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WO2012052423A1 - Polymères aromatiques de vinyle expansibles - Google Patents

Polymères aromatiques de vinyle expansibles Download PDF

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Publication number
WO2012052423A1
WO2012052423A1 PCT/EP2011/068165 EP2011068165W WO2012052423A1 WO 2012052423 A1 WO2012052423 A1 WO 2012052423A1 EP 2011068165 W EP2011068165 W EP 2011068165W WO 2012052423 A1 WO2012052423 A1 WO 2012052423A1
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WO
WIPO (PCT)
Prior art keywords
vinyl aromatic
aromatic polymer
polymer
expandable vinyl
expandable
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.)
Ceased
Application number
PCT/EP2011/068165
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English (en)
Inventor
Stéphane Nowe
Philippe Lodefier
Laetitia Urbanczyk
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Total Petrochemicals Research Feluy SA
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Total Petrochemicals Research Feluy SA
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Priority to US13/879,831 priority Critical patent/US20130320253A1/en
Priority to BR112013008987A priority patent/BR112013008987A2/pt
Priority to EA201370095A priority patent/EA022941B1/ru
Priority to EP11775933.2A priority patent/EP2630186A1/fr
Priority to CN201180060937.2A priority patent/CN103261298B/zh
Publication of WO2012052423A1 publication Critical patent/WO2012052423A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/16—Making expandable particles
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Definitions

  • the present invention relates to expandable vinyl aromatic polymers with an enhanced heat insulation capacity and comprising polyisobutene (PiB).
  • Expandable vinyl aromatic polymers and among these, in particular, expandable polystyrene (EPS), are known products which have been used for a long time for preparing expanded articles which can be adopted in various applicative fields, among which one of the most important is the field of heat insulation.
  • EPS expandable polystyrene
  • These expanded products are obtained by swelling beads of expandable polymer impregnated with a gas and molding the swollen particles contained inside a closed mould by means of the contemporaneous effect of pressure and temperature.
  • the swelling of the particles is generally effected with water vapour, or another gas, maintained at a temperature slightly higher than the glass transition temperature (Tg) of the polymer.
  • a particular applicative field of expanded polystyrene is that of thermal insulation in the building industry where it is generally used in the form of flat sheets.
  • the flat expanded polystyrene sheets are normally used with a density of about 15 to 30 g/l.
  • expandable beads based on vinyl aromatic polymers means vinyl aromatic polymers in the form of granules, containing an expanding system and other additives.
  • thermoplastic polymers in the form of granules are particularly used, after expansion and moulding, in the production of household appliances or other industrial equipment, in packaging and thermal insulation in the building industry, due to their thermo-insulating properties.
  • Thermoplastic vinyl aromatic polymers such as polystyrene can be made expandable by incorporating an expandable agent in the polymeric matrix.
  • Typical expanding agents for vinyl aromatic polymers include at least one liquid hydrocarbon containing from 3 to 7 carbon atoms, a halogenated hydrocarbon, carbon dioxide or water. The quantity of expanding agent usually ranges from 2 to 15% by weight.
  • Expandable polymers are produced in general as beads or granules which, under the action of heat, supplied, for example, by steam, are first expanded until a desired density is reached and, after a certain aging period, are sintered in closed moulds to produce blocks or the desired final products.
  • the flowability of polymer mixtures containing fillers is critical especially if micro-beads have to be produced.
  • a usual method to modify the rheology and decrease the viscosity is to lower the molecular weight. This technique is showing limitations because of the lack of entanglements of the low molecular weight chains.
  • An alternative is to add oil, however when using a material containing oil in foams application the compression resistance is reduced.
  • the present invention uses polyisobutylene (also called polyisobutene or PiB) instead of oil. PiB allows to decrease the viscosity of the polymer while maintaining the same or a higher 10% compression resistance.
  • the MFI see in the examples the measurements standart
  • a higher molecular weight can then advantageously be used.
  • EP 770632 B1 describes a high impact monovinylaromatic polymeric compound comprising an impact resistant rubber modified monovinylaromatic polymer with improved environmental stress crack resistance, said polymeric compound formed by the polymerization of a monovinylaromatic compound in the presence of a rubber and an additive consisting essentially of low/medium to high molecular weight polyisobutylene as measured by a viscosity of from about 48 up to about 4380 est at 99°C.
  • US 3,929,686 describes a composition and process for the preparation of expandable styrene polymers wherein low molecular weight isobutylene polymers are employed in an amount of from about 0.02 to about 0.15% by weight based upon the styrene polymer as a nucleating agent to produce an expanded styrene polymer having a very small average cell size. There is no mention of the insulation boards obtained and compression resistance thereof. [Brief summary of the invention]
  • the present invention is an expandable vinyl aromatic polymer which comprises:
  • MFI from an initial index to a final index such as the 10% compression strength of the foam made with said expandable vinyl aromatic polymer of the final index
  • the expandable vinyl aromatic polymer of the invention is produced in the form of beads or granules.
  • the expandable vinyl aromatic polymer comprises carbon black in a proportion sufficient for the foamed material obtained from the expandable vinyl aromatic polymer to have a thermal conductivity ⁇ of about 34 mW/m°K or lower.
  • the thermal conductivity ⁇ of about 34 mW/m°K means that it could be in the range 33.5 to 34.5 mW/m°K.
  • the thermal conductivity ⁇ is between about 33 and 34 mW/m°K, more advantageously between about 32 and 33 mW/m°K, preferably between about 31 and 32 mW/m°K and more preferably between about 30 and 31 mW/m°K.
  • the present invention also relates to a process for preparing the composition wherein it is carried out by mixing the vinyl aromatic polymer in the melted state with the blowing agent or agents, PiB, optionally carbon black and optionally the fillers.
  • PiB can be introduced in the molten vinyl aromatic polymer or with the expanding agent, or with the carbon black if any or with the fillers if any or any combination thereof.
  • PiB can be introduced during the polymerization of the vinyl aromatic monomer.
