EP1082382A1 - Method for producing water expandable styrene polymers - Google Patents

Method for producing water expandable styrene polymers

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Publication number
EP1082382A1
EP1082382A1 EP99910367A EP99910367A EP1082382A1 EP 1082382 A1 EP1082382 A1 EP 1082382A1 EP 99910367 A EP99910367 A EP 99910367A EP 99910367 A EP99910367 A EP 99910367A EP 1082382 A1 EP1082382 A1 EP 1082382A1
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Prior art keywords
styrene
water
polymerization
solid substance
particle size
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EP99910367A
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German (de)
French (fr)
Inventor
Guiscard Glück
Klaus Hahn
Roland Gellert
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BASF SE
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BASF SE
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    • 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
    • C08J9/16—Making expandable particles
    • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the 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
    • C08F12/00—Homopolymers and 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
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J2325/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the invention relates to a process for the preparation of water-expandable styrene polymers (WEPS) by polymerizing styrene in aqueous suspension, the suspended styrene droplets containing water in a finely dispersed manner emulsified.
  • WEPS water-expandable styrene polymers
  • EPS Particulate expandable styrene polymers
  • Common blowing agents are hydrocarbons, especially pentane.
  • pentane emitted during the manufacture and processing of EPS must be collected again. This is complex and costly. It therefore makes sense to replace these organic substances with harmless blowing agents in the long term, for example with water.
  • This process has the disadvantage that it is carried out in two stages: first water is emulsified in the styrene / polystyrene mixture, then the organic phase is suspended in water with phase reversal.
  • the object of the invention was therefore to develop a simpler, one-step process for the production of WEPS.
  • This object is achieved in that at the beginning or in the course of the suspension polymerization 0.1 to 15 wt .-%, based on the monomers, of a water and styrene insoluble 2 inorganic solid substance with an average particle size of at most 100 microns and a density of more than 1.1 g / cm 3 is added.
  • the particles of the solid Due to gravitational and centrifugal forces during the polymerization, the particles of the solid constantly penetrate the interface between the water and styrene phases and in doing so constantly carry adherent water droplets into the styrene phase. This is probably the basis of the effect of the solids as an emulsifying agent.
  • the preferred solid substance is carbon black with an average particle size of 10 to 500 Nm, depending on the type of carbon black. Carbon black is effective in amounts of preferably 0.2 to 5% by weight. Also suitable is graphite with an average particle size (longest leaflet diameter) of 2 to 20 ⁇ m. The effective amount is preferably 0.4 to 10% by weight.
  • silica gel silicates, for example talc or bentonite
  • metal oxides for example Al 2 0 3 and Ti0 2
  • hydroxides such as AlO (OH) and Mg (OH) 2
  • metal salts such as CaC0 3 , Mg 3 (P0 4 ) and BaS0 suitable.
  • styrene alone is preferably used as the monomer. However, up to 20% of its weight can be replaced by other ethylenically unsaturated monomers, such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenylethene or ⁇ -methylstyrene.
  • the usual auxiliaries such as e.g. Suspension stabilizers, radical initiators, flame retardants, chain transfer agents, expansion aids, nucleating agents and plasticizers are added.
  • inorganic Pickering dispersants e.g. Magnesium pyrophosphate or tricalcium phosphate
  • Preferred flame retardants are organic bromine compounds, such as hexabromocyclododecane, which are added in amounts of 0.1 to 2% by weight, based on the monomers.
  • polystyrene which is expediently used as a styrenic solution.
  • polystyrene recyclate can also be used.
  • the solid substance is preferably added right at the start of the suspension polymerization, but it is also possible to meter in up to a conversion of 90% in the course of the polymerization.
  • the suspension polymerization is expediently carried out in two temperature stages, two peroxide initiators decomposing at different temperatures being used.
  • the first peroxide e.g. Dibenzoyl peroxide
  • the temperature is allowed to rise slowly to 100 to 140 ° C.
  • the second peroxide then breaks down, e.g. Dicumyl peroxide or di-tert. Butyl perbenzoa.
  • the WEPS particles formed in the suspension polymerization contain 2 to 20, in particular 5 to 15,% by weight of water, depending on the amount of EPS recyclate used and their content of coating agent. Their particle size is 0.2 to 5, preferably 0.5 to 2 mm. They can be foamed into foam particles with 110 to 140 ° C hot air or superheated steam. A particularly elegant foaming process, which leads to foam particles with a very low bulk density, is described in German Patent Application P 198 12 854.1.
