EP1572768A2 - Particule a noyau et enveloppe servant a modifier la resilience de matieres moulables de poly(meth)acrylate - Google Patents

Particule a noyau et enveloppe servant a modifier la resilience de matieres moulables de poly(meth)acrylate

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Publication number
EP1572768A2
EP1572768A2 EP03769412A EP03769412A EP1572768A2 EP 1572768 A2 EP1572768 A2 EP 1572768A2 EP 03769412 A EP03769412 A EP 03769412A EP 03769412 A EP03769412 A EP 03769412A EP 1572768 A2 EP1572768 A2 EP 1572768A2
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EP
European Patent Office
Prior art keywords
weight
core
shell
alkyl
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03769412A
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German (de)
English (en)
Inventor
Klaus Schultes
Reiner Müller
Andreas Spiess
Klaus Albrecht
Werner Höss
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication of EP1572768A2 publication Critical patent/EP1572768A2/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
    • 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
    • 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
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • 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
    • C08L51/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the present invention relates to core-shell particles, processes for producing core-shell particles, molding compositions containing core-shell particles and their use.
  • the present invention relates to core-shell particles which can be used for impact modification of poly (meth) acrylate molding compositions. It has long been known that the notched impact strength of molding compositions, in particular poly (meth) acrylate molding compositions, can be improved by adding a suitable amount of so-called impact modifiers to the molding composition.
  • the use of core-shell particles with one or two shells has become established in technology. These generally have an elastomeric phase, in the case of a core-shell particle with one shell usually the core and, in the case of a core-shell particle with two shells, usually the first shell grafted onto the core being the elastomeric phase.
  • US Pat. No. 3,793,402 discloses impact-resistant molding compositions, in particular based on poly (meth) acrylate, which contain 90 to 4% by weight of a multi-stage core-shell particle with a hard core, an elastomeric first shell and a hard one have second shell.
  • Typical main components of the core and the second shell are alkyl methacrylate with 1 to 4 carbon atoms in the alkyl radical, in particular methyl methacrylate.
  • the first shell is essentially composed of butadiene, substituted butadienes and / or alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical.
  • copolymerizable monomer units such as, for example, copolymerizable, monoethylenically unsaturated monomer units.
  • copolymerizable monomer units such as, for example, copolymerizable, monoethylenically unsaturated monomer units.
  • the total diameter of the core-shell particles is in the range from 100 to 300 nm.
  • German patent application DE 41 21 652 A1 describes impact modifiers for thermoplastics, such as polymethyl methacrylate, consisting of an at least three-phase emulsion polymer containing
  • a hard core made of a crosslinked homo- or copolymer of ethylenically unsaturated, free-radically polymerizable monomers
  • a molding compound (example 3) which is mentioned in this publication has an Izod impact strength at room temperature of 6.2 kJ / m 2 , at -10 ° C of 4.7 kJ / m 2 and at -20 ° C of 3.7 kJ / m 2 .
  • the Vicat softening temperature of the molding compound is 97 ° C.
  • German patent application DE 41 36 993 A1 discloses impact-modified molding compositions which contain 10 to 96% by weight of a polymer based on polymethyl methacrylate and 4 to 90% by weight of a multi-stage core-shell-shell particle, the preparation of the Core and the second shell, a monomer mixture is used which essentially contains methyl methacrylate.
  • the monomer mixture for the first shell comprises 60 to 89.99% by weight of acrylic acid alkyl esters with 1 to 20 carbon atoms in the alkyl radical and / or cycloalkylacrylates with 5 to 8 carbon atoms in the cycloalkyl radical and 10 to 39.99% by weight of phenyl acrylic acid.
  • alkyl esters with 1 to 4 carbon atoms in the alkyl radical and optionally further constituents are included in the alkyl esters with 1 to 4 carbon atoms in the alkyl radical and optionally further constituents.
  • the average particle diameter of the core-shell-shell particles is in the range from 50 nm to 1000 nm, in particular in the range from 150 nm to 400 nm.
