WO2011045122A1 - Particules polymères - Google Patents

Particules polymères Download PDF

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Publication number
WO2011045122A1
WO2011045122A1 PCT/EP2010/063138 EP2010063138W WO2011045122A1 WO 2011045122 A1 WO2011045122 A1 WO 2011045122A1 EP 2010063138 W EP2010063138 W EP 2010063138W WO 2011045122 A1 WO2011045122 A1 WO 2011045122A1
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Prior art keywords
polymer particles
weight
polymer
acrylate
meth
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PCT/EP2010/063138
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German (de)
English (en)
Inventor
Sabine Schwarz-Barac
Michael Schnabel
Thorsten Goldacker
Klaus Schultes
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Evonik Röhm Gmbh
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Publication of WO2011045122A1 publication Critical patent/WO2011045122A1/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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • 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
    • C08L51/003—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 by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to polymer particles which are preferably used for the matting of molding compositions, in particular of polyalkyl (meth) acrylate-containing molding compositions, and give them a light-scattering effect.
  • Additives such as barium sulfate, calcium carbonate,
  • Titanium dioxide, silicon dioxide, etc. is only partially suitable for this purpose.
  • the inorganic fillers can usually only be dispersed uniformly uniformly within a polymer matrix. In addition, these sit down
  • inorganic fillers often degrade during polymerization due to their high density, and consequently do not give uniform results and often adversely affect the physical properties of the material produced. Furthermore, they greatly reduce the
  • inorganic agents can be used and give better opacity at high light transmission values.
  • the disadvantage is the poor weatherability and, as a consequence, an increase in the yellowness index and its high level of yellowing
  • the refractive index of the polymer should be greater than that of the polymer matrix and the mean particle size of the beads should be in the range of 20 ⁇ m-50 ⁇ m.
  • the resin composition is extruded into the desired moldings.
  • these beads are comparatively small
  • the patent EP 1 022 115 describes extruded articles which have a matt and textured surface. In order to achieve this effect, light-scattering pearls with a refractive index offset to the matrix of> 0.02
  • the weight average particle size of the beads should be in the range of
  • Polymer particles which are encased by a matrix polymer which is to be homogenized during compounding in the thermoplastic to be matted, while the
  • crosslinked polymer particles should then act as matting agents.
  • Polyacrylic resins such as copolymers of methyl methacrylate, are used in these
  • the crosslinked polymer particles are made of an ethylenically unsaturated monomer, such as. As styrene, constructed. They are used with 0.01 wt .-% to 3.0 wt .-% of a multiple
  • unsaturated monomers such as. B. a Diacrylester of glycol, crosslinked as a primary crosslinker.
  • the polymer particles preferably become a secondary crosslinking or latent crosslinking by means of reactive groups
  • the preparation of the crosslinked polymer particles takes place by means of endopolymerization, by dissolving the matrix polymer in a monomer and subsequently the monomer
  • Obtained polymer product which comprises the matrix polymer as a quasi-continuous phase in which the newly formed crosslinked end-polymerisate is dispersed.
  • the endopolymerization can be different
  • the resulting product is optionally granulated, mixed with further matrix polymer and processed together.
  • the size of the enclosed endopolymers should be in the range of 0.5 .mu.m to 30 .mu.m. These values were determined by light microscopy.
  • Example 1 describes the matting of a polymethacrylate co-ethyl acrylate (85/15).
  • the matrix polymer used is a polymer of the same composition.
  • the crosslinked polymer particles are obtained by endopolymerization in bulk, wherein the monomer mixture styrene (96.65 wt .-% based on all monomers), glycidyl methacrylate (1.96 wt .-% based on all monomers), methacrylic acid (1.29 wt. % based on all monomers) and butylene diacrylate (0.10% by weight based on all monomers). After the polymerization, the product is granulated and added together with the monomer mixture styrene (96.65 wt .-% based on all monomers), glycidyl methacrylate (1.96 wt .-% based on all monomers), methacrylic acid (1.29 wt. % based on all monomers)
  • the size of the granulated polymer particles is given as less than 7.938 mm.
  • the properties of further finely divided polymer mixtures are described in Example 7.
  • the soluble polymer comprises from 87% to 90% by weight of methyl methacrylate units and from 10% to 13% by weight of ethyl acrylate units.
  • the crosslinked particles comprise styrene units and optionally 87% by weight of butyl acrylate units. You have one
  • Size range from 5 ym to 80 ym and an average size ranging from 5 ym to 40 ym.
  • the concentration of cross-linked particles is between 50 and 80%.
  • Polymer particles comprising a crosslinked end copolymer in a matrix polymer are also described in DE 2439542 A
  • thermoplastic polymers in particular to reduce surface gloss and matting.
  • Example 1 a final polymerization is shown in substance.
  • the matrix polymer used is a polymethacrylate-co-ethyl acrylate (91/9).
  • the monomer mixture for the final copolymer comprises styrene (61.83% by weight, based on all monomers), n-butyl methacrylate (32.84% by weight, based on all monomers), ethyl acrylate (3.88% by weight, based on all monomers) Monomers) and allyl methacrylate (1.45% by weight based on all monomers). After the polymerization, the product becomes
  • Endopolymer particles should have a size in the range from 1 ⁇ m to 35 ⁇ m and a mean size of 1.5 ⁇ m, determined by means of electron microscopy.
  • Example 2 The use of the product of Example 1 as an additive for polyvinyl chloride is described in Example 2.
