WO2009141057A1 - Procédé de polymérisation pour production de particules coeur-écorce - Google Patents

Procédé de polymérisation pour production de particules coeur-écorce Download PDF

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Publication number
WO2009141057A1
WO2009141057A1 PCT/EP2009/003243 EP2009003243W WO2009141057A1 WO 2009141057 A1 WO2009141057 A1 WO 2009141057A1 EP 2009003243 W EP2009003243 W EP 2009003243W WO 2009141057 A1 WO2009141057 A1 WO 2009141057A1
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Prior art keywords
core
shell particles
nanoparticles
preparation
particles according
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PCT/EP2009/003243
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German (de)
English (en)
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Gerhard Jonschker
Joerg Pahnke
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Merck Patent Gmbh
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Publication of WO2009141057A1 publication Critical patent/WO2009141057A1/fr

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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to processes for the preparation of core-shell particles and their use in formulations, paints, inks and plastics or their precursors.
  • coating properties can be improved by addition of nanoparticles, but the processing of the nanoparticles poses a challenge since agglomeration and incompatibilities with common coating components can easily occur. Furthermore, the additional introduction of another paint raw material is an undesirable logistical effort, which is associated with costs.
  • the polymers are desirably required to react with the nanoparticles to form covalent bonds.
  • the nanoparticles must be provided with groups which are reactive with respect to the polymers used.
  • the curing of the polymers involving the nanoparticles usually occurs under conditions of rapidly increasing viscosity and thus decreasing mobility of the reactants.
  • the incorporation of the nanoparticles into the polymers is usually incomplete and the desired property improvements do not or do not occur to the desired and theoretically achievable extent.
  • Nanoparticles by virtue of their large interfacial energy, have the property of
  • redispersible nanoparticles with polymers bound via a sulfur bridge which have the structure of core-shell particles and can use these in paints and coatings as an additive in the quantitative range from 1 to usually 20% by weight
  • the main component of these coatings and paints are still conventional binders that can crosslink with the nanoparticles during curing and bring all the disadvantages of traditional binders with them.
  • the object of the present invention was accordingly to provide nanoparticle-containing systems which overcome the disadvantages mentioned.
  • core-shell particles which can be produced by a specific polymerization process, fulfill the complex requirement profile.
  • the core-shell particles of the present application comprise central attachment points (hereinafter referred to as cores) with a diameter of> 1 nm with radially bound oligomers and / or polymers which form the shell.
  • the oligomers and / or polymers are preferably covalently bonded to the surface of the cores.
  • Proportion of oligomers and / or polymers to the core-shell particles is 10 to 99 wt .-%, preferably 30 to 70 wt .-% and in particular 35 to 65 wt .-%, based on the core-shell particles.
  • the determination of the proportions is carried out by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the ignition residue (core portion) of the dried core-shell particles is determined (instrument: TGA V4.OD Dupont 2000), heating rate: 10 K / min, temperature range 25-1000 0 C in air, platinum crucible).
  • binder in the sense of the present invention means compounds which are responsible for film formation in coating materials and inks, for example printing inks.
  • Film formation is the general term for the transition of a applied coating material from liquid or else powdery (with transition via the In the case of paints and varnishes, binders according to DIN EN 971-1: 1996-09 and DIN 55945: 1999-07 are the nonvolatiles or nonvolatiles without pigment and filler but including plasticizers, driers and other nonvolatile excipients some of which are also applied from the melt (for example in the case of powder coating) or reacted by radiation Binder is present in liquid coating materials in solution or as a dispersion, and provides anchoring of pigments and fillers in the film and adhesion of the film on de m substrate.
  • radial in the sense of the present invention means a linear or branched, preferably rectilinear, one-point alignment of the oligomers and / or polymers
  • the core represents the point from which the oligomers and / or or polymers are aligned largely uncrosslinked.
  • the nanodimensioned cores are already fully reacted with reactive polymers to form covalent bonds even before the 3-dimensional crosslinking in the film or film, so that good incorporation and bonding are possible Crosslinking with the polymer target system (matrix), and thereby a maximum effect on the matrix polymer structure can be achieved.
  • This pre-crosslinking is preferably carried out in an upstream step under conditions which guarantee a high reactivity with the particle surface and sufficient mobility of the polymer chains. This can be achieved in different ways.
  • the polymer / oligomer chains may be e.g. by polymerization away from a core element. Another way is the reaction of correspondingly reactively modified polymer / oligomer chains with a core.
  • controlled radical polymerization is particularly suitable for the production of core-shell particles and leads to core-shell particles having improved properties.
  • a first object of the present invention is to provide a process for producing core-shell particles
  • At least 2 different monomers are added separately in time so that the resulting
  • Polymeric block copolymers are. It is further preferred that the last added monomer carries a group capable of further reactions, in particular acrylate, methacrylate, vinyl, amino, cyano, isocyanate, epoxy, carboxy or hydroxy groups.
  • the surface modifiers are e.g. organofunctional silanes, organometallic compounds, e.g. Zirconium tetra-n-propylate, or
  • the surface modifier is covalently bonded to the surface of the core.