  • European patent EP 0 828 772 B1 describes the impact modification of poly (meth) acrylates by means of multi-stage core-shell particles, which consist of a core, a first shell and optionally a second shell, and of vinylically unsaturated compounds with at least two identical reactive double bonds are free.
  • the core contains a first (meth) acrylic polymer.
  • the first shell has a polymer with a low glass transition temperature, which contains 0 to 25% by weight, in particular 5 to 26% by weight, of a styrenic monomer and 75 to 100% by weight of a (meth) acrylic monomer which contains a homopolymer forms a glass transition temperature between -75 ° C and -5 ° C.
  • the optionally present second shell contains a second (meth) acrylic polymer which corresponds to the first (meth) acrylic polymer or can be different from him.
  • the total diameter of the core-shell particles is in the range from 250 nm to 320 nm.
  • suspension polymers are also occasionally used to modify the impact strength of molding compositions.
  • the rubber grafted with, for example, polymethyl methacrylate is present in the matrix of the molding composition, for example polymethyl methacrylate, relatively finely distributed.
  • the elastomeric phase consists of a mostly crosslinked copolymer with a low glass transition temperature below 25 ° C., which usually has alkyl acrylate units with 1 to 8 carbon atoms in the alkyl radical, in particular butyl acrylate units, as the main component.
  • polybutadiene or polybutadiene copolymers are also used as the tough phase.
  • the molding composition should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%.
  • the present invention provides impact modifiers for molding compositions, in particular for poly (meth) acrylate molding compositions, which enable the notched impact strength of molding compositions to be improved, in particular at low temperatures, without simultaneously the noticeable deterioration of the other properties of the molding composition which are important for the application, in particular the modulus of elasticity, the melt viscosity, the Vicat temperature and the strand expansion.
  • the molding compositions should have an Izod impact strength at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s. And advantageously less than 4500 Pa s, a Vicat temperature preferably greater than 93 ° C. and a strand expansion preferably in the range from 0 to 20%.
  • the present invention was also based on the object Specify areas of application and possible uses of the impact modifier according to the invention.
  • a core-shell particle which consists of a core, a first shell and optionally a second shell, wherein: i) the core, based on its total weight, at least 75.0% by weight (meth) repeating acrylate units; ii) the first shell has a glass transition temperature below 30 ° C; iü) the optionally present second shell, based on its total weight, comprises at least 75.0% by weight of (meth) acrylate repeat units; iv) the first shell, based on its total weight, comprises the following components:
  • styrene repeat units of the general formula (I) where the radicals R 1 to R 5 are each independently hydrogen, a halogen, a C- ⁇ - 6 alkyl group or a C 2 - 6 - alkenyl group call and the radical R 6 is hydrogen or an alkyl group having 1 to 6 carbon atoms, wherein the weight percentages of E) and F) add up to 100.0% by weight, v) the radius of the core-shell particle, including any second shell, measured by the Coulter method, in the range of greater than 160.0 up to 240.0 nm,
  • Molding compositions which are particularly suitable according to the invention have a notched impact strength according to Izod at 23 ° C., preferably greater than 6.0 kJ / m 2 , an elastic modulus preferably greater than 1450 MPa, a melt viscosity preferably greater than 2000 Pa s and advantageously less than 4500 Pa s, a Vicat Temperature preferably greater than 93 ° C and a strand expansion preferably in the range of 0 to 20%.
  • a number of important advantages can be achieved by using the core-shell particles according to the invention. These include:
  • molding compositions with significantly improved notched impact strength values are expediently molding compositions with an Izod impact strength according to ISO 180 greater than 3.7 kJ / m 2 at -20 ° C, accessible.
  • the core-shell particles according to the invention can be produced in a simple manner, on an industrial scale and inexpensively.
  • the impact-modified molding compositions according to the invention are distinguished by a significantly improved property profile at low temperatures, in particular at -20 ° C. This makes them ideal for applications at low temperatures, especially at temperatures below 0 ° C.
  • the present invention relates to core-shell particles which have a core, a first shell and optionally a second shell.
