DE3448013A1 - Process for the production of foamed, non-flammable products from polyacrylates - Google Patents

Process for the production of foamed, non-flammable products from polyacrylates

Info

Publication number
DE3448013A1
DE3448013A1 DE3448013A DE3448013A DE3448013A1 DE 3448013 A1 DE3448013 A1 DE 3448013A1 DE 3448013 A DE3448013 A DE 3448013A DE 3448013 A DE3448013 A DE 3448013A DE 3448013 A1 DE3448013 A1 DE 3448013A1
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DE
Germany
Prior art keywords
polymerization
flame
range
added
production
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.)
Granted
Application number
DE3448013A
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German (de)
Inventor
Des Erfinders Auf Nennung Verzicht
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.)
Imc Acrylguss GmbH
Original Assignee
Imc Acrylguss 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 Imc Acrylguss GmbH filed Critical Imc Acrylguss GmbH
Priority to DE3448013A priority Critical patent/DE3448013A1/en
Priority claimed from DE19843412142 external-priority patent/DE3412142A1/en
Publication of DE3448013A1 publication Critical patent/DE3448013A1/en
Granted 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Abstract

The invention relates to a process for the production of foamed, non-flammable, self-extinguishing products from polyacrylates, to whose monomers are added, inter alia, a flameproofing agent, a blowing agent and optionally a crosslinking agent. The polymerisation, which is carried out for from 2 to 10 hours at an elevated temperature in the range 60-140 DEG C, is carried out according to the invention for a short time and under a pressure in the range from 8 to 25 bar. <IMAGE>

Description

JMC Acrylguss GmbH
Kronprinzenstraße 11
5630 Remscheid 1JMC Acrylguss GmbH
Kronprinzenstrasse 11
5630 Remscheid 1

Verfahren zur Herstellung von geschäumten schwer entflammbaren Erzeugnissen aus PolyacrylatenProcess for the production of foamed, flame-retardant products from polyacrylates

Die Erfindung betrifft ein Verfahren zur Herstellung von geschäumten schwer entflammbaren Erzeugnissen aus Polyacrylaten, wie Polymethylmetacrylat und dergleichen.The invention relates to a process for the production of foamed flame-retardant products from polyacrylates, such as polymethyl methacrylate and the like.

Die Herstellung von Erzeugnissen aus Polymeren auf PoIyacrylatbasis, nachfolgend als "Acrylschaum" bezeichnet, wird hier als bekannt unterstellt. Die Monomere werden mit bestimmten Zusätzen unter Energiezufuhr polymerisiert, wodurch sich die Monomermoleküle zu Makromolekülen verketten. Acrylschaum entsteht durch einen Zusatz von Treibmittel. Falls ein stabilerer Schaum gewünscht wird, kann dem Monomer eine Menge von 0,05 % bis 0,2 % Vernetzer beigegeben werden.The manufacture of products from polymers based on polyacrylate, hereinafter referred to as "acrylic foam", is assumed to be known here. The monomers are polymerized with certain additives under the supply of energy, whereby the monomer molecules are linked to form macromolecules. Acrylic foam is created by adding a propellant. If a more stable foam is desired, an amount of 0.05 % to 0.2 % crosslinker can be added to the monomer.

In herkömmlicher Weise hergestellter Acrylschaum erfüllt auch bei Zusatz handelsüblicher Flammschutzmittel nicht die Anforderungen nach DIN 4102-B1. Der Tropfpunkt des Materials liegt über dem Flammpunkt. Dadurch verbrennt das Material, ehe es abtropft.Acrylic foam produced in a conventional manner does not meet these requirements, even with the addition of commercially available flame retardants Requirements according to DIN 4102-B1. The dropping point of the material is above the flash point. This burns the material before it drips off.