  • the surface modifiers used are preferably haloalkane organosilanes, such as, for example, chloropropyltrimethoxysilane, bromopropyltrimethoxysilane, bromoacetyloxypropyltrimethoxysilane or (p-chloromethyl) phenyltrimethoxysilane, or preferably halocycloalkanesilanes or haloaromatic silanes.
  • haloalkane organosilanes such as, for example, chloropropyltrimethoxysilane, bromopropyltrimethoxysilane, bromoacetyloxypropyltrimethoxysilane or (p-chloromethyl) phenyltrimethoxysilane, or preferably halocycloalkanesilanes or haloaromatic silanes.
  • chlorine or iodine-containing alkanes are also preferred.
  • bromine-containing alkanes are also preferred.
  • Bromacetyloxypropyltrimethoxysilane is particularly preferably used. Very particular preference is given to using (p-chloromethyl) phenyltrimethoxysilane.
  • halogen-substituted sulfur-nitrogen or phosphorus compounds such as phosphonic acids are preferred because they can have a high affinity for the particle surface.
  • Further preferred surface-modifying agents are halogen-substituted complexing agents, for example based on acetylacetone, carboxylic acids, beta-diketones or alpha-hydroxycarboxylic acids.
  • Common processes for preparing surface-modified nanoparticles are based on aqueous particle dispersions to which the surface modifier is added.
  • the reaction with the surface modifiers can also be carried out in an organic solvent or in solvent mixtures. This applies in particular to ZnO nanoparticles.
  • Preferred solvents are alcohols or ethers, with the use of methanol, ethanol, diethyl ether, tetrahydrofuran and / or dioxane or mixtures thereof being particularly preferred. In this case, methanol has proved to be a particularly suitable solvent.
  • adjuvants may optionally be present as well, e.g. Surfactants or protective colloids (e.g., hydroxypropyl cellulose).
  • these dispersions are preferred with the indicated solvents.
  • the surface modifiers may be used alone, as mixtures or in admixture with other, optionally non-functional surface modifiers.
  • the described requirements for surface modifiers fulfill an adhesion promoter which carries two or more functional groups.
  • One group of the coupling agent chemically reacts with the oxide surface of the nanoparticle.
  • Alkoxysilyl groups for example methoxy-, ethoxysilanes
  • halosilanes for example chlorine
  • acidic groups of phosphoric acid or phosphonic acids and phosphonic acid esters or carboxylic acids are particularly suitable here.
  • About a more or less long spacer are the groups linked to a second, functional group.
  • the adhesion promoter can have further functional groups, in particular
  • Silane-based surface modifiers are described, for example, in DE 40 11 044 C2.
  • Phosphoric acid-based surface modifiers include i.a. as Lubrizol® 2061 and 2063 from LUBRIZOL (Langer & Co.).
  • amphiphilic silanes of the general formula (R) 3 Si-S P P -Ah -Bhb, where the radicals R may be the same or different and are hydrolytically removable radicals, Sp is -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 C atoms which may be substituted by alkyl groups having 1-6 C atoms, A hp is a hydrophilic block, B hb is a hydrophobic block and wherein at least one group capable of initiating a controlled free-radical polymerization ( US Pat .
  • Halogen is bound to A hp and / or B hb , is.
  • amphiphilic silanes When amphiphilic silanes are used, nanoparticles are obtained which are particularly readily redispersible, in both polar and nonpolar solvents.
  • the amphiphilic silanes contain a head group (R) 3 Si, where the radicals R may be the same or different and represent hydrolytically removable radicals. Preferably, the radicals R are the same.
  • Suitable hydrolytically removable radicals are, for example, alkoxy groups having 1 to 10 C atoms, preferably having 1 to 6 C atoms, halogens, hydrogen, acyloxy groups having 2 to 10 C atoms and in particular having 2 to 6 C atoms or NRV groups, wherein the Radicals R 'may be the same or different and are selected from
  • Suitable alkoxy groups are, for example, methoxy, ethoxy, propoxy or butoxy groups.
  • Suitable halogens are in particular Br and Cl.
  • Examples of acyloxy groups are acetoxy or propoxy groups.
  • Oximes are also suitable as hydrolytically removable radicals.
  • the oximes may hereby be substituted by hydrogen or any organic radicals.
  • the radicals R are preferably alkoxy groups and in particular methoxy or ethoxy groups.
  • a spacer Sp Covalently bonded to the above-mentioned head group is a spacer Sp, which acts as a link between the Si head group and the hydrophilic block A h p and performs a bridging function in the context of the present invention.
  • the group Sp is either -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms.
  • the C 1 -C 8 -alkyl group of Sp is, for example, a methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1-, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl , Dodecyl, tridecyl or tetradecyl group.
  • it may be perfluorinated, for example as difluoromethyl, tetrafluoroethyl, hexafluoropropyl or octafluorobutyl.
