EP0236353A1 - Process for the production of foamed plastics - Google Patents

Process for the production of foamed plastics

Info

Publication number
EP0236353A1
EP0236353A1 EP19860904821 EP86904821A EP0236353A1 EP 0236353 A1 EP0236353 A1 EP 0236353A1 EP 19860904821 EP19860904821 EP 19860904821 EP 86904821 A EP86904821 A EP 86904821A EP 0236353 A1 EP0236353 A1 EP 0236353A1
Authority
EP
European Patent Office
Prior art keywords
component
starting mixture
monomeric
oligomeric
foamed
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.)
Pending
Application number
EP19860904821
Other languages
German (de)
French (fr)
Inventor
Jürgen GUDJONS
Klaus Wollmann
Gerhard Glink
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.)
Erwin Behn Verpackungsbedarf GmbH
Original Assignee
Erwin Behn Verpackungsbedarf GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Erwin Behn Verpackungsbedarf GmbH filed Critical Erwin Behn Verpackungsbedarf GmbH
Publication of EP0236353A1 publication Critical patent/EP0236353A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent

Definitions

  • the invention relates to a process for the production of ge foamed plastics, in which a starting mixture of monomeric, oligomeric or polymeric compounds "polymerized with vinyl grouping in the presence of a blowing agent and a catalyst and then foamed by irradiation.
  • a process for the manufacture of articles from polymethyl methacrylate in which a mixture of methyl methacrylate monomer, preferably liquid blowing agent and catalyst is polymerized to a solid body containing blowing agent in a first stage. This is carried out in a second stage foamed by heating to the softening temperature of the plastic, for example by means of microwaves.
  • the acrylate polymers produced in this way are very difficult to foam with microwaves. In a commercially available microwave oven, the known material only begins after about 30 minutes to become soft and to inflate very slowly.
  • GB-PS 1 348 552 describes a method for producing foams in which compounds containing vinyl groups are polymerized in the presence of a blowing agent, a catalyst and additionally a crosslinking agent.
  • the polymers are foamed using radio waves of approximately 27 MHz. It is particularly pointed out that a crosslinking agent is necessary in order to be able to obtain a foamed material. If microwave radiation is used instead of radio waves in this process, no satisfactory results are obtained either. If the addition of crosslinking agents is dispensed with, the result is products which are too soft and are not stable foams.
  • the present invention is based on the object of specifying a method with which the products can be fully foamed in a maximum of 5 minutes without the addition of crosslinking agents.
  • the starting mixture is composed of at least three components, which consist of a component A of monomeric methyl methacrylate and / or styrene, optionally with a proportion of prepolymerized methyl methacrylate and / or styrene, of a component B consists of monomeric or oligomeric compounds containing a vinyl grouping and microwave-sensitive groups and a component C consists of monomeric, oligomeric or polymeric compounds containing microwave-sensitive groups without vinyl grouping, components B and C containing hydroxyl, thiol , Alkylamino- with 1 to 6 carbon atoms, amino or carboxyl groups are substituted, and that foaming by microwave radiation lung is brought about.
  • a component A of monomeric methyl methacrylate and / or styrene optionally with a proportion of prepolymerized methyl methacrylate and / or styrene
  • a component B consists of monomeric or oligomeric compounds containing a vinyl group
  • the starting mixture has a special composition.
  • the mixture component is methyl methacrylate and / or styrene. Some of these compounds can also be present in prepolymerized form.
  • the amount of component A in the starting mixture is 50 to 95% by weight, preferably 70 to 8% by weight, based on the total weight of the starting mixture, i.e. without taking into account the proportions of blowing agent, catalyst and fillers or dyes that may also be present.
  • the mixture components B and C can be monomeric, oligomeric or polymeric compounds and contain groups which are easily excitable by microwaves. Such groups are hydroxyl, thiol, alkylamino, amino or carboxyl groups.
  • Component B furthermore has at least one vinyl grouping, while component C is free of vinyl groupings. It is also essential that the main part of the starting mixture forms methyl methacrylate and or styrene.
  • the amount of component B i of the starting mixture is 5 to 50% by weight, preferably 10 to 2% by weight. -%, based on the total weight of the starting mixture.
  • the amount of component C is 1 to 20% by weight. preferably 2 to 7% by weight, based on the total weight of the starting mixture.
  • Hydroxyalkyl acrylates or methacrylates and / or hydroxyalkenes are preferably used as component B. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl ethacrylate and allyl alcohol are particularly suitable fetch As component C, for example, hydroxyl-containing silicones, polyesters, ie polyols, melamine resin or urea precondensates are used. Particularly good results are achieved with silicones. Bisphenol A, nonylphenol, decanol and perfluoroalcohol are also suitable.
  • Solid blowing agents can be used, which decompose when the temperature rises and thereby release the expanding gases.
  • Liquid blowing agents are preferably used which have a boiling point of max. 100 ° C., preferably 50 ° C., evaporate when the temperature of the material rises and thereby inflate the material.
  • the products contain 5 to 60 units. -%, preferably 40 to 50 wt. -% blowing agent, based on the total remaining portions in the reaction mixture. Frigen 1 and a mixture of Frigen 11 and Frigen 114 are preferably used.
  • a conventional peroxide catalyst can be used as the polymerization initiator, which is effective when heated. If, for the purpose of polymerization, the reaction mixture has to be heated to a temperature above the evaporation temperature of the blowing agent, the polymerization can be carried out under pressure in order to prevent the blowing agent from being released prematurely.
  • a photoinitiator is preferably used as the polymerization catalyst, which makes it possible to polymerize the mixture at low temperature, in particular at about room temperature, by exposure to radiation matched to a photoinitiator known for acrylate monomer, for example UV light of a wavelength of 350 nm.
  • the polymerization can be controlled by switching the radiation sources on and off or by external cooling so that the temperature in the mass to be polymerized does not rise above a certain value in the course of the exothermic polymerization reaction which is below the evaporation temperature of the liquid blowing agent.
  • fillers and / or dyes can be provided in the starting mixture, which can be selected depending on the area of use of the foamed product.
  • An already polymerized, propellant-containing product can be stored as an intermediate product if it is not immediately fed into the second process stage, in which it is foamed by microwave radiation of approximately 2000 to 3000 MHz.
  • the method according to the invention enables the products to be foamed by means of microwaves in a maximum of 5 minutes. Most of the products are fully foamed after only 2 minutes.
  • non-substituted monomeric or prepolymeric vinyl compounds i.e. Methyl methacrylate and / or styrene, fast foaming products are thus obtained which also have well-formed pores.
  • the foamed polymers according to the invention can also be transparent and in the form of sheets, sheets, moldings and multilayer bodies with a foam core.
  • blowing agent Frigen 11
  • the resulting blowing agent-containing polymer is then foamed by heating by means of high frequency in a commercially available microwave oven (2450 MHz, 720 W output power). The process of exhaustion was over after a minute.
  • Example 1 The procedure of Example 1 is repeated using 4 parts of methyl methacrylate, 0.55 part of hydroxybutyl acrylate, 0.45 part of silicone, 0.05 part of nonylphenol, 0.03 part of UV polymerization initiator and 2.5 parts of blowing agent (Frigen 11) become. The polymer was fully foamed after about 2 minutes.
  • Example 1 The procedure of Example 1 is repeated, except that 2.5 parts of methyl methacrylate, 1 part of styrene, 1 part of hydroxybutyl methacrylate, 0.25 part of nonylphenol, 0.25 part of bisphenol ⁇ , 0.07 part of UV polymerization initiator and 2 , 5 parts of blowing agent can be used.
  • the duration of the foaming process using microwave radiation was less than 2 minutes.

