EP2794673A1 - Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules - Google Patents

Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules

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Publication number
EP2794673A1
EP2794673A1 EP12810201.9A EP12810201A EP2794673A1 EP 2794673 A1 EP2794673 A1 EP 2794673A1 EP 12810201 A EP12810201 A EP 12810201A EP 2794673 A1 EP2794673 A1 EP 2794673A1
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EP
European Patent Office
Prior art keywords
prepolymer
beads
suspension
styrene
polymerization
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Withdrawn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
EP12810201.9A
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German (de)
English (en)
Inventor
Patrick Spies
Pascal Hesse
Bernhard Schmied
Libor SEDA
Rainer Ostermann
Frank Braun
Gregor Haverkemper
Uwe-Johannes Lehnen
Klaus Hahn
Jan Holoch
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12810201.9A priority Critical patent/EP2794673A1/fr
Publication of EP2794673A1 publication Critical patent/EP2794673A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • 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
    • C08J9/12—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 by a physical blowing agent
    • C08J9/14—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 by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08J2325/06—Polystyrene

Definitions

  • the present invention relates to a process for the preparation of particulate additives containing expandable styrene polymers by at least two-stage polymerization in suspension, as well as prepolymer beads, obtainable after the first stage.
  • EPS expandable polystyrene
  • protective colloids such as polyvinylpyrrolidone or so-called Pickering stabilizers, for example magnesium pyrophosphate, as described in EP-A 575 872. Bead size and bead size distribution can be controlled by the amount and dosage of the stabilizer.
  • WO 99/16817 and WO 03/033579 therefore propose, in the suspension polymerization in the presence of graphite particles, special peroxide initiators, such as tert-butyl peroxy-2-ethylhexanoate, which do not form benzoyl or benzyl radicals and use different peroxides with different decomposition temperatures.
  • DE 198 28 250 A1 describes polystyrene foam spheres with a coarse-celled core and a fine-celled edge.
  • the EPS beads obtained by suspension polymerization in particular in the presence of graphite, have a broad particle size distribution and large variations in average particle sizes between different production batches. This required subsequent screening to obtain products with marketable particle sizes. Usually, sieve fractions ranging from 0.5 to 2.0 mm are needed.
  • WO 00/61648 describes a multi-stage seed polymerization process for the preparation of polymer particles having an average particle size of at least 50 ⁇ m, in which an initiator diffuses into the seed and activates it. Processes for the production of carbon black or graphite-containing, expandable polystyrene by seed polymerization are known, for example, from WO 2010/06631, US 2009/0030096 A1 or JP-A 62-13442.
  • a minigranulate obtained by mixing graphite into a polystyrene melt and extruding and granulating is used as seed in a subsequent suspension polymerization.
  • the particle size of the seed is limited by the minimum diameter of the perforated plate.
  • temperature-sensitive additives such as flame retardants such as HBCD or peroxides such as dicumyl peroxide can not be incorporated into the seed without at least partial decomposition. Due to high melt viscosities and blockage of the perforated plate, the extrusion of granules with high graphite content is also problematic.
  • the object of the present invention was to provide a simple and economical process for the preparation of particulate additives, in particular graphite-containing, expandable styrene polymers, which does not have the aforementioned disadvantages.
  • a process for the polymerization in suspension should be found which has no significant instabilities during the entire polymerization time and also allows targeted control of the bead size distribution with high reproducibility even at higher additive contents.
  • the object was achieved by a process for the preparation of expandable styrene polymers, comprising the steps: a) preparation of prepolymer beads by a first suspension polymerization of an aqueous suspension containing styrene monomers and particulate additives, b) separation of the prepolymer beads,
  • Expandable styrene polymers are understood as meaning blowing agent-containing styrene polymer particles.
  • Suitable styrenic polymers are homopolymers or copolymers of styrene, styrene derivatives or copolymerizable ethylenically unsaturated monomers.