  • a straight-chain or branched alkenyl having 2 to 18 C atoms, wherein several double bonds may also be present is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, Hexenyl, heptenyl, octenyl, -C 9 Hi 6 , -CioHi 8 to -C- I sH 34 , preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl.
  • a straight-chain or branched alkynyl having 2 to 18 C atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, Heptynyl, octynyl, -C 9 H 14, -C 10 Hi 6 to C-IsH 32 , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.
  • the spacer group Sp is followed by the hydrophilic block A hp .
  • This may be selected from nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups.
  • the hydrophilic block is to ammonium, sulfonium, phosphonium groups, alkyl chains with carboxyl, sulfate and phosphate side groups, which may also be present as a corresponding salt, partially esterified anhydrides with free acid or salt group, OH-substituted alkyl or cycloalkyl chains (eg Sugar) having at least one OH group, NH- and SH-substituted alkyl or cycloalkyl chains or mono-, di- tri- or oligo-ethylene glycol groups.
  • the length of the corresponding alkyl chains can be 1 to 20 C atoms, preferably 1 to 6 C atoms.
  • nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups can be prepared from corresponding monomers by polymerization in accordance with methods generally known to the person skilled in the art.
  • Suitable hydrophilic monomers contain at least one dispersing functional group which consists of the group consisting of
  • the primary and secondary can be
  • Amino groups also serve as isocyanate-reactive functional groups.
  • hydrophilic monomers having functional groups (i) are acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester, in particular acrylic acid and methacrylic acid.
  • hydrophilic monomers with functional groups (ii) are 2-aminoethyl acrylate and methacrylate or allylamine.
  • hydrophilic monomers having functional groups (iii) are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl, omega-methoxy-polyoxypropylene-1-yl, or omega-methoxy-poly (ethylene oxide-co-poly) polypropylene oxide) -1-yl acrylate or methacrylate, as well as hydroxy-subsitituted ethylene, acrylates or methacrylates, such as, for example, hydroxyethyl methacrylate.
  • Suitable monomers for the formation of zwitterionic hydrophilic polymers are those in which a betaine structure occurs in the side chain.
  • the side group is selected from - (CH 2 ) m - (N + (CH 3 ) 2 ) - (CH 2 ) n -SO 3 -, - (CH 2 ) m - (N + (CH 3 ) 2 ) - (CH 2 ) n -PO 3 2 -, - (CH 2 ) m - (N + (CH 3 ) 2 ) - (CH 2 ) n - O-PO 3 2 " or - (CH 2 ) m - (P + (CH 3 ) 2 ) - (CH 2 ) n -SO 3 " , where m is an integer from the range from 1 to 30, preferably from the range 1 to 6, particularly preferably 2, and n is an integer from the range from 1 to 30, preferably from the range 1 to 8, particularly preferably 3.
  • Structural unit of the hydrophilic block has a phosphonium or sulfonium radical.
  • hydrophilic monomers it is to be noted that it is preferable to combine the hydrophilic monomers having functional groups (i) and the hydrophilic monomers having functional groups (ii) so as not to form insoluble salts or complexes.
  • the hydrophilic monomers having functional groups (i) or functional groups (ii) can be arbitrarily combined with the hydrophilic monomers having functional groups (iii).
  • the monomers having the functional groups (i) are particularly preferably used.
  • the neutralizing agents for the anionic functional groups (i) are selected from the group consisting of ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine, triethanolamine , Diethylenetriamine and triethylenetetramine, and the neutralizing agents for the cation-convertible functional groups (ii) selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid and citric acid.
  • the hydrophilic block is selected from mono- and triethylene glycol structural units.
  • the block B hb is based on hydrophobic groups or, like the hydrophilic group
  • hydrophobic groups are straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds , saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms. Examples of such groups are already mentioned in advance.
  • aryl, polyaryl, aryl-C 1 -C 6 -alkyl or esters having more than 2 C atoms are suitable.
  • the groups mentioned may also be substituted, in particular with halogens, with perfluorinated groups being particularly suitable.
  • Aryl-C 1 -C 6 -alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and the alkylene chain, as described above, may be partially or completely substituted by F, particularly preferably benzyl or phenylpropyl.
  • hydrophobic olefinically unsaturated monomers examples include
  • esters of olefinically unsaturated acids which are substantially free of acid groups such as (meth) acrylic acid, crotonic acid, ethacrylic acid,
  • These may contain minor amounts of higher-functional (meth) acrylic acid, crotonic acid or ethacrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
  • butylene glycol pentane-1, 5-diol, hexane-1, 6-diol, octahydro-4,7-methano-1 H-inden-dimethanol- or cyclohexane-1, 2-, -1, 3- or -1, 4-diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol tetra (meth) acrylate and the analogous ethacrylates or crotonates.