Abstract

Dans un procédé de production de plastiques expansés on utilise un mélange de départ, qui est composé d'au moins trois constituants. Le constituant A est représenté par le méthylméthacrylate et/ou le styrol et peut également contenir des quantités prépolymérisées de ces composés. Le constituant B est un composant monomère ou oligomère, qui possède un groupement vinylique et des groupes sensibles aux micro-ondes. Le constituant C contient également des groupes sensibles aux micro-ondes mais ne comporte pas de groupement vinylique. Les constituants B et C sont, à la différence du constituant A, substitués par des groupes hydroxyle, thiol, alkylamino avec 1 à 6 atomes de carbone, amino ou carboxyle. La polymérisation s'effectue de la manière connue en présence d'un agent moussant et d'un catalyseur. Le polymérisat obtenu est ensuite expansé par le rayonnement à micro-ondes.In a process for producing expanded plastics, a starting mixture is used, which is composed of at least three constituents. Component A is represented by methylmethacrylate and / or styrol and may also contain prepolymerized amounts of these compounds. Component B is a monomer or oligomer component, which has a vinyl group and groups sensitive to microwaves. Component C also contains groups sensitive to microwaves but does not contain a vinyl group. Constituents B and C are, unlike constituent A, substituted by hydroxyl, thiol, alkylamino groups with 1 to 6 carbon atoms, amino or carboxyl. The polymerization is carried out in the known manner in the presence of a foaming agent and a catalyst. The polymerisate obtained is then expanded by microwave radiation.

