WO2011069983A1 - Procédé de polymérisation du styrène - Google Patents

Procédé de polymérisation du styrène Download PDF

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Publication number
WO2011069983A1
WO2011069983A1 PCT/EP2010/069012 EP2010069012W WO2011069983A1 WO 2011069983 A1 WO2011069983 A1 WO 2011069983A1 EP 2010069012 W EP2010069012 W EP 2010069012W WO 2011069983 A1 WO2011069983 A1 WO 2011069983A1
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Prior art keywords
polymerization
initiator
process according
suspension
styrene
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PCT/EP2010/069012
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English (en)
Inventor
Andreas Herman Hogt
Bart Fischer
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Akzo Nobel Chemicals International B.V.
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Priority to MX2012006309A priority Critical patent/MX339691B/es
Priority to US13/513,681 priority patent/US20120245315A1/en
Priority to JP2012542502A priority patent/JP5632926B2/ja
Priority to RU2012127565/04A priority patent/RU2556005C2/ru
Priority to CN201080054319.2A priority patent/CN102639569B/zh
Priority to EP10785446A priority patent/EP2510021A1/fr
Priority to AU2010329986A priority patent/AU2010329986B2/en
Priority to CA2779995A priority patent/CA2779995A1/fr
Publication of WO2011069983A1 publication Critical patent/WO2011069983A1/fr

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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers 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
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—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
    • 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
    • C08F2/44—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
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • 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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • the invention relates to a process for the polymerization of styrene monomer in the presence of a brominated flame retardant for the production of polystyrene, in particular expandable polystyrene (EPS).
  • EPS expandable polystyrene
  • blowing agents are pentane, iso-pentane, butane, propane, and mixtures thereof, the most common being (iso-)pentane.
  • expandable polystyrene copolymer In addition to styrene, other olefinically unsaturated monomers can be present, resulting in an expandable polystyrene copolymer.
  • expanded polystyrene or "EPS” in this specification includes expandable polystyrene homopolymer and expandable polystyrene copolymers.
  • Expandable polystyrene is generally used to prepare polystyrene foam.
  • foam can be obtained from EPS in three steps: prefoaming, intermediate storage, and final foaming (or moulding).
  • prefoaming the particles are heated and the polystyrene is thereby softened, the blowing agent in the polystyrene evaporates to form rapidly growing bubbles until either the heat supply is shut off or the expandability is exhausted.
  • the bead diameter may increase about threefold and the bead volume (bulk volume) about thirtyfold.
  • the objective of the present invention is to provide a process for the polymerization of styrene in the presence of a brominated flame retardant wherein the effect of the flame retardant on the molecular weight is counteracted.
  • the present invention therefore enables the polymerization of styrene in the presence of a brominated flame retardant to produce polystyrene with at least the same molecular weight as obtained in the absence of flame retardant.
  • the present invention relates to a process for the suspension polymerization of styrene monomer to produce polystyrene in the presence of a brominated flame retardant.
  • a polymerization suspension comprising styrene monomer is heated to a temperature of at least 60°C.
  • an initiator is dosed to this heated polymerization suspension during the polymerization reaction over a period of more than 90 minutes to less than 5 hours, in a continuous manner or intermittently in at least 2 portions, said period starting before a monomer conversion of 65% is reached and said initiator having a half-life at the temperature at which it is dosed of not more than 60 minutes.
  • a brominated flame retardant is present in the polymerization suspension during the polymerization reaction.
  • WO 2004/089999 discloses a process for the polymerization of styrene by dosing an initiator continuously or intermittently. However, dosing over a period of more than 90 minutes in the presence of a brominated flame retardant is neither disclosed nor suggested in this document. Monomers
  • the process according to the present invention involves the polymerization of styrene monomer in aqueous suspension.
  • styrene is the sole monomer that is present in the suspension, resulting in polystyrene homopolymer.
  • styrene copolymer In another embodiment, additional co-monomers are present, resulting in a styrene copolymer.
  • styrene is present in the aqueous suspension in an amount of at least 50 wt%, more preferably at least 80 wt%, based on the total weight of monomers.