  • the core-shell particles according to the invention can optionally comprise further shells, although for the purposes of the present invention those core-shell particles which consist of a core, a first shell and preferably a second shell have proven particularly useful.
  • the term “core-shell particles” is best known from the prior art and, in the context of the present invention, denotes polymers which can be obtained by multi-stage emulsion polymerization. This method has long been known in the prior art and is carried out and explained, for example, in Houben-Weyl, Volume E20, Part 2 (1987), p. 1150 ff. The person skilled in the art can also obtain further valuable information from the publications US Pat. No. 3,793,402, DE 41 21 652 A1, DE 41 36 993 A1, EP 828 772 A1, the disclosure of which is hereby expressly incorporated by reference.
  • the core based on its total weight, has at least 75% by weight of (meth) acrylate repeating units.
  • (meth) acrylates denotes acrylates, methacrylates and mixtures of the two. They thus comprise compounds which have at least one group of the following formula
  • R denotes hydrogen or a methyl radical.
  • They include, in particular, alkyl acrylates and / or alkyl methacrylates.
  • the core preferably comprises, based in each case on its total weight, A) 50.0 to 99.9% by weight, suitably 60.0 to 99.9% by weight, preferably 75.0 to 99.9% by weight , particularly preferably 80.0 to 99.0% by weight, in particular 85.0 to 99.0% by weight, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8 carbon atoms in the alkyl radical,
  • the compounds A), B), C) and D) are of course different from one another, in particular the compounds A) and B) do not comprise any crosslinking monomers C).
  • the radicals R 1 to R 5 each independently denote hydrogen, a halogen, in particular fluorine, chlorine or bromine, or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen.
  • the radical R 6 denotes hydrogen or an alkyl group with 1 to 6 carbon atoms, preferably hydrogen.
  • Particularly suitable alkyl groups with 1 to 6 carbon atoms are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl groups and Cyclopentyl and cyclohexyl groups.
  • Styrene repeat units of the general formula (I) thus comprise recurring structural units which can be obtained by polymerizing monomers of the general formula (Ia).
  • Suitable monomers of the general formula (Ia) include, in particular, styrene, substituted styrenes with an alkyl substituent in the side chain, such as, for example, methylstyrene and ⁇ -ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as, for example, vinyl toluo! and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • alkyl methacrylate repeating units (A) mentioned above are taken to mean repeating structural units which can be obtained by polymerizing esters of methacrylic acid.
  • Suitable esters of methacrylic acid include in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-octyl methacrylate, non-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, tert-butylheptyl methacrylate, 3-iso-propylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-
  • the core based on its total weight, contains at least 50% by weight, suitably at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight, of methyl methacrylate repeating units ,
  • alkyl acrylate repeating units (B) are understood to mean recurring structural units which can be obtained by polymerizing esters of acrylic acid.
  • Suitable esters of acrylic acid include in particular methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethyl hexyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-methyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, 2-ethyl acrylate, -tert Butylheptylacrylat, 3-iso-propyl
  • crosslinking repeat units (C) are taken to mean recurring structural units which can be obtained by polymerizing crosslinking monomers.
  • Suitable crosslinking monomers include in particular all the compounds which are able to bring about crosslinking under the present polymerization conditions. These include in particular
  • R is hydrogen or methyl and n denotes a positive integer greater than or equal to 2, preferably between 3 and 20, in particular Di ( meth) acrylates of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol;
  • R is hydrogen or methyl and n is a positive integer between 1 and 14, in particular di (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycols, tetraethylene glycols, dodecaethylene glycols, tetradecaethylene glycols, propylene glycols, dipropyl glycols and tetradecapropylene glycols.
  • Glycerol di (meth) acrylate 2,2'- bis [p- ( ⁇ -methacryloxy- ⁇ -hydroxypropoxy) phenylpropane] or bis-GMA, biphenol-A-dimethacrylate, neopentyl glycol di (meth) acrylate, 2,2'-di (4- methacryloxypolyethoxyphenyl) propane with 2 to 10 ethoxy groups per molecule and 1, 2-bis (3-methacryloxy-2-hydroxypropoxy) butane.