Aus der DE-OS 21 34 327 sind flammhemmende Polymethylmetacrylat-Zusammensetzungen-bekannt, die zur Herstellung von Linsen, Flugzeughauben, Fenstern, Windschutzscheiben, Beleuchtungskörpern und Reklaraeeinrichtungen, aber auch Gebäude-Innenteilen verwendet werden. Zur FlammhemmungFrom DE-OS 21 34 327 flame-retardant polymethyl methacrylate compositions are known, those for the production of lenses, airplane hoods, windows, windshields, lighting fixtures and advertising devices, but also Building interior parts are used. For flame retardancy

COpyCOpy

werden dem Polymermaterial bestimmte 2,3-Dibrompropyl-Hydrogenphosphatester als Additive zugesetzt. Diese Additive beeinträchtigen nicht Klarheit und Härte der Polymere. Versuche mit diesen flammhemmenden Materialien haben jedoch gezeigt, daß zwar ein gewisses flammhemmendes Verhalten erreicht wird, welches jedoch nicht ausreicht, den kriti-' sehen Brandschachttest B1 nach DIN 4102 zu bestehen.certain 2,3-dibromopropyl hydrogen phosphate esters are added to the polymer material added as additives. These additives do not affect the clarity and hardness of the polymers. try with these flame-retardant materials, however, have shown that although a certain flame-retardant behavior is achieved, which, however, is not sufficient to pass the critical 'see Brandschacht test B1 according to DIN 4102.

Aus der FR-PS 1 240 088 ist es bekannt, die Polymerisation raonomerer Acrylverbindungen unter Druck durchzuführen. Dadurch soll die Bildung von Blasen in dem Polymerisat verhindert werden. Die Polymerisation erfolgt bevorzugt durch Zugabe von Katalysatoren und durch geregelte Wärmezufuhr. Irgendwelche Anregungen über die Erzeugung flammhemmender Eigenschaften von Acrylpolymerisaten ist dieser Schrift nicht zu entnehmen.From FR-PS 1 240 088 it is known to carry out the polymerization of monomeric acrylic compounds under pressure. Through this the formation of bubbles in the polymer is to be prevented. The polymerization is preferably carried out by Addition of catalysts and controlled heat supply. Any suggestions about making flame retardant Properties of acrylic polymers is this document not to be found.

Aufgabe der vorliegenden Erfindung ist nun die Schaffung eines Verfahrens zur Herstellung von schwer entflammbaren Erzeugnissen aus Acrylschaum, welche die Anforderungen nach DIN 4102-B1 erfüllen. Insbesondere soll der Flammpunkt bei gleichzeitiger Absenkung des Tropfpunktes so weit angehoben werden, daß er über dem Tropfpunkt liegt, damit das Material unter der Einwirkung einer Flamme abtropft, ehe es zu brennen beginnt.The object of the present invention is now to provide a process for the production of flame-retardant products from acrylic foam, which meets the requirements Meet DIN 4102-B1. In particular, the flash point should be raised so far with a simultaneous lowering of the dropping point be that it is above the dropping point so that the material drips under the action of a flame before it starts to burn.

Zur Lösung dieser Aufgabe werden erfindungsgemäß die Maßnahmen nach Anspruch 1 vorgeschlagen. Bevorzugte Ausgestaltungen sind in den Unteransprüchen gekennzeichnet.According to the invention, the measures are implemented to achieve this object proposed according to claim 1. Preferred configurations are characterized in the subclaims.

Nach dem erfindungsgemäßen Verfahren hergestellte Erzeugnisse aus Acrylschaum erfüllen überraschenderweise die Anforderungen nach DIN 4102-B1. Die kurze radikale Polymerisationszeit ist nur aufgrund des im Autoklaven aufgebauten Überdrucks möglich. Durch den Einbau der Flamm-Products manufactured by the method according to the invention made of acrylic foam surprisingly meet the requirements of DIN 4102-B1. The short radical polymerization time is only possible due to the overpressure built up in the autoclave. By installing the flame

Schutzmittel wird der Flammpunkt angehoben. Gleichzeitig wird der Fließpunkt des Materials durch die bei der radikalen Polymerisation entstehenden kurzen Ketten auf Temperaturen um ca. 1500C abgesenkt. Dadurch wird erreicht, daß das im Brandschacht nach DIN 4102-B1 geprüfte Material brennend abtropft, bevor das Material, das sich oberhalb des abtropfenden Materials befindet, durch die eigene Flamme seinerseits entflammt werden kann. Sobald das so eingestellte Material nicht mehr im Einflußbereich einer fremden Flamme liegt, erlischt es von selbst.Protective agent, the flash point is raised. At the same time, the yield point of the material is lowered by the produced during the radical polymerization of short chains to temperatures of about 150 0 C. This ensures that the material tested in the fire shaft according to DIN 4102-B1 drips while burning before the material above the dripping material can be ignited by its own flame. As soon as the material adjusted in this way is no longer in the area of influence of a foreign flame, it goes out by itself.