  • the WEPS foam particles can be welded to form foam sheets, blocks or molded parts that can be used as insulation or packaging materials.
  • the product could be expanded using air heated to over 100 ° C.
  • the product expanded to 8 times its original bulk density of approx. 600 g / 1.
  • the pre-expanded product was then dried and foamed in a second and third expansion step with steam to a bulk density of 10 g / l.
  • the product could be expanded using air heated to over 100 ° C.
  • the product expanded to 10 times its original bulk density of approx. 600 g / 1.
  • the pre-expanded product was then dried and foamed in a second and third expansion step with steam to a bulk density below 10 g / l.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to a method for producing styrene polymers containing water as only inflating agent by polymerising styrene in an aqueous suspension in the presence of between 0.1 and 15 weight % of a solid matter which is insoluble in water and styrene, for example carbon black or graphite.

Description

Verfahren zur Herstellung wasserexpandierbarer StyrolpolymerisateProcess for the preparation of water-expandable styrene polymers
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung wasserexpandierbarer Styrolpolymerisate (WEPS) durch Polymerisation von Styrol in wässriger Suspension, wobei die suspendierten Styrol- tröpfchen Wasser in feiner Verteilung emulgiert enthalten.The invention relates to a process for the preparation of water-expandable styrene polymers (WEPS) by polymerizing styrene in aqueous suspension, the suspended styrene droplets containing water in a finely dispersed manner emulsified.
Teilchenförmige expandierbare Styrolpolymerisate (EPS) werden normalerweise hergestellt durch Polymerisation von Styrol in wässriger Suspension in Gegenwart eines flüchtigen organischen Treibmittels. Übliche Treibmittel sind Kohlenwasserstoffe, insbesondere Pentan. Aus Umweltschutzgründen muß bei der Herstellung und Verarbeitung von EPS emittiertes Pentan wieder aufgefangen werden. Dies ist aufwendig und kostenintensiv. Es ist daher sinnvoll diese organischen Substanzen längerfristig durch unbedenklichere Treibmittel zu ersetzen, beispielsweise durch Wasser.Particulate expandable styrene polymers (EPS) are normally produced by polymerizing styrene in aqueous suspension in the presence of a volatile organic blowing agent. Common blowing agents are hydrocarbons, especially pentane. For environmental reasons, pentane emitted during the manufacture and processing of EPS must be collected again. This is complex and costly. It therefore makes sense to replace these organic substances with harmless blowing agents in the long term, for example with water.
In einer Dissertation der Universität Eindhoven "Water Expandable Polystyrene" von J.J. Crevecoeur aus dem Jahr 1997 ist ein Verfahren zur Herstellung von WEPS beschrieben, bei dem zunächst Wasser in feiner Verteilung in Styrol mit Hilfe von oberflächenaktiven Substanzen emulgiert, das Styrol bis zu einem Umsatz von 50 % polymerisiert, die Mischung unter Phasenumkehr in Wasser suspendiert und das Styrol schließlich mit Hilfe von Peroxid-Initiatoren auspolymerisiert wird. Als oberflächenaktive Substanzen werden amphiphile Emulgatoren eingesetzt, z.B. Natrium-In a dissertation by the University of Eindhoven "Water Expandable Polystyrene" by J.J. Crevecoeur from 1997 describes a process for the production of WEPS, in which water is first emulsified in fine distribution in styrene with the aid of surface-active substances, the styrene is polymerized up to a conversion of 50%, the mixture is suspended in water with reversed phase and the Styrene is finally polymerized using peroxide initiators. Amphiphilic emulsifiers are used as surface-active substances, e.g. Sodium-
Bis- (2-ethylhexyl) -sulfosuccinat oder Natrium-Styrolsulfonat oder Blockcopolymere aus Polystyrol-Blöcken und Polystyrolsulfonat- Blöcken. Alle diese Substanzen weisen sowohl einen hydrophilen als auch einen hydrophoben Rest auf und sind daher in der Lage, Wasser in Styrol zu emulgieren.Bis- (2-ethylhexyl) sulfosuccinate or sodium styrene sulfonate or block copolymers of polystyrene blocks and polystyrene sulfonate blocks. All of these substances have both a hydrophilic and a hydrophobic residue and are therefore able to emulsify water in styrene.
