vinyl monomers are described in more detail below.
  • the metal salt used in the inventive composition may be any metal salt which may be generally used in the field of the polymerization reactions.
  • the metal salt may be a salt of, but is not limited to, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Zn and the like. It is possible to use two or more metal salts, for example two or more metal salts from the same metal having different oxidation states.
  • the metal of the metal salt is Cu.
  • the corresponding anion o f the metal salt may be selected from any anion which is generally used in the field of polymerization reactions or which is generally used in metal complexes.
  • the anion may be, but is not limited to, a halide, N0 2 , CN, OH, S0 3 H, and the like.
  • the anion is a halide, such as F, CI, Br or I.
  • suitable metal salts include, but are not limited to, TiCL t , ReCl 6 , FeCl 2 , RuCl 2 , RhCl 2 , NiBr 2 , NiCl 2 , CuBr, CuCl, CuBr 2 , CuCl 2 , and the like.
  • the metal salt is a halide of Cu in +1 oxidation state, such as CuBr or CuCl, or a mixture of halides of copper in +1 and +2 oxidation states.
  • the metal salt is typically used in an amount which is smaller than the amount generally used in polymerization chemistry.
  • the metal salt may be used in an amount of about 1 x 10 "6 mol or about 1 x 10 "5 mol.
  • the metal salt may be used in an amount of about 1/10 mg, such as 1/100 mg or 1/1000 mg.
  • the metal salt may also be used in an amount in the ppm range.
  • the compounds of the invention may be used for polymerizing olefins, such as one kind of vinyl monomer or a mixture of two or more different kinds of vinyl monomers.
  • the inventive compound may thus be used for atom transfer radical polymerization (ATRP) of at least one kind of vinyl monomer.
  • ATRP atom transfer radical polymerization
  • the polymerization is carried out using the polymerization composition.
  • the vinyl monomer(s) which may be polymerized in the present invention may be selected from the group of vinyl monomers generally used in the field of polymerizations.
  • the vinyl monomer may be a ⁇ , ⁇ - unsaturated olefin.
  • the vinyl monomer may be, but is not limited to, ethylene, propylene, styrene, C 4 -C 10 olefins, such as 1-butene, isobutene, 1-pentene, 1-hexene, 4- methyl- l ⁇ pentene, 1 -heptene, 1-octene, 1-nonene, 1-decene, as well as diene, such as butadiene, 1,7-octadiene and 1,4-hexadiene, or cyclic olefins, such as norbornene, acrylate, acrylic acid, methacrylate, methacrylic acid, and the like and mixtures of any of such vinyl monomers.
  • ethylene propylene
  • styrene C 4 -C 10 olefins
  • C 4 -C 10 olefins such as 1-butene, isobutene, 1-pentene, 1-hexene, 4- methyl-
  • the vinyl monomer may be styrene, acrylate, acrylic acid, methacrylic acid or one of its derivatives, vinyl sulphonic acid or one of its derivatives or vinyl phosphonic acid or one of its derivatives, acrylonitrile, vinyl pyridine, isobutene, maleimide, isoprene, vinylidene chloride, or any mixture of these monomers.
  • acrylate refers to a group of formula R a -OC(0)C(CH 2 )(H).
  • R a may be Ci-C 20 alkyl, C 2 -Cj 2 ether, vinyl group or allyl group.
  • acrylates include, but are not limited to, acrylate, propargyl acrylate, n-butyl acrylate (nBA), n- isopropyl acrylamide (NIPAAm), allyl acrylate, 2-allyloxyethyl acrylate, 2- propargyloxyethyl acrylate and 1 -hexenylacrylate.
  • methacrylate refers to a group of formula R b - OC(0)C(CH 2 )(CH 3 ).
  • R b may be C 1 -C 20 alkyl, C 2 -d 2 ether, vinyl group or allyl group.
  • methacrylates include, but are not limited to, di(propylene glycol) allyl ether methacrylate, propargyl methacrylate, 2-(methacryloyloxy)ethyl ester, allyl methacrylate, allyl acrylate, propargyl methacrylate and propargyl acrylate.
