EP1824893A1 - Uv stabilizer for pmma - Google Patents

Uv stabilizer for pmma

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Publication number
EP1824893A1
EP1824893A1 EP05806876A EP05806876A EP1824893A1 EP 1824893 A1 EP1824893 A1 EP 1824893A1 EP 05806876 A EP05806876 A EP 05806876A EP 05806876 A EP05806876 A EP 05806876A EP 1824893 A1 EP1824893 A1 EP 1824893A1
Authority
EP
European Patent Office
Prior art keywords
monomer
molding composition
composition according
group
molding
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.)
Withdrawn
Application number
EP05806876A
Other languages
German (de)
French (fr)
Inventor
Thorsten Goldacker
Klaus Koralewski
Alexander Laschitsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1824893A1 publication Critical patent/EP1824893A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate

Definitions

  • the invention relates to a molding composition with UV absorbers, processes for their preparation and applications.
  • UV absorbers Since UV rays often lead to unwanted decomposition reactions, plastics often use UV-absorbing additives. These absorb in the UV region of the spectrum and thus protect either the polymer itself, other constituents of the plastic or an underlying material from such reactions. Such UV absorbers in addition to their advantageous protective function also have a number of disadvantages. Thus, their Absorbtionsbande extends into the visible area, which is why parts of the visible violet and blue light are absorbed and the plastic receives a yellowish hue. This is all the more unsatisfactory, as often only a small portion of the UV absorber used is actually needed to fulfill the protective function.
  • a transparent component consists of a UV-stabilized molding compound, but the UV light can only penetrate into the uppermost layers due to the absorption of the stabilizer.
  • the lower UV absorber has no stabilizing function, but due to its above-described absorption in the visible range, it contributes to increasing the yellowness value.
  • EP 1115792 B1 and EP 939093 B1 describe the use of photo-fries-capable groups as pre-UV absorbers in polyesters and pofycarbonates.
  • resorcinol is incorporated as a diol component in the main chain.
  • Po y (meth) acrylates are not mentioned in these protective rights.
  • EP 120608 describes polymers for coating applications prepared by the reaction of the OH group of resorcinol mono-benzoate with reactive groups of a polymer.
  • polymers containing glycidyl methacrylate are reacted.
  • the resorcinol mono-benzoate group can transform under UV light in a photo-Fries rearrangement to the o-hydroxybenzophenone group, which is an effective UV absorber.
  • the process described has serious disadvantages:
  • the preparation of the polymers can be carried out with this pre-UV absorber exclusively polymer analogous, since a corresponding methacrylic ester would prevent radical polymerization due to its radical scavenging effect.
  • the polymer-analogous conversion to the desired "polymer-bound pre-UV absorber is disadvantageous because of the additional process step Epoxide groups undergo unwanted side reactions such as hydrolysis and cross-linking. Therefore, the method described is unsuitable for molding compositions.
  • the object is achieved with a molding composition, characterized in that at least one monomer A with at least one monomer B, with a pre-UV absorber group, which by the action of UV light significantly increased absorption at a wavelength between 300 and 400 nm contains, is radically copolymerized.
  • the compounds according to the invention can undergo a photo-Fries rearrangement under UV action in the solid polymer, the rearrangement product having the desired UV absorption.
  • monomer B all compounds which, after copolymerization with monomer A under UV light, carry out photo Fries rearrangement reactions are suitable as monomer B.
  • monomer B preference is given to using compounds having acryloyl or methacryloyl or styrenic structures, more preferably p-methylphenyl methacrylate.
  • derivatives are also suitable, which may also contain branched or unbranched alkyl groups with Ci to C-i ⁇ , but also -O-CH 3 in para-position instead of a methyl group.
  • Suitable monomers A are compounds which are selected from the group of free-radically polymerizable monomers. Particularly preferred monomers A are selected from the group of acrylates, methacrylates, substituted or unsubstituted styrenic monomers or acrylonitrile.