  • Example 6 describes a suspension end-polymerization.
  • the matrix polymer used is a polymethacrylate-co-ethyl acrylate (90/10).
  • the monomer mixture for the final copolymer comprises styrene (59.74% by weight, based on all monomers), n-butyl methacrylate (33.41% by weight, based on all monomers), ethyl acrylate (3.84% by weight, based on all monomers) Monomers) and allyl methacrylate (3.01 wt.% Based on all monomers).
  • the size of the resulting polymer particles is reported as 1080 ym to 2160 ym.
  • the endopolymer particles should have a size in the range from 1 .mu.m to 33 .mu.m and a mean size of 6 .mu.m, determined by means of
  • the matrix is made up of approx. 150 ym pearls that are made from
  • PMMA Polymethyl methacrylate
  • Pearls is according to the product data sheet about 7 ym.
  • Matting agents in particular for polymethyl methacrylate-based molding compositions, desired.
  • Acematt OP 278 is not suitable for the matting of polymethylmethacrylate, in particular Plexiglas 7N, since there is no increase in the intensity half-value angle.
  • Acematt is according to the product data sheet
  • polymer particles comprising crosslinked polymer particles derived from a
  • Matrix polymer are coated, wherein
  • the matrix polymer is obtainable by radical polymerization of at least one monoethylenically unsaturated monomer
  • the crosslinked polymer particles are insoluble in the matrix polymer
  • Matrix polymer measured at 20 ° C., is at least 0.01,
  • Luminous efficacy shows and leads to a very effective increase of the intensity half-value angle.
  • the loss due to re-radiation is significantly lower than with conventional matting agents and the scattering effect is significantly higher.
  • the amount of litter additives can be reduced, which in turn reduces costs and conserves resources.
  • the moldings according to the invention have very good mechanical properties, very good roughness and significantly improved weather resistance.
  • the preparation of the molding according to the invention with matt and structured surface finish can be produced in a comparably simple manner on an industrial scale and inexpensively by shaping a composition,
  • polymer particles according to the invention lies in the processability. Due to their size, they can be processed much more easily than conventional matting agents, since the finely divided scattering particles are only released when compounded.
  • the polymer particles of the invention comprise
  • Polymer particles coated by a matrix polymer They are preferably present as end-polymer particles.
  • the polymer particles are within the scope of the present invention.
  • crosslinked means that the particles are only in small amounts in a strong organic compound
  • Solvent such as tetrahydrofuran (THF)
  • THF tetrahydrofuran
  • polymer-soluble fraction is at most 7% by weight, based on the total weight of those used in the measuring method
  • the polymer-soluble portion becomes as follows
  • the polymer particles are dissolved in THF and heated at 21,000 rpm for 3 hours. centrifuged. 15 ml of the supernatant are withdrawn and refilled with approx. 15 ml of THF. This is repeated 3 times. The withdrawn supernatant is filtered through a 0.45 ⁇ membrane filter, then reduced to 60 mL and again centrifuged for 3 hours. After centrifugation, the supernatant is evaporated and analyzed by NMR and GC-MS.
  • the matrix polymer is preferably not crosslinked.
  • non-crosslinked means that the matrix polymer can essentially be dissolved in a strong organic solvent, such as tetrahydrofuran (THF), where "substantially” means that the polymer-soluble fraction is more than 7% by weight, based on the total weight of the particles used in the measurement method.
  • THF tetrahydrofuran
  • the crosslinked polymer particles are free-radical
  • a. 90.00% by weight to 99.99% by weight preferably 95.00% by weight to 99.95% by weight, preferably 97.00% by weight to 99.90% by weight, in particular 98.00 wt .-% to 99.50 wt .-%, of at least one monoethylenically unsaturated monomer and
  • the monoethylenically unsaturated monomers are in principle not subject to further restrictions and include u. a. (Meth) acrylates, fumarates and maleates derived from saturated alcohols, such as
  • n-propyl (meth) acrylate iso-propyl (meth) acrylate
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate,
  • Vinyl halides such as vinyl chloride
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and
  • Alkyl substituents on the ring such as vinyl toluene and p-methylstyrene, halogenated styrenes, such as Monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
  • Maleic acid and maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide;
  • Aryl (meth) acrylates such as benzyl methacrylate or
  • Methacrylates of halogenated alcohols such as 2,3-dibromopropyl methacrylate,
  • Hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl methacrylate
  • carbonyl-containing methacrylates such as 2-carboxyethylmethacrylate, carboxymethylmethacrylate, oxazolidinylethylmethacrylate, N- (Methacryloyloxy) formamide, acetonyl methacrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2-pyrrolidinone, N- (2-methacryloyloxypentadecyl) 2-pyrrolidinone, N- (3-methacryloyloxyheptadecyl) -2-pyrrolidinone;
  • Methacrylates of ether alcohols such as
  • Methoxyethoxyethyl methacrylate 1-butoxypropyl methacrylate, cyclohexyloxymethyl methacrylate,
  • Methoxymethoxyethyl methacrylate benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate,
  • Ethoxymethyl methacrylate and ethoxylated (meth) acrylates which preferably have 1 to 20, in particular 2 to 8, ethoxy groups;
  • Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N- (methacryloyloxyethyl) dihexadecylketimine,
  • Oxiranyl methacrylates such as 2, 3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 10, 11-epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 10, 11-epoxyhexadecyl methacrylate;
  • Particularly suitable monoethylenically unsaturated monomers are alkyl acrylates, preferably having 4 to 8
  • Very particularly preferred systems contain, based on the total weight of the monoethylenically unsaturated
  • At least 50.0 wt .-% suitably at least 75.0 wt .-%, particularly preferably at least 90.0 wt .-%, in particular at least 95.0 wt .-%, styrene and at most 50.0 wt. %, advantageously not more than 25.0% by weight, more preferably not more than 10.0% by weight,
  • Cio-alkyl acrylate in particular C 4 - to Cs-alkyl acrylate.