  • stages a) and d) by suspension polymerization of styrene and the corresponding copoly- merisierbaren monomers, for example alkylstyrenes, divinylbenzene, 1, 4-butanediol dimethacrylate, para-methyl-a-methylstyrene, a-methylstyrene or acrylonitrile, butadiene, acrylic acid esters or methacrylic acid ester formed. Particularly preferably, only styrene is used as the monomer in all polymerization stages.
  • styrene and the corresponding copoly- merisierbaren monomers for example alkylstyrenes, divinylbenzene, 1, 4-butanediol dimethacrylate, para-methyl-a-methylstyrene, a-methylstyrene or acrylonitrile, butadiene, acrylic acid esters or methacrylic acid ester formed.
  • styrene
  • styrene The suspension polymerization of styrene is known per se. It is described in detail in the Plastics Handbook, Volume V, "Polystyrene", Carl Hanser Verlag, 1969, pages 679 to 688. In this case, in general styrene, optionally together with the above-mentioned comonomers, suspended in water and in the presence of polymerized out organic or inorganic suspension stabilizers.
  • the volume ratio of aqueous to organic phase is preferably between 0.5 and 1, 6, in particular between 1, 0 and 1, 4.
  • Suitable additives are any additives which do not dissolve significantly in the styrene polymers.
  • titanium dioxide or carbon particles used.
  • carbon particles various natural or synthetic carbon blacks or graphites can be used.
  • the carbon particles preferably contain at least 1, preferably at least 5,% by weight of graphitic structures.
  • the carbon particles have an ash content, determined according to DIN 51903 of 0.005 to 15 wt .-%, preferably 0.01 to 10 wt .-% to.
  • the preferably used graphite preferably has an average particle size of 1 to
  • the proportion of the sum of all particulate additives is preferably in the range of 5 to 50
  • Weight percent in particular 10 to 30 weight percent, based on the prepolymer beads. Particular preference is exclusively given to using carbon particles, in particular graphite, as particulate additives. 10 to 30 wt .-%, based on the prepolymer beads, graphite particles having an average particle size in the range of 1 to 50 ⁇ are used in step a) as particulate additives.
  • Silane-modified carbon particles which are modified with silane for example, at from 0.01 to 1% by weight, preferably from 0.1 to 0.5% by weight, based on the carbon particles, can also be used as carbon particles.
  • the silane-modified carbon particles preferably have on their surface C 3 -C 16 -alkylsilane or arylsilane groups, in particular C 6 -C 12 -alkylsilane groups or phenylsilane groups.
  • alkyl or aryl silanes having 1 to 3 halogen atoms or methoxy groups on the silicon atom are suitable for modifying the carbon particles.
  • the modification with silanes leads to a hydrophobization of the surface of the carbon particles by silyl groups, so that the interfacial activity of the carbon particles which disturbs the suspension process is markedly reduced.
  • the method known per se for hydrophobicizing hydrophilic surfaces by silane in the gas phase or in solvents, such as toluene surprisingly also works with relatively hydrophobic graphite in order to mask remaining polar groups.
  • the surface modification of the carbon particles allows better compatibility with or even a connection to the polymer matrix.
  • the usual additives for example flame retardants, nucleating agents, UV stabilizers, chain transfer agents, plasticizers, pigments and antioxidants can be added in step a).
  • the customary peroxide initiators and suspension stabilizers such as protective colloids, inorganic pickering salts and anionic and nonionic surfactants, are particularly suitable for the suspension polymerization.
  • Halogen-containing or halogen-free flame retardants are preferably used as additives.
  • Particularly suitable are organic, in particular aliphatic, cycloaliphatic and aromatic bromine compounds, such as hexabromocyclododecane (HBCD), Pentabrommonoch- lorcyclohexan, Pentabromphenylallylether or brominated styrenic polymers, such as styrene-butadiene block copolymers, which can be used alone or as a mixture.
  • the flame retardants used are preferably exclusively brominated styrene polymers or brominated styrene-butadiene block copolymers.
  • the halogenated polymer used as flame retardant preferably has an average molecular weight in the range from 5,000 to 300,000, in particular 30,000 to 150,000, determined by gel permeation chromatography (GPC) in tetrahydrofuran over polystyrene standard.