  • the monomers B represent a pre-UV absorber which has no absorption band extending into the visible range. It has been found that the yellowness of the copolymer of monomer A and monomer B is not significantly worse than that of the yellowness of the pure molding material of monomer A.
  • the polymer can also be processed well thermoplastic.
  • blends with excellent properties can be prepared from the copolymers of monomer A and monomer B with further polymers.
  • core-shell polymers can be prepared whose structure comprises, for example, a hard core, a rubber-elastic middle layer and an outer shell of polymethymethacrylate.
  • the pre-UV absorber can be polymerized into the shell and / or the middle layer as needed.
  • the bond to the polymer also proves to be advantageous over the pure physical interference, since there is no evaporation or sweating during processing. In addition, no migration from the component is to be feared.
  • molded articles can be produced from the novel molding materials or blends. Usually semi-finished products, such as plates, sheets, blocks, profiles, tubes, hoses, rods, are produced.
  • At least one monomer A is copolymerized free-radically.
  • Usual additives e.g. suitable initiators or regulators are added.
  • the reaction mixture is usually heated.
  • Other polymers for the preparation of blends can also be added.
  • the polymer is precipitated with a suitable solvent, dried and further processed.
  • the reaction mixture may also contain dyes, impact modifiers and additives, e.g. Flame retardants, or inhibitors, lubricants or additives against the thermo-oxidative degradation may be added.
  • moldings or semi-finished products are produced. Likewise, the molding compounds or blends can be applied to other materials or coextruded.
  • the molding compositions according to the invention can also be used with other radical polymerization processes, such as e.g. emulsion polymerization,
  • the molding composition according to the invention has a broad field of application. They can be used in the construction sector, in motor vehicles, rail vehicles, aircraft, watercraft, spacecraft and advertising technology. ' A particularly preferred field of application are films, Panels, coextruded layers on panels and exterior parts of motor vehicles.
  • the molding composition according to the invention for UV adsorption by means of photo-floppye rearrangement is an inexpensive alternative to coextrusion in which only the upper layer is to be equipped with UV absorber.
  • much more complicated geometries can be represented with the material according to the invention.
  • the polymer is precipitated in methanol, dried (vac, 12O 0 C, 4h) and processed to a 1mm thick press plate (processing temperature: 18O 0 C).
  • the press plate is irradiated in a SUN test CPS / 10 (ATLAS Material Testing Technology GmbH, D-63589 Linsen amount-Altenhasslau) with a power of 60 W / m 2 (measured in the wavelength range between 300-400 nm) and according to the irradiation times listed below in tabular form measured.
  • the Yellowness Index is determined according to DIN 6167 (D65 / 1O 0).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to a molding compound comprising UV absorbers, to a method for producing the same and to uses thereof.

Description

UV-Stabilisator für PMMA UV stabilizer for PMMA
Die Erfindung betrifft eine Formmasse mit UV-Absorbern, Verfahren zu deren Herstellung und Anwendungen.The invention relates to a molding composition with UV absorbers, processes for their preparation and applications.