  • (Meth) acrylates derived from unsaturated alcohols such as 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, oleyl (meth) acrylate;
  • Glycol dimethacrylates such as 1,2-ethanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate;
  • Dienes such as divinylbenzene, divinylpyridine, divinyltoluenes, divinylnaphthalenes, 1,3-divinylxylene, divinylethylbenzene, divinylsulfone, polyvinyl or polyallyl ethers of glycol, of glycerol, of pentaerythritol, of mono- or dithio derivatives of glycols and of resorcinol, divinyl ketone,
  • R is hydrogen or methyl, preferably methyl
  • R 1 is a linear or branched alkyl radical having 2 to 20 carbon atoms, preferably 2 to 10
  • Carbon atoms means. Very particular preference is given to using ethylene glycol dimethacrylate.
  • At least two different polyunsaturated compounds are used, more preferably at least one polyunsaturated one
  • Non (meth) acrylate compound in particular divinylbenzene used.
  • Compound is preferably at least 10.0% by weight, preferably at least 25.0% by weight, particularly preferably at least 30.0% by weight, advantageously at least 35.0% by weight, advantageously at least 40.0% by weight, very particularly preferably at least 45.0% by weight. -%, In particular 50.0 wt .-%, each based on the total weight of all multiply
  • Very particularly suitable crosslinked polymer particles for the purposes of the present invention are obtainable by free-radical polymerization of a monomer mixture which, based on its total weight,
  • Ci-Cio alkyl (meth) acrylate b. 0.00 wt .-% to 49.99 wt .-% of at least one Ci-Cio alkyl (meth) acrylate
  • the matrix polymer is also free radical
  • unsaturated monomers in particular at least one monoethylenically unsaturated (meth) acrylate, obtainable.
  • unsaturated monomers in particular at least one monoethylenically unsaturated (meth) acrylate, obtainable.
  • Polymer particles are used.
  • Matrix polymer be insoluble or incompatible. "Insoluble” in this context means that the polymers in the present concentration ratio are immiscible.
  • the Gibbs mixing energy (AG m i X ) m is for the
  • Entropieterm -T (AS m i X ) m can not compensate for the positive enthalpy term (AH m i X ) m . It is preferred in this
  • thermoplastically processable polymers are suitable as the matrix polymer. These include, but are not limited to, polyalkyl (meth) acrylates such as polymethyl methacrylate (PMMA), polyacrylonitriles, polystyrenes, polyethers, polyesters, polycarbonates, polyvinyl chlorides.
  • PMMA polymethyl methacrylate
  • Pacrylonitriles such as polystyrenes
  • polyethers such as polyetherstyrenes
  • polyesters such as polycarbonates, polyvinyl chlorides.
  • polyalkyl (meth) acrylates are preferred.
  • Polymers can be used individually or as a mixture. Furthermore, these polymers may also be in the form of copolymers.
  • Ci-Ci8 _ alkyl (meth) acrylates expediently of Ci-Cio-alkyl (meth) acrylates, in particular C1-C4-alkyl (meth) acrylate polymers, which may optionally still contain different monomer units, particularly preferably.
  • the notation (meth) acrylate here means both
  • Methacrylate such as. As methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, such as. For example, methyl acrylate,
  • copolymers which contain 70.0% by weight to 99.0% by weight, in particular 70.0% by weight to 90.0% by weight, of C 1 -C 10 -alkyl (meth) acrylates, has proven very special.
  • Preferred C 1 -C 10 -alkyl methacrylates include
  • MMA Methyl methacrylate
  • ethyl methacrylate ethyl methacrylate
  • C 1 -C 10 -alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, decyl acrylate and ethylhexyl acrylate, and cycloalkyl acrylates such as
  • cyclohexyl acrylate for example, cyclohexyl acrylate, isobornyl acrylate or ethylcyclohexyl acrylate.
  • Very particularly preferred copolymers comprise 80.0% to 99.0% by weight of MMA units and 1.0% to 20.0% by weight, preferably 1.0% to 5% , 0 wt .-%, Ci-Cio-alkyl acrylate units, especially methyl acrylate and / or ethyl acrylate units.
  • Ci-Cio-alkyl acrylate units especially methyl acrylate and / or ethyl acrylate units.
  • PLEXIGLAS ® 7N has proven particularly successful in this context.
  • the matrix polymer preferably has a weight average molecular weight in the range from 10,000 to 1,000,000 g / mol, preferably in the range from 15,000 to 500,000 g / mol,
  • the matrix polymer can be known per se
  • Emulsion polymerization are particularly preferred.