Description

Verfahren zur Herstellung von geschäumten Kunststoffen Process for the production of foamed plastics
Die Erfindung betrifft ein Verfahren zur Herstellung von ge schäumten Kunststoffen, bei dem eine Ausgangsmischung au monomeren, oligomeren oder poly eren Verbindungen "mit Vinyl gruppierung in Anwesenheit eines Treibmittels und eines Ka talysators polymerisiert und anschließend durch Bestrahlun geschäumt werden.The invention relates to a process for the production of ge foamed plastics, in which a starting mixture of monomeric, oligomeric or polymeric compounds "polymerized with vinyl grouping in the presence of a blowing agent and a catalyst and then foamed by irradiation.
Aus der DE-PS 31 24 980 ist ein Verfahren zur Herstellun von Gegenständen aus Polymethylmethacrylat bekannt, bei de in einer ersten Stufe ein Gemisch von Methylmethacrylatmono mer, bevorzugt flüssigem Treibmittel und Katalysator zu ei nem treibmittelhaltigen festen Körper polymerisiert wird Dieser wird in einer zweiten Stufe durch Erwärmen auf di Erweichungstemperatur des Kunststoffes, z.B. mittels Mikro wellenbestrahlung, geschäumt. Die so hergestellten Acrylat polymerisate sind jedoch nur sehr schwer mit Mikrowellen zu Schäumen zu bringen. In einem handelsüblichen Mikrowellen herd beginnt das bekannte Material erst nach etwa 30 Minute weich zu werden und ganz langsam zu blähen.From DE-PS 31 24 980 a process for the manufacture of articles from polymethyl methacrylate is known, in which a mixture of methyl methacrylate monomer, preferably liquid blowing agent and catalyst is polymerized to a solid body containing blowing agent in a first stage. This is carried out in a second stage foamed by heating to the softening temperature of the plastic, for example by means of microwaves. However, the acrylate polymers produced in this way are very difficult to foam with microwaves. In a commercially available microwave oven, the known material only begins after about 30 minutes to become soft and to inflate very slowly.
In der GB-PS 1 348 552 wird eine Methode zur Herstellung von Schäumen beschrieben, bei der Vinylgruppen enthaltende Ver¬ bindungen in Anwesenheit eines Treibmittels, eines Katalysa¬ tors und zusätzlich eines Vernetzungsmittels polymerisiert werden. Die Polymerisate werden mittels Radiowellen von etwa 27 MHz geschäumt. Es wird besonders darauf hingewiesen, daß ein Vernetzungsmittel notwendig ist, um ein verschäumtes Ma¬ terial erhalten zu können. Verwendet man bei diesem Verfah¬ ren statt Radiowellen, Mikrowellenbestrahlung, so werden auch keine zuf iedenstellenden Ergebnisse erhalten. Verzich¬ tet man auf die Zugabe von Vernetzungsmitteln, so resultie¬ ren Produkte, die zu weich sind und keine stabilen Schäume darstellen.GB-PS 1 348 552 describes a method for producing foams in which compounds containing vinyl groups are polymerized in the presence of a blowing agent, a catalyst and additionally a crosslinking agent. The polymers are foamed using radio waves of approximately 27 MHz. It is particularly pointed out that a crosslinking agent is necessary in order to be able to obtain a foamed material. If microwave radiation is used instead of radio waves in this process, no satisfactory results are obtained either. If the addition of crosslinking agents is dispensed with, the result is products which are too soft and are not stable foams.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, mit dem die Produkte ohne Zusatz von Vernetzungsmitteln in einer Zeitspanne von maximal 5 Minuten voll aufgeschäumt werden können.The present invention is based on the object of specifying a method with which the products can be fully foamed in a maximum of 5 minutes without the addition of crosslinking agents.