Da UV-Strahlen oft zu unerwünschten Zersetzungsreaktionen führen, werden in Kunststoffen häufig UV-absorbierende Additive verwendet. Diese absorbieren im UV-Bereich des Spektrums und schützen so entweder das Polymer selbst, andere Bestandteile des Kunststoffs oder ein darunter liegendes Material vor derartigen Reaktionen. Solche UV-Absorber haben neben ihrer vorteilhaften Schutzfunktion auch eine Reihe von Nachteilen. So reicht ihre Absorbtionsbande bis in den sichtbaren Bereich hinein, weshalb Teile des sichtbaren violetten und blauen Lichts absorbiert werden und der Kunststoff einen gelblichen Farbton erhält. Dies ist umso unbefriedigender, als dass oft nur ein kleiner Teil des eingesetzten UV-Absorbers tatsächlich benötigt wird, um die Schutzfunktion zu erfüllen. Dies ist zum Beispiel der Fall, wenn ein transparentes Bauteil aus einer UV-stabilsierten Formmasse besteht, das UV- Licht aber aufgrund der Absorption des Stabilisators nur in die obersten Schichten eindringen kann. Der tiefer liegende UV-Absorber hat keinerlei stabilisierende Funktion, trägt aber aufgrund seiner oben geschilderten Absorption im sichtbaren Bereich zur Erhöhung des Gelbwerts bei.Since UV rays often lead to unwanted decomposition reactions, plastics often use UV-absorbing additives. These absorb in the UV region of the spectrum and thus protect either the polymer itself, other constituents of the plastic or an underlying material from such reactions. Such UV absorbers in addition to their advantageous protective function also have a number of disadvantages. Thus, their Absorbtionsbande extends into the visible area, which is why parts of the visible violet and blue light are absorbed and the plastic receives a yellowish hue. This is all the more unsatisfactory, as often only a small portion of the UV absorber used is actually needed to fulfill the protective function. This is the case, for example, if a transparent component consists of a UV-stabilized molding compound, but the UV light can only penetrate into the uppermost layers due to the absorption of the stabilizer. The lower UV absorber has no stabilizing function, but due to its above-described absorption in the visible range, it contributes to increasing the yellowness value.
Eine etablierte Lösung dieses Problems ist die Beschichtung des Bauteils entweder mit einer Lackschicht oder mit einer coextrudierten Formmasseschicht, die einen UV-Absorber enthält. Oft kann man allerdings die Fertigung einer solchen Schutzschicht aus technischen Gründen nicht bewerkstelligen oder scheut den zusätzlichen Prozessschritt aus wirtschaftlichen Gründen. Lee et al. [Polymer Degradation and Stability 83 (2004) 435] beschreiben Polyphenylacrylat und Poly(p-Methylphenylacrylat) als UV-Stabilisator für PET. Sie verwenden Homopolymere der genannten Monomere, mischen diese mit dem PET und verarbeiten die Mischungen zu Spincoating-Filmen und Fasern. Die verwendeten Mischungen waren nicht transparent, weshalb auch die Absorption im UV- oder sichtbaren Bereich nicht untersucht wurde.An established solution to this problem is coating the component either with a lacquer layer or with a coextruded molding layer containing a UV absorber. Often, however, one can not accomplish the production of such a protective layer for technical reasons or shuns the additional process step for economic reasons. Lee et al. [Polymer Degradation and Stability 83 (2004) 435] describe polyphenyl acrylate and poly (p-methylphenyl acrylate) as a UV stabilizer for PET. They use homopolymers of these monomers, mix them with the PET and process the mixtures into spin-coating films and fibers. The mixtures used were not transparent, which is why the absorption in the UV or visible range was not investigated.
In einer Grund\agenarbeιt untersuchen Li et al. [Macromolecules 10 (1977) 840] die Photo-Fries-Umlagerung von reinem Polyphenylacrylat im Festkörper. Copolymerisation mit MMA oder die Nutzung der Absorption zur UV- Stabilisierung werden nicht erwähnt.In a basic report, Li et al. [Macromolecules 10 (1977) 840] the photo-Fries rearrangement of pure polyphenyl acrylate in the solid state. Copolymerization with MMA or the use of absorption for UV stabilization are not mentioned.
US 2003180542, EP 1115792 B1 und EP 939093 B1 beschreiben die Verwendung von Photo-Fries-fähigen Gruppen als Prä-UV-Absorbern in Polyestern und Pofycarbonaten. Hier wird Resorcinol als Diol-Komponente mit in die Hauptkette eingebaut. Po)y(meth)acrylate werden bei diesen Schutzrechten nicht erwähnt.US 2003180542, EP 1115792 B1 and EP 939093 B1 describe the use of photo-fries-capable groups as pre-UV absorbers in polyesters and pofycarbonates. Here resorcinol is incorporated as a diol component in the main chain. Po ) y (meth) acrylates are not mentioned in these protective rights.