Die Menge an zugesetztem Flammschutzmittel soll 13 bis 22 Massen-^, vorzugsweise 15 bis 17 Massen-% betragen.The amount of flame retardant added should be 13 to 22% by mass, preferably 15 to 17% by mass.

Die Ergebnisse wurden erzielt mit handelsüblichem Flammschutzmittel, wie tris-(ß,ßf dichlorisopropyD-phosphat, tris-Cß-chloraethyD-phosphat oder dimethylmethylphosphonat. Gleiche Ergebnisse dürften jedoch auch mit anderen handelsüblichen Flammschutzmitteln erreichbar sein.The results were achieved with commercially available flame retardants, such as tris- (ß, ß f dichloroisopropyD-phosphate, tris-Cß-chloroethyD-phosphate or dimethylmethylphosphonate. However, the same results should also be achievable with other commercially available flame retardants.

Der Überdruck liegt im Bereich von 8 bis 25 bar, vorzugssweise im Bereich von 10 bis 20 bar.The overpressure is in the range from 8 to 25 bar, preferably in the range from 10 to 20 bar.

Die Polymerisationsdauer liegt zwischen 2 und 10 h, insbesondere 7 bis 8 Stunden.The polymerization time is between 2 and 10 hours, in particular 7 to 8 hours.

Während der gesamten Polymerisationsdauer wird der Überdruck aufrechterhalten. Die Zufuhr von Wärme beginnt, nachdem der Druck im Autoklaven aufgebaut ist. Die Temperaturerhöhung kann stufenweise erfolgen derart, daß das in Formen befindliche Material zunächst.auf 40 bis 6O0C erwärmt und dort einige Zeit gehalten wird. Dann wird die Temperatur auf 1000C angehoben, anschließend erfolgt noch unter Überdruck die Temperaturabsenkung auf 2O0C, jeweils währendThe overpressure is maintained during the entire duration of the polymerization. The supply of heat begins after the pressure in the autoclave has built up. The temperature increase can take place gradually in such a manner that the material being heated and forms zunächst.auf 40 to 6O 0 C is held there for some time. Then the temperature is raised to 100 0 C, then the temperature reduction still takes place under overpressure to 2O 0 C, respectively during

etwa zwei Stunden. Unmittelbar vor der Entnahme der Formen aus dem Autoklaven wird der Druck auf Atmosphärendruck abgesenkt. Danach können die Polyacrylat-Erzeugnisse entformt werden.about two hours. Immediately before the molds are removed from the autoclave, the pressure is reduced to atmospheric pressure. The polyacrylate products can then be removed from the mold.

In Fig. 1 ist ein Polymerisationszyklus für Acrylschaum aufgezeichnet. Dieser Polymerisationszyklus ist nur beispielhaft und nicht beschränkend zu verstehen. Abweichungen in Temperatur, Zeit und Ablauf sind möglich.In Fig. 1, a polymerization cycle for acrylic foam is plotted. This polymerization cycle is only to be understood as an example and not in a restrictive manner. Deviations in Temperature, time and sequence are possible.

Claims (6)