Dieses Verfahren hat den Nachteil, daß es in zwei Stufen durchgeführt wird: Erst wird Wasser in der Styrol/Polystyrol-Mischung emulgiert, dann wird unter Phasenumkehr die organische Phase in Wasser suspendiert.This process has the disadvantage that it is carried out in two stages: first water is emulsified in the styrene / polystyrene mixture, then the organic phase is suspended in water with phase reversal.
Aufgabe der Erfindung war es daher, ein einfacheres, einstufiges Verfahren zur Herstellung von WEPS zu entwickeln.The object of the invention was therefore to develop a simpler, one-step process for the production of WEPS.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß zu Beginn oder im Verlauf der Suspensionspolymerisation 0,1 bis 15 Gew.-%, bezogen auf die Monomeren, einer wasser- und styrolunlöslichen 2 anorganischen Festsubstanz mit einer mittleren Teilchengröße von höchstens 100 μm und einer Dichte von höher als 1,1 g/cm3 zugesetzt wird.This object is achieved in that at the beginning or in the course of the suspension polymerization 0.1 to 15 wt .-%, based on the monomers, of a water and styrene insoluble 2 inorganic solid substance with an average particle size of at most 100 microns and a density of more than 1.1 g / cm 3 is added.
Durch Schwer- und Zentrifugalkräfte während der Polymerisation bedingt, durchdringen die Partikel der Festsubstanz ständig die Grenzfläche zwischen Wasser- und Styrolphase und schleppen dabei ständig anhaftende Wassertröpfchen in die Styrolphase ein. Darauf beruht vermutlich die Wirkung der Feststoffe als Emulgierhilfs- mittel.Due to gravitational and centrifugal forces during the polymerization, the particles of the solid constantly penetrate the interface between the water and styrene phases and in doing so constantly carry adherent water droplets into the styrene phase. This is probably the basis of the effect of the solids as an emulsifying agent.
Bevorzugte Festsubstanz ist Ruß mit einer mittleren Teilchengröße von 10 bis 500 Nm, je nach Rußsorte. Ruß ist schon in Mengen von vorzugsweise 0,2 bis 5 Gew.-% wirksam. Geeignet ist ferner Graphit mit einer mittleren Teilchengröße (längster Blättchendurchmesser) von 2 bis 20 μm. Die wirksame Menge beträgt vorzugsweise 0,4 bis 10 Gew.-%.The preferred solid substance is carbon black with an average particle size of 10 to 500 Nm, depending on the type of carbon black. Carbon black is effective in amounts of preferably 0.2 to 5% by weight. Also suitable is graphite with an average particle size (longest leaflet diameter) of 2 to 20 μm. The effective amount is preferably 0.4 to 10% by weight.
Ferner sind Kieselgel, Silikate, z.B. Talkum oder Bentonit, Metalloxide, z.B. Al203 und Ti02, Hydroxide, wie AlO(OH) und Mg(OH)2, sowie Metallsalze, wie CaC03, Mg3(P04) und BaS0 geeignet.Furthermore, silica gel, silicates, for example talc or bentonite, metal oxides, for example Al 2 0 3 and Ti0 2 , hydroxides, such as AlO (OH) and Mg (OH) 2 , and metal salts, such as CaC0 3 , Mg 3 (P0 4 ) and BaS0 suitable.
Bei der erfindungsgemäßen Suspensionspolymerisation wird als Monomer bevorzugt Styrol allein eingesetzt. Es kann jedoch zu bis zu 20 % seines Gewichts durch andere ethylenisch ungesättigte Monomere, wie Alkylstyrole, Divinylbenzol, Acrylnitril, 1,1-Di- phenylethen oder α-Methylstyrol ersetzt sein.In the suspension polymerization according to the invention, styrene alone is preferably used as the monomer. However, up to 20% of its weight can be replaced by other ethylenically unsaturated monomers, such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenylethene or α-methylstyrene.