  • Co-monomers that can be used are of the conventional type and are preferably selected from the group consisting of divinyl benzene, vinyl acetate, ethylene, propylene, acrylonitrile, butadiene, (meth)acrylates, and ethylenically unsaturated polymers, such as polybutadiene and styrene butadiene rubber.
  • vinylidene chloride can be present as co-monomer.
  • Suitable brominated flame retardants for use in the process according to the present invention are hexabromocyclododecane (HBCD), pentabromobenzyl- bromide, tetrabromobisphenyl A bis(allylether), tetrabromobisphenyl A bis(2,3- dibromopropyl ether), dibromohexahydrophthalimide, N-methyl-dibromohexa- hydrophthalimide, N,N 2,3-dibromopropyl-4,5-dibromohexahydrophthalimide, bis(2,3-dibromopropyl)tetrabromophthalate, tris(2,3-dibromoisopropyl)- isocyanurate, tribromophenyl allyl ether, and brominated styrene (co)polymers.
  • HBCD hexabromocyclododecane
  • brominated flame retardants examples include pentabromo- benzylbromide, tetrabromobisphenyl A bis(allylether), tris(2,3-dibromoisopropyl)- isocyanurate, and brominated styrene (co)polymers.
  • Flame retardant synergists may also be present.
  • Examples of such synergists are dicumyl peroxide, di-(t-butylperoxyisopropyl)benzene, 2,3-dimethyl-2,3-diphenyl- butane, 3,4-dimethyl-3,4-diphenylhexane, and poly(1 ,4-diisopropyl benzene).
  • Commercially available synergists can be obtained under trade names such as Perkadox® BC and Perkadox® 30.
  • the polymerization suspension preferably comprises 0.3-6 wt%, more preferably 0.4-3 wt%, and most preferably 0.5-1 .5 wt% of brominated flame retardant, based on the weight of styrene.
  • the brominated flame retardant is preferably pre- charged to the polymerization suspension, before heating the suspension to the desired temperature. Alternatively, it may be dosed to the reaction mixture during the polymerization reaction as a solution in styrene.
  • an initiator is dosed to the polymerization suspension after it has been heated to a temperature of at least 60°C.
  • the polymerization suspension has been heated to at least 75°C, and more preferably at least 80°C before dosing the initiator.
  • the initiator is dosed to the heated polymerization reaction over a period of more than 90 minutes, preferably more than 120 minutes to less than 5 hours, preferably less than 4 hours in a continuous manner or intermittently in at least 2, preferably at least 4, more preferably at least 10, and most preferably at least 20 portions.
  • the time intervals between the portions may be the same or different. If intermittent dosing is applied, the last portion must be added more than 90 and preferably more than 120 minutes after the first portion. If many portions are added at short intervals, continuous dosing is approached.
  • Continuous dosing which is the preferred manner of dosing, may be performed at constant or variable rate.
  • the addition of initiator at variable rate is beneficial for using the cooling capacity of the polymerization reaction in the most optimal way and to reduce the risk of a so-called "run away" during the polymerization reaction.
  • the rate at which initiator is continuously dosed is preferably in the range 1 -100 meq/kg styrene/hour, more preferably 2-50 meq/kg styrene/hour, and most preferably 5-25 meq/kg styrene/hour; wherein meq refers to milli-equivalent and 1 equivalent is defined as 1 mole of peroxide or azo groups.
  • the dosing period does not start before the temperature of the polymerization suspension has reached 60°C, but does start before the monomer conversion has reached a level of 65%.
  • dosing of initiator starts before a conversion level of 60%, more preferably 40%, even more preferably 20%, even more preferably 10% is reached.
  • initiator dosing starts at 0% conversion. This means that the first portion of the initiator is added after reaching the indicated temperature but below the indicated conversion level and that dosing of initiator subsequently continues over a period of more than 90 minutes.
  • the initiator is dosed to the aqueous suspension during the polymerization reaction, i.e. when polymerization proceeds and monomers actually react.