  • Trifunctional or polyfunctional (meth) acrylates in particular trimethylolpropane tri (meth) acrylates and pentaerythritol tetra (meth) acrylate.
  • aromatic crosslinkers in particular 1,2-divinylbenzene, 1,3-divinylbenzene and 1,4-divinylbenzene.
  • the proportions by weight of constituents A) to D) of the core are preferably selected such that the core has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C.
  • the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC). Furthermore, the glass transition temperature Tg can also be calculated approximately in advance using the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • the first shell of the core-shell particles according to the invention has a glass transition temperature of less than 30 ° C., preferably less than 10 ° C., in particular in the range from 0 to -75 ° C.
  • the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation.
  • the first shell based on its total weight, contains the following components:
  • the first shell comprises
  • E-1) 90.0 to 97.9% by weight alkyl acrylate repeat units with 3 to 8 carbon atoms in the alkyl radical and / or alkyl methacrylate repeat units with 7 to 14 carbon atoms in the alkyl radical, in particular butyl acrylate and / or dodecyl methacrylate repeat units, and
  • the compounds E-1), E-2) and F) are of course different from one another, in particular the compounds E-1) do not comprise any crosslinking monomers E-2).
  • the second shell if present, includes, based on it
  • G 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100.0% by weight, in particular 85.0 to 99.5% by weight .-%, alkyl methacrylate repeating units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
  • alkyl acrylate repeat units with 1 to 20, preferably 1 to 12, in particular 1 to 8, carbon atoms in the alkyl radical,
  • the second shell contains, based on its total weight, at least 50% by weight, expediently at least 60% by weight, preferably at least 75% by weight, in particular at least 85% by weight of methyl methacrylate. repeating units.
  • the constituents of the second shell are advantageously selected in such a way that the second shell has a glass transition temperature Tg of at least 10 ° C., preferably of at least 30 ° C.
  • the glass transition temperature Tg of the polymer can be determined by means of differential scanning calorimetry (DSC) and / or can be calculated approximately in advance using the Fox equation.
  • the total radius of the core-shell particle, including the optionally present second shell is in the range from greater than 160 to 240 nm, preferably in the range from 170 to 220 nm, in particular in the range from 175 to 210 nm. The total radius is determined according to the Coulter Procedure determined.
  • the first shell 20.0 to 75.0% by weight, preferably 30.0 to 60.0
  • % By weight, expediently 35.0 to 55.0% by weight, in particular 40.0 to 50% by weight, and iii) the second shell 0.0 to 50.0% by weight, preferably 5, 0 to 40.0
  • % By weight, expediently 10.0 to 30.0% by weight, in particular 15.0 to 25.0% by weight, the weight percentages preferably adding up to 100.0% by weight.
  • the core-shell particles according to the invention can be produced in a manner known per se, for example by means of multi-stage emulsion polymerization. It is expediently carried out by a process in which water and emulsifier are initially introduced.
  • the template preferably contains 90.00 to 99.99 parts by weight of water and 0.01 to 10.00 parts by weight of emulsifier Advantageously add parts by weight to 100.00 parts by weight.
  • the monomers for the core are then added to this template step by step in the following order b) in the desired ratios and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95 , 0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, c) the monomers for the first shell are added in the desired ratios and up to a conversion of at least 85.0% by weight , preferably at least 90.0% by weight, expediently at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized, d) optionally the monomers for the second shell in the desired ratios added and up to a conversion of at least 85.0% by weight, preferably at least 90.0% by weight, advantageously at least 95.0% by weight, in particular at least 99% by weight, in each case based on their total weight, polymerized.
  • polymers refer to compounds which have at least ten times the molecular weight in comparison with the respective starting compound A) to I), the so-called monomer.
  • the progress of the polymerization reaction in each step can be monitored in a known manner, for example gravimetrically or by means of gas chromatography.
  • the polymerization in steps b) to d) is preferably carried out at a temperature in the range from 0 to 120 ° C., preferably in the range from 30 to 100 ° C.
  • Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, especially sodium and potassium peroxodisulfate.
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate, or particularly preferably peroxides.