Bei der Suspensionspolymerisation können die üblichen Hilfsmittel, wie z.B. Suspensionsstabilisatoren, Radikalinitiatoren, Flammschutzmittel, Kettenüberträger, Expandierhilfsmittel, Keimbildner und Weichmacher zugesetzt werden. Es ist vorteilhaft, als Suspensionsstabilisatoren anorganische Pickering-Dispergatoren, z.B. Magnesiumpyrophosphat oder Tricalciumphosphat, in Kombination mit geringen Mengen Alkylsulfonaten einzusetzen. Bevorzugte Flammschutzmittel sind organische Bromverbindungen, wie Hexabrom- cyclododecan, die in Mengen von 0,1 bis 2 Gew.-%, bezogen auf die Monomeren zugesetzt werden.In suspension polymerization, the usual auxiliaries such as e.g. Suspension stabilizers, radical initiators, flame retardants, chain transfer agents, expansion aids, nucleating agents and plasticizers are added. It is advantageous to use inorganic Pickering dispersants, e.g. Magnesium pyrophosphate or tricalcium phosphate, in combination with small amounts of alkyl sulfonates. Preferred flame retardants are organic bromine compounds, such as hexabromocyclododecane, which are added in amounts of 0.1 to 2% by weight, based on the monomers.
Es ist günstig, die Polymerisation in Gegenwart von 1 bis 30, vorzugsweise 3 bis 15 Gew.-% Polystyrol durchzuführen, welches zweckmäßigerweise als styrolische Lösung eingesetzt wird. Statt reinem Polystyrol kann auch Polystyrol-Recyclat verwendet werden. 3It is advantageous to carry out the polymerization in the presence of 1 to 30, preferably 3 to 15,% by weight of polystyrene, which is expediently used as a styrenic solution. Instead of pure polystyrene, polystyrene recyclate can also be used. 3
Die Festsubstanz wird bevorzugt gleich zu Beginn der Suspensionspolymerisation zugesetzt, man kann aber auch im Verlauf der Polymerisation bis zu einem Umsatz von 90 % zudosieren.The solid substance is preferably added right at the start of the suspension polymerization, but it is also possible to meter in up to a conversion of 90% in the course of the polymerization.
Die Suspensionspolymerisation wird zweckmäßigerweise in zwei Temperaturstufen durchgeführt, wobei zwei bei unterschiedlichen Temperaturen zerfallende Peroxid-Initiatoren eingesetzt werden. Zunächst wird die Suspension auf 80° bis 90°C erhitzt, wobei das erste Peroxid, z.B. Dibenzoylperoxid, zerfällt und die Polymeri- sation einleitet. Dann läßt man die Temperatur langsam auf 100 bis 140°C ansteigen. Dabei zerfällt dann das zweite Peroxid, z.B. Dicumylperoxid oder Di-tert .butylperbenzoa .The suspension polymerization is expediently carried out in two temperature stages, two peroxide initiators decomposing at different temperatures being used. First the suspension is heated to 80 ° to 90 ° C, the first peroxide, e.g. Dibenzoyl peroxide, breaks down and initiates the polymerization. Then the temperature is allowed to rise slowly to 100 to 140 ° C. The second peroxide then breaks down, e.g. Dicumyl peroxide or di-tert. Butyl perbenzoa.
Die bei der Suspensionspolymerisation entstandenen WEPS-Partikel enthalten je nach der eingesetzten EPS-Recyclatmenge und deren Gehalt an Beschichtungsmittel 2 bis 20, insbesondere 5 bis 15 Gew. -% Wasser. Ihre Partikelgröße beträgt 0,2 bis 5, vorzugsweise 0,5 bis 2 mm. Sie können mit 110 bis 140°C heißer Luft oder überhitzten Wasserdampf zu Schaumstoffpartikeln geschäumt werden. Ein besonders elegantes Schäumverfahren, welches zu Schaumpartikeln mit sehr niedriger Schüttdichte führt, ist in der Deutschen Patentanmeldung P 198 12 854.1 beschrieben.The WEPS particles formed in the suspension polymerization contain 2 to 20, in particular 5 to 15,% by weight of water, depending on the amount of EPS recyclate used and their content of coating agent. Their particle size is 0.2 to 5, preferably 0.5 to 2 mm. They can be foamed into foam particles with 110 to 140 ° C hot air or superheated steam. A particularly elegant foaming process, which leads to foam particles with a very low bulk density, is described in German Patent Application P 198 12 854.1.
Die WEPS-Schaumpartikel können wie herkömmliche EPS-Schaumparti- kel zu Schaumstoff-Platten, -Blöcken oder -Formteilen verschweißt werden, die als Isolier- oder Verpackungsmaterialien verwendet werden können.Like conventional EPS foam particles, the WEPS foam particles can be welded to form foam sheets, blocks or molded parts that can be used as insulation or packaging materials.