Diese Aufgabe ist erfindungsgemäß dadurch gelöst, daß die Ausgangsmischung aus mindestens drei Komponenten zusammenge¬ setzt wird, die aus einer Komponente A aus monomerem Methyl¬ methacrylat und/oder Styrol, gegebenenfalls mit einem Anteil an vorpolymerisiertem Methylmethacrylat und/oder Styrol, ei¬ ner Komponente B aus monomeren oder oligomeren, eine Vinyl- gruppierung und mikrowellenempfindliche Gruppen enthaltenden Verbindungen und einer Komponente C aus monomeren, oli¬ gomeren oder polymeren, mikrowellenempfindliche Gruppen ent¬ haltenden Verbindungen ohne Vinylgruppierung bestehen, wobei die Komponenten B und C mit Hydroxyl-, Thiol-, Alkylamino- mit 1 bis 6 C-Atomen, Amino- oder Carboxylgruppen substitu¬ iert sind, und daß das Verschäumen durch Mikrowellenbestrah- lung herbeigeführt wird. Bevorzugte Ausführungsformen de erfindungsgemäßen Verfahrens sind in den Unteransprüchen bis 7 beschrieben.This object is achieved according to the invention in that the starting mixture is composed of at least three components, which consist of a component A of monomeric methyl methacrylate and / or styrene, optionally with a proportion of prepolymerized methyl methacrylate and / or styrene, of a component B consists of monomeric or oligomeric compounds containing a vinyl grouping and microwave-sensitive groups and a component C consists of monomeric, oligomeric or polymeric compounds containing microwave-sensitive groups without vinyl grouping, components B and C containing hydroxyl, thiol , Alkylamino- with 1 to 6 carbon atoms, amino or carboxyl groups are substituted, and that foaming by microwave radiation lung is brought about. Preferred embodiments of the method according to the invention are described in the subclaims to 7.
Erfindungsgemäß wird eine schnelle Schäumung in erster Linie dadurch erreicht, daß die Ausgangsmischung eine spe zielle Zusammensetzung aufweist. Die Mischungskomponente ist Methylmethacrylat und/oder Styrol. Diese Verbindunge können auch teilweise in präpolymerisierter Form vor¬ liegen. Die Menge der Komponente A in der Ausgangsmi¬ schung beträgt 50 bis 95 Gew. -% , vorzugsweise 70 bis 8 Gew.- , bezogen auf das Gesamtgewicht der Ausgangsmischung d.h. ohne Berücksichtigung der Anteile an Treibmittel, Kata lysator und Füll- oder Farbstoffe, die ebenfalls anwesend sein können. Die Mischungskomponenten B und C können monomere, oligomere oder polymere Verbindungen sein un enthalten Gruppen, die durch Mikrowellen gut anregbar sind. Solche Gruppen sind Hydroxyl-, Thiol-, Alkylamino- Amino- oder Carboxylgruppen. Bevorzugt werden Verbindunge mit Hydroxylgruppen eingesetzt. Ferner weist die Komponente B mindestens eine Vinylgruppierung auf während die Komponen C frei von Vinylgruppierungen ist. Wesentlich ist auch, da den Hauptanteil der Ausgangsmischung Methylmethacrylat und oder Styrol bildet. So beträgt die Menge der Komponente B i der Ausgangsβiischung 5 bis 50 Gew.-/., vorzugsweise 10 bis 2 Gevr . -% , bezogen auf das Gesamtgewicht der Ausgangsmischuπg Die Menge an Komponente C beläuft sich auf 1 bis 20 Gew.-?. vorzugsweise 2 bis 7 Gew.-?., bezogen auf das Gesamtgewich der Ausgangsmischung.According to the invention, rapid foaming is primarily achieved in that the starting mixture has a special composition. The mixture component is methyl methacrylate and / or styrene. Some of these compounds can also be present in prepolymerized form. The amount of component A in the starting mixture is 50 to 95% by weight, preferably 70 to 8% by weight, based on the total weight of the starting mixture, i.e. without taking into account the proportions of blowing agent, catalyst and fillers or dyes that may also be present. The mixture components B and C can be monomeric, oligomeric or polymeric compounds and contain groups which are easily excitable by microwaves. Such groups are hydroxyl, thiol, alkylamino, amino or carboxyl groups. Compounds with hydroxyl groups are preferably used. Component B furthermore has at least one vinyl grouping, while component C is free of vinyl groupings. It is also essential that the main part of the starting mixture forms methyl methacrylate and or styrene. The amount of component B i of the starting mixture is 5 to 50% by weight, preferably 10 to 2% by weight. -%, based on the total weight of the starting mixture. The amount of component C is 1 to 20% by weight. preferably 2 to 7% by weight, based on the total weight of the starting mixture.
Als Komponente B werden vorzugsweise Hydroxyalkylacrylate oder -methacrylate und/oder Hydroxyalkene verwendet. Besond geeignet sind Hydroxyethylacrylat , Hydroxyethylmethacrylat Hydroxybutylacrylat, Hydroxybutyl ethacrylat und Allylalko hol. Als Komponente C werden z.B. hydroxylgruppenhaltige Si likone, Polyester, d.h. Polyole, Melaminharz- oder Harn stoffvorkondensate eingesetzt. Besonders gute Ergebniss werden mit Silikonen erzielt. Gut geeignet sind auch Bisphe nol A, Nonylphenol, Decanol und Perfluoralkohol.Hydroxyalkyl acrylates or methacrylates and / or hydroxyalkenes are preferably used as component B. Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl ethacrylate and allyl alcohol are particularly suitable fetch As component C, for example, hydroxyl-containing silicones, polyesters, ie polyols, melamine resin or urea precondensates are used. Particularly good results are achieved with silicones. Bisphenol A, nonylphenol, decanol and perfluoroalcohol are also suitable.