  • Particularly suitable for this purpose initiators include in particular azo compounds, such as 2,2'-azobis (isobutyronitrile) or 2, 2 'azobis (2, 4 dimethylvaleronitrile), redox systems, such as the combination of tertiary amines with peroxides or
  • Dibenzoyl peroxide or 2, 2-bis (tert-butylperoxy) butane Dibenzoyl peroxide or 2, 2-bis (tert-butylperoxy) butane. It is also possible to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, for example dilauroyl peroxide and 2,2-bis- (tert-butylperoxy) -butane, in order to control the free radical flow in the course of the polymerization and at different temperatures
  • amounts of polymerization initiator used are generally from 0.01 wt .-% to 2.0 wt .-% based on the monomer mixture.
  • the polymerization can be carried out both continuously and batchwise. After polymerization, the polymer is over conventional insulation and
  • Copolymerizats can be carried out by polymerization of the monomer or monomer mixture in the presence of molecular weight regulators, in particular from those known
  • Mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol or 2-ethylhexyl thioglycolate, pentaerythritol tetrathioglycolate;
  • the molecular weight regulators generally in amounts of 0.05 wt .-% to 5.0 wt .-%, based on the monomer or monomer mixture, preferably in amounts of 0.1 wt .-% to 2.0 % By weight and more preferably in amounts of from 0.2% by weight to 1.0% by weight, based on the monomer or monomer mixture (cf., for example, H. Rauch-Puntigam, Th. Völker, " Acrylic and Methacrylic Compounds ", Springer, Heidelberg, 1967; Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, page 66, Georg Thieme, Heidelberg, 1961 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. Pages 296ff, J. Wiley, New York, 1978).
  • Preference is given to using n-dodecylmercaptan as molecular weight regulator.
  • Pentaerythritol tetrathioglycolate particularly favorable. It may also be a combination of two or more regulators, in particular mixtures of n-dodecylmercaptan and
  • Pentaerythritol tetrathioglycolate used in an advantageous manner.
  • the matrix polymer preferably has one
  • Light transmittance T D 65 according to DIN 5033/7 in the range of 40% to 93%, preferably greater than 75%, in particular greater than 85%.
  • the crosslinked polymer particles are in the
  • Polymer particles according to the invention preferably spherical.
  • Spherical in this context means that the ratio of the diameter of the crosslinked polymer particles in the direction of the shortest extension divided by the
  • Diameter of the crosslinked polymer particles in the direction of the longest extent greater than 80%, preferably greater than 90%, more preferably greater than 95%, in particular greater than 99%.
  • the mean particle size of the crosslinked polymer particles is in the range from 0.9 ⁇ m to 6.0 ⁇ m, preferably in the range from 1.5 ⁇ m to 5.0 ⁇ m, expediently in the range from 2.0 ⁇ m to 4.0 ⁇ m, in particular in Range from 2.2 ym to 3.0 ym.
  • the mean particle size of the coated polymer particles is in the range from 50 ⁇ m to 300 ⁇ m, preferably in the range from 100 ⁇ m to 250 ⁇ m, expediently in the range from 125 ⁇ m to 225 ⁇ m, in particular in the range from 150 ⁇ m to 200 ⁇ m.
  • the stated average particle sizes are preferably based on the corresponding weight average.
  • All polymer particles preferably have a particle size in the range from 25 ⁇ m to 400 ⁇ m, preferably in the range from 30 ⁇ m to 350 ⁇ m, expediently in the range from 35 ⁇ m to 325 ⁇ m, in particular in the range from 39 ⁇ m to 320 ⁇ m.
  • All crosslinked polymer particles preferably have a particle size in the range from 0.5 .mu.m to 8.0 .mu.m, preferably in the range from 0.6 .mu.m to 7.5 .mu.m, expediently in the range from 0.7 .mu.m to 7.0 .mu.m, in particular Range from 0.75 ym to 6.5 ym.
  • Polymer particles can be done in a known per se, such as. B. by light scattering methods or by microscopy suitably colored samples. For the determination of
  • polymer particles have scattering studies on the preferably in a solvent such.
  • a solvent such as water
  • dispersed polymer samples particularly proven, in particular measurements by means of Mastersizer.
  • crosslinked polymer particles is preferably by means of
  • Electron microscopy determined. If the crosslinked polymer particles and / or the endopolymer particles have no spherical shape, the corresponding values are based on the maximum
  • the content of the matrix polymer based on the total weight of the coated polymer particles of the present invention is desirably 1.0 wt% to 50.0 wt%, preferably 5.0 wt% to 30.0 wt%, desirably 10.0 wt .-% to 25.0 wt .-%, in particular 15.0 wt .-% to 20.0 wt .-%.
  • Polymer particles is suitably 50.0% by weight to 99.0% by weight, preferably 70.0% by weight to 95.0% by weight,
  • the matrix polymer is partially connected to the crosslinked polymer particles. This can be
  • coated polymer particles according to the invention can be prepared in a manner known per se.
  • the preferred method comprises a final polymerization technique wherein the monomers which ultimately form the crosslinked polymer particles are in the presence of a soluble preformed polymer
  • crosslinked polymer particles are in the so-called
  • soluble matrix polymer is preferably insoluble and the latter becomes a carrier polymer in this technique, i. the original preformed matrix polymer used in the
  • Monomer system is dissolved, remains intact and after the polymerization of the monomer system, which merges into the crosslinked polymer particles, the continuous phase, which contains dispersed therein the crosslinked polymer particles.
  • the endopolymerization takes place as
  • Suspension polymerization process (bead polymerizations).