  • the temperature may be kept constant during a certain period, and may be increased and kept constant again for another period. This may be repeated one or more times. Alternatively, the temperature may be increased gradually to a certain maximum temperature which is kept constant for a certain period. Combinations of (subsequent) periods with continuous polymerization temperature increases and constant polymerization temperatures are also possible.
  • the temperature during the polymerization reaction is at most 160°C, more preferably at most 150°C, and most preferably at most 140°C.
  • the temperature is at least 60°C, preferably at least 75°C, and most preferably at least 80°C.
  • a part of the total initiator amount used may be pre- charged to the reaction mixture, prior to reaching a temperature of at least 60°C.
  • the reaction mixture is formulated at or near the temperature that is desired for the polymerization reaction to proceed, which is called the warm-start process, it is not required to pre-charge a certain amount of initiator.
  • the warm-start process it may be beneficial to at once add up to 20 wt%, preferably up to 10 wt% of initiator, based on the combined weight of the monomers, to the reaction mixture prior to reaching a temperature of 60°C.
  • the total amount of initiator to be used in the process according to the invention is within the range conventionally used in polymerization processes. Typically, it is preferred to use at least 0.01 wt%, more preferably at least 0.05 wt%, and most preferably at least 0.1 wt%, and preferably at most 5 wt%, more preferably at most 3 wt%, and most preferably at most 2 wt%, based on the weight of the monomers to be polymerized.
  • Dosing to the reactor is typically effected by dosing the initiator as such (neat) or as a mixture or solution with one or more solvents, in the form of a solution, emulsion, or suspension.
  • Suitable solvents are preferably selected from the group consisting of water, conventional organic solvents, monomers (such as styrene), blowing agents (such as pentane, isopentane, and the like), and mixtures thereof. Mixtures with monomer may not be preferred for safety or quality control reasons.
  • dispersions of the initiator more preferably aqueous dispersions, are used.
  • a suspension of the initiator in water is used, such as a 40 wt% dibenzoyl peroxide suspension in water.
  • Said suspension can be obtained commercially from Akzo Nobel Polymer Chemicals under the trade name Perkadox® L W-40.
  • the dispersion can be a dispersion of the initiator as such or a dispersion of a solution of said initiator.
  • the dispersion is an aqueous dispersion.
  • dilute initiator solutions or dispersions are used that ensure rapid mixing of the initiator and the polymerization mixture, which leads to a more efficient use of the initiator.
  • solutions, emulsions, or suspensions of the initiator having an initiator concentration of at least 1 , more preferably at least 5, and most preferably at least 10 wt%, up to at most 70, more preferably at most 60 wt%.
  • Initiators suitable for dosing to the aqueous suspension during the process according to the present invention are initiators that at the temperature at which they are dosed have a half-life, as measured in monochlorobenzene, of 60 minutes or less, preferably 50 minutes or less, even more preferably 30 minutes or less, and most preferably 15 minutes or less. At the same time, this half-life is preferably more than 0.5 minutes, more preferably more than 1 minute, even more preferably more than 2.5 minutes, and most preferably more than 5 minutes.
  • the half-life of the initiators is determined by differential scanning calorimetry- thermal activity monitoring (DSC-TAM) of a dilute solution of the initiator in monochlorobenzene, as is known in the art.
  • DSC-TAM differential scanning calorimetry- thermal activity monitoring
  • initiator is used here in the classical sense to denominate those compounds that generate free radicals, which, in turn, initiate the polymerization reaction.
  • certain thermally labile compounds are used for the purpose of (wholly or partially) surviving the polymerization conditions, e.g. such that they are present in the final polymer as a flame retardant synergist, the part that does not decompose is not to be seen as an initiator in accordance with the present invention.
  • initiators for dosing to the aqueous suspension during the process according to the invention are peroxydicarbonates, peroxycarbonates, peroxyesters, peroxyketals, diacylperoxides, dialkylperoxides, azo-initiators, ketone peroxides, and mixtures thereof. These initiators may have one or more peroxy and/or azo moieties per molecule. Optionally, these initiators are further functional ized with one or more functional groups, such as amide, chloride, phosphate, ester, ether and/or alcohol groups.