  • GPC gel permeation chromatography
  • the halogenated polymer has a weight loss of 5 wt .-% at a temperature of 250 ° C or higher, preferably in the range of 270 to 370 ° C in the thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • Preferred halogenated polymers as flame retardants are brominated polystyrene or styrene-butadiene block copolymer having a bromine content in the range of 40 to 80 wt .-%.
  • the effect of the bromine-containing flame retardants can be improved by adding CC or OO-labile organic compounds.
  • suitable flame retardant synergists are dicumyl and dicumyl peroxide.
  • a preferred combination consists of 0.6 to 5 wt .-% of organic bromine compound and 0.1 to 1, 0 wt .-% of CC or OO-labile organic compound.
  • the plasticizers used in stage a) are generally 0.1-10% of white oil or hexamine dinch in order to improve the expandability of the end product.
  • a phosphate preferably magnesium pyrophosphate or tricalcium phosphate, in amounts of from 0.3 to 5 wt .-%, based on water.
  • Magnesium pyrophosphate is particularly preferably used.
  • magnesium sulfate heptahydrate is added in addition to magnesium pyrophosphate. Preference is given to an addition of 0.05 to 1% by weight of magnesium sulfate heptahydrate, based on water.
  • the addition of magnesium sulfate heptahydrate is particularly preferably also in the range from 0.1 to 0.5% by weight, based on the organic phase.
  • the organic phase is composed of the monomers and optionally styrene polymers and non-water-soluble additives.
  • the magnesium pyrophosphate is preferably prepared immediately prior to the polymerization by combining highly concentrated solutions of pyrophosphate and magnesium ions using the stoichiometric amount of a magnesium salt required for the precipitation of Mg.sub.2P.sub.2O.sub.7.
  • the magnesium salt may be in solid form or in aqueous solution.
  • the magnesium pyrophosphate is prepared by combining aqueous solutions of sodium pyrophosphate (Na 4 P 2 O 7) and magnesium sulfate (MgSO 4 7H 2 O).
  • the magnesium salt is added in at least the stoichiometrically required amount, preferably in a stoichiometric amount. For the process according to the invention, it is favorable if there is no excess of alkali pyrophosphate.
  • Emulsifiers called extender used. These extenders include, for example, sodium dodecyl benzene sulfonate, long chain alkyl sulfonates, vinyl sulfonate, diisobutyl naphthalene sulfonate.
  • the extenders used are preferably alkali metal salts of dodecylbenzenesulfonic acid and / or alkali metal salts of a mixture of C 12 -C 17 -alkylsulfonic acids.
  • a particularly suitable mixture of C 12 -C 17 -alkyl sulfonates consists predominantly of secondary sodium alkyl sulfonates having the average chain length C 15. Such a mixture is sold under the name E30 by Leuna Tenside GmbH.
  • the extenders increase the ability to stabilize the suspension in the presence of sparingly soluble inorganic compounds.
  • the extenders are usually in amounts between 0.5 and 15, preferably 2 to
  • the average power input is preferably above 0.2 kg kg reactor charge.
  • the amount of extender used can be reduced or the stirrer speed can be lowered after the extender metering, so that the average power input assumes a value of less than 0.2 W / kg.
  • a high-temperature peroxide is a peroxide which in Cumene has a half-life of 1 hour in the range from 110 to 160 ° C., preferably in the range from 120 to 140 ° C., particularly preferably in the range from 125 to 135 ° C.
  • Suitable peroxides are di-tert-amyl peroxides, tert-butyl peroxybenzoate, di (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexanes and dicumyl peroxide.
  • Dicumyl peroxide is particularly preferably used as high-temperature peroxide.
  • the at least one high-temperature peroxide in stage a) is generally used in amounts of at least 0.5 wt .-%, preferably in the range of 1, 1 to 5.0 wt .-%, particularly preferably in the range of 1, 3 bis 4 wt .-%, based on the Repolymerisatperlen used.
  • step a) 5 to 50% by weight of graphite and 0.5 to 5% by weight of at least one high-temperature peroxide, in particular dicumyl peroxide, in each case based on the prepolymer beads are used in step a) and the suspension polymerization in step a) is less than 1.5 h at a temperature in the range of 120-130 ° C.