  • minor amounts of higher-functional monomers (1) are amounts which do not lead to crosslinking or gelation of the polymers;
  • Hydroxymethylamino carry per molecule and are substantially free of acid groups, such as
  • Hydroxyalkyl esters of alpha, beta-olefinically unsaturated carboxylic acids such as hydroxyalkyl esters of acrylic acid, methacrylic acid and ethacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-hydroxybutyl acrylate, methacrylate or ethacrylate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products of cyclic esters, such as epsilon-caprolactone and these hydroxyalkyl esters; - olefinically unsaturated alcohols such as allyl alcohol
  • Allyl ethers of polyols such as trimethylolpropane monoallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • monomers are used only in minor amounts.
  • minor amounts of higher-functional monomers are amounts which do not lead to crosslinking or gelation of the polymers,
  • reaction products of alpha, beta-olefinic carboxylic acids with glycidyl esters of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms in the molecule may be carried out before, during or after the polymerization reaction.
  • the monomer (2) used is preferably the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid. This glycidyl ester is commercially available under the name Cardura® E10. In addition, it will open
  • Carboxylic acid amides such as N-methylol and N, N-dimethylol aminoethyl acrylate, aminoethyl methacrylate, acrylamide and methacrylamide; such as
  • Acryloxysilane groups and hydroxyl-containing olefinically unsaturated monomers preparable by reaction of hydroxy-functional silanes with epichlorohydrin 30 and subsequent reaction of the intermediate with an alpha, beta-olefinically unsaturated Carboxylic acid, especially acrylic acid and methacrylic acid, or their hydroxyalkyl esters;
  • vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule such as the vinyl esters of Versatic®
  • cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
  • amides of alpha.beta.-olefinically unsaturated carboxylic acids such as (meth) acrylamide, N-methyl-, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl and / or N, N-cyclohexylmethyl (meth) acrylamide;
  • monomers containing epoxide groups such as the glycidyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
  • vinyl aromatic hydrocarbons such as styrene, vinyltoluene or alpha-alkylstyrenes, especially alpha-methylstyrene;
  • nitriles such as acrylonitrile or methacrylonitrile
  • vinyl compounds selected from the group consisting of vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; Vinylamides, such as N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and vinyl cyclohexyl ether; and vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate; (10) allyl compounds selected from the group consisting of allyl ethers and esters, such as propyl allyl ether, butyl allyl ether, ethylene glycol diallyl ether, trimethylolpropane triallyl ether, or allyl acetate or allyl propionate; As far as the higher-functional monomers are concerned, what has been said above applies mutatis mutandis;
  • Siloxane or polysiloxane monomers which may be substituted with saturated, unsaturated, straight-chain or branched alkyl groups or other hydrophobic groups already mentioned above.
  • polysiloxane macromonomers which are a number average
  • Molecular weight Mn of 1,000 to 40,000 and having on average 0.5 to 2.5 ethylenically unsaturated double bonds per molecule such as polysiloxane macromonomers having a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule exhibit; especially
  • Polysiloxane macromonomers having a number average molecular weight Mn of 2,000 to 20,000, more preferably 2,500 to 10,000 and especially 3,000 to 7,000 and an average of 0.5 to 2.5, preferably 0.5 to 1, 5, ethylenically unsaturated double bonds per molecule such in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US Pat. No. 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line 10; and
  • carbamate or allophanate group-containing monomers such as acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; Further examples of suitable monomers containing carbamate groups are described in patents US 3,479,328 A 1, US 3,674,838 A 1, US 4,126,747 A 1, US 4,279,833 A 1 or US 4,340,497 A 1.
  • the polymerization of the abovementioned monomers can be carried out in any manner known to those skilled in the art, for example by polyadditions or cationic, anionic or free-radical polymerizations.
  • the amphiphilic silanes have an HLB value in the range of 2-19, preferably in the range of 4-15.
  • the HLB value is defined as
  • the HLB value is calculated theoretically and results from the mass fractions of hydrophilic and hydrophobic groups.
  • An HLB value of 0 indicates a lipophilic compound, a chemical compound with an HLB value of 20 has only hydrophilic moieties.
  • Suitable amphiphilic silanes are furthermore distinguished by the fact that at least one group which is capable of initiating a controlled radical polymerization and is bonded to Ah P and / or Bh b is present.
  • the reactive functional group is preferably present at the hydrophobic block Bh b, and more preferably bound there at the end of the hydrophobic block.
  • the head group (R 1) Si and the group capable of initiating a controlled radical polymerization have the greatest possible spacing, allowing a particularly flexible design of the chain lengths of the blocks A hp and B hb , without the possible reactivity of initiating a controlled radical polymerization capable group, for example, with the surrounding medium significantly.
  • further reactive functional groups may be present, in particular selected from silyl groups with hydrolytically removable radicals, OH, carboxy, NH, SH groups, halogens or double bonds containing reactive groups, such as
  • the additional reactive group is an OH group.
  • oligomers and / or polymers are radially bound to the cores.
  • the polymer or oligomer chains may be reacted with any of the methods known to those skilled in the art to form the core material, preferably to form at least one covalent bond.
  • the polymerization method in the process according to the invention of claim 1 operates with a halogen from the surface modifier and the elemental metals mentioned below in finely divided form.
  • adding the monomers and the radical initiator to the dispersion of surface-modified nanoparticles can be done in one step, this is the preferred embodiment.