EP 120608 beschreibt Polymere für Coating-Anwendungen, die durch die Reaktion der OH-Gruppe von Resorcinol-mono-benzoat mit reaktiven Gruppen eines Polymers hergestellt werden. In den Beispielen werden Polymere, die Glycidylmethacrylat enthalten, umgesetzt. Die Resorcinol-mono-benzoatgruppe kann sich unter UV-Licht in einer Photo-Fries-Umlagerung zur o-Hydroxybenzo- phenon-Gruppe umwandeln, die ein effektiver UV-Absorber ist.EP 120608 describes polymers for coating applications prepared by the reaction of the OH group of resorcinol mono-benzoate with reactive groups of a polymer. In the examples, polymers containing glycidyl methacrylate are reacted. The resorcinol mono-benzoate group can transform under UV light in a photo-Fries rearrangement to the o-hydroxybenzophenone group, which is an effective UV absorber.
Das beschriebene Verfahren hat allerdings gravierende Nachteile: Die Herstellung der Polymere kann mit diesem Prä-UV-Absorber ausschließlich polymeranalog erfolgen, da ein entsprechender Methacrylsäureester aufgrund seiner radikalfangenden Wirkung die radikalische Polymerisation unterbinden würde. Die polymeranaloge Umsetzung zu dem gewünschten "polymergebundenen Prä-UV-Absorber ist aufgrund des zusätzlichen Prozessschritts nachteilig. Zudem können nicht vollständig umgesetzte Epoxidgruppen unerwünschte Nebenreaktionen wie Hydrolyse und Vernetzung eingehen. Daher ist die beschriebene Methode für Formmassen ungeeignet.However, the process described has serious disadvantages: The preparation of the polymers can be carried out with this pre-UV absorber exclusively polymer analogous, since a corresponding methacrylic ester would prevent radical polymerization due to its radical scavenging effect. The polymer-analogous conversion to the desired "polymer-bound pre-UV absorber is disadvantageous because of the additional process step Epoxide groups undergo unwanted side reactions such as hydrolysis and cross-linking. Therefore, the method described is unsuitable for molding compositions.
Aufgabe der Erfindung war es daher, eine Formmasse zu entwickeln, die nur unter Einwirkung von UV-Strahlen eine Absorption im UV-Bereich sowie den damit verbundenen Absorptionsausläufern im sichtbaren Bereich entwickelt.It was therefore an object of the invention to develop a molding composition which develops absorption in the UV range and the associated absorption tailings in the visible range only under the action of UV rays.
Die Aufgabe wird gelöst mit einer Formmasse, dadurch gekennzeichnet, dass mindestens ein Monomer A mit mindestens einem Monomer B, mit einer Prä- UV-Absorber-Gruppe, welches durch die Einwirkung von UV-Licht eine deutlich erhöhte Absorption bei einer Wellenlänge zwischen 300 und 400 nm aufweist, enthält, radikalisch copolymerisiert wird.The object is achieved with a molding composition, characterized in that at least one monomer A with at least one monomer B, with a pre-UV absorber group, which by the action of UV light significantly increased absorption at a wavelength between 300 and 400 nm contains, is radically copolymerized.
Die erfindungsgemäßen Verbindungen können unter UV-Einwirkung im festen Polymer eine Photo-Fries-Umlagerung vollziehen, wobei das Umlagerungsprodukt die gewünschte UV-Absorption aufweist.The compounds according to the invention can undergo a photo-Fries rearrangement under UV action in the solid polymer, the rearrangement product having the desired UV absorption.