  • PiB can be introduced in part during the polymerization of the vinyl aromatic monomer and in part in the already polymerized vinyl aromatic monomer as explained above or with the expanding agent, or with the carbon black if any or with the fillers if any or any combination thereof.
  • the mixing is carried out in a chamber equipped with at least one stirring means and under temperature and pressure conditions which are capable of preventing expansion of the composition, preferably in an extruder, in particular a single-screw or twin-screw extruder, or in one or more static mixers at a temperature greater than the glass transition temperature of the polymer, in particular a temperature ranging from 120 to 250°C and under an absolute pressure ranging from 0.1 to 10 MPa.
  • the present invention also relates to the use of the expandable vinyl aromatic polymer to make expanded articles, in particular insulation boards.
  • a step of pre-expansion by contacting and mixing the composition, which is in the form in particular of expandable particles or, preferably, expandable beads, with water vapour, in particular in a stirred tank, under pressure and temperature conditions capable of forming expanded particles or expanded beads having in particular a bulk density ranging from 5 to 200 kg/m3, preferably from 5 to 100kg/m3 and in particular from 5 to 50 kg/m3,
  • step (iii) a step of moulding the particles or beads thus stabilized, by introducing them into a mould and by heating the mould so as to weld the particles or beads to one another and so to produce a moulded and expanded article having in particular the desired bulk density and, preferably a bulk density substantially identical to that of the expanded particles or expanded beads obtained in step (i).
  • the present invention also relates to a process to increase the Melt Flow Index of an expandable vinyl aromatic polymer while maintaining the same or a higher 10% compression resistance.
  • the present invention is a process to increase the Melt Flow Index of an expandable vinyl aromatic polymer while maintaining the same or a higher 10% compression resistance, comprising,
  • MFI from an initial index to a final index such as the 10% compression strength of the foam made with said expandable vinyl aromatic polymer of the final index
  • the expandable vinyl aromatic polymer can be recovered as beads by any means, advantageously through an under water pelletizer.
  • vinyl aromatic polymer mention may be made of : polystyrene, elastomer-modified polystyrene,
  • copolymers of styrene and acrylonitrile SAN
  • SAN acrylonitrile
  • ABS elastomer-modified SAN
  • ABS which is obtained, for example, by grafting (graft polymerization) of styrene and acrylonitrile on a backbone of polybutadiene or of butadiene-acrylonitrile copolymer, mixtures of SAN and ABS,
  • copolymers with styrene blocks and blocks made of butadiene or isoprene or of a mixture butadiene /isoprene these block copolymers can be linear blocks copolymers or star blocks copolymers, they can be hydrogenated and/or functionalized.
  • These copolymers are described in ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, fith edition (1995) Vol A26, pages 655-659, They are sold by Total Petrochemicals under the trade mark Finaclear®, by BASF under the trade mark Styrolux®, under the trade mark K- Resin® by Chevron Phillips Chemical,
  • Elastomers Possible examples of the abovementioned elastomers are EPR (the abbreviation for ethylene-propylene rubber or ethylene- propylene elastomer), EPDM (the abbreviation for ethylene- propylene-diene rubber or ethylene- propylene-diene elastomer), polybutadiene, acrylonitrile- butadiene copolymer, polyisoprene, isoprene-acrylonitrile copolymer and copolymers with styrene blocks and blocks made of butadiene or isoprene or of a mixture butadiene /isoprene.
  • block copolymers can be linear blocks copolymers or star blocks copolymers, they can be hydrogenated and/or functionalized (see above).
  • part of the styrene may be replaced by unsaturated monomers copolymerizable with styrene, for example alpha- methylstyrene or (meth)acrylates
  • styrene copolymers which may be mentioned are chloropolystyrene, poly-alpha- methylstyrene, styrene- chlorostyrene copolymers, styrene-propylene copolymers, styrenebutadiene copolymers, styrene-isoprene copolymers, styrene-vinyl chloride copolymers, styrene-vinyl acetate copolymers, styrene- alkyl acrylate copolymers (methyl, ethyl, butyl, octyl, phenyl acrylate), styrene- al
  • the vinyl aromatic polymer comprises : i) from 60 to 100 weight % of one or more Cs-12 vinyl aromatic monomers; and
  • ii) from 0 to 40 weight % of one or more monomers selected from the group consisting of Ci -4 alkyl esters of acrylic or methacrylic acid and acrylonitrile and methacrylonitrile; which polymer may be grafted onto or occluded within from 0 to 20 weight % of one or more rubbery polymers.
  • rubbery polymers can be selected from the group consisting of:
  • copolymers comprising from 60 to 85 weight % of one or more C 4- 6 conjugated diolefins and from 15 to 40 weight % of a monomer selected from the group consisting of acrylonitrile and methacrylonitrile and
  • copolymers comprising from 20 to 60, preferably from 40 to 50 weight % of one or more Cs-12 vinyl aromatic monomers which are unsubstituted or substituted by a Ci -4 alkyl radical and from 60 to 40, preferably from 60 to 50 weight % of one or more monomers selected from the group consisting of C 4- 6 conjugated diolefins.
  • the rubber may be prepared by a number of methods, preferably by emulsion or solution polymerization. These processes are well known to those skilled in the art.
  • the vinyl aromatic polymers may be prepared by a number of methods. This process is well known to those skilled in the art.
  • the rubber is present in an amount from about 3 to 10 weight %.
  • Polybutadiene is a particularly useful rubber.
  • the vinyl aromatic polymer is polystyrene
  • it could be a crystal polystyrene or a rubber modified polystyrene.
  • the rubber modified polystyrene is called HIPS (High Impact Polystyrene) .
  • HIPS High Impact Polystyrene
  • the process for making HIPS is well known to those skilled in the art.
  • the rubber is "dissolved” in the styrene monomer (actually the rubber is infinitely swollen with the monomer). This results in two co- continuous phases.
  • the resulting "solution” is fed to a reactor and polymerized typically under shear. When the degree of polymerization is about equal to the weight % of rubber in the system it inverts (e.g.