Die zur Polymerisation von Monomeren mit Vinylgruppen, z.B. Acrylaten, einsetzbaren Treibmittel und Katalysatoren sin bekannt. Es können feste Treibmittel verwendet werden, di sich bei Temperaturerhöhung zersetzen und dabei di blähenden Gase freisetzen. Vorzugsweise werden flüssig Treibmittel verwendet, die einen Siedepunkt von maxima 100°C, vorzugsweise 50°C, aufweisen, bei Temperaturerhöhung des Materials verdampfen und dabei das Material aufblähen. Die Produkte enthalten 5 bis 60 Gevt. -% , vorzugsweise 40 bis 50 Gew . -% Treibmittel, bezogen auf die gesamten restliche Anteile im Reaktionsgemisch. Vorzugsweise wird Frigen 1 sowie eine Mischung aus Frigen 11 und Frigen 114 verwendet .Those for polymerizing monomers with vinyl groups, e.g. Acrylates, propellants and catalysts that can be used are known. Solid blowing agents can be used, which decompose when the temperature rises and thereby release the expanding gases. Liquid blowing agents are preferably used which have a boiling point of max. 100 ° C., preferably 50 ° C., evaporate when the temperature of the material rises and thereby inflate the material. The products contain 5 to 60 units. -%, preferably 40 to 50 wt. -% blowing agent, based on the total remaining portions in the reaction mixture. Frigen 1 and a mixture of Frigen 11 and Frigen 114 are preferably used.
Als Polymerisationsinitiator kann insbesondere ein übliche Peroxidkatalysator verwendet werden, der beim Erwärmen wirk sam wird. Wenn zum Zwecke der Polymerisation die Reaktions mischung auf eine Temperatur über der Verdampfungstemperatu des Treibmittels erwärmt werden muß, kann das Polymerisiere unter Druck vorgenommen werden ,* um ein vorzeitiges Freiwer den des Treibmittels zu verhindern. Vorzugsweise wird al Polymerisationskatalysator ein Fotoinitiator verwendet welcher es ermöglicht, das Gemisch bei niedriger Temperatur insbesondere etwa bei Raumtemperatur, durch Belichten mi einer auf einen für Acrylat-Monomer bekannten Fotoinitiator abgestimmten Strahlung, z.B. UV-Licht einer Wellenlänge vo 350 nm, zu polymerisieren. Die Polymerisation kann durc Ein- und Ausschalten der Strahlenguellen oder durch eine externe Kühlung so gesteuert werden, daß die Temperatur in der zu poly erisierenden Masse im Verlauf der exothermen Polymerisationsreaktion nicht über einen bestimmten Wert steigt, der unterhalb der Verdampfungstemperatur des flüs¬ sigen Treibmittels liegt.A conventional peroxide catalyst can be used as the polymerization initiator, which is effective when heated. If, for the purpose of polymerization, the reaction mixture has to be heated to a temperature above the evaporation temperature of the blowing agent, the polymerization can be carried out under pressure in order to prevent the blowing agent from being released prematurely. A photoinitiator is preferably used as the polymerization catalyst, which makes it possible to polymerize the mixture at low temperature, in particular at about room temperature, by exposure to radiation matched to a photoinitiator known for acrylate monomer, for example UV light of a wavelength of 350 nm. The polymerization can be controlled by switching the radiation sources on and off or by external cooling so that the temperature in the mass to be polymerized does not rise above a certain value in the course of the exothermic polymerization reaction which is below the evaporation temperature of the liquid blowing agent.
Weiter können in der Ausgangsmischung Füllstoffe und/ode Farbstoffe vorgesehen werden, die je nach Einsatzgebiet de geschäumten Produkts ausgewählt werden können.Furthermore, fillers and / or dyes can be provided in the starting mixture, which can be selected depending on the area of use of the foamed product.
Ein bereits polymerisiertes, treibmi telhaltiges Produk kann als Zwischenprodukt gelagert werden, falls es nicht gleich in die zweite Verfahrensstufe zugeführt wird in welcher es durch Mikrowellenbestrahlung von etwa 2000 bi 3000 MHz geschäumt wird.An already polymerized, propellant-containing product can be stored as an intermediate product if it is not immediately fed into the second process stage, in which it is foamed by microwave radiation of approximately 2000 to 3000 MHz.