Als Monomer B sind prinzipiell alle Verbindungen geeignet, die nach Copolymerisation mit Monomer A unter UV-Licht Einwirkung Photo-Fries- Umlagerungen durchführen. Dabei wird eine ortho-Hydroxybenzoylstruktur ausgebildet. Als Monomer B werden vorzugsweise Verbindungen mit Acryloyl- oder Methacryloyl- oder styrolischen Strukturen, besonders bevorzugt p- Methylphenylmethacrylat, eingesetzt. Es sind jedoch auch Derivate geeignet, die in para-Stellung statt einer Methylgruppe auch verzweigte oder nicht verzweigte Alkylgruppen mit Ci bis C-iβ, aber auch -O-CH3 enthalten können.In principle, all compounds which, after copolymerization with monomer A under UV light, carry out photo Fries rearrangement reactions are suitable as monomer B. In this case, an ortho-hydroxybenzoyl structure is formed. As monomer B, preference is given to using compounds having acryloyl or methacryloyl or styrenic structures, more preferably p-methylphenyl methacrylate. However, derivatives are also suitable, which may also contain branched or unbranched alkyl groups with Ci to C-iβ, but also -O-CH 3 in para-position instead of a methyl group.
Als Monomer A sind Verbindungen geeignet die ausgewählt sind aus der Gruppe der radikalisch polymerisierbaren Monomere. Besonders bevorzugt werden Monomere A ausgewählt aus der Gruppe der Acrylate, Methacrylate, substituierten oder unsubstituierten styrolischen Monomere oder Acrylnitril. Die Monomere B stellen einen Prä-UV-Absorber dar, der keine in den sichtbaren Bereich hineinreichenden Absorptionsbande aufweist. Es wurde gefunden, dass der Gelbwert des Copolymerisats aus Monomer A und Monomer B nicht signifikant schlechter ist, als der der Gelbwert der reinen Formmasse aus Monomer A.Suitable monomers A are compounds which are selected from the group of free-radically polymerizable monomers. Particularly preferred monomers A are selected from the group of acrylates, methacrylates, substituted or unsubstituted styrenic monomers or acrylonitrile. The monomers B represent a pre-UV absorber which has no absorption band extending into the visible range. It has been found that the yellowness of the copolymer of monomer A and monomer B is not significantly worse than that of the yellowness of the pure molding material of monomer A.
Herkömmliche Materialien mit UV-Absorbern sind optisch immer schlechter, weil die Absorber im sichtbaren Bereich arbeiten. Bei den erfindungsgemäßen Materialien erfolgt die UV-Absorption nur in den oberen Schichten. Damit werden wesentlich bessere optische Ergebnisse erzielt, da ein Maß für die Qualität auch immer die Gelbfärbung ist.Conventional materials with UV absorbers are optically worse, because the absorbers work in the visible range. In the case of the materials according to the invention, the UV absorption takes place only in the upper layers. Thus, much better optical results are achieved, since a measure of the quality is always the yellowing.
Überraschend wurde gefunden, dass die Monomere B aus der Gruppe der Verbindungen mit Acryloyl- oder Methacryloyl- oder styrolischen Strukturen, besonders bevorzugt p-Methylenphenylmethacrylat, gut mit Monomeren A aus der Gruppe der radikalisch polymerisierbaren Monomere, bevorzugt aus der Gruppe der Acrylate, Methacrylate, substituierten oder unsubstituierten styrolischen Monomere und Acrylnitril, besonders bevorzugt Methylmethacrylat, copolymerisierbar sind. Das Polymerisat lässt sich zudem gut thermoplastisch verarbeiten.Surprisingly, it has been found that the monomers B from the group of compounds having acryloyl or methacryloyl or styrenic structures, more preferably p-methylenephenyl methacrylate, good with monomers A from the group of free-radically polymerizable monomers, preferably from the group of acrylates, methacrylates, substituted or unsubstituted styrenic monomers and acrylonitrile, particularly preferably methyl methacrylate, are copolymerizable. The polymer can also be processed well thermoplastic.