  • the addition of the monomers and the radical initiator takes place stepwise, for example with re-initiation and portionwise addition of the monomers.
  • the hydrophilic and hydrophobic monomers are suitable, as defined above.
  • the metal catalyst for example Cu (O)
  • Cu (II) is required for the polymerization cycle.
  • the monomers react in the presence of modified nanoparticles, with only catalytic amounts of Cu (O).
  • Another object of the invention is a process for the preparation of core-shell particles, comprising the a) controlled radical polymerization of organofunctional silanes with monomers in the presence of a metal catalyst and b) crosslinking of the polymerized silanes to core-shell particles.
  • the crosslinking is preferably carried out in the presence of hydrolyzable organometail compounds.
  • hydrolyzable organometail compounds particularly preferred are tetraalkoxysilanes such as tetraethyl orthosilicate or alkoxides of Ti, Zr, Al or Sn.
  • silane-modified polymers can be produced with particular preference.
  • the polymers / oligomers forming the shell can be composed of all known polymeric substance groups, or mixtures thereof.
  • the oligomers and / or polymers are selected from the group comprising poly (meth) acrylates, polyesters, polyurethanes, Polyureas, silicones, polyethers, polyamides, polyimides, or mixtures thereof and hybrids.
  • Suitable monomers for forming corresponding oligomers and / or polymers having functional groups are acrylic acid,
  • Such monomers with functional groups are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl, omega-methoxy-polypropylene oxide-1-yl or omega-methoxy-poly (ethylene oxide-co-polypropylene oxide) -1- yl acrylate or methacrylate, and hydroxy subsitituted Ethylene, acrylates or methacrylates, such as hydroxyethyl methacrylate or hydroxypropyl methacrylate.
  • Suitable monomers for the formation of zwitterionic hydrophilic polymers are those in which a betaine structure occurs in the side chain.
  • the side group is selected from - (CH 2 ) m - (N + (CH 3 ) 2) -
  • the polymers consist of a monomer or (preferably) of monomer mixtures.
  • the monomers may also preferably carry reactive groups in the side chains, e.g. Hydroxy, epoxy, allyl, blocked isocyanate, etc.
  • the side chains can be additionally functionalized: e.g. Hydroxybenzophenone, benzotriazole as UV absorber or fluorescent dyes that are incorporated into the polymer chain via acrylate function.
  • the polymer / oligomer shell is reactive with other components of the lacquers, e.g. Crosslinker (in particular isocyanate or melamine crosslinker) or curable by energy irradiation (for example UV light, electron beam curing or heat), e.g. by contained blocked isocyanates.
  • the polymers bound to the core material desirably have further reactive groups with which they can then react to form a 3-dimensionally crosslinked polymer. This can e.g. unsaturated groups such as acrylic or vinyl, or also groups which can react with an external crosslinker, e.g. Epoxy groups, NH, COOH, alkoxysilyl or OH groups, which with
  • Isocyanates can be crosslinked.
  • the functional group is an OH group.
  • the nanoparticles are preferred! inorganic or organic or comprise a mixture of inorganic or organic constituents which form the cores.
  • These nanoparticles are particularly preferably based on sulfates or carbonates of alkaline earth compounds or on oxides or hydroxides of silicon, titanium, zinc, aluminum, cerium, cobalt, chromium, nickel, iron, yttrium or zirconium or mixtures thereof, which are optionally coated with metal oxides or oxides .
  • Hydroxides may be coated, or on with metal
  • Oxides or hydroxides coated metals such as Ag, Cu, Fe, Au, Pd, Pt or alloys based.
  • Dispersions of the nanoparticles used in the process according to the invention are preferably selected from SiO 2 silica sols, organo silica sols. Particular preference is given to dispersions of SiO 2 particles, ZnO or cerium oxide particles or TiO 2 particles, which may optionally be coated with metal oxides or hydroxides. Very particular preference is given to using nanoparticles of SiO 2 or ZnO.
  • the inventive method according to claim 1 is therefore preferably directed to the production of core-shell particles with a core of SiO 2 , evidenced by Example 2.
  • the inventive method according to claim 1 is therefore preferably directed to the production of core-shell particles having a core of ZnO, evidenced by Example 1.
  • the solvent is preferably selected from water, organic solvents or mixtures thereof.
  • the solvent or solvent mixture is preferably selected from water, organic solvents or mixtures thereof. If the solvent mixture and monomers are chosen so that the monomers but the polymers formed therefrom are no longer soluble beyond a certain chain length, the desired core
  • the precipitated core-shell particles can be separated from the free polymer or unreacted surface modifier present in the reaction medium. This can be done by conventional methods known in the art.
  • the polymerization is carried out in a solvent or solvent mixture in which the monomers are soluble, the polymers formed above a certain
  • an external trigger e.g. Temperature change, salt addition or addition of a non-solvent induces a phase separation at a certain time.
  • the core-shell particle synthesis can thus be interrupted at any time, for example to control the surface coverage.