PATENTANWALTSBÜRO SCHUMANNSTR. 97 D-4000 DÜSSELDORF 1 Telefon:(0211) 683346 Telex:08586513copd PATENTANWÄLTE DipL-lng. W. COHAUSZ · Dipl-Ing. R. KNAUF · Dipl.-Ing. H. B. COHAUSZ DipHng D. H. WERNER 15.07.1985 We/Ka 44242 PatentansprüchePATENT AGENCY OFFICE SCHUMANNSTR. 97 D-4000 DÜSSELDORF 1 Telephone: (0211) 683346 Telex: 08586513copd PATENTANWÄLTE DipL-lng. W. COHAUSZ Dipl-Ing. R. KNAUF Dipl.-Ing. H. B. COHAUSZ DipHng D. H. WERNER 07/15/1985 We / Ka 44242 claims 1. Verfahren zur Herstellung von geschäumten schwer entflammbaren Erzeugnissen aus Polyacrylaten, deren Monomeren u.a. ein Flammschutzmittel, Treibmittel und Vernetzer zugesetzt werden, wobei die Polymerisation bei erhöhter Temperatur erfolgt,
dadurch gekennzeichnet, daß die Polymerisation während 2 bis 10 h und unter einem Druck im Bereich von 8 bis 25 bar bei Temperaturen im Bereich von 60 bis 14O0C vorgenommen wird.1. Process for the production of foamed, flame-retardant products from polyacrylates, the monomers of which, among other things, a flame retardant, blowing agent and crosslinking agent are added, the polymerization taking place at elevated temperature,
characterized in that the polymerization for 2 to 10 hours and is carried out under a pressure in the range of 8 to 25 bar at temperatures in the range of 60 to 14O 0 C. 2. Verfahren nach Anspruch 1,2. The method according to claim 1, dadurch gekennzeichnet, daß dem Monomer 13 bis 22 Massen-? Flammschutzmittel zugesetzt wird.characterized in that the monomer 13 to 22 mass? Flame retardants is added. ■20 ■ 20 3. Verfahren nach Anspruch 2,3. The method according to claim 2, dadurch gekennzeichnet, daß dem Monomer 15 bis 17 Massen-% Flammschutzmittel zugesetzt wird.characterized in that the monomer contains 15 to 17% by mass of flame retardant is added. 4. Verfahren nach Anspruch 1,4. The method according to claim 1, dadurch geken.nz. e lehnet, daß die Polymerisation bei einem Druck im Bereich von bis 20 bar erfolgt.thereby geken.nz. e refuses, that the polymerization takes place at a pressure in the range of up to 20 bar. 1 1 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Polymerisation während 7 bis 8 h vorgenommen wird.5. The method according to claim 1, characterized in that that the polymerization is carried out for 7 to 8 hours. 6. Verfahren nach Anspruch 1,6. The method according to claim 1, dadurch gekennzeichnet, daß bei der Polymerisation während zwei- Stunden eine Temperatur von 1000C eingestellt wird. 10characterized in that a temperature of 100 ° C. is set for two hours during the polymerization. 10
DE3448013A 1984-03-31 1984-03-31 Process for the production of foamed, non-flammable products from polyacrylates Granted DE3448013A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE3448013A DE3448013A1 (en) 1984-03-31 1984-03-31 Process for the production of foamed, non-flammable products from polyacrylates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843412142 DE3412142A1 (en) 1984-03-31 1984-03-31 Process for the production of flame-retardant products from acrylic polymer
DE3448013A DE3448013A1 (en) 1984-03-31 1984-03-31 Process for the production of foamed, non-flammable products from polyacrylates

Publications (1)

Publication Number Publication Date
DE3448013A1 true DE3448013A1 (en) 1986-02-27

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ID=25819941

Family Applications (1)

Application Number Title Priority Date Filing Date
DE3448013A Granted DE3448013A1 (en) 1984-03-31 1984-03-31 Process for the production of foamed, non-flammable products from polyacrylates

Country Status (1)

Country Link
DE (1) DE3448013A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2134327A1 (en) * 1970-01-02 1973-01-18 Stauffer Chemical Co FLAME RETARDANT POLYMETHYL METHACRYLATE COMPOSITIONS
DE2520635A1 (en) * 1975-05-09 1976-11-18 Basf Ag FINE PARTITION, EXPANDABLE STYRENE POLYMERIZED WITH GOOD PROCESSABILITY

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2134327A1 (en) * 1970-01-02 1973-01-18 Stauffer Chemical Co FLAME RETARDANT POLYMETHYL METHACRYLATE COMPOSITIONS
DE2520635A1 (en) * 1975-05-09 1976-11-18 Basf Ag FINE PARTITION, EXPANDABLE STYRENE POLYMERIZED WITH GOOD PROCESSABILITY

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