  • the monomer / matrix polymer solution is treated as a disperse phase by the action of mechanical forces (stirring) in a non-solvent (continuous
  • the polymer formed is predominantly soluble in the monomer. Under the influence of the interfacial tension the monomer forms spherical drops, which are successively polymerized, whereby in the individual drops the
  • Matrix polymer and the monomers increasingly segregate and, as a result, the matrix polymer to the crosslinked
  • the "distributor" causes the monomer droplets once formed are stabilized to the extent that a combination of drops practically
  • the distributors used are preferably (water-insoluble) salts of inorganic acids, such as barium sulfate or barium carbonate, or high molecular weight natural products or synthetic polymers.
  • the group of high molecular weight distributors includes water-soluble colloids, such as polyvinyl alcohol, partially saponified polyvinyl acetate, methyl cellulose, starch,
  • Monomeric phase is preferably 2: 1 to 4: 1.
  • initiators which are, to a first approximation, soluble in the monomer but insoluble in water.
  • the amount of starter used is from 0.1% by weight to 1.0% by weight, preferably by 0.5% by weight, based on the monomers.
  • starters are preferably the usual monomer-soluble organic peroxides or corresponding azo compounds used, such as. B. dibenzoyl peroxide, lauroyl peroxide,
  • Decay temperatures can additionally be used if towards the end of the reaction as complete as possible Polymerization the temperature is increased.
  • the bead size can be adjusted in the stressed frame.
  • lubricants commonly used such as fatty alcohols, stearic acid esters, palmitic acid esters or natural waxes may be added, preferably before polymerization.
  • the practice of the polymerization may be such that the water, the monomers, the matrix polymer, the initiator, optionally the dispersant and
  • the lubricant is placed together and then heated, for example to about 90 ° C.
  • the excess heat of polymerization especially from 95 ° C, dissipated by external cooling. Temperatures above 115 ° C should be avoided if possible.
  • the duration of the polymerization is usually in the range of 1 to 5 hours.
  • Polymerization temperature is generally in the range between 800 mPas and 8,000 mPas.
  • the partially reactive lubricants are preferably added only from about 20% conversion.
  • the addition of regulators can also take place during the polymerization.
  • the beads are generally separated by filtration or centrifugation. adherent
  • Additives can be suitably, e.g. B. be removed by washing with dilute acid and water.
  • the beads are often heated, preferably with
  • Initiator polymerized which is soluble in the monomer mixture.
  • the weight ratio of matrix polymer to monomer mixture is preferably in the range from 1: 1.28 to 1: 5.6. Furthermore, the weight ratio of water to solution is preferably in the range from 1: 2 to 1: 4, preferably in
  • the distributor used is conveniently a polyvinyl alcohol, particularly preferably a partially hydrolyzed polyvinyl acetate, preferably having a degree of hydrolysis greater than 50 mol%.
  • the polymer particles of the invention are characterized by a high thermal stability. They preferably have a temperature resistance of at least 200 ° C, in particular of at least 250 ° C, without thereby causing a
  • temperature resistance means that the particles are essentially not subject to any thermal degradation
  • Temperature stability can be determined by thermogravimetric
  • Determination determined The determination method is familiar to the person skilled in the art. When the method is used, a mass loss of not more than 2.0% by weight of the plastic sample to be measured occurs up to the indicated temperature under protective gas.
  • Secondary crosslinking in this context means a subsequent crosslinking via groups which do not react during the initial polymerization, but which can later be brought to reaction by suitable measures, in particular by increasing the temperature.
  • polymer particles according to the invention preferably have less than 1.0% by weight, based on their total weight,
  • polar groups which can be subsequently crosslinked, in particular by increasing the temperature.
  • polar groups include in particular hydroxy groups, primary or secondary
  • Polymer particles include, in particular, the matting of thermoplastic polymers.
  • Corresponding molding compositions can be obtained by introducing the invention
  • Polymer particles in a thermoplastic polymer eg. B.
  • the molding composition by mixing the components, wherein the Components are preferably distributed homogeneously in the molding composition.
  • the polymer particles according to the invention are in principle suitable for all known thermoplastics
  • processable polymers include, among others
  • Polyalkyl (meth) acrylates such as
  • PMMA Polymethyl methacrylate
  • polyacrylonitriles polystyrenes
  • polyethers polyethers
  • polyesters polycarbonates
  • polyvinyl chlorides polyvinyl chlorides
  • polyalkyl (meth) acrylates are preferred.
  • Polymers can be used individually or as a mixture. Furthermore, these polymers may also be in the form of copolymers.
  • Ci-Ci8 _ alkyl (meth) acrylates expediently of Ci-Cio-alkyl (meth) acrylates, in particular C1-C4-alkyl (meth) acrylate polymers, which may optionally still contain different monomer units, particularly preferably.
  • copolymers which contain 70.0% by weight to 99.0% by weight, in particular 70.0% by weight to 90.0% by weight, of C 1 -C 10 -alkyl (meth) acrylates, has proven very special.
  • Preferred C 1 -C 10 -alkyl methacrylates include
  • C 1 -C 10 -alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate,
  • cyclohexyl acrylate for example, cyclohexyl acrylate, isobornyl acrylate or ethylcyclohexyl acrylate.
  • Very particularly preferred copolymers comprise 80.0% to 99.0% by weight of MMA units and 1.0% to 20.0% by weight, preferably 1.0% to 5% , 0 wt .-%, Ci-Cio-alkyl acrylate units, especially methyl acrylate and / or ethyl acrylate units.
  • Ci-Cio-alkyl acrylate units especially methyl acrylate and / or ethyl acrylate units.
  • PLEXIGLAS ® 7N has proven particularly successful in this context.