  • the suspension polymerization in step a) is less than 1.5 h at a temperature in the range of 120-130 ° C.
  • a prepolymer is obtained which contains sufficient undecomposed dicumyl peroxide, and enables a suspension polymerization in stage d) without the addition of further peroxides.
  • it can also act as a flame retardant synergist in the expandable styrene polymer.
  • the high-temperature peroxide is preferably present in the prepolymer in amounts of from 50 to 100% by weight, more preferably in quantities of from 60 to 80% by weight, of the amount used in undecomposed form. This remaining high-temperature peroxide may act as the sole polymerization initiator in the main polymerization (step d).
  • the invention therefore also prepolymer beads which 5 to 50 wt .-%, preferably 10 to 30 wt .-% graphite and 0.5 to 5 wt .-%, preferably 1 to 4 wt .-% dicumyl peroxide, respectively based on prepolymer, included.
  • the resulting prepolymer beads are first isolated from the aqueous phase. Subsequently, the prepolymer beads are used directly or after splitting and selecting a particle size fraction (stage c) in a main polymerization (stage d). Stage c)
  • the prepolymer beads are divided into fractions of different particle size and one or more fractions are selected for subsequent steps. As a rule, fractionation takes place by sieving one or more sieve fractions. By suitable choice of the screening of the prepolymer beads, the bead size of the expandable styrene polymer can be controlled in a targeted manner.
  • step d) at least one second suspension polymerization is carried out.
  • the process can be carried out in two or more stages.
  • stages b) to d) can be carried out several times, at least one suspension polymerization being carried out in the presence of blowing agent and with metering in of further styrene monomers.
  • the process according to the invention is preferably carried out in two stages with a single execution of stages a), b), c) and d).
  • the one or more fractions of the prepolymer beads separated in step b) or selected in step c) are initially introduced in aqueous suspension.
  • the styrene monomer is preferably metered in continuously.
  • from 10 to 60% by weight, preferably from 15 to 35% by weight, particularly preferably from 25 to 35% by weight, based on expandable styrene polymer are initially introduced as prepolymer beads in the aqueous phase and the remaining portion is used as monomers, particularly preferably metered in continuously as styrene monomer.
  • the prepolymer beads may initially be allowed to swell below the polymerization temperature with an organic peroxide, such as tert-butyl peroxy-2-ethylhexanoate. Furthermore, it has proved to be advantageous to meter a portion of the styrene monomer to be metered or a white oil also already below the polymerization temperature.
  • step d) if appropriate, the particulate additives and additives described for step a) can be used.
  • a phosphate preferably magnesium pyrophosphate or tricalcium phosphate is also used.
  • Magnesium pyrophosphate is generally initially charged at the beginning of the polymerization and in stage d) generally in a concentration of between 0.03 and 2.0% by weight, preferably between 0.05 and 0.5% by weight and more preferably between 0 and 0 , 1 and 0.2 wt .-%, based on the aqueous phase used.
  • an extender is likewise initially introduced in the aqueous phase before the beginning of the polymerization in stage d).
  • the extenders are usually used in amounts of between 0.5 and 15, preferably 2 to 10 wt .-%, based on magnesium pyrophosphate.
  • the blowing agents used are usually aliphatic hydrocarbons having 3 to 10, preferably 4 to 6 carbon atoms, for example n-pentane, iso-pentane or mixtures thereof.
  • the blowing agent is added in the usual amounts of from 1 to 10% by weight, preferably from 3 to 8% by weight, based on the weight of the styrene polymers present in the expandable styrene polymer.
  • the prepolymer is usually used in a proportion in the range of 10 to 60 wt .-%, preferably in the range of 20 to 40 wt .-%, based on expandable styrene polymer, in the aqueous phase.
  • the metering of styrene monomer in stage d) is generally carried out continuously, preferably over a period in the range from 1 to 5 hours. It has proven to be advantageous to dose 5 to 15 wt .-% of the styrene monomer to be metered already in the heating phase at temperatures below 100 ° C in the reactor.