  • the at least one kind of vinyl monomer may comprise one or more functional groups.
  • any functional group may be attached to the at least one kind of vinyl monomer.
  • the final properties of the prepared polymer may be influenced in the desired manner.
  • the vinyl monomers used in the present invention may comprise a functional group such as, but not limited to, a carboxylic acid, a sulphonic acid, a phosphoric acid group or also combinations of such groups and the like.
  • both homopolymers and copolymers may be prepared.
  • Polymers that contain only a single type of vinyl monomers are known as homopolymers, while polymers containing a mixture of different vinyl monomers are known as copolymers.
  • every combination of different vinyl monomers mentioned above may be polymerized.
  • the compound and the composition of the present invention it is possible to control the polymerization reaction and to control the composition and the properties of the finally obtained polymer.
  • the polymerization may be controlled by varying the ratio between monomer and initiator.
  • control may also be ensured by the quantities of comonomers used and by the mode of addition, such as for example sequential addition of monomers or addition of all monomers at the beginning of the reaction process.
  • the polymers obtained using the inventive composition may have a molecular weight in the range of about 1.000 to about 1.000.000, such as about 1.000 to about 100.000, or about 1.000 to about 10.000.
  • the molecular weight of the polymers may be below about 10.000, such as below about 7.500 or below about 5.000 in case they are used as additives.
  • additives are those compounds/components which impart a particular property when used in combination with various other components.
  • additives may provide hydrophobic or hydrophilic propertiesor may influence viscosity or dispersing capabilities.
  • low molecular weight polymers or high molecular weight polymers may be used as additives.
  • the molecular weight of the polymers may be about 100.000 to about 900.000, such as about 100.000 to about 750.000 in case they were used as resins.
  • resin is a polymer which is used as structured material like some components of automotive or airplane parts, wind shields made up of polymers and the like.
  • the polymers obtained may comprise at least one polar carboxylic acid group wherein the weight percentage of residual metal is less than about 0.02%.
  • the residual metal may be present in an amount of less than about 500 ppm, such as less than about 250 ppm, less than about 100 ppm, less than about 50 ppm, less than about 10 ppm, less than about 1 ppm or even less than about 0.1 ppm.
  • ATRP polymerization using the compound and/or composition of the present invention may be carried out in solution phase using an organic solvent or may be conducted under a solvent-free reaction conditions.
  • the organic solvent may be, but is not limited to, aromatic or a mixture of aromatic and aliphatic hydrocarbons, such as substituted and unsubstituted benzenes, for example toluene and the xylenes, methanol, ethanol, acetone, anisol, diphenyl ether, ethyl acetate, DMF, ethylene carbonate, supercritical carbon-di-oxide and the like. It is also advantageous to carry out this process in water or preferably in surfactant solution so that the polymers are obtained as fine powders dispersed in water or as emulsions thereby enhancing their separation and making them closer to application.
  • PS is prepared, wherein n may be any number from 2 to 200.
  • Method 1 Preparation of PS in the presence of tertiary amine
  • PMMA was prepared in the same way as that of PS-MI in Example 2.
  • CuBr (0.0062g, 4.32x10 "5 mol), II (0.149g, 0.3 mmol), MMA (3.2 mL, 2.995g, 0.03 mol) and toluene (3 mL) were heated overnight (15h) at 100°C. Yield: 2.5g (79.52%).
  • PAA-MI was prepared in the same way as that of PS-MI in Example 2.
  • CuBr (0.005g, 3,48xl0 "5 mol), II (0.36g, 0.72 mmol), AA (5 mL, 5.255g, 0.0729 mol) and toluene (5 mL) were heated overnight (15h) at 110°C.
  • the reaction mixture turned to white solid during this period.
  • a small fraction was scrapped out of the flask and dissolved in CD3OD to determine monomer conversion.
  • the reaction flask containing the solid was then soaked in methanol (50 mL) for two days and then the swollen polymer was transferred to a beaker. The swollen polymer was allowed to dry under ambient conditions.