  • the initiators mentioned can be used either individually or in a mixture. They are preferably used in an amount of 0.05 to 3.0% by weight, based on the total weight of the monomers in the respective stage.
  • the polymerization can also preferably be carried out with a mixture of different polymerization initiators with different half-lives in order to keep the radical stream constant during the course of the polymerization and at different polymerization temperatures.
  • the batch is preferably stabilized by means of emulsifiers and / or protective colloids. Stabilization by emulsifiers is preferred in order to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1 to 5% by weight, in particular 0.5 to 3% by weight, based on the total weight of the monomers A) to I).
  • Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular:
  • Alkyl sulfates preferably those with 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates with 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
  • Sulfonates preferably alkyl sulfonates with 8 to 18 carbon atoms in the alkyl radical, alkylarylsulfonates with 8 to 18 carbon atoms in the alkyl radical, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms in the alkyl radical; optionally these alcohols or alkylphenols can also be ethoxylated with 1 to 40 ethylene oxide units;
  • Partial phosphoric acid esters and their alkali and ammonium salts preferably alkyl and alkylaryl phosphates with 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
  • Alkyl polyglycol ethers preferably with 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
  • Alkylaryl polyglycol ethers preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units;
  • Ethylene oxide / propylene oxide copolymers preferably block copolymers, advantageously with 8 to 40 ethylene oxide or propylene oxide units.
  • Mixtures of anionic emulsifier and nonionic emulsifier are preferably used according to the invention.
  • the emulsifiers can also be used in a mixture with protective colloids.
  • Suitable protective colloids include u. a. partially saponified polyvinyl acetates, polyvinyl pyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and copolyether. If protective colloids are used, this is preferably done in an amount of 0.01 to 1.0% by weight, based on the total amount of monomers A) to I).
  • the protective colloids can be introduced or metered in before the start of the polymerization.
  • the initiator can be introduced or metered in. Furthermore, it is also possible to introduce part of the initiator and to meter in the rest.
  • the polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution.
  • the dosages of emulsifier and monomers can be carried out separately or as a mixture.
  • the procedure is such that the emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor.
  • the remainder of emulsifier and the remainder of monomer are preferred were not submitted, metered in separately from one another after the start of the polymerization. Dosing is preferably started 15 to 35 minutes after the start of the polymerization.
  • the template contains a so-called "seed latex", which is preferably obtainable by polymerizing alkyl (meth) acrylates and moreover advantageously has a particle radius in the range from 3.0 to 20 0 nm.
  • seed latex preferably obtainable by polymerizing alkyl (meth) acrylates and moreover advantageously has a particle radius in the range from 3.0 to 20 0 nm.
  • These small radii can be calculated after a defined polymerisation of the seed latex, in which a shell is built up around the seed latex and the radii of the particles produced in this way were measured using the Coulter method.
  • This method for particle size determination known in the literature is based on the measurement of the electrical resistance, which changes in a characteristic manner when particles pass through a narrow measurement opening. Further details can be found, for example, in Chem. Tech. Lab. 43, 553-566 (1995).
  • the monomer components of the actual core ie the first composition
  • the polymer formed in the first stage of the process is stored in a shell-like manner around the seed latex.
  • the monomer components of the first shell material (second composition) are added to the emulsion polymer under conditions such that the formation of new particles is avoided.
  • the polymer produced in the second stage is stored in a shell-like manner around the existing core. This procedure is appropriate for each additional bowl. - to repeat.
  • the core-shell particles according to the invention are obtained by an emulsion polymerization process in which, instead of the seed latex, a long-chain, aliphatic alcohol, preferably having 12 to 20 carbon atoms, is initially emulsified.
  • a long-chain, aliphatic alcohol preferably having 12 to 20 carbon atoms
  • stearyl alcohol is used as the long-chain, aliphatic alcohol.
  • the core-shell structure is obtained analogously to the procedure described above by stepwise addition and polymerization of the corresponding monomers while avoiding the formation of new particles.
  • the person skilled in the art can obtain further details on the polymerization process from the patents DE 3343766, DE 3210891, DE 2850105, DE 2742178 and DE 3701579.