  • the polymerization in stage d) is preferably carried out at least partly at a temperature in the range from 15 to 130 ° C.
  • step d) no peroxidic initiator is added.
  • a conventional low-temperature initiator such as tert-butyl peroxy-2-ethylhexanoate
  • a high-temperature initiator for example dicumyl peroxide.
  • the expandable styrene polymer particles obtained by the processes according to the invention can be coated with the usual coating agents, for example metal stearates, glyceryl esters and finely divided silicates.
  • the propellant-containing styrene polymer particles produced according to the invention generally have a diameter between 0.2 and 4 mm, preferably between 0.7 and 2.5 mm. They can be prefoamed by conventional methods, for example with steam, into foam particles with a diameter of between 0.1 and 2 cm and a bulk density of between 5 and 100 kg / m 3 .
  • the prefoamed particles can then be foamed by conventional methods to foam moldings having a density of 5 to 100 kg / m 3 .
  • the expandable styrene polymers obtained by the processes according to the invention can be processed into polystyrene foams having densities of 5 to 35 g / l, preferably 8 to 25 g / l and especially 10 to 15 g / l.
  • the expandable particles are prefoamed. This is usually done by heating the particles with water vapor in so-called pre-expanders.
  • the pre-expanded particles are then welded into shaped bodies.
  • the pre-expanded particles are filled in non-gas-tight molds and subjected to steam. After cooling, the moldings can be removed.
  • the foams produced from the expandable styrene polymers according to the invention are distinguished by excellent thermal insulation. This effect is particularly evident at low densities.
  • the thermal conductivity is so low that it meets the requirements of the heat conductivity class 035 (according to DIN 18164, Part 1 Tab. 4).
  • the embodiment of the suspension polymerization of the method according to the invention is characterized by a significantly increased stability of the suspension without phase inversion.
  • the improved stability of the suspension leads to a safer and more efficient process. Due to the lower amount of stabilizer a better control of the bead size distribution reached.
  • the internal water content of the obtained, expandable styrene polymers can be significantly reduced.
  • the process according to the invention makes it possible to increase the yield of the fractions having a desired and marketable bead size distribution of, in particular, graphite-containing expandable styrene polymers. If a screening of the prepolymer beads is dispensed with, narrower particle size distributions can nevertheless be achieved. achieve higher yield of value fraction compared to a classical suspension polymerization in the presence of graphite.
  • Demineralised water demineralized water
  • Emulsifier K30 Blend of linear alkyl sulfonates (Ci 5 H 3 o.9 (S0 3 Na) i .i, HLB 1 1 -12), 1% by weight aqueous solution
  • the bead size distribution was determined by sieve analysis (standard 1) and evaluated as grain size KG and relative fraction (R).
  • sieve mesh size of the respective sieve bottom
  • d ' average particle diameter at 63% by weight of the integral particle size distribution according to Rosin, Rammler, Sterling, Bennet.
  • Mg2P2Ü7 suspension a freshly prepared amorphous magnesium pyrophosphate precipitate (MPP suspension) was used as the Pickering stabilizer.
  • 931.8 g of sodium pyrophosphate Na 4 P207, Giulini Co.
  • An aqueous suspension of magnesium pyrophosphate (MPP) was formed.
  • the suspension was heated to 80 ° C. in the course of 1.2 hours and then to 134 ° C. over 4.5 hours. 140 minutes after reaching 80 ° C., 63.2 g of a 2% solution of the emulsifier E30 (prepared from E30-40 from Leuna Tenside GmbH, 40% by weight of a mixture of C 12 -C 17 -alkylsulfonates in Water). After a further 30 minutes, 1.17 kg of pentane-S (from Haltermann / Exxon) were metered in. Finally, it was polymerized at a final temperature of 134 ° C.
  • the resulting expandable polystyrene beads were decanted off and dried to remove the internal water and coated with a coating of glycerol monostearate, Glycerintristea- rat and precipitated silica.
  • the EPS beads have a content of dicumyl peroxide of 0.2% by weight and have the following sieve distribution:
  • Comparative Experiment 1 was repeated with the difference that 636 g of graphite (4% by weight) were added to the organic phase.