  • M n (NMR) 6912. Conversion based on ⁇ -NMR analysis was 85.63 %.
  • Example 8 Preparation of copolymers of acrylic acid and styrene by stepwise addition of monomers (PAA-b/ra»-PS)
  • the solid mass in the reaction flask was dissolved in THF (30 mL) and precipitated in 20% HC1 (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 2.2g (70.64%).
  • the polymer composition based on ⁇ -NMR analysis was PAAo. 13 PS 0 , 87-The polymer composition was estimated by comparing the integral ratio of proton signal at 2.2- 2.4 ppm (CH unit of PAA) with the aromatic proton signals of PS unit appearing at 6.4-7.3 ppm.
  • Example 9 Preparation of copolymers of acrylic acid and n-butyl acrylate by stepwise addition of monomers (PAA-b/raw-PnBA)
  • nBA 2.5 mL, 2.235g, 0.017 mol
  • toluene (2 mL) were added via syringe into the reaction medium.
  • the reaction mixture was heated for an additional 18h under nitrogen atmosphere and cooled.
  • the solid mass in the reaction flask was dissolved in THF (50 mL) and precipitated in 20% HC1 (v/v).
  • the aqueous layer was decanted off and the residue was washed repeatedly with water and dried.
  • the dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 3g (56.08%)).
  • the polymer composition - based on ⁇ -NMR analysis was S 0 3 7 5 PAAo.3 7 5PnBAo. 2 5. The composition of this polymer was estimated as described above for other copolymers.
  • Example 1 1 Preparation of PAA containing terpolymers by mixed monomer approach - PS-rflK-PnBA-ran-PAA [0086] Compound II (0.035g, 7.02x 10 "5 mol), CuBr (0.005g, 3.48x 10 "5 mol), styrene (4 mL, 3.636g, 0.035 mol), nBA (4.9 mL, 4.3806g, 0.034 mol), AA (1.2 mL, 1.2612g, 0.0175 mol) and toluene (10 mL) were heated at 110°C for 22h after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. The reaction mixture became highly viscous during this period.
  • Example 15 Crossliriked poly(acrylic acid) using diethylene glycol dimethacrylate (DEGDMA) as crosslinker
  • the swollen solid was washed repeatedly with methanol and dried. Yield: 2.02g (91.25%).
  • the acid showed a swelling ratio of 110 in 0.9 wt% NaCl solution.
  • the sodium salt of the cross- linked polymer showed a swelling ratio of 1031 in 0.9 wt% NaCl solution.
  • the polymer also swells in sodium hydroxide solution.
  • Example 61 Dispersion ' of inorganic compounds
  • Table 1 provides comparison of the residual metal salts in the polymer by normal reported ATRP process with the ATRP carried out using UMLIDFS.
  • FIG. 4 shows the homopolymers formed using the UMLIDFS are not colored, unlike products obtained from typical ATRP processes, indicating the low concentration of metal impurities present in the polymers formed.
  • the copolymers of acrylic acid (AA) as well as methacrylic acid (MAA) were prepared and the appearance of the copolymers is illustrated in FIGs. 5-7- Samples shown in FIG. 7 are as prepared and collected from the reaction flask at the end of polymerization.
  • Aqueous solutions of polymers were prepared by dissolving lOOmg of polymer in 5 mL of alkali solution, prepared by dissolving 0.08g of NaOH (one pellet) in 5 mL of water IV. These prepared solutions are illustrated in FIG. 8.
  • Example 63 Composition and other characteristics of specific copolymers
  • Table 2 shows the characteristics of copolymers of carboxylic acid bearing vinyl monomers like AA and MAA. Many vinyl monomers could be employed as comonomers to make a variety of copolymers including terpolymers. All of these acid containing copolymers are soluble in weakly basic solutions to yield aqueous solutions without any aid of volatile or non-volatile organic solvents. It is possible to obtain thin films from these aqueous solutions. It is also possible to make carboxylic acid containing cross-linked polymers. The cross-linked poly(acrylic acid) upon neutralization shows swelling tendency in 0.9 wt% NaCl solution, a prerequisite for superabsorbent polymer. These results may be viewed by keeping in mind that it is not possible to directly polymerize vinyl monomers bearing labile protons under ATRP conditions at present.