  • the chain lengths, in particular the (co) polymers of the second shell, can be adjusted by polymerizing the monomer or the monomer mixture in the presence of molecular weight regulators, such as, in particular, the mercaptans known for this, such as, for example, n-butyl mercaptan, n-dodecyl mercaptan, 2- Mercaptoethanol or 2-ethylhexylthioglycolate, pentaerythritol tetrathioglycolate; the molecular weight regulators generally in amounts of 0.05 to 5% by weight, based on the monomer mixture, preferably in amounts of 0.1 to 2% by weight and particularly preferably in amounts of 0.2 to 1% by weight be used on the monomer mixture (see, for example, H.
  • molecular weight regulators such as, in particular, the mercaptans known for this, such as, for example, n-butyl mercaptan, n-dodecyl
  • the molecular weight regulator used is preferably n-dodecyl mercaptan.
  • postpolymerization can be carried out using known methods to remove residual monomers, for example by means of initiated postpolymerization.
  • the process according to the invention is particularly suitable for the production of aqueous dispersions with a high solids content of more than 50% by weight, based on the total weight of the aqueous dispersion
  • the relative proportions of all substances are expediently chosen such that the total weight of the monomers, based on the Total weight of the aqueous dispersion, greater than 50.0% by weight, suitably greater than 51.0% by weight, preferably greater than 52.0% by weight.
  • the substances to be considered in this connection also include all other substances used, such as water, emulsifier, initiator, possibly regulators and protective colloids, etc.
  • the aqueous dispersions obtainable by the process according to the invention are characterized by a low coagulum content which, based on the total weight of the aqueous dispersion, is preferably less than 5.0% by weight, advantageously less than 3.0% by weight, in particular less than 1.5 wt%.
  • the aqueous dispersion based on its total weight, has less than 1.0% by weight, preferably less than 0.5% by weight, suitably less than 0.25% by weight , in particular 0.10 wt .-% or less, coagulate.
  • the term “coagulate” denotes water-insoluble constituents which can preferably be filtered off, preferably by filtration of the dispersion, using a filter sleeve with clamped filter fabric No. 0.90 DIN 4188.
  • the core-shell particle according to the invention can be obtained from the dispersion, for example, by spray drying, freeze coagulation, precipitation by adding electrolyte or by mechanical or thermal stress, as can be carried out according to DE 27 50 682 A1 or US 4 110 843 by means of a degassing extruder.
  • the spray drying process is the most common, although the other processes mentioned have the advantage that the water-soluble polymerization auxiliaries are at least partially separated from the polymer.
  • the core-shell particle according to the invention serves to improve the notched impact strength of hard thermoplastics which are compatible with the hard phase, preferably of poly (meth) acrylate molding compositions, in particular of polymethyl methacrylate.
  • the poly (meth) acrylate molding compositions preferably contain further polymers in order to modify the properties in a suitable manner.
  • polyacrylonitriles include in particular polyacrylonitriles, polystyrenes, polyethers, polyesters, polycarbonates and polyvinyl chlorides.
  • These polymers can be used individually or as a mixture, copolymers which can be derived from the aforementioned polymers being added to the molding compositions in the context of a very particularly preferred embodiment of the present invention.
  • These include, in particular, styrene-acrylonitrile copolymers (SAN), which are preferably added to the molding compositions in an amount of up to 45% by weight.
  • SAN styrene-acrylonitrile copolymers
  • Particularly preferred styrene-acrylonitrile copolymers can be obtained through the
  • 100 parts of the molding composition to be modified are admixed with 10 to 60 parts of the impact modifier.
  • particularly preferred molding compositions contain, in each case based on their total weight:
  • the (meth) acrylic polymer comprises, in each case based on its total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100, 0% by weight, in particular 85.0 to 99.5% by weight, of repeating alkyl methacrylate units with 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0, 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, of alkyl acrylate repeating units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0 wt .-% styrene repeat units of the general
  • Formula (I) the percentages by weight adding up to 100.0% by weight.