Die in den Beispielen genannten Prozente beziehen sich auf das Gewicht.The percentages given in the examples relate to the weight.
Beispiel 1example 1
In 17,03 kg Styrol werden 2,55 kg Polystyrol (PS 158 K der BASF) gelöst und 510 g (3 %) pulverförmiges Graphit (Graphitwerk Kropf- mühle KG, UF2 96/97, mittlere Teilchengröße 4,5 μm) homogen suspendiert unter Beimischung von 59,6 g Dicumylperoxid und 20,4 g Dibenzoylperoxid. Die organische Phase wird in 19,5 1 vollentsalztes Wasser in einem 50 1 Rührkessel eingebracht. Die wässrige Phase enthält 69,8 g Natriumpyrophosphat und 129,5 g2.55 kg of polystyrene (PS 158 K from BASF) are dissolved in 17.03 kg of styrene and 510 g (3%) of powdered graphite (Graphitwerk Kropfmühle KG, UF2 96/97, average particle size 4.5 μm) are homogeneously suspended with the addition of 59.6 g of dicumyl peroxide and 20.4 g of dibenzoyl peroxide. The organic phase is introduced into 19.5 l of demineralized water in a 50 l stirred kettle. The aqueous phase contains 69.8 g sodium pyrophosphate and 129.5 g
Magnesiumsulfat. Man erhitzt die Suspension unter Rühren auf 80°C und gibt 3,51 g Natrium-sec. -Cis-Alkylsulfonat zu, wobei sich das Suspensionsstabilisatorsystem bildet. Die Rührerdrehzahl betrug hierbei 140 Upm. Schließlich wird bei 134°C auspolymerisiert. Nach dem Abtrennen der wässrigen Phase erhält man ein perlförmiges Granulat, welches 8 % Wasser enthält. 4Magnesium sulfate. The suspension is heated to 80 ° C. with stirring and 3.51 g of sodium sec. -Cis alkyl sulfonate, the suspension stabilizer system being formed. The stirrer speed was 140 rpm. Finally, polymerization is carried out at 134 ° C. After the aqueous phase has been separated off, pearl-shaped granules are obtained which contain 8% water. 4
Das Produkt konnte mittels auf über 100°C erhitzter Luft expandiert werden. Dabei expandierte das Produkt auf das 8-fache seines ursprünglichen Schüttgewichtes von ca. 600 g/1. Das vorgeschäumte Produkt wurde anschließend getrocknet und in einem zweiten und dritten Expansionsschritt mit Wasserdampf auf eine Schüttdichte von 10 g/1 geschäumt.The product could be expanded using air heated to over 100 ° C. The product expanded to 8 times its original bulk density of approx. 600 g / 1. The pre-expanded product was then dried and foamed in a second and third expansion step with steam to a bulk density of 10 g / l.
Beispiel 2Example 2
In 17,03 kg Styrol werden 2,55 kg Polystyrol (PS 158 K der BASF) gelöst und 340 g (2 %) pulverförmiger Ruß (MT N 990, Degussa AG, mittlere Teilchengröße 320 Nm) homogen suspendiert unter Beimischung von 59,6 g Dicumylperoxid und 20,4 g Dibenzoylperoxid. Die organische Phase wird in 19,5 1 vollentsalztes Was- ser in einem 50 1 Rührkessel eingebracht. Die wäßrige Phase enthält 69,8 g Natriumpyrophosphat und 129,5 g Magnesiumsulfat. Man erhitzt die Suspension unter Rühren auf 80°C. Die Rührerdrehzahl betrug hierbei 140 Upm. Nach 140 Minuten wird 3,51 g Alkyl- sulfonat zugegeben. Schließlich wird bei 134°C auspolymerisiert. Nach dem Abtrennen der wäßrigen Phase erhält man ein perlförmiges Granulat, welches 11 % Wasser enthält.2.55 kg of polystyrene (PS 158 K from BASF) are dissolved in 17.03 kg of styrene and 340 g (2%) of powdered carbon black (MT N 990, Degussa AG, average particle size 320 Nm) are homogeneously suspended with the addition of 59.6 g dicumyl peroxide and 20.4 g dibenzoyl peroxide. The organic phase is introduced into 19.5 l of completely demineralized water in a 50 l stirred kettle. The aqueous phase contains 69.8 g of sodium pyrophosphate and 129.5 g of magnesium sulfate. The suspension is heated to 80 ° C. with stirring. The stirrer speed was 140 rpm. After 140 minutes, 3.51 g of alkyl sulfonate is added. Finally, polymerization is carried out at 134 ° C. After the aqueous phase has been separated off, pearl-shaped granules are obtained which contain 11% of water.