  • the film shown in FIG. 10 was obtained by casting the 2 wt% aqueous alkali solution on a plate glass and allowing the water to evaporate under ambient conditions.

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Abstract

La présente invention a pour objet la polymérisation de monomères vinyliques par polymérisation radicalaire par transfert d'atomes (ATRP) au moyen de sels métalliques dans des quantités molaires mesurées en ppm. Elle concerne la polymérisation dans des conditions d'ATRP au moyen de systèmes bifonctionnels ligand - initiateur unimoléculaires (UMLIDFS) dans lesquels l'initiateur et le ligand pour la complexation du métal font partie de la même molécule.
PCT/SG2010/000362 2009-09-29 2010-09-27 Systèmes bifonctionnels ligand - initiateur unimoléculaires (umlidfs) et leur utilisation WO2011040881A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052944A1 (fr) * 2002-12-11 2004-06-24 3M Innovative Properties Company Amorceurs azlactone a cycle ouvert pour la polymerisation radicalaire par transfert d'atomes
WO2006003352A1 (fr) * 2004-07-06 2006-01-12 Warwick Effect Polymers Limited Initiateur de polymerisation de radicaux vivants comprenant un groupe fonctionnel capable de reagir avec des polypeptides ou analogues, polymere en peigne obtenu avec cet initiateur, conjugues polypeptidiques et medicaments obtenus a base de cet initiateur
US20070129239A1 (en) * 2005-11-14 2007-06-07 Maciej Radosz Highly active catalyst for atom transfer radical polymerization
WO2009122220A1 (fr) * 2008-04-04 2009-10-08 Ulive Enterprises Ltd Hybrides polymère-dendrimère

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052944A1 (fr) * 2002-12-11 2004-06-24 3M Innovative Properties Company Amorceurs azlactone a cycle ouvert pour la polymerisation radicalaire par transfert d'atomes
WO2006003352A1 (fr) * 2004-07-06 2006-01-12 Warwick Effect Polymers Limited Initiateur de polymerisation de radicaux vivants comprenant un groupe fonctionnel capable de reagir avec des polypeptides ou analogues, polymere en peigne obtenu avec cet initiateur, conjugues polypeptidiques et medicaments obtenus a base de cet initiateur
US20070129239A1 (en) * 2005-11-14 2007-06-07 Maciej Radosz Highly active catalyst for atom transfer radical polymerization
WO2009122220A1 (fr) * 2008-04-04 2009-10-08 Ulive Enterprises Ltd Hybrides polymère-dendrimère

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE CAS 18 October 2007 (2007-10-18), accession no. STN Database accession no. 950906-45-3 *
HUANG ET AL.: "Polypeptide Diblock Copolymer: Syntheses and Properties of Poly(N-isopropyllacrylamide)-b-Polylysine", MACROMOLECULES, vol. 41, 2008, pages 7041 - 7052 *
LEE ET AL.: "Synthesis of Complementary Host and Guest Functionalized polymeric Building block and Their Self Assembling Behavior", MACROMOLECULES, vol. 42, no. 17, 2009, pages 6483 - 6494 *
LOOS ET AL.: "Construction of functional porphyrin polystyrene nano-architectures by ATRP", CHEM. COMMUN., 2005, pages 60 - 62, Retrieved from the Internet <URL:http://pubs.rsc.org.> [retrieved on 20041201] *
NIEHOFF ET AL.: "One-Pot Procedure for the Preparation of Rod-Coil Block Copolymers via a Bifunctional Initiator", MACROMOL. SYMP, vol. 275-276, no. 1, - 2009, pages 82 - 89, Retrieved from the Internet <URL:10.1002/masy.200950110> *

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