  • the styrene/styrene polymer phase becomes continuous and the rubber phase becomes discontinuous.
  • the polymer is finished in a manner essentially similar to that for finishing polystyrene.
  • the polymer is prepared using conventional bulk, solution, or suspension polymerization techniques.
  • the vinyl aromatic polymers of the present invention may be co- or homopolymers of Cs-12 vinyl aromatic monomers.
  • Some vinyl aromatic monomers may be selected from the group consisting of styrene, alpha methyl styrene and para methyl styrene.
  • the vinyl aromatic monomer is styrene.
  • the vinyl aromatic polymer may be a copolymer comprising from 60 to 100 weight % of one or more Cs-12 vinyl aromatic monomers; and from 0 to 40 weight % of one or more monomers selected from the group consisting of Ci -4 alkyl esters of acrylic or methacrylic acid and acrylonitrile and methacrylonitrile.
  • Suitable esters of acrylic and methacrylic acid include methyl acrylate, ethyl acyrlate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
  • the vinyl aromatic polymers of the present invention may be rubber modified.
  • the vinyl aromatic polymer is a monovinylaromatic polymer.
  • the vinyl aromatic polymer can be a branched aromatic ionomer.
  • the branched aromatic ionomer comprises the product of co- polymerizing a first monomer comprising an aromatic moiety and an unsaturated alkyl moiety and a second monomer comprising an ionic moiety and at least two unsaturated moieties, wherein the ionic moiety has at least two ionizable groups, a cationic group that ionizes to form cations and an anionic group that ionizes to form anions, and wherein the cationic group is polyvalent and one capable of forming bridges to other molecules.
  • the first monomer is selected from the group consisting of styrene, alphamethyl styrene, t-butylstyrene, p-methylstyrene, vinyl toluene, and mixtures thereof.
  • the first monomer is styrene.
  • Components that may be used as the second monomer include, but are not limited to: zinc diacrylate, zinc dimethacrylate, zinc di-vinylacetate, zinc di- ethylfumarate, and the like; copper diacrylate, copper dimethacrylate, copper di- vinylacetate, copper di-ethylfumarate, and the like; aluminum triacrylate, aluminum trimethacrylate, aluminum tri-vinylacetate, aluminum tri- ethylfumarate, and the like; zirconium tetraacrylate, zirconium tetramethacrylate, zirconium tetra-vinylacetate, zirconium tetra-ethylfumarate, and the like.
  • the second monomer may be sodium acrylate, sodium methacrylate, silver methacrylate, and the like. These components and any component useful as the second monomer may be prepared by, for example, reacting an organic acid or an anhydride with a metal or metal salt.
  • the second monomer is selected from the group consisting of: zinc diacrylate, zinc dimethacrylate, zinc di-vinylacetate, zinc di- ethylfumarate, and the like; copper diacrylate, copper dimethacrylate, copper di- vinylacetate, copper di-ethylfumarate, and the like; aluminum triacrylate, aluminum trimethacrylate, aluminum tri-vinylacetate, aluminum tri- ethylfumarate, and the like; zirconium tetraacrylate, zirconium tetramethacrylate, zirconium tetra-vinylacetate, zirconium tetra-ethylfumarate, and mixtures thereof.
  • the second ionomer is zinc diacrylate or zinc dimethacrylate.
  • the first monomer can be a mixture of various aromatic monomers comprising an aromatic moiety and an unsaturated alkyl moiety and /or can be used alone or in a mixture of up to 50% by weight with other co-polymerizable monomers.
  • said monomers are (meth) acrylic acid, Ci-C4 alkyl esters of methacrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid, such as acrylamide, methacrylamide, acrylonitrile, methacrylinitrile , butadiene, ethylene, divinyl benzene, maleic anhydride, etc..
  • Preferred co polymerizable monomers are acrylonitrile and methyl methacrylate.
  • the monomers used to prepare the branched aromatic ionomers may interact in several ways to affect the physical properties of the ionomers.
  • a first way is the formation of covalent bonds due to the polymerization of the unsaturated moieties.
  • a second way that the monomers used to prepare the branched aromatic ionomers may interact is by the formation of a bridge wherein a polyvalent cationic group is coordinated to two anionic groups which are integrated into the backbones of at least two separate chains. This coordination may, in effect, cross link the two chains thereby increasing that segment's total effective molecular weight to the sum of the two chains.
  • a third way that that the monomers used to prepare the branched aromatic ionomers may interact is by the formation of multiple bridges as described immediately above. The more crosslinking that occurs, the less flexible the three dimensional structure of the ionomer, which may result in lower melt flow values and increased melt strength.
  • the ionic moieties when the cationic groups are mono-valent, the ionic moieties, while not fully bridged, may still associate due to hydrophobic-hydrophilic forces.
  • this weaker but still measurable force may result from the comparatively non-polar hydrophobic, non-ionic parts of the molecule being mutually attracted and repelled from the polar hydrophilic ionic parts of the ionomer. These forces are more noticeable as the proportion of the second monomer is increased in concentration. These four are not all of the possible interactions of the monomers. In addition, most of the properties of the ionomers associated with its primary, secondary, and even tertiary structure, such as the ionomers' glass transition temperatures "Tg" may be affected.
  • the amount of second monomer and the type of interaction with the first monomer will dictate the amount of second monomer used. Therefore, in some embodiments where the interaction is weak, such as when the cationic group of the second monomer is mono-valent, and a significant amount of effect is desired from the second monomer, the branched ionomers are prepared with a comparatively large amount of the second monomer, typically with a ratio of first monomer to second monomer of from about 999: 1 to about 40:60. In other such embodiments, the ratio is from about 95:5 to about 50:50. In still other such embodiments, the ratio is from about 90: 10 to about 60:40. Other embodiments have a ratio of from 80:20 to 70:30.
  • the amount of the second monomer is quite small ranging from about 10 parts per million "ppm" to about 10,000 ppm. In other such ionomers, the range is from about 100 ppm to about 1000 ppm. In still other such ionomers, the range is from about 250 ppm to about 800 ppm.