  • the suspension was heated to 95 ° C. in the course of 1.5 hours and then to 127 ° C. over 4.2 hours. 100 minutes after reaching 80 ° C., 240 g of a 2% strength solution of the emulsifier E30 (prepared from E30-40 from Leuna Tenside GmbH, mixture of Ci2-Ci7-Natriumalkylsulfonaten) are metered. Finally, it was polymerized at a final temperature of 127 ° C.
  • the prepolymer had an internal water content of 5.23% and an average diameter of 0.8 mm.
  • the resulting prepolymer beads were filtered through a suction filter (pore size 40 ⁇ m) and dried to remove the surface water.
  • reaction mixture was heated to 130 ° C. From a temperature of 120 ° C., 67 g of pentane-S (from Craigrmann / Exxon Co.) were added over a period of 40 minutes. For complete monomer conversion was polymerized with stirring for a further 2 hours at a temperature of 130 ° C.
  • the propellant-containing polystyrene beads obtained were decanted off, dried by internal water and coated with a coating composition of glycerol monostearate, glycerol tristearate and precipitated silica.
  • the resulting EPS beads showed the following bead size distribution
  • Example 1 was repeated with the difference that the prepolymer beads were screened through a sieve from Fritsch (Analysette 18). In the subsequent main polymerization, a sieve cut between 0.4 mm and 1, 25 mm was used. 2,00 mm 0,23 g 0,76
  • Example 2a was repeated with the difference that 2.92 g of dicumyl peroxide dissolved in 5 g of styrene were metered into the cold reactor within 2 minutes in the main polymerization before the start of the heating phase. From the dried polymer the following sieve distribution could be obtained:
  • Example 1 was repeated with the difference that the prepolymer beads were screened through a sieve from Fritsch (Analysette 18) (step c). In the subsequent main polymerization, a sieve cut between 0.5 mm and 1, 25 mm was used.
  • Example 2 was repeated using instead of white oil 420 g 1, 2-
  • Example 2 was repeated using 420 g of alkyl sulfonic acid ester of phenol (ASE) (Mesamoll 2, Lanxess AG) instead of white oil.
  • ASE alkyl sulfonic acid ester of phenol
  • the internal water content of the prepolymer was 3.16%.
  • a sieve cut between 0.4 mm and 1, 25 mm was used.
  • Example 2 was repeated using instead of HBCD 1, 06 kg brominated styrene-butadiene block copolymer (Br-SBS) were used.
  • the internal water content of the prepolymer was 2.56%.
  • a sieve cut between 0.4 mm and 1, 25 mm was used.
  • Example 7 Stage a)
  • the suspension was heated to 95 ° C. in the course of 1.5 hours and then to 125 ° C. in the course of 4.2 hours. 100 minutes after reaching 80 ° C., 240 g of a 2% solution of the emulsifier E30 (prepared from E30-40 from Leuna Tenside GmbH, mixture of C 12 -C 17 -alkylsulfonates) were metered in. Finally, it was polymerized at a final temperature of 125 ° C.
  • E30 prepared from E30-40 from Leuna Tenside GmbH, mixture of C 12 -C 17 -alkylsulfonates
  • the obtained prepolymer beads were decanted off and dried and sieved to remove the surface water.
  • the propellant-containing polystyrene beads obtained were decanted off, dried by internal water and coated with a coating composition of glycerol monostearate, glycerol tristearate and precipitated silica.
  • the resulting EPS beads showed the following bead size distribution.
  • Example 8 Stage a)
  • the suspension was heated to 95 ° C. in the course of 1.5 hours and then to 125 ° C. within 4.2 hours. 89 minutes after reaching 80 ° C., 4.00 kg of a 2% solution of the emulsifier E30 (prepared from E30-40 from Leuna Tenside GmbH, mixture of C12-C17 sodium alkyl sulfonates) were metered in. After the emulsifier was metered, the stirrer speed was lowered to 42 rpm (this corresponds to an average power input of 0.070 W / kg). Finally, it was polymerized at a final temperature of 125 ° C. Stage b)
  • the prepolymer obtained is isolated by means of a Siebschleuder from Siebtechnik (type Contourbex H 320) (sieve 0.2 mm), antistatically equipped with 200 ppm emulsifier E30 via a screw conveyor and dried via a flash dryer (average temperature: 70 ° C.) from the surface water ,
  • the prepolymer obtained had an internal water content of 7.56% and a content of dicumyl peroxide of 1, 44 wt .-%.