  • aqueous dispersions of nanoparticles can be effectively provided with a polymer shell.
  • the conversion rates are at least twice as high as compared to conventional free-radical chemistry. This also provides a special advantage in economic terms.
  • the nanoparticles which form the cores are particularly preferably inorganic nanoparticles ⁇ 20 nm.
  • the cores may preferably also consist of organic constituents of a mixture of inorganic or organic constituents.
  • the cores preferably have diameters determined by means of a Malvern ZETASIZER (particle correlation spectroscopy, PCS) or transmission electron microscope from 1 to 20 nm in at least one dimension, preferably at most 500 nm in a maximum of two dimensions, such as, for example in phyllosilicates. Particularly preferred are substantially round cores of a diameter of 1 to 25 nm, in particular 1 to 10 nm.
  • PCS particle correlation spectroscopy
  • the investigation is carried out with a Malvern Zetasizer according to the operating instructions.
  • the diameter of the particles is determined as dOW value.
  • the term "average particle diameter" in the present specification refers to this d50 value.
  • the distribution of particle sizes is narrow, i. the fluctuation range is less than 100% of the mean value, in particular preferably not more than 50% of the mean value.
  • Suitable cores may be nanoparticles prepared separately or in an upstream step, as are well known to those skilled in the art, such as: SiO 2 , ZrO 2 , TiO 2 , CeO 2 , ZnO, etc. but also 3-dimensional crosslinked organosilsesquioxane structures and metal oxides / hydroxides, in particular silsesquioxane structures (known, for example, under the trade name POSS TM from Hybrid Plastics), or heteropolysiloxanes, in particular cubic or other 3-dimensional representatives of this class of materials.
  • SiO 2 , ZrO 2 , TiO 2 , CeO 2 , ZnO, etc. but also 3-dimensional crosslinked organosilsesquioxane structures and metal oxides / hydroxides, in particular silsesquioxane structures (known, for example, under the trade name POSS TM from Hybrid Plastics), or heteropolysiloxanes, in particular cubic or other 3-dimensional representatives of this class of materials
  • Hybrids of nanoparticles and silsesquioxane structures can also be used as nuclei.
  • cores based on phyllosilicates, sulfates, silicates, carbonates, nitrides, phosphates, sulfides of appropriate size can in principle be used.
  • Another suitable core material are cores selected from organic polymers / oligomers, in particular organic nanoparticles, for example consisting of free-radically polymerized monomers. Dendrimers or hyperbranched polymers can in principle also serve as core material.
  • the core can also be built in situ from suitable polymer chains.
  • preferably terminally reactive modified polymers are suitable, which form the core or relevant parts of the core in a linking step.
  • alkoxysilane-modified polymer chains particularly preferably trialkoxysilane-modified.
  • the nucleation in these polymers is preferably carried out under reaction conditions which are suitable for the formation of spherical structures. In silane modification, these are above all basic reaction conditions, comparable to the Stöber synthesis known to the person skilled in the art.
  • other suitable metal compounds for. B. of Ti 1 Zr, AI are used and are reacted under optimum conditions for each species. The reaction can also occur in the presence of an already formed template (germ, nanoparticles, etc) or others
  • Reactants silanes, metal alkoxides, salts
  • Preferred cores are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, cores based on sulfates or carbonates of alkaline earth compounds or of oxides or hydroxides of silicon, titanium, zinc, aluminum, cerium, cobalt,
  • Chromium, nickel, iron, yttrium or zirconium or mixtures thereof which may optionally be coated with metal oxides or hydroxides, for example of silicon, zirconium, titanium, aluminum or with metal oxides or hydroxides, for example of silicon, Zirconium, titanium, aluminum, coated metals such as Ag, Cu, Fe, Au, Pd, Pt or alloys.
  • the individual oxides can also be present as mixtures.
  • the metal of the metal oxide or hydroxide is silicon.
  • the cores are particularly preferably selected from SiO 2 particles, or they are selected from ZnO or cerium oxide particles or TiO 2 particles), which are optionally doped with metal oxides or hydroxides, for example of silicon, zirconium, titanium, Aluminum, can be coated.
  • the core-shell particles according to the invention may be particles due to the
  • Core-shell particles are used.
  • Suitable zinc oxide particles with a particle size of 3 to 50 nm are obtainable, for example, by a process in which one or more precursors for the ZnO nanoparticles in an organic solvent are converted to the nanoparticles in a step a), and in step b) the growth of the nanoparticles is terminated by the addition of at least one modifier which is a precursor for silica, when in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value.
  • the method and the suitable modifiers and process parameters are described in DE 10 2005 056622.7.
  • suitable zinc oxide particles can be produced by a process in which one or more precursors for the ZnO nanoparticles in an organic solvent are converted to the nanoparticles in a step a), and in a step b) the growth of the nanoparticles by addition at least one copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals is terminated when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value.
  • This process and the suitable copolymers, monomers and process parameters are described in DE 10 2005 056621.9.
  • nanohectorites which are sold for example by Südchemie branded Optigel® ® or by Laporte under the brand name Laponite ®, are used.