  • the (meth) acrylic polymer based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
  • the (meth) acrylic polymer preferably has a number average molecular weight in the range from 1,000 to 100,000,000 g / mol, preferably in the range from 10,000 to 1,000,000 g / mol, in particular in the range from 50,000 to 500,000 g / mol.
  • the molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
  • the dispersion of the core-shell particle can be mixed with an aqueous dispersion of the mixing component and the mixture coagulated, the water phase separated and the coagulate melted into a molding compound.
  • a particularly uniform mixing of the two masses can be achieved.
  • the components can also be prepared and isolated separately and mixed in the form of their melts or as powders or granules and homogenized in a multi-screw extruder or on a roller mill.
  • Usual additives can be mixed in at any suitable processing stage. These include dyes, pigments, fillers, reinforcing fibers, lubricants, UV protection agents, etc.
  • the molding composition contains, based in each case on its total weight, 0.1 to 10% by weight, preferably 0.5 to 5.0% by weight, in particular 1.0 to 4, 0% by weight of a further polymer (AP) which, in comparison with the (meth) acrylic polymer, has a weight average molecular weight which is at least 10%, preferably at least 50%, in particular at least 100% higher.
  • the molecular weight can be determined, for example by means of gel permeation chromatography with calibration for polystyrene.
  • Polymers (AP) which are particularly suitable according to the invention comprise, based on their total weight, preferably a) 50.0 to 100.0% by weight, advantageously 60.0 to 100.0% by weight, particularly preferably 75.0 to 100 , 0 wt .-%, in particular 85.0 to 99.5 wt .-%, alkyl methacrylate repeating units having 1 to 20, preferably 1 to 12, advantageously 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical, b) 0 , 0 to 40.0% by weight, preferably 0.0 to 25.0% by weight, in particular 0.1 to 15.0% by weight, repeating alkyl acrylate units with 1 to 20, preferably 1 to 12, expediently 1 to 8, in particular 1 to 4, carbon atoms in the alkyl radical and c) 0.0 to 8.0% by weight of styrene repeat units of the general formula (I), the weight percentages adding up to 100.0% by weight.
  • alkyl methacrylate repeating units having 1 to 20,
  • the polymer (AP), based on its total weight, contains at least 50.0% by weight, advantageously at least 60.0% by weight, preferably at least 75.0% by weight, in particular at least 85.0% by weight methyl methacrylate repeat units.
  • the polymer (AP) preferably has a weight average molecular weight in the range from 10,000 to 100,000,000 g / mol, preferably in the range from 50,000 to 5,000,000 g / mol, advantageously in the range from 100,000 to 1,000,000 g / mol, in particular in the range from 250,000 to 600,000 g / mol.
  • the molecular weight can be, for example, by means of
  • Mixtures of the core-shell particles, in particular with polymethyl methacrylate, are particularly suitable for the production of moldings, expediently with a wall thickness of more than 1 mm, such as extruded webs of 1 to 10 mm in thickness, which can be easily punched and for example for the production of printable screens for Electrical devices are useful, or for the production of molded high-quality moldings, for. B. automotive windows. Thinner films, for example 50 ⁇ m thick, can also be produced therefrom.
  • the molded articles obtainable according to the invention stand out
  • KSZ notched impact strength KSZ (Izod 180 / 1eA) according to ISO 180 of at least 5.8 kJ / m 2 , advantageously greater than 6.0 kJ / m 2 , at 23 ° C and preferably of at least 3.7 kJ / m 2 at -20 ° C and
  • the moldings according to the invention are used as a mirror housing or spoiler of a vehicle, as a tube, as a film for sports articles, as a cover or as a component of a refrigerator.
  • a seed latex was made by emulsion polymerization of a monomer composition containing 98% by weight of ethyl acrylate and 2% by weight of allyl methacrylate. These particles, about 20 nm in diameter, were about 10% by weight in water.
  • All of the core-shell particles described below were produced by means of emulsion polymerization in accordance with the general preparation instructions below.
  • the emulsions I to III given in Table 1 were used.