  • the branched aromatic ionomer is prepared by co-polymerizing the first and second monomers. Each of these monomers has at least one polymerizable unsaturation.
  • the polymerization may be carried out using any method known to those of ordinary skill in the art of performing such polymerizations.
  • the polymerization may be carried out by using a polymerization initiator.
  • the polymerization initiators are, for instance, radical polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate and 1 , 1 -di-t-butylperoxy-2,4-di-t- butylcyclohexane.
  • the amount of the polymerization initiator is from about 0 to about 1 percent by weight of the monomers. In one embodiment, the amount of polymerization initiator is from about 0.01 to about 0.5 percent by weight of the monomers. In another embodiment, the amount of polymerization initiator is from about 0.025 to about 0.05 percent by weight of the monomers.
  • the ionomer may be prepared using heat as an initiator.
  • the ionomer may be prepared using a non- conventional initiator such as a metallocene catalyst as is disclosed in US. Patent No. 6,706,827 to Lyu, et al., which is incorporated herein in its entirety by reference.
  • the monomers may be admixed with a solvent and then polymerized.
  • one of the monomers is dissolved in the other and then polymerized.
  • the monomers may be fed concurrently and separately to a reactor, either neat or dissolved in a solvent, such as mineral oil.
  • the second monomer may be prepared in- situ or immediately prior to the polymerization by admixing the raw material components, such as an unsaturated acid or anhydride and a metal alkoxide, in-line or in the reactor.
  • the raw material components such as an unsaturated acid or anhydride and a metal alkoxide
  • Any process for polymerizing monomers having polymerizable unsaturation know to be useful to those of ordinary skill in the art in preparing such polymers may be used.
  • the process disclosed in U.S. Patent No. 5,540,813 to Sosa, et al. may be used and is incorporated herein in its entirety by reference.
  • the processes disclosed in U.S. Patent No. 3,660,535 to Finch, et al., and U. S. Patent No. 3,658,946 to Bronstert, et al. may be used and are both incorporated herein in their entirety.
  • Any process for preparing general purpose polystyrene may be used to prepare the branched
  • the branched aromatic ionomer can be mixed with up to 50%w of a
  • the ionomers may be admixed with additives prior to being used in end use applications.
  • the ionomers may be admixed with fire retardants, antioxidants, lubricants, UV stabilizers, antistatic agents, and the like. Any additive known to be useful to those of ordinary skill in the art of preparing ionomers to be useful may be used with the branched ionomers.
  • polystyrene such as crystal polystyrene and HiPS.
  • Polystyrene has advantageously a Mw from 130000 to 210000 and a MFI (Measured at 200°C with a weight of 5Kg, according to norm DIN ISO 1 133) ranging from 4 to 20.
  • the expanding agent is selected from aliphatic or cyclo- aliphatic hydrocarbons containing from 3 to 6 carbon atoms such as n-pentane, iso-pentane, cyclopentane or blends thereof; halogenated derivatives of aliphatic hydrocarbons containing from 1 to 3 carbon atoms, such as, for example, dichlorodifluoromethane, 1 ,2,2- trifluoroethane, 1 , 1 ,2-trifluoroethane; carbon dioxide and water.
  • pentane advantageously a mixture of n and iso is used. The proportion of pentane is advantageously in the range 4 to 7w%.
  • the isobutylene polymers according to the present invention are preferably homopolymers of isobutylene but include also C2-C5 lower olefin hydrocarbons containing at least about 85% isobutylene monomer units and typically including minor amounts of normal-butylene monomer units and relatively small amounts of other lower olefins.
  • the isobutylene polymers employed in the present invention are those having a molecular weight (number average) of between about 500 and 5000, although it is preferred that the molecular weight thereof range between about 900 and 3000.
  • the polymers are characterized as long chain hydrophobic molecules with methyl side group chains. The proportion of PiB can be adjusted easily by checking the MFI of the expandable vinyl aromatic polymer.
  • the proportions (w% with respect to polymer (a)) of PiB are from 0.5 to 2.5, preferably from 0.8 to 2.2 more preferably from 1 to 2.
  • the isobutylene polymers employed in accordance with the present invention can be prepared by means of known procedures, and suitable products are available commercially.
  • a hydrocarbon feed consisting essentially of isobutylene monomer is contacted with a Friedel-Crafts catalyst at a temperature above about -45°F, whereupon a suitable low molecular weight polymer is produced. See, for example, the disclosure of U.S. Pat. No. 2,957,930.
  • Polymers falling within the upper portion of the molecular weight range specified hereinabove may be produced by further contacting the foregoing low molecular weight polyisobutylene with about 1 to 10% of a Friedel-Crafts catalyst for periods of about 15 minutes to 2 hours and at a temperature of from about 10° to 200°F see, for example, U.S. Pat. No. 3,375,295.
  • a Friedel-Crafts catalyst for the preparation of low molecular weight isobutylene polymers are described in U.S. Pat. Nos. US 3, 501 ,551 , US 3,073, 876, US 3,242, 158, and US 3,356,661 .
  • the proportion can be determined easily by the man skilled in the art.
  • the thermal conductivity of the foam decreases with the increasing proportion of carbon black.
  • the range can be from about 1 to about 5 w%. It is easy with a reduced number of experiments to find the proportion to get a thermal conductivity ⁇ of about 34 mW/m°K or lower of the foam.
  • the carbon black has advantageously a surface area (preferably the BET nitrogen surface area), measured according to ASTM D-6556, ranging from 5 to 1000 m2/g, more advantageously from 5 to 800 m2/g . Preferably said surface area ranges from 50 to 100m2/g and more preferably from 45 to 75 m2/g.
  • fillers one can cite any material capable to reduce the thermal conductivity and/or to enhance the properties of the expanded vinyl aromatic polymer.