Das erfindungsgemäße Verfahren ermöglicht die Aufschäumun der Produkte mittels Mikrowellen in maximal 5 Minuten. Ei Großteil der Produkte werden schon nach 2 Minuten voll auf geschäumt. Durch Zugabe von ήichtsubstituierten monomeren oder vorpolymeren Vinylverbindungen in die Ausgangsmischung d.h. Methylmethacrylat und/oder Styrol, werden somit schnellschäumende Produkte erhalten, die zusätzlich auch gu ausgebildete Poren aufweisen. Die erfindungsgemäß geschäum ten Polymere können auch transparent und in Form von Bah nen, Platten, Formkörpern und Mehrschichtkörpern mit Schaumstoffkern ausgebildet sein.The method according to the invention enables the products to be foamed by means of microwaves in a maximum of 5 minutes. Most of the products are fully foamed after only 2 minutes. By adding non-substituted monomeric or prepolymeric vinyl compounds to the starting mixture i.e. Methyl methacrylate and / or styrene, fast foaming products are thus obtained which also have well-formed pores. The foamed polymers according to the invention can also be transparent and in the form of sheets, sheets, moldings and multilayer bodies with a foam core.
Die Erfindung wird anhand nachfolgender Beispiele näher er läutert.The invention is explained in more detail using the following examples.
Beispiel _Example _
4 Teile Me thyl methacryl at , 0 , 8 Teile Hyd roxybutyl acryl at 0 , 1 5 Teile Bisphenol A, 0 , 03 Teile UV-Po lymerisationsstarte und 2,5 Teile Treibmittel (Frigen 11) werden unter Beachtung der Temperatur gemischt und anschließend unter Kühlung bei 18°C fotopolymerisiert.4 parts methyl methacrylate, 0.8 part hydroxybutyl acrylate 0.15 parts bisphenol A, 0.03 part UV-polymerisation start and 2.5 parts of blowing agent (Frigen 11) are mixed while observing the temperature and then photopolymerized with cooling at 18 ° C.
Das resultierende, treibmittelhaltige Polymerisat wird dann durch Erwärmen mittels Hochfrequenz, in einem handelsübli¬ chen Mikrowellenherd (2450 MHz, 720 W Ausgangsleistung) ge¬ schäumt. Der Schäu ungsprozeß war schon nach einer Minute zu Ende.The resulting blowing agent-containing polymer is then foamed by heating by means of high frequency in a commercially available microwave oven (2450 MHz, 720 W output power). The process of exhaustion was over after a minute.
Beispiel 2_Example 2_
Das Verfahren des Beispiels 1 wird wiederholt, wobei jedcch 4 Teile Methylmethacrylat, 0,55 Teile Hydroxybutylacrylat, 0,45 Teile Silikon, 0,05 Teile Nonylphenol, 0,03 Teile UV- Polymerisationsstarter und 2,5 Teile Treibmittel (Frigen 11) verwendet werden. Das Polymerisat war nach etwa 2 Minuten voll aufgeschäumt.The procedure of Example 1 is repeated using 4 parts of methyl methacrylate, 0.55 part of hydroxybutyl acrylate, 0.45 part of silicone, 0.05 part of nonylphenol, 0.03 part of UV polymerization initiator and 2.5 parts of blowing agent (Frigen 11) become. The polymer was fully foamed after about 2 minutes.
Beispiel _3_Example _3_
Das Verfahren des Beispiels 1 wird wiederholt, wobei jedoch 2,5 Teile Methylmethacrylat, 1 Teil Styrol, 1 Teil Hydroxy- butylmethacrylat, 0,25 Teile Nonylphenol, 0,25 Teile Bisphe¬ nol Ä, 0,07 Teile UV-Polymerisationsstarter und 2,5 Teile Treibmittel verwendet werden. Die Dauer des Schäumungspro- zesses mittels Mikrowellenbestrahlung lag unter 2 Minuten. The procedure of Example 1 is repeated, except that 2.5 parts of methyl methacrylate, 1 part of styrene, 1 part of hydroxybutyl methacrylate, 0.25 part of nonylphenol, 0.25 part of bisphenol Ä, 0.07 part of UV polymerization initiator and 2 , 5 parts of blowing agent can be used. The duration of the foaming process using microwave radiation was less than 2 minutes.