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WO2010057654A1 - Compositions comprenant des copolymères de glycidyléther - Google Patents

Compositions comprenant des copolymères de glycidyléther Download PDF

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Publication number
WO2010057654A1
WO2010057654A1 PCT/EP2009/008281 EP2009008281W WO2010057654A1 WO 2010057654 A1 WO2010057654 A1 WO 2010057654A1 EP 2009008281 W EP2009008281 W EP 2009008281W WO 2010057654 A1 WO2010057654 A1 WO 2010057654A1
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Prior art keywords
radical
composition according
glycidyl ether
block
structural unit
Prior art date
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Ceased
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PCT/EP2009/008281
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German (de)
English (en)
Inventor
Bernd Göbelt
Jürgen OMEIS
Guillaume Jaunky
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BYK Chemie GmbH
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BYK Chemie GmbH
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Priority to JP2011536787A priority Critical patent/JP6063124B2/ja
Priority to CN200980155062.7A priority patent/CN102292377B/zh
Priority to EP09760107.4A priority patent/EP2367865B1/fr
Priority to ES09760107T priority patent/ES2419660T3/es
Priority to KR1020117014558A priority patent/KR101660355B1/ko
Publication of WO2010057654A1 publication Critical patent/WO2010057654A1/fr
Priority to US13/113,525 priority patent/US8367762B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols

Definitions

  • compositions comprising glycidyl ether copolymers
  • the present invention relates to a composition
  • a composition comprising at least one amphiphilic glycidyl ether copolymer constructed from the structural units I to V listed in the present application, wherein the structural units can be arranged in a gradient, random or blocky manner as described in the present application, as a dispersing agent and a dispersed Solid, preferably a dispersed pigment, or as an emulsifier and a cured, unsaturated polymer system in the form of a water-in-oil emulsion.
  • aqueous or organic solvents containing dispersions or polymer molding compositions to distribute stable and homogeneous, dispersants are required as auxiliaries.
  • dispersants must fulfill two different functions.
  • hydrophilic adhesive groups are tertiary amino groups, ammonium salts, phosphoric acid groups, carboxylic acid groups, sulfonic acid, amide, urethane or urea groups.
  • hydrophobic groups such as alkyl radicals, phenyl or benzyl radicals, as described for. In Adv. Mater. 1998, 10, 1215-1218.
  • dispersants must be well-tolerated with the dispersing medium.
  • hydrophobic radicals such. B. have longer chain alkyl radicals or aryl radicals.
  • the dispersants should contain water-soluble, hydrophilic radicals, such as e.g. B. have salified carboxylic acids.
  • dispersants show very good solids-wetting properties, but in comparison to dispersants with a gradient-like or blocky structure, a poorer stabilization of the solid dispersion.
  • block-like structure of dispersants having very good stabilizing properties can lead to micelle formation of the polymer chains in strongly differently polar blocks, which leads to a poorer wetting behavior of the solid surface of the solid to be dispersed.
  • a large group of dispersants is based on polymers of ethylenically unsaturated monomers such.
  • acrylates or methacrylates wherein the polymers used can have both a statistical, gradient-like or block-like structure. If polymers or copolymers have a statistical structure, they are prepared by free radical polymerization using conventional starters. If they have a gradient-like or block-like structure, they are controlled by a controlled polymerization such. Atom transfer radical polymerization (ATRP), group transfer polymerization (GTP), nitroxyl mediated polymerization (NMP) or reversible addition fragmentation chain transfer process (RAFT).
  • ATRP Atom transfer radical polymerization
  • GTP group transfer polymerization
  • NMP nitroxyl mediated polymerization
  • RAFT reversible addition fragmentation chain transfer process
  • dispersants are based on polyalkylene oxides (US 2002/0011183, US2005 / 0085563, US 6,552,091, WO2007087961). By polymerization of ethylene oxide, these dispersants show a hydrophilic character, while by copolymerization of propylene, butylene or styrene oxide hydrophobic groups can be incorporated into the dispersant-based polymers. Since there is only a small selection of commercially available alkylene oxides and only terminal OH groups are suitable as functional groups for modifications in these polymers, there is only a limited possibility for modifying the polymers and thus for their use as dispersants.