  • talc in an embodiment, one can cite those having a mean diameter above about 8 pm, said mean diameter being measured by Laser Mastersizer according to standard ISO 13320-1 , one can cite the 20M00S supplied by the company Rio Tinto Minerals (Talcs de Luzenac).
  • the talc has a mean diameter above about 8 pm and under 100 pm, more advantageously in the range 8-50 pm, preferably in the range 8-30 pm, more preferably in the range 9-12 pm.
  • the D(95) is around 100 pm or below, more advantageously around 50 pm, much more advantageously around 40 pm, preferably around 30 pm. D(95) means that 95% of particles are smaller than this value.
  • the BET of the talc is in the range 0.5-5 m2/g and preferably in the range 3-4 m2/g.
  • the proportion of talc is advantageously from 0.1 to 2w% and preferably around 1 %.
  • flame retardants include nucleating agents, plasticizers and agents which facilitate the demoulding of the moulded and expanded articles.
  • it may comprise at least one flame retardant selected in particular from halogenated hydrocarbons, preferably brominated hydrocarbons, in particular C6 to C12 hydrocarbons, such as hexabromocyclohexane, penta- bromomonochlorocyclohexane or hexabromocyclododecane, in an amount which can range from 0.05 to 2 parts, preferably from 0.1 to 1 .5 parts, by weight, per 100 parts by weight of the styrene polymer.
  • halogenated hydrocarbons preferably brominated hydrocarbons, in particular C6 to C12 hydrocarbons, such as hexabromocyclohexane, penta- bromomonochlorocyclohexane or hexabromocyclododecane
  • the composition may further comprise at least one nucleating agent selected in particular from synthetic waxes, in particular Fischer-Tropsch waxes and polyolefin waxes such as polyethylene waxes or polypropylene waxes, in an amount which can range from 0.05 to 1 part, preferably from 0.1 to 0.5 part, by weight per 100 parts by weight of the vinyl aromatic polymer.
  • the composition may likewise comprise at least one plasticizer, selected in particular from mineral oils and petroleum waxes such as paraffin waxes, in an amount which can range from 0.1 to 1 part, preferably from 0.1 to 0.8 part, by weight per 100 parts by weight of the vinyl aromatic polymer.
  • the composition may additionally comprise at least one agent which facilitates the demoulding of the moulded and expanded articles, selected in particular from inorganic salts and esters of stearic acid, such as glycerol mono-, di or tristearates and zinc stearate, calcium stearate or magnesium stearate, in an amount which can range from 0.05 to 1 part, preferably from 0.1 to 0.6 part, by weight per 100 parts by weight of the vinyl aromatic polymer.
  • inorganic salts and esters of stearic acid such as glycerol mono-, di or tristearates and zinc stearate, calcium stearate or magnesium stearate
  • a parameter of importance is the 10% compression strength as a function of the density of the foam.
  • the advantage of the compositions of the invention is they have a high 10% compression strength.
  • the proportion of PiB is adjusted to increase the Melt Flow Index (MFI) from an initial index to a final index such as the 10% compression strength of the foam made with said expandable vinyl aromatic polymer of the final index is essentially the same or higher than the foam made with said expandable vinyl aromatic polymer of the initial index.
  • MFI Melt Flow Index
  • a final index such as the 10% compression strength of the foam made with said expandable vinyl aromatic polymer of the final index
  • essentially the same means that the difference is less than 5%, advantageously less than 4%, more advantageously less than 3% and preferably less than 2%.
  • the 10% compression strength (or strain value at 10% deformation) in kPa which is at least [7.14x density of the foam in kg/m3 - 28]. Which means about 50 kPa for a density of 1 1 kg/m3 and about 150 kPa for a density of 25 kg/m3.
  • the process to make said expandable polymer it is carried out by mixing the vinyl aromatic polymer in the melted state with the blowing agent or agents, PiB, talc if any, carbon black if any and the fillers.
  • the mixing is carried out in a chamber equipped with at least one stirring means and under temperature and pressure conditions which are capable of preventing expansion of the composition, preferably in an extruder, in particular a single-screw or twin-screw extruder, or in one or more static mixers at a temperature greater than the glass transition temperature of the polymer, in particular a temperature ranging from 120 to 250°C and under an absolute pressure ranging from 0.1 to 10 MPa.
  • the present invention relates to a process for preparing in mass and in continuous, expandable vinyl aromatic polymers, which comprises the following steps in series: (i) feeding the vinyl aromatic polymer, as described above, to an extruder, optionally together with fillers, (ii) heating the vinyl aromatic polymer to a temperature higher than the relative melting point; (iii) injecting the expanding agent and possible additives (PiB) into the molten polymer before extrusion through a die; and (iv) forming expandable beads, through a die, with an average diameter ranging from 0.2 to 2 mm and advantageously made with an underwater pelletizer.
  • the expandable beads produced are subjected to pre-treatment generally applied to conventional expandable beads and which essentially consists in: 1 . coating the beads with an antistatic agent such as amines, tertiary ethoxylated alkylamines, ethylene oxide-propylene oxide copolymers, etc. The purpose of this agent is to facilitate the adhesion of the coatings
  • said coating essentially consisting of a mixture of mono-, di-and tri-esters of glycerin (or other alcohols) with fatty acids and of metallic stearates such as zinc and/or magnesium stearate.
  • melt index of polystyrene is measured at 200°C under a 5kg load (DIN ISO 1 133).
  • a coating agent like zinc stearate and optionally glycerol mono- bi- or tri- stearate.
  • the treated beads are pre-expanded with steam at 100°C, left to age for 1 day and finally used to mold the board. After 1 day, the density of the board, determined by weighing the board and measuring its dimensions, is 19 g/l. After at least 30 ageing days, the sample is subjected to compression test. The strain value at 10% deformation, evaluated following EN826 standart, is 1 13 kPa. The thermal conductivity of the board, measured according to norm ISO 8301 , is 0.035 W/mK
  • a coating agent like zinc stearate and optionally glycerol mono- bi- or tri-stearate.