  • Preferred initiators are substituted or unsubstituted dibenzoyl peroxides, 1 ,1 - di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-di(tert-butylperoxy)butane, 1 ,1 -di(tert-butylperoxy)cyclohexane, dicetylperoxydicarbonate, dimyristyl peroxy- dicarbonate, 1 ,1 ,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneo- decanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di(3,5,5- trimethylhexanoyl)peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,2'- azobis(isobutyronitrile), 2,2'-azobis(2-methylbuty
  • dibenzoyl peroxide dicetyl- peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, and 2,2'-azobis(isobutyro- nitrile).
  • the amount of residual monomer content in the polymer product can be reduced in the usual manner; preferably by adding an additional initiator which decomposes at a relatively high temperature, typically in the range 1 10-170°C.
  • This additional initiator also called second stage initiator, may be added at the start of or during the polymerization process, as such or dissolved in a solvent, for instance the blowing agent.
  • suitable additional initiators are tert-butylperoxy- benzoate, tert-butyl peroxy-2-ethylhexyl carbonate, dicumylperoxide, and tert-amyl peroxy-2-ethylhexyl carbonate.
  • blowing agent In order to make polystyrene expandable, a blowing agent has to be introduced.
  • the blowing agent can be added to the aqueous suspension in the process of the present invention or can be added at a later stage, after the polystyrene has been prepared, by impregnation of the produced polystyrene with said blowing agent, or by extrusion of the produced polystyrene in the presence of blowing agent.
  • the blowing agent can be added to the aqueous suspension in the process of the present invention or be added afterwards. Preferably, part or all of the blowing agent is introduced into the aqueous suspension when the degree of polymerization of the monomer is less than 90%, preferably less than 80%, and most preferably less than 70%. A suitable process was found to be one where the blowing agent was dosed or added within one hour of the start of the polymerization.
  • the blowing agent can be added as such, or in admixture with the optional additional initiator mentioned above.
  • Suitable blowing agents are freons, linear or branched saturated hydrocarbons and cyclic saturated hydrocarbons, preferably C3-7 hydrocarbons, in particular C 4- 6 hydrocarbons, such as n-butane, isobutane, n-pentane, isopentane, n-hexane or isohexane, carbon dioxide, and mixtures of two or more of these compounds.
  • the most preferred blowing agents are pentane and isopentane.
  • the blowing agent is preferably used in the process of the present invention in such an amount that the resulting EPS comprises, per 100 parts by weight of styrene (co)polymer, from 2 to 20 parts, preferably from 2 to 15 parts, and in particular from 2 to 10 parts by weight of blowing agent.
  • carbon particulates e.g. carbon black
  • carbon black can be added to the polymerization suspension.
  • particulate carbon examples include carbon black, graphite, and activated carbon.
  • types of carbon black are oil furnace black (petroleum black), gas furnace black, acetylene black, lamp black, flame black (smoke black), channel black (carbon black obtained by small-flame combustion), thermal black, and electrically conductive carbon black.
  • Electrically conductive carbon black differs from the other carbon blacks in particular in an extremely high specific surface area.
  • the carbon particulates preferably have an average particle size of 0.1 -300 microns, more preferably 0.5-150 microns, and most preferably 1 -100 microns.
  • Examples of commercially available carbon blacks are N550 ex-Cabot and Lampblack FW101 ex Degussa.
  • Examples of commercially available electrically conductive carbon blacks are Ketjenblack® EC-300JD and Ketjenblack® EC-600JD (ex Akzo Nobel) and Ensaco® and Super P® conductive carbon black (ex Timcal).
  • Examples of commercially available graphites are Graphit UFZ 99.5, Graphit UF2 96/96, expandable graphite ES200 A5 (all ex Graphit Kropfmuhl AG), expandable graphite type 2151 (ex Bramwell Graphite AG), and Timtex® graphite (ex Timcal).
  • the particulate carbon may be added to the styrene and homogeneously dispersed, it may be added to the polymerization suspension before the polymerization process, or it may be added to the polymerization suspension during the polymerization reaction.