  • compositions according to the invention comprising at least one amphiphilic glycidyl ether copolymer composed of the following structural unit I and at least one of the following structural units H-V, wherein the structural unit IV always together with at least one of the structural units II, III and V is arranged
  • R 1 is a linear or branched alkyl radical having preferably 1-20 C atoms or a cyclic alkyl radical having preferably 4-10 C atoms, or is an aryl radical, an arylalkylene radical, a heteroaryl radical or heteroarylalkylene radical in which in each case the Aryl or heteroaryl ring may be substituted;
  • R 2 represents hydrogen and / or a carboxymethylene group or a corresponding salt or a corresponding alkyl ester group, a monoester residue of maleic acid or a corresponding mono salt, a phosphoric acid residue or a corresponding salt, a sulfonic acid residue or a corresponding salt or a sulphosuccinic acid radical or a corresponding salt or up to at most 20% of the radicals
  • R 2 are an OH protecting group, preferably an acetal group or a t-butyl group
  • R 3 is hydrogen and / or a linear or branched alkyl radical having 1 to 6 C atoms and / or a cyclic alkyl radical having 4-6 C atoms;
  • R 4 is a linear, branched or cyclic alkyl radical which may be substituted by at least one aryl radical or arylalkylene radical, a substituted or unsubstituted aryl radical or arylalkylene radical or a polyalkylene oxide radical which preferably contains at least 2, more preferably 2 to 20 repeating units having an alkoxy group preferably has 1-5 C atoms;
  • R 5 identical or different from R 2 , has the meaning of R 2, with the exception of an OH protecting group,
  • structural units are arranged gradient-like, random or block-like, and
  • the structural unit I is at least 2-fold, preferably 2 to 100, more preferably 2 to 50 times, of which at least one of the structural units I carries an aromatic radical, and wherein the proportion of optionally present structural units IV 0 to at most 50% of the total of the structural units II to V is
  • dispersing agent as dispersing agent and at least one dispersed solid, preferably at least one dispersed pigment,
  • polyglycidyl ether block copolymers are already known from the prior art, they are by no means used as dispersants as in the compositions according to the invention.
  • US Pat. No. 4,485,211 describes polyglycidyl ether block copolymers by means of cationic ring-opening polymerization and optionally modification into quaternary ammonium salts. These block copolymers are gem. Disclosure in this US patent specification preferably as a difunctional chain extender for the preparation of linear, relatively high molecular weight polymers. Its use as a viscosity-increasing agent, as a dispersing additive for polymerizations or as a mineral release agent is also mentioned there.
  • EP-A-0406168 describes a product in which a phenylglycidyl ether unit is attached as end group to a polyalkylene oxide. Such products, which may have been still modified and possibly used in combination with other anionic or nonionic additives, may u. a. used as a dyeing aid.
  • aqueous composition of a glycidyl block copolymer of 5-phenylglycidyl ether units and 67 ethylene oxide units and a pharmaceutical agent such as griseofulvin is therefore excluded from the present invention, as is an aqueous composition of a glycidyl block copolymer consisting of 2 blocks of either 71 or 62 or 38 ethylene oxide units and an intervening block of 7, 8 or 12 phenylglycidyl ether units and a sparingly soluble pharmaceutical agent such as griseofulvin.
  • the glycidyl ether copolymers which are present in the compositions according to the invention as a dispersant or emulsifier are random or gradient-like or block-like, preferably gradient-like or block-like, particularly preferably block-like.
  • the glycidyl ether copolymers used according to the invention have the repeating structural unit I, wherein the glycidyl ether copolymer preferably has at least one block of this repeating structural unit and at least one of the repeating structural unit I contains an aryl radical radical.
  • the glycidyl ether copolymer has the repeating structural unit I and the repeating structural unit II, wherein particularly preferably the glycidyl ether copolymer has at least one block of the repeating structural unit I and at least one block of the repeating structural unit II or at least one block from the repeating structural unit I and at least one block of copolymerized structural units I and II.
  • the glycidyl ether copolymer used according to the invention can also be composed of recurring structural units I and repeating structural units III, preferably of at least one block of repeating structural unit I and at least one repeating structural unit III block or at least one block of interpolymerized structural units I and III be.
  • Glycidyl ether copolymers of the recurring structural units I to III can also be present in the compositions according to the invention.
  • the glycidyl ether copolymers preferably have at least one block of the repeating structural unit I and at least one block of the copolymerized repeating structural units II and III or in each case at least one block of the repeating structural unit II or the repeating structural unit IM.
  • Branched glycidyl ether copolymers contain, in addition to the repeating structural units I, at least one optionally recurring structural unit IV which is copolymerized at least with a repeating structural unit II and / or III and / or V, the recurring structural units being arranged gradient-like or random, particularly preferably random could be. If the structural unit IV is present in the glycidyl ether copolymer, its proportion is at most 50%, preferably at most 30%, very particularly preferably at most 20% of the total number of structural units II to V.
  • the glycidyl ether copolymers used according to the invention have the preferably hydrophobic structural unit I, preferably 2 to 100, more preferably 2 to 50, most preferably 2 to 20 times, of which at least one of the structural units I carries an aromatic radical.
  • Particularly preferred glycidyl ether copolymers are those in which the number of structural units II to V at least equal to the number of structural unit I, preferably the number of structural units II to V is at least 20%, more preferably at least 50% higher than the number of Structural units I.