  • the treated beads are pre-expanded with steam at 100°C, left to age for 1 day and finally used to mold the board. After 1 day, the density of the board, determined by weighing the board and measuring its dimensions, is 19.1 g/l. After at least 30 ageing days, the sample is subjected to compression test. The strain value at 10% deformation, evaluated following EN826 standart, is 101 .4 kPa.
  • Glissopal 1000 is a polyisobutene of Mn 1000.
  • the melt flow index of this melt equals 8.5 g/10min, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 19.9 g/l. After at least 30 ageing days, the sample is subjected to compression test.
  • the strain value at 10% deformation, evaluated following EN826 standart, is 1 17.3 kPa.
  • Primol 352 is a white mineral oil (CAS number: 8042-47-5 EINECS number: 232-455-8) of average Molecular Weight 480 (ASTM D 2502) having a percentage carbon Paraffinic / Naphthenic/ Aromatic 66 / 34 / 0 (ASTM D 2140).
  • the melt flow index of this melt equals 8.1 g/1 Omin, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 18.8 g/l. After at least 30 ageing days, the sample is subjected to compression test. The strain value at 10% deformation, evaluated following EN826 standart, is 103.8 kPa.
  • the melt flow index of this melt equals 9 g/1 Omin, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 19.5 g/l. After at least 30 ageing days, the sample is subjected to compression test.
  • the melt flow index of this melt equals 8.9 g/1 Omin, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 20 g/l. After at least 30 ageing days, the sample is subjected to compression test.
  • the strain value at 10% deformation, evaluated following EN826 standart, is 99 kPa.
  • the melt flow index of this melt equals 9.3 g/1 Omin, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 20.2 g/l. After at least 30 ageing days, the sample is subjected to compression test.
  • the strain value at 10% deformation, evaluated following EN826 standart, is 1 16 kPa.
  • the thermal conductivity of the board measured according to norm ISO 8301 , is 0.0318 W/mK.
  • the melt flow index of this melt equals 9.6 g/1 Omin, according to DIN ISO 1 133.
  • the board obtained after pre-expansion and molding steps has a density of 20 g/l. After at least 30 ageing days, the sample is subjected to compression test.
  • the strain value at 10% deformation, evaluated following EN826 standart, is 95.1 kPa.
  • the thermal conductivity of the board measured according to norm ISO 8301 , is 0.0324 W/mK.
  • Example 1 illustrates the preparation of white EPS beads with a standard polystyrene grade by extrusion with the use of an underwater pelletizer.
  • a good control over the melt flow is critical in order to facilitate melt cutting and to obtain spherical beads of narrow size distribution.
  • increasing the temperature leads to irregular beads shape and broad size distribution. Therefore, the strategy envisaged is to find a way to lower the melt viscosity, which would allow an easy granulation without plugging issues or beads deformation.
  • Another classical way of reducing melt viscosity is to add some oil (see Comparative Examples 3 and 4). With 1 and 2wt% of oil, the MFI is successfully increased to 8.1 and 8.9 g/10min respectively, which greatly facilitates underwater peptization. However, the oil added decreases the foam mechanical resistance (103.8 and 99 kPa respectively).
  • polyisobutene addition can increase the melt flow index of the PS while not negatively impacting the final foam mechanical resistance.
  • the addition of 0.5 and 1wt% of PiB leads to Ml of 8.5 and 9 g/10min, respectively. This higher melt flow facilitates the underwater granulation step (no plugging observed).
  • the mechanical resistance of the boards prepared is similar than boards of Example 1 , where no plasticizer is added (1 17.3 and 1 12.2 kPa, respectively). Polyisobutene addition thus helps the granulation process without negatively impacting the final foam mechanical properties.
  • Example 5 The same experiment has been performed with the addition of a filler able to decrease the foam thermal conductivity, namely carbon black, for insulation purpose.
  • a satisfactory MFI is obtained with the addition of 1 % of PiB and 3% of carbon black (9.3 g/10min).
  • the compression resistance of the boards prepared is not affected by these additives (1 16 kPa) and the thermal conductivity of the boards is lowered (0.0318 W/mK compared to 0.035 W/mK without carbon black, see Example 1 ).
  • Comparative Example 5 shows that mechanical resistance of foams containing 1 % of oil and 3% of carbon black is detrimentally affected (95.1 kPa), while the thermal conductivity remains acceptable (0.0324 W/mK).

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Abstract

L'objet de la présente invention est un polymère aromatique de vinyle expansible qui comprend : a) une matrice de polymère aromatique de vinyle, b) de 1 à 10 % en poids, calculés par rapport au polymère (a), d'un agent d'expansion incorporé dans la matrice polymère, c) de 0,1 à 5 % en poids, calculés par rapport au polymère (a), de PiB (polyisobutène), distribué de manière homogène dans la matrice polymère, d) de 0 à 20 % en poids, calculés par rapport au polymère (a), d'une ou de plusieurs charges, autres que PiB, distribuées de manière homogène dans la matrice polymère. La proportion de PiB est ajustée pour porter l'indice de fluidité à chaud (MFI) d'un indice initial à un indice final de telle façon que la résistance à la compression à 10 % de la mousse obtenue avec ledit polymère aromatique de vinyle expansible à l'indice final soit sensiblement égale ou supérieure à celle de la mousse obtenue avec ledit polymère aromatique de vinyle expansible à l'indice initial. Le polymère aromatique de vinyle expansible selon l'invention est produit sous la forme de billes ou de granulés. Dans un mode de réalisation, le polymère aromatique de vinyle expansible comprend du noir de carbone en une proportion suffisante pour que le matériau expansé obtenu à partir du polymère aromatique de vinyle expansible ait une conductivité thermique λ d'environ 34 mW/m°K ou moins.
