Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—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
  • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
  • C08J9/008—Nanoparticles
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—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
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—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
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene
  • C08J2325/06—Polystyrene
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/02—Polyalkylene oxides
• • 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
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08J2371/12—Polyphenylene oxides
• • 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
  • C08J2425/00—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
  • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

• a particulate, expandable polymer a method for the production thereof and applications thereof.
• the present invention relates to a particulate, expandable polymer that can be processed into a flame-retardant foam with a fine cellular structure and a low density, which contains a carbon-based material that increases the thermal insulation value to improve the thermal insulation value thereof.
• the present invention also relates to a method for producing a particulate, expandable polymer, and to a foam material obtained with it.
• a composition for producing a thermoplastic polymer foam comprising a foamable polymer material, 1 , 1 ,2,2-tetrafluoroethane as the only desired blowing agent and nanographite in concentrations ranging between 80 and 99%, 3.0 and 12% and 0.05 and 5.0%, respectively, said percentages being based on dry weight.
• the employed nanographite is to be regarded as a multilayer nanographite, at least one dimension of which has a thickness of less than 100 nm and is preferably contained in a carrier, viz. a polyethylene methyl acrylate copolymer.
• the addition of the nanographite is claimed to improve the thermal, mechanical and flame-retardant properties of the ultimate foamed product.
• US 2002/01 17769 relates to foamed cellular polymer particles to which additives, such as carbon black, titanium dioxide, aluminum and graphite, can be added to lower the thermal conductivity.
• additives such as carbon black, titanium dioxide, aluminum and graphite
• US 2012/0123007 relates to a styrene polymer composition to which a brominated flame retardant has been added.
• EPS expandable polystyrene
• the relevant active carbon has a particle size of ⁇ 12 micrometres.
• a foam obtained with such a material increasing the thermal insulation value meets the fire resistance requirements according to the B2 test, viz. DI N 4102, part 2.
• EPS expandable polystyrene
• a method for increasing the thermal insulation of EPS is also known per se from International patent application WO 00/43442, in which styrene polymer is melted in an extruder and is mixed with at least a blowing agent and aluminium particles, which are predominantly in the form of plates, and are jointly extruded, the employed concentration of aluminium particles being at most 6 wt.%, after which the extrudate is cooled and reduced to particles.
• Such polymers contain at least aluminium in the form of particles to improve their thermal-insulation properties, the aluminium particles being homogeneously distributed and incorporated as a material reflecting infrared radiation.
• the aluminium particles have a plate-like shape of a size varying from 1 to 15 pm.
• the raw material that is used to produce expandable polystyrene (EPS) can be obtained not only via the extrusion process known from the aforementioned international patent application, but also via suspension polymerisation.
• the EPS granulate thus obtained is generally used as a raw material in the packaging industry and in construction.
• the method for further processing comprises prefoaming, in which an amount of steam is passed through a layer of EPS granules in an expansion vessel, causing the blowing agent contained in the EPS granules, usually pentane, to evaporate and the foaming of the granules to take place.
• the granule thus prefoamed is introduced into a mould in which the granules are further expanded under the influence of steam.
• the employed mould has small openings allowing the blowing agent still present during the expansion to escape while the granules fuse into the desired shape.
• the size of this shape is in principle not limited, with it being possible to obtain both blocks for the building industry and packaging material for the food and non-food industries.
• the aforementioned method differs substantially from the method known from WO20081 19059, which relates to a continuously foamed foam in a single-step process in a continuous extruder.
• a flame retardant is often added to the production of a foam. Such foam materials are further processed into products and objects whose fire or flame retardancy must meet a requirement stipulated by the national authorities. It is assumed that such flame retardants have an unacceptable chemical impact on humans and the environment. Because of this, certain flame retardants are being phased out.
• One object of the present invention is to prove a particulate, expandable polymer granule with which, after further processing, a flame-retardant foam is obtained that has a practically desired, sufficiently low thermal conductivity coefficient to make it suitable for use for the intended thermal insulation properties.
• Another aspect of the present invention is the provision of a method for producing expandable polymer granules in which styrene polymers can, in the presence of one or more additional components, be converted into a material that has an increased thermal insulation value after foaming and moulding.