  • the weight-average molecular weight of the polymer to be matted is preferably in the range of 10,000 to
  • 1,000,000 g / mol preferably in the range of 15,000 to 500,000 g / mol, in particular in the range of 20,000 to 200,000 g / mol. It is preferably determined by means of gel permeation chromatography (GPC).
  • thermoplastic polymer may contain other additives well known to those skilled in the art. To be favoured
  • impact modifiers external lubricants, antioxidants, flame retardants, UV stabilizers,
  • Mold release agents dyes, pigments, adhesion promoters, weathering agents, plasticizers, fillers and the like. Furthermore, the addition of inorganic nanoparticles is particularly advantageous.
  • the preparation of impact modifiers is preferably carried out by
  • Emulsion polymerization process In this way, a stable latex having an arithmetic weight average particle size in the range of 0.05 ym to 5 ym is obtained, which is usually spray dried or
  • suitable emulsifiers include in particular conventional soaps, alkylbenzenesulfonates, such as
  • Particularly preferred emulsifiers include hydrocarbon groups having 8 to 22 carbon atoms attached to highly polar solubilizing groups such as alkali metal and ammonium carboxylate groups.
  • thermoplastic polymer such as B. by
  • thermoplastic polymer is used, or in a monomer / polymer syrup mixture, which together the
  • thermoplastic polymer results.
  • Dispersion in water or in an organic carrier are given.
  • the water or organic carrier can then be removed before or after casting into the final polymer form.
  • the impact modifiers may also be compounded with the polymer by extrusion molding.
  • thermoplastic polymers reference is made to U.S. Patent 3,793,402.
  • thermoplastic polymer is polymethylmethacrylate, which is commercially available from Evonik Röhm GmbH under the
  • Plexiglas ® zk6BR is available.
  • thermoplastic polymer preferably has one
  • Light transmittance T D 65 according to DIN 5033/7 in the range of 40% to 93%, preferably greater than 75%, in particular greater than 85%.
  • thermoplastic polymer is preferably at least 0.01, advantageously at least 0.02,
  • the content of the thermoplastic polymer is favorably 20.0 wt .-% to 99.9 wt .-%, preferably 50.0 wt .-% to 99.8 wt .-%, particularly preferably 75.0 wt .-% to 99.5 wt .-%, most preferably 80.0 wt .-% to 95.8 wt .-%, more preferably 90.0 wt .-% to 99.5 wt. % and most preferably 95.0% to 99.0% by weight.
  • the content of the polymer particles according to the invention is advantageously 0.1% by weight to 80% by weight, preferably 0.1% by weight to 50.0% by weight, particularly preferably 0, 2 wt .-% to 50 wt .-%, most preferably 0.5 wt .-% to 25 wt .-%, especially preferably 0.2 wt .-% to 20.0 wt .-%, very specifically
  • the molding composition of the invention may be as conventional
  • Preferred forming processes include profile extrusion, sheet and film extrusion, injection molding and
  • the product which is obtained by injection molding, has a matte
  • the average roughness Ra is preferably at least 0.05 ⁇ m, preferably at least 0.15 ⁇ m, particularly preferably at least 0.25 ⁇ m, in particular at least 0.30 ⁇ m.
  • the average roughness Rz is preferably
  • the roughness Rt is preferably at least 0.50 ⁇ m, preferably at least 1.00 ⁇ m, particularly preferably
  • the surface roughness is determined according to DIN EN ISO 4287 and DIN EN ISO 4288.
  • TWLT Transmission
  • ASTM E1331 and E1164
  • Forward scattering can be determined by measuring the transmission in combination with the energy half-angle of moldings containing the particles.
  • the matted appearance can be determined by means of an opacity or opacity measurement (turbidity measurement). The higher the opacity value, the better the opacity or unrecognizability.
  • the opacity should be at least 10%.
  • the loading of the polymer particles and the difference in refractive indices affects the opacity of the sample, which is determined by the opacity number
  • the determination of the opacity values is preferably carried out according to the standards ASTM D2805-80, ASTM D589-65, TAPPI T-425 and TAPPI T-519.
  • the molding composition according to the invention and the moldings obtainable therefrom preferably have a light transmittance T D65 according to DIN 5033/7 in the range of 40.0% to 93.0%, preferably of at least 50.0%, particularly preferably
  • At least 55.0% suitably at least 70.0%, in particular in the range from 80.0% to less than 90.0%.
  • Moldings obtainable from the molding compositions according to the invention preferably have an intensity half-value angle (IHW), measured in accordance with DIN 5036 with a LMT goniometer measuring station GO-T-1500 from the company LMT, in the range from 1 ° to 55 °, preferably greater than 2.0 ° , in particular greater than 4.0 °, on.
  • IHW values in the range of greater than 10 ° and less than 50 ° are particularly expedient. Especially useful are values in the range of greater than 15 ° and less than 45 °, even more preferred are values for the IHW in the range of greater than 20 ° and less than 40 °.
  • Moldings available are preferably at least 20 MPa, preferably at least 40 MPa, more preferably at least 50 MPa, in particular at least 60 MPa.
  • the modulus of elasticity of moldings available according to ISO 527 is when impact resistant
  • Polymer matrices favorably greater than 1600 MPa, preferably greater than 1700 MPa.
  • Moldings according to ISO 179 available when using impact-resistant polymer matrices is preferably at least 30 kJ / m 2 , preferably at least 40 kJ / m 2 , in particular at least 50 kJ / m 2 .