  • the structural unit I is preferably derived from a glycidyl ether of the general formula (X)
  • R 1 is a linear or branched alkyl radical, preferably having C 1 to C 20, particularly preferably a methyl, ethyl, propyl, butyl, 2-ethylhexyl radical, or a cyclic alkyl radical having preferably 4 to 12 C atoms, particularly preferably a cyclohexyl radical, for an aryl radical having 6 to 10 C atoms, with a short-chain alkyl radical, preferably a methyl, ethyl and / or propyl radical or a halogen atom, preferably chlorine , may be substituted, particularly preferably a phenyl radical or naphthyl radical, or an aryl-alkylene radical having preferably 7 to 10 C atoms, where the aryl radical is substituted by short-chain alkyl radicals, preferably with a methyl, ethyl and / or propyl radical may be, more preferably for a benzyl radical,
  • the structural unit II is derived from a glycidyl ether of the general formula (Y)
  • R 2 is a protective group for the OH group, preferably a t-butyl and / or ethoxy-ethyl radical.
  • the OH groups protected by the radicals R 2 can be partially or completely converted to the above-mentioned functional groups.
  • the structural unit IM is preferably derived from an alkylene oxide, more preferably from a linear, branched or cyclic alkylene oxide having 2 to 10 C atoms, very particularly preferably from ethylene oxide, 1, 2-propylene oxide and / or 1, 2-butylene oxide.
  • the structural unit IV which is present in branched glycidyl ether copolymers, is preferably derived from oxirane compounds of the general formula (Z)
  • R 6 is hydrogen or an alkyl group having 1 to 4 C atoms, preferably methyl, and
  • R 7 is a C 1 to C 6 alkylene radical having at least one hydroxyl group, preferably a terminal hydroxyl group.
  • the structural unit V is derived from Gylcidol. It may be partially or fully modified by further reaction of the -OH functional group as outlined below.
  • R 2 is H in the structural unit, it may also be derived from gylcidol and may be partially or fully modified by further reaction of the -OH group as set forth below.
  • the end group OR 4 are derived from the starter compounds for the glycidyl copolymers used according to the invention, where R 4 is a linear, branched or cyclic alkyl radical having C 1 to C 10, preferably a C 1 to C 5 radical containing at least one, preferably terminal Aryl radical, particularly preferably with a phenyl radical or a preferably terminal arylalkylene radical, particularly preferably with a benzyl radical which may be substituted, or a Alkoxypolyalkyenoxidrest, preferably from at least 2, preferably from 2 to 20, more preferably from 2 to 12 repeating units of an alkylene - Oxids, preferably an ethylene oxide and / or propylene oxide.
  • R 4 is a linear, branched or cyclic alkyl radical having C 1 to C 10, preferably a C 1 to C 5 radical containing at least one, preferably terminal Aryl radical, particularly preferably with a phenyl radical or a preferably terminal arylalky
  • the end group R 5 has the meaning of R 2 , except for an OH-protecting group, and may represent H, a carboxymethylene group or a corresponding C 1 to C 6 alkylester group, a monoester radical of maleic acid or succinic acid or a corresponding monosalt, a phosphoric acid residue or a corresponding salt, a sulfonic acid residue or a corresponding salt, a sulfosuccinic acid residue or a corresponding salt.
  • the glycidyl ether copolymers used according to the invention preferably have no ester groupings with the exception of the maleic acid monoester residues which may be present.
  • the glycidyl ether block copolymers used according to the invention are preferably obtained by polymerization with ring opening, very particularly preferably by anionic polymerization with ring opening.
  • the anionic polymerization is carried out by customary methods known to the person skilled in the art. Suitable process parameters, catalysts and reaction media are u. a. in the following publication and in the citations listed there:
  • Nonionic Surfactants Organic Chemistry, Surfactant Science Series Volume 72 (Edited by Nico M. Van Os).
  • a glycidyl ether, an alkylene oxide or an oxirane compound can be used to prepare the respective structural unit or its mixture.
  • the starter molecule may first be polymerized with a starting compound which leads to hydrophilic structural units, preferably a corresponding glycidyl ether, or with a glycidyl ether, preferably an aryl glycidyl ether, which leads to a hydrophobic structural unit.
  • a starting compound which leads to hydrophilic structural units
  • a glycidyl ether preferably an aryl glycidyl ether
  • the glycidyl ether copolymers thus obtained may have at least one hydrophilic and at least one hydrophobic block or a further alternating block arrangement between hydrophobic and hydrophilic blocks.
  • the polymerization is carried out so that the hydroxy groups of the starting compound are partially deprotonated by alkali metal hydroxides or alkoxides of from 0.1% to 80%, preferably from 2% to 20%. After removal of the water or alcohol by distillation, a mixture of starter and starter alcoholate is obtained.
  • the polymerization is carried out with ring opening in the presence of a catalyst without addition of a solvent.
  • the polymerization can, however, also be carried out with the concomitant use of an inert solvent under the alkoxylation conditions.