• Another aspect of the present invention is the provision of a method for producing expandable polymer granules in which use is made of a flame retardant showing little biotoxicity, which is safe for humans and animals and meets the safety requirements prevailing in the building industry.
• the invention as referred to in the preamble is characterised in that the polymer particles contain carbon with a particle size of ⁇ 1 ⁇ m as the material increasing the thermal insulation value and a brominated SBS (styrene-butadiene- styrene) as the flame retardant.
• SBS styrene-butadiene- styrene
• One or more aspects of the present invention is/are met by using such a type of carbon as the material increasing the thermal insulation value.
• the aforementioned flame retardant may moreover be regarded as a means for meeting the safety requirements prevailing in the building industry and also has little impact on humans and the environment.
• a preferred value of 0.1 ⁇ m is specified as a lower limit for the particle size.
• the present invention excludes in particular the use of carbon black as the source of carbon.
• the particle size D50 is particularly desirable for the particle size D50 to be at most 1 ⁇ , more specifically the particle size D 50 to be at most 0.8 ⁇ m.
• the D 90 value and D 50 value are understood to be the 90 th and 50 th percentile, respectively, being the particle sizes below which fall 90% and 50% of the population, respectively.
• the D10 the size below which falls 10% of the population
• D50 the size below which falls half of the population
• D90 the size below which falls 90% of the population
• the D10 can be easily inferred from a cumulative distribution curve obtained by Malvern Instruments using the products Mastersizer and Lazersizer, and these three values (D10, D50 and D90) can be used to characterise the particle size distribution in powder.
• the (D90- D10)/D50 ratio also referred to as particle size distribution
• the 10 th percentile is the particle size for which 10% of the particles are smaller than or equal to this value, and therefore 90% of the particles are larger than said value.
• the 50 th percentile is the particle size for which 50% of the particles are smaller than or equal to this value, and therefore 50% of the particles are larger than said value.
• the D50 is preferably at most 1 .0 ⁇ m, in particular at most 0.8 ⁇ m.
• the 90 th percentile is the particle size for which 90% of the particles are smaller than or equal to this value, and therefore 10% of the particles are larger than said value.
• a block copolymer of polystyrene and brominated polybutadiene it is preferable for a block copolymer of polystyrene and brominated polybutadiene to be used as the brominated SBS (styrene-butadiene-styrene) in the present particulate, expandable polymer.
• the weight percent of bromine preferably ranges between 60 and 70 wt.%, based on the brominated SBS (styrene-butadiene-styrene).
• the molecular weight of the brominated SBS (styrene-butadiene-styrene) preferably ranges between 60,000 and 150,000.
• the amount of brominated SBS styrene-butadiene-styrene preferably ranges between 0.7 and 2.2 wt. %, based on the total weight of the particulate, expandable polymer.
• the amount of hexabromocyclododecane (H BCD) is less than 1 .0 wt.%, in particular less than 0.6 wt.%, more specifically less than 0.2 wt.%, and preferably less than 0.05 wt.%, calculated on the basis of the total weight of the particulate, expandable polymer.
• the polymer used in the present invention is selected from the group comprising polystyrene, expanded polypropylene (EPP), expanded cellular polyethylene (EPE), polyphenylene oxide (PPO), polypropylene oxide and polylactic acid, or a combination thereof.
• Polylactic acid is a collective noun for polymers based on lactic acid monomers, with it being possible for the structure of the polylactic acid to vary from completely amorphous to semi-crystalline or crystalline, depending on its composition.
• Polylactic acid can be produced for example from milk products, starch, flour and maize.
• Lactic acid is the monomer of which polylactic acid is composed, and this monomer occurs in two stereoisomers, viz. L-lactic acid and D- lactic acid.
• Polylactic acid therefore contains a certain proportion of L-lactic acid monomers and a certain proportion of D-lactic acid monomers. The ratio of the L- and D-lactic acid monomers in polylactic acid determines its properties.
• D-value and "D-content” (percentage of D-lactic acid-monomers) are also used.
• the polylactic acid that is currently commercially available has an L: D ratio of between 100:0 and 75:25; in other words, a D-content of between 0 and 25%, or between 0 and 0.25.
• PLA granulate is foamed at a pressure of for example 20 bar. Then the PLA is once again as a foam impregnated with for example 6 % CO 2 and shaped in a mould at a steam pressure of between 0.2 and 0.5 bar. This way the moulded part is obtained in the same way as discussed for EPS granules above.