  • Starck example Levasil® ® from HC or dispersions of deposited from the gas phase particles such as: very especially preferred is silica sols (S1O 2 in water) made of ion-exchanged water glass.
  • the core does not already have a high reactivity and the possibility of forming covalent bonds with the oligomers / polymers, it is advantageous to apply a coupling agent or other suitable surface modification.
  • the halo-substituted alkanes are cycloalkanes having more than two halo radicals.
  • the core in this case preferably consists of the cycloalkane structural unit, so that only optional inorganic nanoparticles are required.
  • Controlled radical polymerization is particularly preferably carried out using SET-DTLRP (Single Electron Transfer-Degenerative Transfer Radical Polymerization). This is a recent polymerization process by Percec et al., Which allows the core-shell particles to surprisingly exhibit novel properties (Percec et al, J. Am. Chem. Soc., 2006, 128, 14156-14165).
  • Controlled free-radical polymerization makes it possible to successively polymerize different monomers / monomer mixtures onto a core and thereby to build core / shell particles which are specifically tailored to the requirements of the invention. Thus, it is preferable to introduce the polymer reactive components at the end of the chain. In addition, reactive groups in the vicinity of the core, which are not accessible due to steric hindrance, can thus be avoided.
  • the metal catalyst is particularly preferably copper.
  • the metal catalyst is iron, aluminum, cadmium, zinc, samarium, chromium, molybdenum, tungsten, cobalt, nickel, rhodium, ruthenium, palladium or titanium.
  • the surface modifier contains at least one carbon-bonded halogen atom, preferably Br, Cl, more preferably Br. More preferably, however, Cl.
  • the core-shell particles consists of a SiO 2 core and the polymer shell as a block copolymer of alkyl (meth) acrylates and / or styrene and at least one OH-functional monomer (preferably HEMA), wherein the / the OH-functional monomers are designed as the last, nuclear far block.
  • OH-functional monomer preferably HEMA
  • the core-shell particles thus produced or have a very advantageous, star-like structure, which in the 3-dimensional
  • Crosslinking to a polymer nanocomposite with optimal incorporation of the nanoparticles can react and are suitable binders, as previously defined.
  • the homogeneously incorporated nanoparticles are not only improvements of the structure and the mechanical / chemical
  • nanoparticles By incorporating suitable nanoparticles further property improvements are possible, for example an increased UV stability by means of nanoscale UV absorbers or weather-resistant colors by nanoscale pigments. It is also possible, by selecting the size and refractive index of the cores, to achieve targeted scattering of short-wave light (UV) while maintaining transparency in the visible wavelength range.
  • UV short-wave light
  • the described core-shell particles preferably prepared by the process according to the invention, can be used alone or as a mixture with free polymers.
  • the cores with radially bound oligomers and / or polymers obtainable from the abovementioned processes are particularly suitable for use as binders, as described above.
  • the use of the core-shell particles having improved properties in formulations, paints (preferably clearcoats), paints, foams, adhesives, potting compounds and plastics or in their precursors is likewise an object of the present invention. Particularly preferred is the use as a coating raw material in solvent and water-based paints, as well as in Pulveriacken.
  • the improvement in scratch resistance and chemical resistance of clearcoats for example in commercial powder coatings, UV-curing paints, dual-cure paints, very high-solid paints or VOC-free paints
  • plastics such as e.g. Polycarbonate or PMMA
  • the core-shell particles serve as a replacement for conventional binders. In the property of core-shell particles this already carries the known advantages of nanoadditives in itself.
  • the viscosity of core-shell particles is significantly reduced compared to the viscosity of conventional binders of the same molecular weight, since instead of one long, several shorter chains originate from a central point. This is particularly advantageous in the formulation of high solids and especially in very high solid paints, which have to do with a very low solvent content.
  • conventional polymers short-chain polymers and the mechanical properties of deteriorating reactive diluents often have to be used here.
  • the use of the reactive diluents can be reduced.
  • the schematic representation of a direct comparison between a polymer having 30 monomer units (corresponding to approximately 3000-4000 g / mol average molecular weight) with a core-sheathed core-shell particles likewise having 30 monomer units shows that the long, linear polymer chain will have a higher viscosity, as the approximately spherical shape of the core-shell particle according to the invention, which can also show Newtonian behavior.
  • the core-shell particles are particularly suitable for use in clearcoats or adhesives. Also and especially in the field of powder coatings, the core-shell particles can be used. The reduced viscosity allows better flow and therefore better
  • nanoparticle core into the paint matrix.
  • electromagnetic radiation can be influenced (UV absorption, IR absorption), catalytic effects can be exerted, inorganic nanocolour pigments can be used or e.g. Nanophosphors are used as an inorganic core.
  • the use of the core-shell particles as opacifiers for short-wave radiation in paints, foams, adhesives, potting compounds and plastics or in their precursors is preferred.
  • the Ken core shell particles may be present together with surface-modified particles with a diameter ⁇ 1 .mu.m, which are homogeneously distributed or in the form of a gradient in a cured coating material.