  • To the mixture are preferably added gradually to be polymerized G lycidylether and polymerized at a temperature between 40 0 C and 120 0 C, preferably 50 0 C and 100 ° C, particularly preferably 60 0 C and 90 ° C.
  • Living, anionic, ring opening polymerization is controlled by the rapid exchange of protons between the alcohol and alkoxide groups of the growing chains.
  • it is neutralized with acid and the resulting products are filtered off. This can also be achieved with the help of acidic ion exchangers.
  • Branched structures can be obtained by polymerization of glycidol or copolymerization of glycidol with the abovementioned glycidyl ethers and / or the alkylene oxides mentioned. Further details on reactions, reactants and procedures can be found in the following publications: Macromolecules 1999, 32, 4240-4246 or US 2003/0120022. The relevant disclosures in the publication are hereby incorporated by reference and are considered part of the disclosure of the present application.
  • branched structural units are also to be polymerized in the case of anionic polymerization with ring opening, it is preferable to begin the anionic polymerization with the aid of a hydroxyl terminated starter molecule, preferably by polymerizing hydrophobic glyidyl ethers to form a corresponding hydrophobic block.
  • the glycidyl ether copolymers used according to the invention preferably have from 1 to 50%, especially from 1 to 30% and very particularly preferably from 1 to 10%, based on the hydrophobic structural units, of branched structural units IV.
  • the polymerization of the alkylene oxides can be carried out by known processes.
  • References to and descriptions of suitable reaction conditions for customary methods known to the person skilled in the art and suitable apparatuses for working under pressure can be found, for example, in Huaweius Schonfeldt, Grenz inhabitassitule ⁇ thylenoxid adducts, psychologistliche Verlagsgesellschaft mbH, Stuttgart 1984 and in the citations cited therein.
  • the glycidyl ether copolymers used in accordance with the invention are preferably post-treated after the polymerization with ring opening in order, for example, to undergo ring-opening.
  • ring opening for example, to cleave the ether moiety of the preferably hydrophilic glycidyl ether derived structural units and to obtain functional hydroxyl groups for further reactions.
  • Corresponding protective groups which remain stable during the anionic polymerization with ring opening are, for example, ethoxyethyl groups of ethoxyethyl glycidyl ether. This also applies to the t-butyl groups of t-butyl glycidyl ether, which can be used for the preparation of hydrophilic structural units II.
  • the structural units II very particularly preferably have the easily removable acetal groups as protective groups, provided that an ethoxyethyl glycidyl ether is used as the starting compound.
  • the glycidyl ether used may also have an allyl group, so that an allyl glycidyl ether can be used to prepare the structural units II. From the prior art (macromolecule 2007, 40, 3070-3079), the removal of protective groups, in particular the necessary reaction condition and reactants can be found.
  • a copolymer preferably a block copolymer, is obtained which, in addition to the structural units I, has structural units with free hydroxyl groups as intermediate.
  • This intermediate can be further functionalized via the free hydroxyl groups in order, for. B. introduce anionic groups.
  • a phosphorylation of the hydroxyl groups take place, just as the introduction of sulfonic acid groups can take place with the aid of concentrated sulfuric acid, oleum, sulfur trioxide or chlorosulfonic acid.
  • a sulfosuccinic acid residue can be introduced via the reaction with the free hydroxyl groups of the glycidyl copolymer.
  • the introduction of a carboxymethylene group can be carried out with the aid of sodium hydride and sodium chloroacetate.
  • Suitable salts are ammonium salts, prepared by reaction with ammonium or a suitable organic amine, tertiary amines, preferably triethylamine, alkanolamines, such as. For example, triethanolamine, ammonium hydroxide or tetraalkylammonium hydroxide.
  • suitable for the reaction with the acid groups alkali metal hydroxides such. As lithium hydroxide, sodium hydroxide, potassium hydroxide or corresponding carbonates such. As potassium carbonate or dicarbonates such as potassium dicarbonate.
  • compositions of the invention comprise the above-defined copolymers, preferably modified copolymers, as dispersants for solids, preferably for pigments, with the exception of silver halides.
  • These compositions are aqueous or solvent-containing dispersed solids systems, preferably dispersed pigments.
  • compositions according to the invention are suitable for numerous applications.
  • pigment dispersions are preferably required which give stable dispersions in different liquid media such as in organic solvents or in water and accordingly also in aqueous media or in solvent-containing media can be incorporated for further formulation.
  • So z As required by a color resist during its processing that it is readily soluble in an organic solvent such as methoxypropyl acetate and dissolves quickly in an alkaline aqueous solution which may contain surfactants.
  • the corresponding composition according to the invention has a direct influence on the properties of the end product.
  • compositions of the invention meet these and other requirements, so that they can be used for a variety of applications easily and with improved properties.
  • the compositions z. B. in the production or processing of paints, printing inks, paper coating, leather and textile dyes, pastes, pigment concentrates, ceramics or cosmetic preparations are used, if they contain as solids pigments and / or fillers.