  • the particulate carbon can be added as powder, as dispersion or slurry in styrene, as dispersion or slurry in water, in admixture with both styrene and water, or as polystyrene granules in which the carbon has been incorporated by, e.g., a melt-mixing process.
  • the particulate carbon is preferably added to the polymerization suspension in an amount of 0.1 -25 wt%, more preferably 0.5-8 wt%, based on the weight of monomers.
  • suspension stabilizers e.g. tricalcium phosphate, magnesium pyrophosphate, sodium dodecylbenzene sulphonate, persulphate, bisulphite, polyvinylalcohol, polyvinylpyrrolidone
  • buffer salt e.g. polyethylene wax
  • surfactants e.g. polyethylene wax
  • chain transfer agents e.g. polyethylene wax
  • protective colloids e.g. anti-fouling agents
  • pH- buffers e.g. pH- buffers, etc.
  • the combined weight of these additives preferably is at most 20 wt%, based on the combined weight of all monomers.
  • the polystyrene resulting from the process according to the present invention preferably has a weight-average molecular mass, Mw, in a range of from 140,000 to 300,000 daltons, more preferably from 160,000 to 280,000 daltons, and most preferably from 180,000 to 260,000 daltons.
  • the weight-average molecular mass is typically measured using conventional Gel Permeation Chromatography (GPC) using polystyrene standards.
  • the molecular weight distribution of the styrene polymer preferably ranges from 1 .5 to 4.0, more preferably from 1 .7 to 3.5, and most preferably from 1 .8 to 3.0.
  • the polystyrene resulting from the process according to the present invention preferably has a relatively low level of residual styrene monomer and, where appropriate, of residual comonomer(s).
  • the residual monomer content is preferably not more than 5,000 mg/kg of monomer, preferably less than 2,000 mg/kg of monomer, more preferably less than 1 ,000 mg/kg of monomer.
  • the polystyrene resulting from the process of the present invention may be in the form of particles or, preferably, of expandable beads.
  • beads are meant, generally, spherical or substantially spherical particles, in particular spheroidal particles which may have a large diameter and a small diameter, with a ratio between the large diameter and the small diameter ranging in particular from 1 .0 to 1 .3, preferably from 1 .0 to 1 .2.
  • the expandable particles or beads may have an average size ranging from 0.2 to 3 mm, preferably from 0.3 to 2 mm, in particular from 0.4 to 1 .5 mm.
  • the process according to the present invention does not require the use of a pre-polymerization process or the addition of seed particles.
  • polymer particles especially particles of an undesired particle size resulting from earlier polymerization batches, may be recycled.
  • the particles are preferably dissolved in the monomer before or during the heating of the polymerization suspension to the desired temperature.
  • Preferred is an addition of 0.5-30, most preferably of 3-20 wt.% of polystyrene in styrene monomer.
  • styrene may be prepolymerized in a suspension polymerization process and the resulting beads are added to the polymerization suspension used in the process of the present invention.
  • a solution of dibenzoyl peroxide (Perkadox® L- W75 ex AkzoNobel; 1 .00 meq/100g styrene), tert-butylperoxy 2-ethylhexyl carbonate (Trigonox® 1 17 ex Akzo Nobel; 0.46 meq/100g total styrene), and optionally hexabromocyclododecane (HBCD) and dicumyl peroxide (Perkadox® BC ex Akzo Nobel; 0.2% based on total weight of styrene) was made in 250 g styrene and charged to the reactor.
  • Trigonox® 1 17 served as a second stage initiator, generally causing initiation at higher temperatures
  • Perkadox® BC served as a flame retardant synergist and was only added in combination with HBCD.
  • the temperature was raised to 90°C at a rate of 1 .56°C/min and kept at 90°C for 4.25 hours. Subsequently, the temperature was increased to 130°C at a rate of 0.67°C/min, at which temperature the reactor was maintained for 3 hours. About 15 minutes before the temperature increase to 130°C, 20 g pentane were added from a vessel by pressurizing the reactor with nitrogen (5 bar).
  • the reaction mixture was acidified with HCI (10%) to pH 1 .5 and stirred for about 1 hour.