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von geschäumten Kunststoffen, bei dem eine Ausgangsmischung aus monomeren, oligomeren oder po- lymeren Verbindungen mit Vinylgruppierung in Anwesenheit ei¬ nes Treibmittels und eines Katalysators polymerisiert und anschließend durch Bestrahlung geschäumt wird, dadurch ge¬ kennzeichnet, daß die Ausgangsmischung aus mindestens drei Komponenten zusammengesetzt wird, die aus einer Komponente aus monomerem Methylmethacrylat und/oder Styrol, gegebenen¬ falls mit einem Anteil an vorpolymerisiertem Methylmethacry lat und/oder Styrol, einer Komponente B aus monomeren oder oligomeren, Vinylgruppierung und mikrowellenempfindliche Gruppen enthaltenden Verbindungen und einer Komponente C aus monomeren, oligomeren oder polymeren, mikrowellen¬ empfindliche Gruppen enthaltenden Verbindungen ohne Vinyl¬ gruppierung bestehen, wobei die Komponenten B und C mi Hydroxyl-, Thiol-, Alkylamino- mit 1 bis 6 C-Atomen, Amino- oder Carboxylgruppen substituiert sind, und daß die Schäu mung durch Mikrowellenbestrahlung herbeigeführt wird.1. A process for the production of foamed plastics, in which a starting mixture of monomeric, oligomeric or polymeric compounds with vinyl grouping is polymerized in the presence of a blowing agent and a catalyst and is then foamed by irradiation, characterized in that the starting mixture consists of at least three components are composed, consisting of a component of monomeric methyl methacrylate and / or styrene, optionally with a proportion of prepolymerized methyl methacrylate and / or styrene, a component B of monomeric or oligomeric, vinyl grouping and compounds containing microwave-sensitive groups and a component C consist of monomeric, oligomeric or polymeric, microwave-sensitive group-containing compounds without vinyl grouping, components B and C being substituted with hydroxyl, thiol, alkylamino with 1 to 6 C atoms, amino or carboxyl groups, and that the foaming is brought about by microwave radiation.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß al Komponente B Hydroxyalkylacrylate oder -methacrylate und/ oder Hydroxyalkene, vorzugsweise Hydroxyethylacrylat, Hydr oxyethylmethacrylat, Hydroxybutylacrylat , Hydroxybutylmeth- acrylat und/oder Allylalkohol verwendet werden. 2. The method according to claim 1, characterized in that al component B hydroxyalkyl acrylates or methacrylates and / or hydroxyalkenes, preferably hydroxyethyl acrylate, hydr oxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate and / or allyl alcohol are used.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Menge der Komponente B in der Ausgangsmischung 5 bis 50 Gew.-?., vorzugsweise 10 bis 25 Gew.-?., bezogen auf das Gesamtgewicht der Ausgangsmischung, beträgt.3. The method according to claim 1 or 2, characterized in that the amount of component B in the starting mixture 5 to 50 wt .-?., Preferably 10 to 25 wt .-?., Based on the total weight of the starting mixture.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß als Komponente C Bisphenol A, Nonylphenol, De- canol, Perfluoralkohol , Hydroxylgruppen enthaltende Siliko¬ ne, Polyole, Melaminharzvorkondensate und/oder Harnstoff¬ vorkondensate verwendet werden.4. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that as component C bisphenol A, nonylphenol, decanol, perfluoroalcohol, hydroxyl-containing silicones, polyols, melamine resin precondensates and / or urea precondensates are used.
5.. Verfahren nach einem der Ansprüche 1 bis , dadurch gekenn¬ zeichnet, daß die Menge der Komponente C in der Ausgangsmi¬ schung 1 bis 20 Gew.-?., vorzugsweise 2 bis 7 Gew.-/.. bezo¬ gen auf das Gesamtgewicht der Ausgangsmiεchung, beträgt.5 .. The method according to any one of claims 1 to, characterized gekenn¬ characterized in that the amount of component C in the starting mixture 1 to 20 wt .-?., Preferably 2 to 7 wt .- / .. based on the total weight of the starting mixture.
'6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekenn¬ zeichnet, daß die Menge der Komponente A in der Ausgangsmi¬ schung 50 bis 95 Gew. -% , vorzugsweise 70 bis 80 Gew.-?., bezogen auf das Gesamtgewicht der Ausgangsmischung, beträgt. '6. A method according to any one of claims 1 to 5, characterized gekenn¬ characterized in that the amount of component A in the Ausgangsmi¬ Research 50 to 95 wt -.?.%, Preferably 70 to 80 wt .-, based on the total weight the starting mixture.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekenn¬ zeichnet, daß die Polymerisation in Gegenwart von Füll¬ stoffen und/oder Farbstoffen durchgeführt wird. 7. The method according to any one of claims 1 to 6, characterized gekenn¬ characterized in that the polymerization is carried out in the presence of fillers and / or dyes.
EP19860904821 1985-09-11 1986-08-08 Process for the production of foamed plastics Pending EP0236353A1 (en)