  • compositions according to the invention which comprise dispersed pigments, fillers and, if appropriate, other additives can be used in casting compounds, PVC plastisols, gelcoats, polymer concrete, printed circuit boards, industrial coatings, wood and furniture coatings, vehicle finishes, marine paints, anticorrosive paints, can and coil coatings. Coatings, paints and architectural paints may be spread very well after addition of binder.
  • binders are resins based on polyurethanes, cellulose nitrate, cellulose acetobutyrate, alkyd, melamine, polyester, chlorinated rubber, epoxy and acrylate.
  • water-based coatings examples include cathodic or anodic electrodeposition coatings, for example for automobile bodies. Further examples are plasters, silicate paints, emulsion paints, water-based paints based on water-dilutable alkyds, alkyd emulsions, hybrid systems, 2-component systems, polyurethane and acrylate dispersions.
  • compositions of the invention are also particularly suitable as a basis for solid concentrates, such as pigment concentrates.
  • the copolymers described above are initially charged in a dispersing medium, such as organic solvents, plasticizers and / or water, and the solids to be dispersed, preferably pigments, are added with stirring.
  • a dispersing medium such as organic solvents, plasticizers and / or water
  • binders and / or other adjuvants may be added to these compositions.
  • binder-free compositions already ensure stable pigment concentrates. It is likewise possible to use the compositions according to the invention as flowable solid concentrates.
  • pigment presscakes which may still contain organic solvents, plasticizers and / or water, are mixed with the glycidyl ether copolymer and the mixture thus obtained is dispersed.
  • the erfindungeadoren solid concentrates prepared in various ways can then be divided into different substrates such. For example, alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins may be incorporated.
  • pigments can also be dispersed directly in water or solvent-free manner with the glycidyl ether copolymers. These compositions of the invention are then particularly suitable for the pigmentation of thermoplastic and thermoset plastic formulations.
  • compositions according to the invention can also be advantageously used in the production of inks for "non-impacf printing processes such as” thermal inkjet “and the” Bubblejet process ".
  • These inks may be, for example, aqueous ink formulations, solvent-based ink formulations, solvent-free or low-viscosity inks for UV applications, as well as waxy inks.
  • compositions of the present invention may also be used in the manufacture of color filters for liquid crystal displays, screens, color resolvers, sensors, plasma screens, surface-conduction electron emitter display (SED) and multi-layer ceramic compound (MLCC) displays.
  • the liquid color filter varnish which is also called color resist can be applied by a variety of application methods such as spin coating, knife coating, combination of both or "non-impacf printing method such as inkjet method.
  • MLCC technology is used in the manufacture of microchips and printed circuit boards.
  • compositions of the invention can also be used in cosmetic preparations such as make-up, powders, lipsticks, hair dyes, creams, nail polishes and sunscreen preparations. These may be in the usual forms.
  • cosmetic preparations such as make-up, powders, lipsticks, hair dyes, creams, nail polishes and sunscreen preparations. These may be in the usual forms.
  • the preparations according to the invention containing the copolymers defined above as dispersants for pigments such as titanium dioxide or iron oxide can be incorporated into the carrier media customary in cosmetics, for example in water, castor oils or in silicone oils.
  • Another object of the present invention is therefore also the use of a glycidyl ether copolymer as a dispersant for solids, preferably for pigments, or as a phase mediator.
  • These pigment dispersions according to the invention comprising compositions according to the invention can be used to produce a pigmented coating on a substrate, the pigmented paint being applied to the substrate and baked thereon or cured or crosslinked.
  • a further subject of the present invention are therefore coating compositions comprising the compositions according to the invention or coatings produced therefrom.
  • Pigment pastes according to the invention based on the pigment dispersions according to the invention can also be prepared based thereon.
  • compositions according to the invention can be used alone or together with conventional binders.
  • it may, for. B. be advantageous to add appropriate low molecular weight polyolefins as support materials to the compositions of the invention.
  • a composition according to the invention also relates to powdered particle and / or fibrous particulate solids, especially pigments or plastic fillers coated with the glycidyl ether copolymers.
  • This coating of organic or inorganic solids can be carried out in a known manner, as z. As described in EP-AO 270 126.
  • the dispersing medium may either be removed or left to form pastes.
  • this coating of the pigment surface may take place during or after the synthesis of the pigments, e.g. By addition of the glycidyl ether copolymers to the pigment suspension or during or after the pigment finish.
  • compositions according to the invention obtained in this way are suitable as pretreated pigments very well for incorporation and are characterized by an improved viscosity, flocculation and gloss behavior and by higher color strength over untreated pigments.
  • pigments are mono-, di-, tri- and polyazo-pigments, oxazine, dioxazine, thiazine pigments, diketo-pyrrolo-pyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane, triarylmethane, xanthan , Acridine, quinacridone, methine pigments, anthraquinone, pyranthrone, perylene and other polycyclic carbonyl pigments.