PCT/EP2011/068165 2010-10-18 2011-10-18 Polymères aromatiques de vinyle expansibles Ceased WO2012052423A1 (fr)

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US13/879,831 US20130320253A1 (en) 2010-10-18 2011-10-18 Expandable vinyl aromatic polymers
BR112013008987A BR112013008987A2 (pt) 2010-10-18 2011-10-18 polímeros aromáticos de vinil expansíveis
EA201370095A EA022941B1 (ru) 2010-10-18 2011-10-18 Способ увеличения индекса текучести расплава вспениваемого винилароматического полимера
EP11775933.2A EP2630186A1 (fr) 2010-10-18 2011-10-18 Polymères aromatiques de vinyle expansibles
CN201180060937.2A CN103261298B (zh) 2010-10-18 2011-10-18 能膨胀的乙烯基芳族聚合物

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014118643A2 (fr) 2013-02-04 2014-08-07 Vascular Biogenics Ltd. Procédés visant à induire une réactivité à un agent anti-angiogénique
EP3441089A1 (fr) 2012-10-17 2019-02-13 Vascular Biogenics Ltd. Procédés de traitement utilisant un adénovirus
WO2019077593A1 (fr) 2017-10-20 2019-04-25 Vascular Biogenics Ltd. Méthodes diagnostiques pour traitement par agent anti-angiogénique
US10639829B2 (en) 2015-01-14 2020-05-05 Synthos S.A. Process for the production of expandable vinyl aromatic polymer granulate having decreased thermal conductivity
WO2020183424A1 (fr) 2019-03-13 2020-09-17 Vascular Biogenics Ltd. Procédés de thérapie antitumorale
WO2020208612A1 (fr) 2019-04-12 2020-10-15 Vascular Biogenics Ltd. Méthodes de thérapie antitumorale
US10808093B2 (en) 2015-01-14 2020-10-20 Synthos S.A. Combination of silica and graphite and its use for decreasing the thermal conductivity of vinyl aromatic polymer foam
US10961154B2 (en) 2015-01-14 2021-03-30 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
US11859066B2 (en) 2015-01-14 2024-01-02 Synthos S.A. Use of a mineral having perovskite structure in vinyl aromatic polymer foam

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957930A (en) 1956-08-27 1960-10-25 Cosden Petroleum Corp Process for the production of polyisobutylene
US3073876A (en) 1960-12-29 1963-01-15 California Research Corp Process for the manufacture of polybutenes
US3242158A (en) 1961-06-15 1966-03-22 Texaco Inc Method for preparing polyisobutylene
US3356661A (en) 1966-11-28 1967-12-05 Lubrizol Corp Process of polymerizing isobutene in presence of titanium tetrahalide and a trihaloacetic acid
US3375295A (en) 1964-08-31 1968-03-26 Cosden Oil & Chem Co Bodying polymer liquid
DE1282938B (de) * 1963-08-17 1968-11-14 Basf Ag Flammwidrige verschaeumbare Formmassen aus Styrolpolymerisaten
US3501551A (en) 1969-03-19 1970-03-17 Standard Oil Co Process for producing normal butene polymers
DE2019945A1 (de) 1970-04-24 1971-11-04 Basf Ag Formmassen zur Herstellung von Schaumstoff-Formkoerpern aus Styrolpolymerisaten
US3658946A (en) 1968-05-11 1972-04-25 Basf Ag Production of rubber-modified vinylaromatic polymers
US3660535A (en) 1970-09-23 1972-05-02 Dow Chemical Co Process for the production of alkenyl aromatic polymers containing a reinforcing polymer therein
US3660321A (en) * 1968-09-30 1972-05-02 Hans Eberhard Praetzel Shaped articles comprising self-extinguishing compositions of plastics and microcapsules containing flame-abating compounds and process for producing the same
US3929686A (en) 1973-08-31 1975-12-30 Cosden Oil & Chem Co Polyisobutylene nucleating agents for expandable styrene polymer compositions
DE2621448A1 (de) * 1976-05-14 1977-12-01 Basf Ag Verfahren zur herstellung kugelfoermiger, expandierbarer polymermischungen auf basis polystyrol
EP0126459A2 (fr) 1983-05-19 1984-11-28 Montedison S.p.A. Procédé pour la fabrication de granulés expansibles en polymères thermoplastiques et dispositif
EP0397001A1 (fr) * 1989-05-12 1990-11-14 BASF Aktiengesellschaft Polymère styrénique expansible
US5540813A (en) 1994-01-19 1996-07-30 Fina Technology, Inc. Method for reducing volatiles in polymerized styrene
EP0770632B1 (fr) 1995-10-25 2002-10-02 Fina Technology, Inc. Polymère monovinylaromatique à la fissuration sous contrainte améliorée
US6706827B1 (en) 1998-06-08 2004-03-16 Samsung Atofina Co. Ltd. Metallocene catalysts for olefin or styrene polymerization and polymerization method using the metallocene catalysts
US6783710B1 (en) 1994-02-21 2004-08-31 Sulzer Chemtech Ag Method for the production of expandable plastics granulate
US20050156344A1 (en) 2002-06-14 2005-07-21 Franz-Josef Dietzen Method for producing expandable polystyrene
WO2005123816A1 (fr) * 2004-06-16 2005-12-29 Basf Aktiengesellschaft Mousses particulaires a base de polymeres styreniques, a conductivite thermique reduite
WO2006081295A2 (fr) 2005-01-26 2006-08-03 Fina Technology, Inc. Ionomeres ramifies
US20060211780A1 (en) 2005-03-17 2006-09-21 Claude Passaplan Method and apparatus for the continuous manufacture of expandable plastic granulate
WO2008141766A1 (fr) 2007-05-18 2008-11-27 Polimeri Europa S.P.A. Procédé de préparation de granulés à base de polymères thermoplastiques expansibles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19629791A1 (de) * 1996-07-24 1998-01-29 Basf Ag Expandierbare Styrolpolymerisate
US6428297B1 (en) * 1998-10-28 2002-08-06 Dart Container Corporation Apparatus for making a corrugation-free foam
DE102004058586A1 (de) * 2004-12-03 2006-06-14 Basf Ag Halogenfrei flammgeschützte, expandierbare Styrolpolymerisate
BRPI1007842A2 (pt) * 2009-03-05 2016-10-25 Basf Se processo para produzir materiais de espuma em partículas por sinterização de uma mistura contendo partículas de espuma, e, material de espuma em partículas.