  • the product was filtered and the EPS beads obtained were washed with water to pH>6 and with an aqueous solution of 25 ppm Armostat 400 (antistatic), respectively.
  • the EPS was dried at room temperature for about 24 hours.
  • the same equipment and ingredients were used as described above, except for the following.
  • the reaction mixture with all ingredients but without initiators was heated to 1 10°C.
  • the dosing of the dibenzoyl peroxide (Perkadox® L-W40) was started.
  • the peroxide - 1 meq dibenzoyl peroxide/100 g styrene suspension - was dosed continuously to the reactor during a certain time period (dosing time) using a peristaltic pump.
  • pentane and the second stage initiator, Trigonox® 1 17, were added, the reaction mixture was heated to 130°C, and the procedure was finished as described above.
  • the weight average molecular weight of the obtained polystyrene - size exclusion chromatography (SEC) - using different dosing times is listed in Table 1 .
  • HBCD 0.56% (0.42% Br) w/w on styrene.
  • a 1 -liter stirred reactor was charged with 1 .125 g tricalcium phosphate, 10 g of a 0.2 wt% sodium dodecylbenzenesulphonate solution (Nacconol 90G), and 365 g water. This mixture was stirred for 5 minutes at 500 rpm. Next, a solution of 0.550 g dicumyl peroxide (Perkadox® BC-FF) and 1 .663 g hexabromocyclododecane (HBCD) in 228.26 g styrene was added to the reactor and the temperature was raised to 90°C in 45 minutes.
  • Perkadox® BC-FF dicumyl peroxide
  • HBCD hexabromocyclododecane
  • dibenzoyl peroxide (Perkadox® L-W75).
  • dibenzoyl peroxide (1 .097 g, dissolved in 21 .74 g styrene) was added to the reaction mixture in 12 portions at regular time intervals during 2 hours. This addition was started when the temperature reached 90°C. After adding the complete amount of initiator, the temperature was kept at 90°C for another 4 hours, followed by cooling the reactor down to 25°C in 45 minutes.
  • the styrene conversion in Examples 8 and 9 was determined by gravimetrical measurement of the solids content of the organic phase of the reaction mixture. Molecular weights were determined by SEC, as described above.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé de polymérisation en suspension de monomères de styrène afin de produire un polystyrène, le procédé comprenant l'étape (a) consistant à chauffer une suspension de polymérisation contenant les monomères de styrène à une température d'au moins 60 °C, et l'étape (b) consistant à ajouter un initiateur à ladite suspension de polymérisation chauffée pendant la réaction de polymérisation sur une période de plus de 90 minutes et de moins de 5 heures, de manière continue ou par intermittence en au moins 2 portions. Ladite période commence quand la conversion en monomères est de 65 % de moins, la demi-vie dudit initiateur à la température à laquelle il est ajouté est de 60 minutes au maximum, et un ignifuge bromé est présent dans la suspension de polymérisation lors de la réaction de polymérisation.
PCT/EP2010/069012 2009-12-10 2010-12-07 Procédé de polymérisation du styrène WO2011069983A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
MX2012006309A MX339691B (es) 2009-12-10 2010-12-07 Proceso para la polimerizacion de estireno.