Es wurde gefunden, dass sich Blends mit hervorragenden Eigenschaften aus den Copolymerisaten von Monomer A und Monomer B mit weiteren Polymeren herstellen lassen.It has been found that blends with excellent properties can be prepared from the copolymers of monomer A and monomer B with further polymers.
Außerdem wurde gefunden, dass gezielte Einpolymerisationen erfolgen können. So können z.B. Kern-Schale-Polymerisate dargestellt werden, deren Aufbau beispielsweise einen harten Kern, eine gummielastische Mittelschicht und eine äußere Hülle aus Polymethymethacrylat umfasst. Der Prä-UV- Absorber kann je nach Bedarf in die Hülle und/oder die mittlere Schicht einpolymerisiert werden. Die Bindung an das Polymer erweist sich zudem als vorteilhaft gegenüber der reinen physikalischen Einmischung, da es zu keinem Ausdampfen oder Ausschwitzen bei der Verarbeitung kommt. Zudem ist keine Migration aus dem Bauteil zu befürchten. Somit können verschiedenste Formkörper aus den erfindungsgemäßen Formmassen oder Blends hergestellt werden. Üblicherweise werden Halbzeuge, wie z.B. Platten, Tafeln, Blöcke, Profile, Rohre, Schläuche, Stäbe, hergestellt.It has also been found that targeted polymerizations can be carried out. Thus, for example, core-shell polymers can be prepared whose structure comprises, for example, a hard core, a rubber-elastic middle layer and an outer shell of polymethymethacrylate. The pre-UV absorber can be polymerized into the shell and / or the middle layer as needed. The bond to the polymer also proves to be advantageous over the pure physical interference, since there is no evaporation or sweating during processing. In addition, no migration from the component is to be feared. Thus, a wide variety of molded articles can be produced from the novel molding materials or blends. Usually semi-finished products, such as plates, sheets, blocks, profiles, tubes, hoses, rods, are produced.
Zur Herstellung der erfindungsgemäßen Polymermatrix wird mindestens ein Monomer A, gegebenenfalls unter Schutzgasatmosphäre, in einem geeigneten Lösungsmittel mit mindestens einem Monomer B radikalisch copolymerisiert. Es werden übliche Zusätze, wie z.B. geeignete Initiatoren oder Regler zugegeben. Das Reaktionsgemisch wird üblicherweise erwärmt. Auch weitere Polymere, zur Herstellung von Blends, können zugegeben werden. Nach Beendigung der Polymerisation wird das Polymerisat mit einem geeigneten Lösungsmittel ausgefällt, getrocknet und weiterverarbeitet. Dem Reaktionsgemisch können auch Farbstoffe, Schlagzähmodifier und Additive, wie z.B. Flammschutzmittel, oder -hemmer, Gleitmittel oder Additive gegen den thermooxidativen Abbau zugegeben werden. Je nach Anwendung werden Formkörper bzw. Halbzeuge hergestellt. Ebenso können die Formmassen oder Blends auf andere Materialien aufgetragen oder coextrudiert werden.For the preparation of the polymer matrix according to the invention, at least one monomer A, optionally under a protective gas atmosphere, in a suitable solvent with at least one monomer B is copolymerized free-radically. Usual additives, e.g. suitable initiators or regulators are added. The reaction mixture is usually heated. Other polymers for the preparation of blends can also be added. After completion of the polymerization, the polymer is precipitated with a suitable solvent, dried and further processed. The reaction mixture may also contain dyes, impact modifiers and additives, e.g. Flame retardants, or inhibitors, lubricants or additives against the thermo-oxidative degradation may be added. Depending on the application, moldings or semi-finished products are produced. Likewise, the molding compounds or blends can be applied to other materials or coextruded.
Neben dem beschriebenen Lösungspolymerisationsverfahren können die erfindungsgemäßen Formmassen auch mit anderen radikalischen Polymerisationsverfahren, wie z.B. Emulsionspolymerisation,In addition to the solution polymerization process described, the molding compositions according to the invention can also be used with other radical polymerization processes, such as e.g. emulsion polymerization,
Suspensionspolymerisation oder Substanzpolymerisation, dargestellt werden.Suspension polymerization or bulk polymerization.