  • Shaped articles according to ISO 527 are advantageously greater than 3%, preferably greater than 4%.
  • Shaped bodies according to ISO 527 is preferably at least 2%, preferably at least 15%, in particular at least 30%.
  • the Vicat softening temperature VET (ISO 306-B50) of the molding composition according to the invention and the moldings obtainable therefrom is not impact-resistant when used
  • Polymer matrices preferably at least 95 ° C, preferably at least 97 ° C, more preferably at least 103 ° C, especially greater than 104 ° C.
  • melt index MVR (ISO 1133, 230 ° C / 3.8 kg)
  • molding composition of the invention and the shaped body obtainable therefrom is the use of impact-resistant polymer matrices preferably at least 1.0 cm 3/10 min, preferably at least 1.3 cm 3/10 min, more preferably at least 3.0 cm 3/10 min, in particular at least 4 , 5 cm 3/10 min.
  • Sales outlets and cosmetic vendors, containers, home and office decorations, furniture applications, shower doors and office doors can be used.
  • the specified measured variables were determined as follows.
  • T Transmission
  • G yellowness index
  • IHW intensity half-value angle
  • the values given for the particle size relate in each case to the volume average particle size distribution.
  • This particle size distribution can be determined, for example, by a Mastersizer 2000 from Malvern Instruments Ltd.
  • the exact measuring method for determining the particle size is included in the user manual.
  • the standard ISO 13320-1 applies, the calculation is based on the Fraunhof model and Mie theory.
  • the parameters used are the refractive index n D of 1.489 (polymethymethacrylate) and the absorption coefficient of 0. This method is particular to the purposes of the present invention
  • particle size can be measured by measuring and
  • Plexiglas 7N was dissolved in styrene at 50 ° C within 2h. The mixture was allowed to stand at room temperature overnight. Subsequently, the crosslinker glycol dimethacrylate and the initiators dilauryl peroxide and dibenzoyl peroxide (75% strength) were added at 250 rpm. Meanwhile, in a second Schmizoreaktor the water with the distributor (Mowiol 40-88, 5%, 35.4g, 16.2% ba monomers) and the excipients butyl phosphate (0.27g) and sodium sulfate (1.47 g) weighed and the mixture dissolved. While stirring (blade stirrer), the aqueous phase (at 250 rev / min) was heated to about 50 ° C (bath temperature
  • aqueous phase is added dropwise.
  • the reaction mixture was stirred at 50 ° C. for 60 minutes (bath temperature 55 ° C.) and then the bath temperature was adjusted to 85 ° C. It was stirred for 4.5 h at this temperature. Subsequently, the
  • Reactor content cooled to about 45 ° C and over a 250 ym Filtered sieve.
  • the peribular polymers were transferred to a filter chute and washed with 5 L of distilled water. The drying took place over 20 h at 50 ° C in
  • Polymer particle was visually estimated and partially the volume average particle size distribution (Malvern
  • the polymerization was carried out analogously to Example Bl, except that instead of 1 wt .-% glycol dimethacrylate per 1 wt .-% divinylbenzene and 1 wt .-% glycol dimethacrylate was used.
  • Round styrene domains are provided in a 7N matrix by endopolymerization.
  • Table 1c Evaluation of the orders of magnitude of the endopolymer carrier beads, of the finely divided end-polymers in the carrier beads and of the scattering agent in the molding compound C2 on the injection-molded die; Determining the sizes by means of SEM on exemplary beads or areas of the injection-molded sheet.
  • Crosslinker allyl methacrylate (instead of glycol dimethacrylate), initiator: dilauryl peroxide and tert-butyl per-2-ethylhexanoate 0.59 g / 0.02 g
  • Crosslinker allyl methacrylate (instead of glycol dimethacrylate),
  • Polymethacrylic acid copolymers as distributors are obtained only crosslinked beads (see Table 3) which swell in acetone but do not disintegrate.
  • suspension polymerization using a polyvinyl alcohol (Mowiol 40-88) as a distributor resulted
  • thermostability of the polymers were determined by means of
  • thermogravimetric analysis Therd thermogravimetric analysis (TGA).
  • T c temperature of the mass point at the midpoint
  • Mass changes of a sample which is subjected to a mostly linear heating (DIN EN ISO 11358,
  • the additives B2 and B4 were each prepared with only 1 wt .-% crosslinker.
  • Theroret. Content of scattering agent 1.0 or 0.50 wt .-%
  • Acematt OP 278 is not a suitable additive for light-scattering a Plexiglas molding compound. Additionally were on
  • Extruded plates of thickness 3.05 mm at a temperature of 210 ° C made.
  • the weathering behavior was assessed by yellowness and transmission changes as well as visual assessment after 500h, 1000h and 2000h Xenotest.
  • the device name is Xenotest 1200 (45 W / m 2 ).