  • organic pigments can be found in the monograph: W. Herbst, K.
  • inorganic pigments are pigments on Base of carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithophones, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, cobalt zincate, antimony oxide, antimony sulfide, chromium oxide, zinc chromate, mixed metal oxides based on nickel, bismuth, vanadium , Molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (for example nickel titanium yellow, bismuth vanadate molybdate yellow or chromium titanium yellow), preferably with the exception of silver halides.
  • Inorganic pigments may also be magnetic pigments based on pure iron, iron oxides and chromium oxides or mixed oxides, metallic effect pigments of aluminum, zinc, copper or brass as well as pearlescent pigments, fluorescent and phosphorescent luminescent pigments.
  • nanoscale organic or inorganic solids with particle sizes below 100 nm, such as certain carbon black types or particles which consist of a metal or semimetal oxide or hydroxide, as well as particles which consist of mixed metal and / or semimetal oxides or consist of hydroxides.
  • the oxides and / or oxide hydroxides of aluminum, silicon, zinc, titanium, etc. may be used to produce such extremely fine particulate solids.
  • the production process of these oxidic or hydroxidic or oxidic hydroxide particles can be carried out by a wide variety of processes, such as, for example, ion exchange processes, plasma processes, sol-gel processes, precipitation, comminution (for example by grinding) or flame hydrolysis.
  • These nanoscale solids may also be so-called hybrid particles, which consist of an inorganic core and an organic shell - or vice versa.
  • pulverulent or fibrous fillers are, for example, those which are composed of pulverulent or fibrous particles of aluminum oxide, aluminum hydroxide, silicon dioxide, diatomaceous earth, silica, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, slate powder, calcium sulfate, Barium sulfate, calcium carbonate, calcite, dolomite, glass or carbon.
  • pigments or fillers can be found, for example, in EP-A-0 270 126.
  • flame retardants such.
  • aluminum or magnesium hydroxide and matting agents such.
  • As silicas can also be dispersed and stabilized excellent.
  • paints, pastes and molding compositions comprising the preparations according to the invention comprising glycidyl ether copolymers and one or more dispersed pigments, organic solvents and / or water, and optionally binders and conventional auxiliaries.
  • glycidyl ether copolymer based on the solids content, preferably the pigment content used.
  • compositions according to the invention as water-in-oil emulsions may contain the glycidyl ether copolymers described above, preferably glycidyl ether block copolymers as emulsifier. Since emulsions are usually unstable systems which do not form spontaneously, but rather a distribution of the phases are obtained by shaking, stirring, homogenization or spraying processes, in order to stabilize these unstable structures, emulsifiers are usually used. Despite the use of emulsifiers, conventional emulsifiers still present the danger that separation of the phases takes place in that the dispersed water droplets separate into a coherent phase from the oil phase. Such water in oil emulsions, which are difficult to stabilize, include so-called water-extended polyester resins, in which water droplets are emulsified in the polyester phase.
  • This continuous phase includes unsaturated polyesters and ⁇ , ⁇ unsaturated monomers such as styrene.
  • the emulsion or the unsaturated polyester is cured by means of radical initiators and transition metal catalysts with the aid of the ⁇ , ß unsaturated monomer.
  • the water-extended polyester emulsions are stable even with the addition of various bases only for a few hours, as z.
  • the emulsions according to the invention preferably have 0.10, preferably 0.25, very particularly preferably 0.5 to 10, particularly preferably up to 5 and very particularly preferably up to 2% by weight of the glycidyl ether copolymer, based on the total weight of the emulsion , on.
  • the glycidyl ether copolymers according to the invention can be used as emulsifiers together with water and a mixture of unsaturated polyester resins and styrene to keep a water-in-oil emulsion stable for months.
  • a glycidyl ether (block) copolymer is incorporated into the polyester formulation together with water without difficulty, using a styrene-containing, water-extended polyester with a glycidyl ether (block) copolymer as emulsifier as a water-in-oil emulsion is obtained.
  • a corresponding composition in the form of a water-in-oil emulsion is a further subject of the present invention.
  • the chromatography was at 40 0 C using a Hochdruck glacikeitschromatographiepumpe (Bishoff HPLC 2200) with a refractive index detector (Waters 410) is performed.
  • the eluent was tetrahydrofuran at a flow rate of 1 mm / min.
  • a conventional calibration was achieved.
  • the NMR measurements were carried out on a Bruker DPX 300 at 300 MHz ( 1 H) and 75 MHz ( 13 C), respectively.
  • a solvent deuterated chloroform (CDCb) and deuterated dimethylsulfoxide (DMSO-o * 6 ) were used.
  • the glycidyl ether block copolymers shown in the following structural formula list were synthesized.
  • the block copolymers of Examples 1 to 3 were prepared in 3 process steps, which are described below.