Die erfindungsgemäße Formmasse hat ein breites Anwendungsgebiet. Sie können im Baubereich, in Kraftfahrzeugen, Schienenfahrzeugen, Luftfahrzeugen, Wasserfahrzeugen, Raumfahrzeugen und der Werbetechnik eingesetzt werden.' Ein besonders bevorzugtes Anwendungsgebiet sind Folien, Platten, coextrudierte Schichten auf Platten und Außenteilen von Kraftfahrzeugen.The molding composition according to the invention has a broad field of application. They can be used in the construction sector, in motor vehicles, rail vehicles, aircraft, watercraft, spacecraft and advertising technology. ' A particularly preferred field of application are films, Panels, coextruded layers on panels and exterior parts of motor vehicles.
Die erfindungsgemäße Formmasse zur UV-Adsorption mittels Photo-Fries- Umlagerung ist eine preiswerte Alternative zur Coextrusion, bei der auch nur die obere Schicht mit UV-Absorber ausgerüstet werden soll. Zudem sind mit dem erfindungsgemäßen Material wesentlich kompliziertere Geometrien darstellbar.The molding composition according to the invention for UV adsorption by means of photo-frieze rearrangement is an inexpensive alternative to coextrusion in which only the upper layer is to be equipped with UV absorber. In addition, much more complicated geometries can be represented with the material according to the invention.
Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken. The examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein.
BeispieleExamples
Beispiel 1example 1
Herstellung von UV-Absorber CopolymerisatProduction of UV absorber copolymer
Zu 540g Methylmethacrylat, 60g 4-Methylphenylmethacrylat und 1 ,38g Methyl- 3-mercaptopropionat werden unter Argon bei 98°C 0,6g 2,2'-Azobis- (isobutyronitril) gelöst in 490,9g Toluol während eines Zeitraums von 360min zudosiert. Anschließend wird für 60min nachgerührt, auf ca. 500C abgekühlt und mit 329,1g Toluol verdünnt. (Umsatz 100%, V.N. = 46,3ml/g).To 540 g of methyl methacrylate, 60 g of 4-methylphenyl methacrylate and 1, 38 g of methyl 3-mercaptopropionate are added under argon at 98 ° C, 0.6 g of 2,2'-azobis (isobutyronitrile) dissolved in 490.9 g of toluene over a period of 360min. The mixture is then stirred for 60 min, cooled to about 50 0 C and diluted with 329.1 g of toluene. (Conversion 100%, VN = 46.3 ml / g).
Das Polymer wird in Methanol ausgefällt, getrocknet (vac, 12O0C, 4h) und zu einer.1mm dicken Pressplatte verarbeitet (Verarbeitungstemperatur: 18O0C).The polymer is precipitated in methanol, dried (vac, 12O 0 C, 4h) and processed to a 1mm thick press plate (processing temperature: 18O 0 C).
Die Pressplatte wird in einem Suntest CPS/10 (ATLAS Material Testing Technology GmbH, D-63589 Linsengericht-Altenhaßlau) mit einer Leistung von 60 W/m2 (gemessen im Wellenlängenbereich zwischen 300-400 nm) bestrahlt und nach den unten tabellarisch aufgeführten Bestrahlungszeiten vermessen. Der Gelbwert wird nach DIN 6167 (D65/1O0) bestimmt.The press plate is irradiated in a SUN test CPS / 10 (ATLAS Material Testing Technology GmbH, D-63589 Linsengericht-Altenhasslau) with a power of 60 W / m 2 (measured in the wavelength range between 300-400 nm) and according to the irradiation times listed below in tabular form measured. The Yellowness Index is determined according to DIN 6167 (D65 / 1O 0).