  • the prepolymer beads were prescreened with a screen cut between 0.4 mm and 1.25 mm.
  • the propellant-containing polystyrene beads obtained were decanted off, dried by internal water and coated with a coating composition of glycerol monostearate, glycerol tristearate and precipitated silica.
  • the resulting EPS beads showed the bead size distribution summarized in Table 3.
  • the organic phase was dissolved in 3.04 l of deionized water with 1.60 kg of MPP suspension and 7.90 g of magnesium sulfate heptahydrad (epsom salt) (Kali and salt) in a 10 l stirred tank (blade stirrer, 300 rpm, corresponds to an average power input of 0.584 W / kg) introduced.
  • the suspension was heated to 95 ° C. within 1.5 hours and then to 125 ° C. within 4.20 hours. 85 minutes after reaching 80 ° C., 37 g of a 2% strength solution of the emulsifier E30 (from Leuna Tenside GmbH) were metered in. Finally, it was polymerized at a final temperature of 125 ° C.
  • the resulting prepolymer beads were decanted off and dried by surface water.
  • Stage c) Screening The prepolymer beads were prescreened with a sieve cut between 0.45 mm and 1.00 mm stage d) main polymerization
  • the propellant-containing polystyrene beads obtained were decanted off, dried by internal water and coated with a coating composition of glycerol monostearate, glycerol tristearate and precipitated silica.
  • the resulting EPS beads showed the bead size distribution summarized in Table 3.
  • the organic phase was introduced into 15 l of demineralized water containing 5.22 kg of MPP suspension in a 50 l stirred tank (paddle stirrer, 240 rpm, corresponding to an average power input of 0.579 W / kg).
  • the suspension was heated to 95 ° C. in the course of 1.5 hours and then to 125 ° C. within 4.20 hours. 100 (+/- 5 min) minutes after reaching 80 ° C, 240 g of a 2% solution of the emulsifier E30 (prepared from E30-40 from Leuna Tenside GmbH). Finally, it was polymerized at a final temperature of 125 ° C.
  • the resulting prepolymer beads were decanted off and dried by surface water by flash drying.
  • the prepolymer had a viscosity number VZ of 74.6, which corresponds to a weight-average molecular weight of about 200,000 g / mol.
  • the residual water content was 1.48 wt .-% and the residual monomer content 0.02 wt .-%.
  • the EPS beads had the following bead distribution:
  • the prepolymer beads were prescreened with a wire cut between 0.4 mm and 1, 12 mm and then used in the main polymerization.
  • the propellant-containing polystyrene beads obtained were decanted off, dried from internal water and coated with a coating composition of glycerol monostearate, glycerol tristearate and precipitated silica.
  • the weight-average molecular weight was M w : 338 200 g / mol.
  • the EPS beads obtained showed the following bead size distribution.
  • Table 4 shows the relationship between the average particle size of the prepolymerizer beads (x50, seed) and the yield of product ordered by particle size classes after the main polymerization. Since the prepolymer is also obtained as a particle size distribution, the ⁇ value is given as a measure of the width of the distribution.
  • the obtained product of the two-stage suspension polymerization contains polymer particles having a particle diameter between 0.8 mm and 2.0 mm.
  • the complete product can be used in the typical application fields for EPS.
  • the described process is extremely economical and produces less unsellable side fractions compared to a classical suspension polymerization:
  • 15 to 20% by weight of side fractions are obtained, which are separated by sieving.
  • 30% by weight of prepolymer beads are used, which means that, based on the overall process, only 6% by weight of unsoldable side fractions are formed.