US13/513,681 US20120245315A1 (en) 2009-12-10 2010-12-07 Process for the polymerization of styrene
JP2012542502A JP5632926B2 (ja) 2009-12-10 2010-12-07 スチレンの重合方法
RU2012127565/04A RU2556005C2 (ru) 2009-12-10 2010-12-07 Способ полимеризации стирола
CN201080054319.2A CN102639569B (zh) 2009-12-10 2010-12-07 苯乙烯的聚合方法
EP10785446A EP2510021A1 (fr) 2009-12-10 2010-12-07 Procédé de polymérisation du styrène
AU2010329986A AU2010329986B2 (en) 2009-12-10 2010-12-07 Process for the polymerization of styrene
CA2779995A CA2779995A1 (fr) 2009-12-10 2010-12-07 Procede de polymerisation du styrene

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US28531609P 2009-12-10 2009-12-10
EP09178690 2009-12-10
US61/285,316 2009-12-10
EP09178690.5 2009-12-10

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US (1) US20120245315A1 (fr)
EP (1) EP2510021A1 (fr)
JP (1) JP5632926B2 (fr)
KR (1) KR20120117980A (fr)
CN (1) CN102639569B (fr)
AU (1) AU2010329986B2 (fr)
CA (1) CA2779995A1 (fr)
MX (1) MX339691B (fr)
MY (1) MY161062A (fr)
RU (1) RU2556005C2 (fr)
TW (1) TWI507421B (fr)
WO (1) WO2011069983A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
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US20140364524A1 (en) * 2011-12-21 2014-12-11 Basf Se Method for producing expandable styrene polymers containing graphite and flame retardant
US10227531B2 (en) 2014-07-08 2019-03-12 Bromine Compounds Ltd. Preparation of bromine-containing polymers and their application as flame retardants

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US8671221B2 (en) 2010-11-17 2014-03-11 Hola Networks Ltd. Method and system for increasing speed of domain name system resolution within a computing device
KR102397588B1 (ko) * 2013-12-30 2022-05-12 아버리스 에이에스 고체 입자상 비닐 방향족 폴리머 조성물의 제조 방법
KR101919506B1 (ko) * 2016-11-21 2018-11-16 금호석유화학 주식회사 수분 함량이 높은 발포성 폴리스티렌 비드의 제조 방법
JP7227466B2 (ja) * 2019-01-16 2023-02-22 株式会社ジェイエスピー 発泡性スチレン系樹脂粒子及びその製造方法
JP7385518B2 (ja) 2020-03-30 2023-11-22 Ykk Ap株式会社 扉体および建具
US20240150504A1 (en) * 2022-01-17 2024-05-09 Lg Chem, Ltd. Method of preparing polymer

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DE1285730B (de) * 1966-03-25 1968-12-19 Basf Ag Thermoplastische Formmassen aus Styrolpolymerisaten zur Herstellung selbstverloeschender Formkoerper
DE2304028A1 (de) * 1973-01-27 1974-08-01 Huels Chemische Werke Ag Schwerentflammbare blaehfaehige formmassen aus styrolpolymerisaten
DE2840355B1 (de) * 1978-09-16 1979-10-18 Huels Chemische Werke Ag Feinteilige expandierbare Styrolpolymerisate zur Herstellung von Schaumstoffkoerpern mit kurzen Mindestformverweilzeiten
EP0476256A1 (fr) * 1990-09-15 1992-03-25 Hüls Aktiengesellschaft Procédé pour régler la granulation lors de la préparation de polymères expansibles de styrène par polymérisation en suspension
WO1999054391A1 (fr) * 1998-04-17 1999-10-28 Nova Chemicals (International) S.A. Procede de preparation de particules de polymere expansible
WO2004089999A2 (fr) 2003-04-14 2004-10-21 Akzo Nobel N.V. Dosage du peroxyde utilise dans un procede de polymerisation en suspension de styrene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140364524A1 (en) * 2011-12-21 2014-12-11 Basf Se Method for producing expandable styrene polymers containing graphite and flame retardant
US10227531B2 (en) 2014-07-08 2019-03-12 Bromine Compounds Ltd. Preparation of bromine-containing polymers and their application as flame retardants

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AU2010329986A1 (en) 2012-05-31
MY161062A (en) 2017-04-14
JP2013513680A (ja) 2013-04-22
CN102639569B (zh) 2014-07-02
CN102639569A (zh) 2012-08-15
AU2010329986B2 (en) 2014-12-04
EP2510021A1 (fr) 2012-10-17
MX339691B (es) 2016-06-06
TWI507421B (zh) 2015-11-11
CA2779995A1 (fr) 2011-06-16
MX2012006309A (es) 2012-06-19
RU2012127565A (ru) 2014-01-20
JP5632926B2 (ja) 2014-11-26
RU2556005C2 (ru) 2015-07-10
KR20120117980A (ko) 2012-10-25
US20120245315A1 (en) 2012-09-27
TW201134835A (en) 2011-10-16

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