  • the block copolymer obtained after the 1st step is dissolved in technical grade THF and treated with concentrated hydrochloric acid solution (37% by weight). After 20 minutes, anhydrous K 2 CO 3 is added and stirred for a further 5 min. Thereafter, the solid constituents are filtered off and the solution is evaporated in vacuo. The oily residue is dried by means of an oil vacuum pump at 45 0 C overnight to a dark oil.
  • Table 2 the quantities of the starting compounds for the treatment of the block copolymers are obtained according to indicated in the first step and listed in the treatment yields and molecular weights and the molecular weight distribution (polydispersity).
  • the block copolymer obtained in the third process step was carboxymethylated after the second process step and then the salts were salified.
  • the reaction was carried out in a dry 500 ml flask in which a sodium hydride (NaH) suspension (60% in mineral oil) was charged and washed with pentane under a nitrogen atmosphere.
  • a solution of the block copolymer respectively obtained in N, N-dimethylformamide (DMF) in the 2nd process step was added slowly (during 30 to 35 minutes) to this dispersion with stirring and stirring was continued at room temperature for 2 ⁇ A hours.
  • sodium chloroacetate (NaOAcCl) was added.
  • the reaction mixture was stirred at 60 ° C. for 24 hours.
  • the residue of NaH was neutralized by the addition of solid ammonium chloride.
  • the solvent was removed under reduced pressure and the residue was dissolved in water.
  • the polymer was precipitated with the addition of aqueous HCl solution (5% by weight) and washed with water. After washing, 30 ml of water was added and the pH was adjusted to a value of 7 to 8 with the aid of an aqueous sodium hydroxide solution (12 mol / l). The solution was then concentrated by evaporation to a volume of 60 ml. From this solution, polymers were taken to determine the concentration of the polymer. Table 3 below shows the amounts of the starting compounds for the third process step and the concentration of the sodium chloroacetate groups introduced thereby. Table 3
  • block copolymers shown below were gem. the above-described 1 to 3 process steps produced with the exception of the use of other initiator compounds and the sequence of polymerization of the various monomers.
  • the corresponding structure of the block copolymers is as follows:
  • the dispersant was synthesized in a manner similar to EXAMPLE 10 except that benzyl glycidyl ether was used instead of phenyl glycidyl ether monomer.
  • the dispersant (not according to the invention) was synthesized according to the preparation procedure given for EXAMPLE 10, except that styrene oxide was used instead of phenylglycidyl ether monomer.
  • Table 4 shows the number average molecular weight or polydispersity of the block copolymer n according to Examples 10 and 11 and Comparative Example 12, respectively, according to the above-mentioned chromatographic method.
  • a first process step 38 g (0.28 mol) of 3-phenylpropan-1-ol was introduced as a starter in a 4-neck round bottom flask equipped with a reflux condenser, a thermometer and a nitrogen inlet and at room temperature under a nitrogen atmosphere 3.2 g (0.028 mol) of potassium tert-butoxide was added. The temperature of the reaction mixture was increased to 110 0 C and the formed t-butanol evaporated under nitrogen. Subsequently, 85.6 g (0.57 mol) of phenylglycidyl ether monomer was added dropwise over one hour and the mixture was polymerized for a further 2 hours until fully reacted (as determined by 1 H NMR analysis).
  • the block copolymer EXAMPLE 13 ' was further modified by cleaving off the acetal protecting groups of the block copolymer.
  • the intermediate (EXAMPLE 13 ' ) was dissolved 120 g of the intermediate (EXAMPLE 13 ' ) in 360 ml of THF and 30 ml of H 2 O.
  • To the clear solution was added 16 g of HCl (37% by weight). The solution was stirred at 40 ° C. for 1 hour. Subsequently, the mixture was neutralized by adding Na 2 CO 3 with stirring. After the addition of sodium chloride, the THF phase was separated. The resulting THF solution was evaporated to dryness. THF was then added again and the solution was dried over magnesium sulfate.
  • a poly (phenylglycidyl ether) macroinitiator (macroinitiator 14) started with 3-phenylpropan-1-ol was prepared in a first stage.
  • This alkoxylation was carried out in a pressure reactor equipped with stirrer and thermostat. 392.8 g (0.9 mol) of macroinitiator were charged, the reactor was closed, evacuated and inertized with N2. After heating to 135 ° C., 396.0 g (9.0 mol) of ethylene oxide were metered in so that a maximum pressure of 5 bar was not exceeded. After completion of the addition and post-reaction at 135 ° C until the pressure remained constant, was cooled to room temperature. The resulting block copolymer was then dissolved in methanol and neutralized with an acid ion exchanger Amberlite IR-120H. After filtering off the ion exchanger, the methanol was removed in vacuo.
  • Example 16 a To prepare the dispersant, the poly (phenylglycidyl ether) macroinitiator started according to Example 14 a) was used as initiator for an alkoxylation reaction, starting with 3-phenylpropan-1-ol.