Applications Claiming Priority (2)

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DE19853532347 DE3532347A1 (en) 1985-09-11 1985-09-11 METHOD FOR PRODUCING FOAMED PLASTICS
DE3532347 1985-09-11

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EP0236353A1 true EP0236353A1 (en) 1987-09-16

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DE3842305A1 (en) * 1988-12-16 1990-06-21 Basf Ag METHOD FOR PRODUCING STYRENE POLYMERISATE FOAM PARTICLES
US5700844A (en) * 1996-04-09 1997-12-23 International Business Machines Corporation Process for making a foamed polymer

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US3432413A (en) * 1964-11-02 1969-03-11 Dow Chemical Co Method for carrying out chemical reactions using microwave energy
GB1348552A (en) * 1971-06-01 1974-03-20 Dow Chemical Co Composite sheet
US3923705A (en) * 1974-10-30 1975-12-02 Dow Corning Method of preparing fire retardant siloxane foams and foams prepared therefrom
US4352854A (en) * 1980-03-28 1982-10-05 Phillips Petroleum Company Molded sponge-like thermoplastic elastomer articles having thin, dense skins and a process for their production
DE3124980C1 (en) * 1981-06-25 1987-07-09 Fa. August Hohnholz, 2000 Hamburg Process for the manufacture of articles from foamed polymethyl methacrylate

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DE3532347C2 (en) 1989-03-02
DE3532347A1 (en) 1987-03-12

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