  • Emulsion I was then metered in over 1 h. 10 minutes after the end of emulsion I, emulsion II was metered in over a period of about 2 hours. Then about 90 min after the end of the emulsion II, emulsion III was metered in over a period of about 1 h. 30 minutes after the end of the emulsion III was cooled to 30 ° C.
  • the dispersion was frozen for 2 d at -20 ° C., then thawed again and the coagulated dispersion was separated off using a filter cloth.
  • the solid was dried at 50 ° C. in a drying cabinet (duration: approx. 3 d).
  • the particle size of the core-shell particles was determined using a Coulter N4 device, the particles being measured in dispersion.
  • Table 1 Composition of the individual emulsions (all figures in fine)
  • Aerosol OT 75 65.88 65.88 65.88 65.88 65.88 65.88 65.88
  • Aerosol OT 75 84.71 84.71 84.71 84.71 84.71
  • Aerosol OT 75 10.59 10.59 10.59 10.59 10.59
  • Test specimens were produced from the mixed molding compositions.
  • the molding compounds and the corresponding test specimens were tested according to the following measurement methods:
  • the notched impact strength of the molding compositions according to the invention is significantly higher at -20 ° C. than that of the comparative molding compositions. All mixtures have a comparable impact strength at room temperature. Even a tough phase without styrene does not improve the
  • the good low-temperature impact strength is achieved without the other important properties of the molding compositions, in particular the
  • Modulus of elasticity [MPa] 1660 1550 1620 1650

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract

L'invention concerne une particule à noyau et enveloppe, comportant un noyau, une première enveloppe et éventuellement une deuxième enveloppe. Le noyau est composé d'au moins 75,0 % en poids, relativement à son poids total, d'unités récurrentes de (méth)acrylate. La première enveloppe a une température de transition vitreuse inférieure à 30 DEG C. La deuxième enveloppe éventuelle est constituée pour au moins 75,0 % en poids, relativement à son poids total, par des unités récurrentes de (méth)acrylate. Relativement à son poids total, la première enveloppe comprend les éléments suivants: E) 92,0 à 98,0 % en poids d'unités récurrentes de (méth)acrylate et F) 2,0 à 8,0 % en poids d'unités récurrentes de styrène de formule (I), dans laquelle les groupes R<1> à R<6> sont comme définis dans la description et les pourcentages en poids de E) et F) s'additionnent pour former 100,0 % en poids. Le rayon de la particule à noyau et enveloppe, y compris la deuxième enveloppe éventuelle, et mesuré selon le principe Coulter, est dans une fourchette dépassant 160,0 à 240,0 nm. La présente invention porte également sur un procédé pour produire ladite particule à noyau et enveloppe, sur une matière moulable contenant cette particule à noyau et enveloppe et sur son utilisation.
EP03769412A 2002-12-19 2003-10-18 Particule a noyau et enveloppe servant a modifier la resilience de matieres moulables de poly(meth)acrylate Withdrawn EP1572768A2 (fr)

Applications Claiming Priority (3)

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DE10260065 2002-12-19
DE10260065A DE10260065A1 (de) 2002-12-19 2002-12-19 Kern-Schale-Teilchen zur Schlagzähmodifizierung von Poly(meth)acrylat-Formmassen
PCT/EP2003/011541 WO2004056892A2 (fr) 2002-12-19 2003-10-18 Particule a noyau et enveloppe servant a modifier la resilience de matieres moulables de poly(meth)acrylate

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KR100781068B1 (ko) 2007-11-30
AU2003278101A1 (en) 2004-07-14
RU2005122819A (ru) 2006-01-20
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JP2006510758A (ja) 2006-03-30
US20060147714A1 (en) 2006-07-06
CN1726238A (zh) 2006-01-25
KR20050085769A (ko) 2005-08-29
TW200422342A (en) 2004-11-01
WO2004056892A3 (fr) 2005-03-17
WO2004056892A2 (fr) 2004-07-08
US7695813B2 (en) 2010-04-13
DE10260065A1 (de) 2004-07-01
JP4582638B2 (ja) 2010-11-17

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