  • Table 8 shows that the relative increase in yellowness of the particles according to the invention is significantly lower for the same weight in each case than for the Sekisui SBX particles. Molding compositions comprising the inventive
  • Endopolymers thus have a significantly better weathering behavior.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne des particules polymères comprenant des particules polymères réticulées, qui sont enrobées d'un polymère formant matrice. Selon la présente invention, i.) les particules polymères réticulées sont obtenues par la polymérisation radicalaire d'un mélange de monomères qui comprend, rapporté au poids total, a. de 90,00 % en poids à 99,99 % en poids d'au moins un monomère monoéthyléniquement insaturé et b. de 0,01 % en poids à 10,00 % en poids d'au moins un monomère polyinsaturé, ii.) le polymère formant matrice est obtenu par la polymérisation radicalaire d'au moins un monomère monoéthyléniquement insaturé, iii.) les particules polymères réticulées sont insolubles dans le polymère formant matrice. En outre, selon l'invention, I.) la taille moyenne de particule des particules polymères réticulées étant comprise entre 0,9 µm et 6,0 µm, II.) la taille moyenne de particule des particules polymères enrobées étant comprise entre 50 µm et 300 µm, et III.) la différence entre l'indice de réfraction des particules polymères réticulées et l'indice de réfraction du polymère formant matrice, respectivement mesurés à 20 °C, étant au moins de 0,01.
PCT/EP2010/063138 2009-10-13 2010-09-08 Particules polymères WO2011045122A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727528A (zh) * 2018-04-18 2018-11-02 汪晓娅 一种无机纳米晶掺杂高分子微球调控折射率及光子晶体颜色的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017217212A1 (fr) 2016-06-17 2017-12-21 Ｎｉｓｓｈａ株式会社 Feuille de transfert, feuille décorative et produit décoratif

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2146628A1 (de) 1970-09-22 1972-09-07 Rohm & Haas Polymerisationsverfahren zur Her stellung von feinteihgen Polymerpartikeln
US3793402A (en) 1971-11-05 1974-02-19 F Owens Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer
DE2439542A1 (de) 1973-08-31 1975-03-06 Rohm & Haas Extrudierbare, pressbare oder warmverformbare gemische aus thermoplastischen polymeren und einem oberflaechenveraendernden mittel sowie verfahren zu deren herstellung
US4000216A (en) * 1970-09-22 1976-12-28 Rohm And Haas Company Surface altering agent for thermoplastic polymers
US4876311A (en) 1985-08-06 1989-10-24 Rohm Gmbh Chemische Fabrik Opaque synthetic resins
EP1022115A1 (fr) 1999-01-21 2000-07-26 Elf Atochem S.A. Articles polymères ayant une surface texturée et un aspect mat

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5636535A (en) * 1979-08-21 1981-04-09 Mitsubishi Rayon Co Ltd Matte thermoplastic resin composition
DE4237209A1 (de) * 1992-11-04 1994-05-05 Basf Ag Rauhe Überzugsmassen auf der Basis von Polymethylmethacrylat
IT1282651B1 (it) * 1996-02-19 1998-03-31 Atohaas Holding Cv Processo per la preparazione di perle di polimeri a base acrilica
DE102004045296A1 (de) * 2004-09-16 2006-03-23 Röhm GmbH & Co. KG Verwendung von Polyalkyl (meth) acrylat-Perlpolymerisaten und Formmasse zur Herstellung von extrudierten Formteilen mit mattierter Oberfläche
DE102007059632A1 (de) * 2007-12-10 2009-06-18 Evonik Röhm Gmbh Formkörper mit matter und strukturierter Oberflächenbeschaffenheit

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2146628A1 (de) 1970-09-22 1972-09-07 Rohm & Haas Polymerisationsverfahren zur Her stellung von feinteihgen Polymerpartikeln
US4000216A (en) * 1970-09-22 1976-12-28 Rohm And Haas Company Surface altering agent for thermoplastic polymers
US3793402A (en) 1971-11-05 1974-02-19 F Owens Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer
DE2439542A1 (de) 1973-08-31 1975-03-06 Rohm & Haas Extrudierbare, pressbare oder warmverformbare gemische aus thermoplastischen polymeren und einem oberflaechenveraendernden mittel sowie verfahren zu deren herstellung
US4876311A (en) 1985-08-06 1989-10-24 Rohm Gmbh Chemische Fabrik Opaque synthetic resins
EP1022115A1 (fr) 1999-01-21 2000-07-26 Elf Atochem S.A. Articles polymères ayant une surface texturée et un aspect mat

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
BRUNO VOLLMERT, E: "Grundriss der Makromolekularen Chemie", vol. IV, 1988, VOLLMERT VERLAG, pages: 222 - 224
H. RAUCH-PUNTIGAM; TH. VÖLKER: "Acryl- und Methacrylverbindungen", 1967, SPRINGER
HANS-GEORG ELIAS: "Makromolekule 5. Auflage", vol. 1, 1990, pages: 680 - 681
HOUBEN-WEYL: "Makromolekulare Stoffe, 4. Auflage,", 1961, G. THIEME-VERLAG, pages: 406 - 433
HOUBEN-WEYL: "Methoden der organischen Chemie", vol. XIV/1, 1961, GEORG THIEME, pages: 66
J. BRANDRUP.; E. H. IMMERGUT: "Polymer Handbook,3. Auflage,", 1989, article "Refractive Indices of Polymers"
KIRK-OTHMER: "Encyclopedia of Chemical Technology", vol. 1, 1978, J. WILEY, pages: 296FF
KIRK-OTHMER: "Encyclopedia of Chemical Technology", vol. 1, 1978, J. WILEY, pages: 386FF

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727528A (zh) * 2018-04-18 2018-11-02 汪晓娅 一种无机纳米晶掺杂高分子微球调控折射率及光子晶体颜色的方法
CN108727528B (zh) * 2018-04-18 2020-05-19 汪晓娅 一种无机纳米晶掺杂高分子微球调控折射率及光子晶体颜色的方法

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