Claims

Patentansprüche claims
1. Formmasse, dadurch gekennzeichnet, dass mindestens ein Monomer A mit mindestens einem Monomer B mit einer Prä-UV-Absorber-Gruppe, welches durch die Einwirkung von UV-Licht eine deutlich erhöhte Absorption bei einer Wellenlänge zwischen 300 und 400nm aufweist, enthält, radikalisch copolymerisiert wird.1. molding composition, characterized in that contains at least one monomer A with at least one monomer B with a pre-UV absorber group which has a significantly increased absorption at a wavelength between 300 and 400 nm by the action of UV light, is radically copolymerized.
2. Formmasse gemäß der Anspruch 1 , dadurch gekennzeichnet, dass das Monomer B nach Copolymerisation mit Monomer A unter UV-Licht Einwirkung durch die Photo-Fries-Umlagerung eine ortho- Hydroxybenzoylstruktur ausbildet.2. Molding composition according to claim 1, characterized in that the monomer B forms an ortho-hydroxybenzoyl structure after copolymerization with monomer A under UV light exposure to the photo-Fries rearrangement.
3. Formmasse gemäß der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das Monomer B eine Acryloyl- oder Methacryloyl- oder styrolische Struktur enthält.3. Molding composition according to claims 1 and 2, characterized in that the monomer B contains an acryloyl or methacryloyl or styrenic structure.
4. Formmasse gemäß der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Monomer B p-Methylphenylmethacrylat ist.4. Molding composition according to claims 1 to 3, characterized in that the monomer B is p-methylphenyl methacrylate.
5. Formmasse gemäß der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Monomer A ausgewählt ist aus der Gruppe der radikalisch polymerisierbaren Monomere.5. Molding composition according to claims 1 to 4, characterized in that the monomer A is selected from the group of free-radically polymerizable monomers.
6. Formmasse gemäß Anspruch 5, dadurch gekennzeichnet, dass das Monomer A ausgewählt ist aus der Gruppe der Acrylate, Methacrylate, substituierten oder unsubstituierten styrolischen Monomere und Acrylnitril.6. Molding composition according to claim 5, characterized in that the monomer A is selected from the group of acrylates, methacrylates, substituted or unsubstituted styrenic monomers and acrylonitrile.
7. Blend bestehend aus einer Formmasse gemäß der Ansprüche 1 bis 6 und mindestens eines weiteren Polymers.7. blend consisting of a molding composition according to claims 1 to 6 and at least one further polymer.
8. Formkörper hergestellt aus einer Formmasse gemäß der Ansprüche 1 bis 7. 9. Verfahren zur Herstellung einer Formmasse gemäß Anspruch 1 , dadurch gekennzeichnet, dass mindestens ein Monomer A mit mindestens einem Monomer B radikalisch copolymerisiert wird.8. molded body produced from a molding composition according to claims 1 to 7. 9. A process for the preparation of a molding composition according to claim 1, characterized in that at least one monomer A is copolymerized with at least one monomer B radically.
•1 O.Verwendung der Formmasse nach Anspruch 1 im Baubereich, in Kraftfahrzeugen, Schienenfahrzeugen, Wasserfahrzeugen,1 O.Use of the molding composition according to claim 1 in the construction sector, in motor vehicles, rail vehicles, watercraft,
Luftfahrzeugen, Raumfahrzeugen und in der Werbetechnik.Aircraft, spacecraft and advertising technology.
11. Verwendung der Formmassen nach Anspruch 10 als Folien, Platten, coextrudierte Schichten auf Platten und Außenteilen von Kraftfahrzeugen. 11. Use of the molding compositions according to claim 10 as films, plates, coextruded layers on plates and exterior parts of motor vehicles.
EP05806876A 2004-12-16 2005-10-29 Uv stabilizer for pmma Withdrawn EP1824893A1 (en)

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DE102004061126A DE102004061126A1 (en) 2004-12-16 2004-12-16 UV stabilizer for PMMA
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