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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)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un procédé de production de polymères de styrène, contenant des additifs sous forme de particules, ledit procédé consistant en a) la production de perles de prépolymérisat par une première polymérisation d'une suspension aqueuse contenant des monomères de styrène et des additifs sous forme de particules, b) la séparation des perles de prépolymérisat, c) éventuellement la division des perles de prépolymérisat en fractions de tailles de particule différentes et la sélection d'une ou de plusieurs fractions pour les étapes suivantes, et d) la production d'une suspension aqueuse des perles de prépolymérisat et l'exécution d'au moins une deuxième polymérisation en suspension en présence d'agents d'expansion et par dosage d'autres monomères.
EP12810201.9A 2011-12-21 2012-12-17 Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules Withdrawn EP2794673A1 (fr)

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EP12810201.9A EP2794673A1 (fr) 2011-12-21 2012-12-17 Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules

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EP11194873 2011-12-21
EP12810201.9A EP2794673A1 (fr) 2011-12-21 2012-12-17 Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules
PCT/EP2012/075730 WO2013092468A1 (fr) 2011-12-21 2012-12-17 Procédé de production de polymères de styrène expansibles, contenant des additifs sous forme de particules

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EP2794673A1 true EP2794673A1 (fr) 2014-10-29

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US (1) US20150005402A1 (fr)
EP (1) EP2794673A1 (fr)
KR (1) KR20140105845A (fr)
CN (1) CN104011086A (fr)
BR (1) BR112014015248A8 (fr)
MX (1) MX2014006977A (fr)
WO (1) WO2013092468A1 (fr)

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CN109312108A (zh) 2016-05-11 2019-02-05 欧文斯科宁知识产权资产有限公司 包含低水平溴化阻燃剂的聚合物泡沫及其制备方法

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JPS6213442A (ja) 1985-07-12 1987-01-22 Mitsubishi Yuka Badische Co Ltd カ−ボン含有発泡性スチレン系樹脂粒子の製法
DE4029298A1 (de) * 1990-09-15 1992-03-19 Huels Chemische Werke Ag Verfahren zur koernungssteuerung bei der herstellung von expandierbaren styrolpolymerisaten durch suspensionspolymerisation
DE4220225A1 (de) 1992-06-20 1993-12-23 Basf Ag Verfahren zur Herstellung von perlförmigen expandierbaren Styrolpolymerisaten
ES2151268T3 (es) * 1997-05-14 2000-12-16 Basf Ag Polimeros de estireno expandibles que contienen particulas de grafito.
JP3954112B2 (ja) 1997-05-14 2007-08-08 ビーエーエスエフ アクチェンゲゼルシャフト グラファイト粒子含有発泡性スチレン重合体の製造
DE19742910A1 (de) 1997-09-29 1999-04-01 Basf Ag Verfahren zur Herstellung von expandierbaren Styrolpolymerisaten
DE19828250B4 (de) * 1998-06-25 2007-08-16 Basf Ag Polystyrol-Schaumstoffkugeln und ihre Verwendung für Dränageplatten
WO2000061648A1 (fr) 1999-04-09 2000-10-19 Polymer Systems As Preparation de particules polymeres
DE10150405A1 (de) 2001-10-11 2003-04-17 Basf Ag Verfahren zur Herstellung von expandierbaren Styrolpolymerisaten
DE102004028768A1 (de) * 2004-06-16 2005-12-29 Basf Ag Styrolpolymer-Partikelschaumstoffe mit verringerter Wärmeleitfähigkeit
KR100801275B1 (ko) 2006-03-31 2008-02-04 금호석유화학 주식회사 단열 특성이 우수한 발포성 폴리스티렌 입자의 2단계 제조방법
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EP2300793B1 (fr) 2008-07-16 2012-03-14 Siemens Aktiengesellschaft Agencement avec une machine électrique et procédé de fonctionnement d'une machine électrique
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MX2014006977A (es) 2014-08-26
KR20140105845A (ko) 2014-09-02
US20150005402A1 (en) 2015-01-01
BR112014015248A8 (pt) 2017-07-04
CN104011086A (zh) 2014-08-27
WO2013092468A1 (fr) 2013-06-27
BR112014015248A2 (pt) 2017-06-13

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