  • the alkoxylation was carried out in a pressure reactor equipped with stirrer and thermostat. 392.8 g (0.9 mol) macroinitiator 14 were charged, the reactor was closed, evacuated and inertized with N 2. After heating to 135 ° C., 396.0 g (9.0 mol) of ethylene oxide were metered in so that a maximum pressure of 5 bar was not exceeded. After completion of the addition and post-reaction at 135 C C until the pressure remained constant, 104.4 g (1, 8 mol) of propylene oxide were added in the same manner. After completion of the addition and post-reaction at 135 ° C until the pressure remained constant, was cooled to room temperature. The resulting block copolymer was then dissolved in methanol and neutralized with an acid ion exchanger Amberlite IR-120H. After filtering off the ion exchanger, the methanol was removed in vacuo.
  • the dispersants (not according to the invention) were synthesized in the same manner as the dispersants corresponding to EXAMPLE 14, EXAMPLE 16 and EXAMPLE 18, respectively, except that styrene oxide was used instead of the phenyl glycidyl ether monomer.
  • Table 6 shows the number average molecular weight determined by the abovementioned chromatographic method and the polydispersity of the block copolymers according to Example 14 and Example 16 and Comparative Examples 15 and 17, respectively.
  • Dispersion 60 min at 40 0 C and 8000 rev / min, Dispermat CV, glass beads 1 mm
  • Dispersion 40 min at 40 0 C and 10000 U / min, Dispermat CV, glass beads 1 mm
  • Dispersion 40 min at 40 0 C and 10000 U / min, Dispermat CV, glass beads 1 mm (with DMEA adjusted to pH 8) Proxel GLX Biocide, Manufacturer ICI Hostaperm Pink E Pigment, Manufacturer Clariant Hellogen Blue L 7101 F Pigment, Manufacturer BASF Flammruß 101 Pigment, Manufacturer Degussa Bayferrox 130M Pigment, Manufacturer Lanxess BYK ⁇ -017 Defoamer, Manufacturer Byk Chemie
  • Caparol white paint, solvent-based, alkyd resin base (Capalac high-gloss colored paint, manufacturer Caparol)
  • Examples 10-11 and 14 or 16 and 18 show that with the aid of the glycidyl ether block copolymers can be obtained as dispersants pigment concentrates or paints with a lower viscosity, but high pigment concentration with otherwise unchanged properties such as storage stability.
  • the lower viscosity and high storage stability of a pigment paste has the advantage that a high degree of pigment filling in the concentrate can be achieved.
  • the emulsion rested for 30 seconds to allow the entrapped air to escape before transferring to a glass vial and sealingly stored at room temperature.
  • V. 2 The water-in-oil emulsion had a viscosity (Brookfield RVT type viscometer, spindle 5, 50 rpm, 23 0 C of 288 M.Pa.s. The emulsion was stable on storage at least 3 months.

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Abstract

La présente invention porte sur une composition comprenant au moins un copolymère amphiphile de glycidyléther, constitué de motifs structuraux spéciaux I à V, où au moins l'un des motifs structuraux I porte un reste aromatique et les motifs structuraux peuvent être disposés en gradient, d'une manière statistique ou chacun sous forme de bloc, comme dispersant et une matière solide dispersée, ou comme émulsifiant et un système polymère insaturé durcissable sous forme d'une émulsion eau-dans-huile.
PCT/EP2009/008281 2008-11-24 2009-11-20 Compositions comprenant des copolymères de glycidyléther Ceased WO2010057654A1 (fr)

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ES09760107T ES2419660T3 (es) 2008-11-24 2009-11-20 Composiciones que contienen copolímeros de glicidil-éter
KR1020117014558A KR101660355B1 (ko) 2008-11-24 2009-11-20 글리시딜 에테르 공중합체를 포함하는 조성물
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WO2012025582A3 (fr) * 2010-08-26 2012-09-07 Basf Se Procédé pour produire des solutions hautement concentrées de protéines à auto-assemblage
CN103209991A (zh) * 2010-08-26 2013-07-17 巴斯夫欧洲公司 用于产生自组装蛋白质的高浓缩溶液的方法
US10202636B2 (en) 2013-12-24 2019-02-12 General Electric Company Electrospun fibers for protein stabilization and storage

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KR101660355B1 (ko) 2016-09-27
CN102292377B (zh) 2014-06-04
JP2012509946A (ja) 2012-04-26
CN102292377A (zh) 2011-12-21
EP2367865B1 (fr) 2013-04-17
EP2367865A1 (fr) 2011-09-28
ES2419660T3 (es) 2013-08-21
DE102009040068A1 (de) 2010-05-27
KR20110097904A (ko) 2011-08-31
US8367762B2 (en) 2013-02-05
US20110257326A1 (en) 2011-10-20

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