  • Formulations, lacquers, paints, foams, adhesives, potting compounds and plastics containing core-shell particles according to the present invention are preferred, in particular with core-shell particles having improved properties produced by the method according to the invention.
  • ⁇ Q For the polymerization, 20 ml (0.19 mol) of methyl methacrylate (MMA), 400 ul (1, 9 mmol) ⁇ /, / VX / V; ⁇ T-pentamethyldiethylenetriamine (PMDTA) and 120 mg (1, 9 mmol) Added copper powder. After the reaction mixture was rendered inert for 10 min via an argon stream, the mixture is stirred for 3 h at room temperature. The onset of polymerization causes a large increase in viscosity.
  • MMA methyl methacrylate
  • PMDTA ⁇ T-pentamethyldiethylenetriamine
  • the zinc oxide nanoparticles are precipitated in 300 ml of ice-cold methanol and filtered off.
  • the prepared composite material may be dispersed in various organic solvents (eg, butyl acetate, acetone, THF, toluene). In all cases, transparent and colorless dispersions are obtained.
  • Solids yield is 12.3 g (52%) and refers to the theoretical yield of zinc oxide and poly (methyl methacrylate) at full conversion.
  • Zinc oxide is detected by UV / VIS spectroscopy.
  • the composite material is dissolved in dichloromethane and examined in the wavelength range 5 from 250 to 600 nm in the UV / VIS spectrometer.
  • the UV / VIS spectrum in transmission shows the typical adsorption property of zinc oxide in the range from 350 nm.
  • FIG. 1 UV / VIS spectrum of core-shell particles (ZnO-PMMA). 0
  • MMA methyl methacrylate
  • PMDTA methyl methacrylate
  • 120 mg (1, 9 mmol) of copper powder are added.
  • the reaction mixture was rendered inert for 10 min via an argon stream, the mixture is stirred for 3 h at room temperature.
  • the onset of polymerization causes a large increase in viscosity.
  • the SiO 2 nanoparticles are precipitated in 500 ml of ice-cold methanol and filtered off.
  • the prepared composite lateol may be dispersed in various organic solvents (eg, butyl acetate, acetone, THF, toluene). In all cases, transparent and colorless dispersions are obtained.
  • the solids yield is 15.4 g (65%) and refers to the theoretically expected yield of SiO 2 and poly (methyl methacrylate) at full conversion.

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  • Health & Medical Sciences (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production de particules de type coeur-écorce, comprenant l'application sur des nanoparticules en dispersion d'au moins un agent de modification de surface contenant un groupe capable d'amorcer une polymérisation radicalaire contrôlée, puis la polymérisation radicalaire contrôlée des monomères en présence des nanoparticules modifiées et d'un catalyseur métallique, les oligomères et/ou polymères résultants étant attachés aux nanoparticules modifiées par une liaison covalente.
PCT/EP2009/003243 2008-05-23 2009-05-06 Procédé de polymérisation pour production de particules coeur-écorce WO2009141057A1 (fr)

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CN106633574A (zh) * 2016-12-30 2017-05-10 华东理工大学 一种有机玻璃专用二氧化钛的制备方法
CN106699958A (zh) * 2016-12-30 2017-05-24 华东理工大学 一种用丙烯酸酯有机硅在二氧化钛表面聚合的方法
CN109503783A (zh) * 2018-12-10 2019-03-22 万华化学集团股份有限公司 一种端基硅氧烷改性聚丙烯酸酯嵌段共聚物及其制备方法
CN112029362A (zh) * 2020-08-21 2020-12-04 帝斯曼先达合成树脂(佛山)有限公司 一种核壳结构纳米粒子及增硬水性丙烯酸树脂涂料的制备方法

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WO2010118343A1 (fr) * 2009-04-10 2010-10-14 Rensselaer Polytechnic Institute Composites nanoparticules/polymères modifiés avec un copolymère diblocs
CN106633574A (zh) * 2016-12-30 2017-05-10 华东理工大学 一种有机玻璃专用二氧化钛的制备方法
CN106699958A (zh) * 2016-12-30 2017-05-24 华东理工大学 一种用丙烯酸酯有机硅在二氧化钛表面聚合的方法
CN109503783A (zh) * 2018-12-10 2019-03-22 万华化学集团股份有限公司 一种端基硅氧烷改性聚丙烯酸酯嵌段共聚物及其制备方法
CN109503783B (zh) * 2018-12-10 2021-07-23 万华化学集团股份有限公司 一种端基硅氧烷改性聚丙烯酸酯嵌段共聚物及其制备方法
CN112029362A (zh) * 2020-08-21 2020-12-04 帝斯曼先达合成树脂(佛山)有限公司 一种核壳结构纳米粒子及增硬水性丙烯酸树脂涂料的制备方法
CN112029362B (zh) * 2020-08-21 2021-11-30 帝斯曼先达合成树脂(佛山)有限公司 一种核壳结构纳米粒子及增硬水性丙烯酸树脂涂料的制备方法

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