EP2484717B1 (fr) * 2009-09-30 2014-12-31 Kuraray Co., Ltd. Bouchon de récipient comprenant un article produit par moulage de mousse

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957930A (en) 1956-08-27 1960-10-25 Cosden Petroleum Corp Process for the production of polyisobutylene
US3073876A (en) 1960-12-29 1963-01-15 California Research Corp Process for the manufacture of polybutenes
US3242158A (en) 1961-06-15 1966-03-22 Texaco Inc Method for preparing polyisobutylene
DE1282938B (de) * 1963-08-17 1968-11-14 Basf Ag Flammwidrige verschaeumbare Formmassen aus Styrolpolymerisaten
US3375295A (en) 1964-08-31 1968-03-26 Cosden Oil & Chem Co Bodying polymer liquid
US3356661A (en) 1966-11-28 1967-12-05 Lubrizol Corp Process of polymerizing isobutene in presence of titanium tetrahalide and a trihaloacetic acid
US3658946A (en) 1968-05-11 1972-04-25 Basf Ag Production of rubber-modified vinylaromatic polymers
US3660321A (en) * 1968-09-30 1972-05-02 Hans Eberhard Praetzel Shaped articles comprising self-extinguishing compositions of plastics and microcapsules containing flame-abating compounds and process for producing the same
US3501551A (en) 1969-03-19 1970-03-17 Standard Oil Co Process for producing normal butene polymers
DE2019945A1 (de) 1970-04-24 1971-11-04 Basf Ag Formmassen zur Herstellung von Schaumstoff-Formkoerpern aus Styrolpolymerisaten
US3660535A (en) 1970-09-23 1972-05-02 Dow Chemical Co Process for the production of alkenyl aromatic polymers containing a reinforcing polymer therein
US3929686A (en) 1973-08-31 1975-12-30 Cosden Oil & Chem Co Polyisobutylene nucleating agents for expandable styrene polymer compositions
DE2621448A1 (de) * 1976-05-14 1977-12-01 Basf Ag Verfahren zur herstellung kugelfoermiger, expandierbarer polymermischungen auf basis polystyrol
EP0126459A2 (fr) 1983-05-19 1984-11-28 Montedison S.p.A. Procédé pour la fabrication de granulés expansibles en polymères thermoplastiques et dispositif
EP0397001A1 (fr) * 1989-05-12 1990-11-14 BASF Aktiengesellschaft Polymère styrénique expansible
US5540813A (en) 1994-01-19 1996-07-30 Fina Technology, Inc. Method for reducing volatiles in polymerized styrene
US6783710B1 (en) 1994-02-21 2004-08-31 Sulzer Chemtech Ag Method for the production of expandable plastics granulate
EP0770632B1 (fr) 1995-10-25 2002-10-02 Fina Technology, Inc. Polymère monovinylaromatique à la fissuration sous contrainte améliorée
US6706827B1 (en) 1998-06-08 2004-03-16 Samsung Atofina Co. Ltd. Metallocene catalysts for olefin or styrene polymerization and polymerization method using the metallocene catalysts
US20050156344A1 (en) 2002-06-14 2005-07-21 Franz-Josef Dietzen Method for producing expandable polystyrene
WO2005123816A1 (fr) * 2004-06-16 2005-12-29 Basf Aktiengesellschaft Mousses particulaires a base de polymeres styreniques, a conductivite thermique reduite
WO2006081295A2 (fr) 2005-01-26 2006-08-03 Fina Technology, Inc. Ionomeres ramifies
US20060211780A1 (en) 2005-03-17 2006-09-21 Claude Passaplan Method and apparatus for the continuous manufacture of expandable plastic granulate
WO2008141766A1 (fr) 2007-05-18 2008-11-27 Polimeri Europa S.P.A. Procédé de préparation de granulés à base de polymères thermoplastiques expansibles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY", vol. A26, 1995, pages: 655 - 659

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EP3441089A1 (fr) 2012-10-17 2019-02-13 Vascular Biogenics Ltd. Procédés de traitement utilisant un adénovirus
WO2014118643A2 (fr) 2013-02-04 2014-08-07 Vascular Biogenics Ltd. Procédés visant à induire une réactivité à un agent anti-angiogénique
US10808093B2 (en) 2015-01-14 2020-10-20 Synthos S.A. Combination of silica and graphite and its use for decreasing the thermal conductivity of vinyl aromatic polymer foam
US10639829B2 (en) 2015-01-14 2020-05-05 Synthos S.A. Process for the production of expandable vinyl aromatic polymer granulate having decreased thermal conductivity
US10961154B2 (en) 2015-01-14 2021-03-30 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
US11267170B2 (en) 2015-01-14 2022-03-08 Synthos S.A. Process for the production of expandable vinyl aromatic polymer granulate having decreased thermal conductivity
US11447614B2 (en) 2015-01-14 2022-09-20 Synthos S.A. Combination of silica and graphite and its use for decreasing the thermal conductivity of vinyl aromatic polymer foam
US11708306B2 (en) 2015-01-14 2023-07-25 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
US11859066B2 (en) 2015-01-14 2024-01-02 Synthos S.A. Use of a mineral having perovskite structure in vinyl aromatic polymer foam
US12195397B2 (en) 2015-01-14 2025-01-14 Synthos S.A. Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same
WO2019077593A1 (fr) 2017-10-20 2019-04-25 Vascular Biogenics Ltd. Méthodes diagnostiques pour traitement par agent anti-angiogénique
WO2020183424A1 (fr) 2019-03-13 2020-09-17 Vascular Biogenics Ltd. Procédés de thérapie antitumorale
WO2020208612A1 (fr) 2019-04-12 2020-10-15 Vascular Biogenics Ltd. Méthodes de thérapie antitumorale

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