Da Produkt konnte mittels auf über 100°C erhitzter Luft expandiert werden. Dabei expandierte das Produkt auf das 10-fache seines ursprünglichen Schüttgewichtes von ca. 600 g/1. Das vorgeschäumte Produkt wurde anschließend getrocknet und in einem zweiten und dritten Expansionsschritt mit Wasserdampf auf eine Schüttdichte unter 10 g/1 geschäumt. The product could be expanded using air heated to over 100 ° C. The product expanded to 10 times its original bulk density of approx. 600 g / 1. The pre-expanded product was then dried and foamed in a second and third expansion step with steam to a bulk density below 10 g / l.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Wasser als einzigem Treibmittel enthaltenden Styrolpolymerisaten durch Polymerisation von1. Process for the production of water as the only blowing agent-containing styrene polymer by polymerization of
Styrol, gegebenenfalls zusammen mit Comonomeren, in wässriger Suspension, wobei die suspendierten Styroltropfchen Wasser in feiner Verteilung emulgiert enthalten und ein Emulgierhilfs- mittel anwesend ist, dadurch gekennzeichnet, daß zu Beginn oder im Verlauf der Suspensionspolymerisation 0,1 bisStyrene, optionally together with comonomers, in aqueous suspension, the suspended droplets of styrene containing water in finely divided emulsified form and an emulsifying aid being present, characterized in that 0.1 to. At the beginning or in the course of the suspension polymerization
15 Gew.-%, bezogen auf die Monomeren, einer wasser- und styrolunlöslichen anorganischen Festsubstanz mit einer mittleren Teilchengröße von höchstens 100 μm und einer Dichte von höher als 1,1 g/cm3 zugesetzt werden.15% by weight, based on the monomers, of a water and styrene-insoluble inorganic solid substance with an average particle size of at most 100 μm and a density of more than 1.1 g / cm 3 are added.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Festsubstanz Ruß mit einer mittleren Teilchengröße von 10 bis 500 Nm oder Graphit mit einer mittleren Teilchengröße (längster Blättchendurchmesser) von 2 bis 20 μm ist.2. The method according to claim 1, characterized in that the solid substance is carbon black with an average particle size of 10 to 500 Nm or graphite with an average particle size (longest leaf diameter) from 2 to 20 microns.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Festsubstanz Kieselgel, ein Silikat, ein Metalloxid, ein Metallhydroxid oder ein Metallsalz ist.3. The method according to claim 1, characterized in that the solid substance is silica gel, a silicate, a metal oxide, a metal hydroxide or a metal salt.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die4. The method according to claim 1, characterized in that the
Festsubstanz bei einem Umsatz zwischen 0 und 90 % dem Polymerisationsansatz zugesetzt wird.Solid substance is added to the polymerization batch at a conversion between 0 and 90%.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Polymerisation in Gegenwart von 1 bis 30 Gew.-%, bezogen auf die Monomeren, an Polystyrol, welches im Monomeren gelöst ist, durchgeführt wird.5. The method according to claim 1, characterized in that the polymerization in the presence of 1 to 30 wt .-%, based on the monomers, of polystyrene, which is dissolved in the monomer, is carried out.
6. Verwendung der nach Anspruch 1 hergestellten, 2 bis 20 Gew.-% Wasser enthaltenden Styrolpolymerisate zur Herstellung von6. Use of the styrene polymers containing 2 to 20% by weight of water prepared according to claim 1 for the production of
Schaumstoffen. Foams.
EP99910367A 1998-03-24 1999-03-19 Method for producing water expandable styrene polymers Withdrawn EP1082382A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19812856 1998-03-24
DE19812856A DE19812856A1 (en) 1998-03-24 1998-03-24 Process for the preparation of water-expandable styrene polymers
PCT/EP1999/001838 WO1999048957A1 (en) 1998-03-24 1999-03-19 Method for producing water expandable styrene polymers

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