• PLA granules are produced using a die plate in an extrusion device. Solid PLA is to this end introduced into an extrusion device and melted.
• liquid PLA is supplied directly to the extrusion device in an in-line polymerisation process, so without having to be melted first.
• a twin-screw extruder is used as the extrusion device.
• the polylactic acid or the mixture of polylactic acid and optionally one or more other biodegradable polymers with optionally one or more chain extenders, nucleating agents and lubricants can be processed into particles.
• Such particulate polylactic acid is also described in PCT/N L2008/000109 of the present inventors.
• blowing agent is added by impregnating the PLA granules to obtain expandable PLA (EPLA).
• blowing agents that may be used are CO 2 , MTBE, nitrogen, air, (iso)pentane, propane, butane and the like or one or more combinations thereof.
• the first way is for the polylactic acid to be shaped into particles, for example by means of extrusion, which particles are subsequently made expandable through impregnation with a blowing agent.
• the second way is for the polylactic acid to be mixed with a blowing agent, which is subsequently directly shaped into expandable particles, for example by means of extrusion.
• graphene or exfoliated graphite which former material is to be conceived as a single-atom-thick flat layer of sp2-bound carbon atoms, which carbon atoms are arranged in a honeycomb-like flat crystal grid, can be used to obtain a certain thermal insulation value in a smaller amount than the usual state-of-the-art materials for increasing the thermal insulation value, in particular in comparison with other carbon sources, such as graphite or active carbon.
• Supplementary experiments have shown that the material here referred to as "graphene” may also be regarded as exfoliated graphite with a particle size of 0.1-0.8 ⁇ m.
• exfoliated graphite with an aspect ratio of ⁇ 10: 1 , more specifically ⁇ 100: 1 .
• Such a layered structure has an especially good influence on increasing the thermal insulation value.
• the amount of carbon is 1 -15 wt.%, based on polymer, preferably 2-8 wt.%, based on polymer.
• one or more other agents for increasing the thermal insulation value to be additionally present in the particulate expandable polymer, selected from the group comprising graphite, carbon black, aluminium powder, AI(OH) 3 , Mg(OH) 2 and Al 2 O 3 , iron, zinc, copper and alloys thereof.
• hexabromocyclododecane was used as a fire retardant to obtain a good fire-retardant effect.
• the present invention focuses in particular on the use of a replacement for HBCD that results in an end product that is comparable with a polymer product containing HBCD, in particular in terms of fire requirements.
• the object of the present invention is to minimise the amount of HBCD, more specifically to reduce the amount of HBCD to zero.
• fire retardants selected from the group comprising dicumyl peroxide, brominated polymer compounds, in particular polystyrene compounds, and 2,3-dimethyl-2,3-diphenylbutane, in an amount of between 1 .0 and 8 wt.%, based on the amount of polymer. It is also possible to add as an auxiliary a phosphorus compound selected from the group comprising polyphosphonates, diphenylphosphonate, bisphenol A-bis(diphenyl phosphate) and resorcinol aromatic polyphosphate compounds, or a combination thereof.
• the exfoliated graphite referred to in the present application can be obtained by subjecting a carbon source to mechanical shearing forces, in particular by subjecting graphite to such a treatment.
• a carbon source to mechanical shearing forces
• graphite to such a treatment.
• An example of such a treatment is the extrusion process in which graphite is in the extruder subjected to substantial shearing forces causing the graphite to be converted into flat carbon plates, in particular exfoliated graphite.
• the present inventors assume of the aforementioned flat carbon plates that such plates are responsible for reflection through a mirror effect of the thermal radiation. This makes it desirable for the employed carbon to have a somewhat flat dimension or a geometric shape to realise the intended mirror effect.
• the carbon source may be dosed as a masterbatch or directly as a powdery material, which powdery material has been pretreated to obtain the desired particle size as specified in the claims.
• the present invention also relates to a method for producing a particulate, expandable polymer in which polymer is supplied to an extruder and is mixed with at least a blowing agent, brominated SBS (styrene-butadiene-styrene), a carbon source and one or more other auxiliaries as referred to in the enclosed subclaims, and is subsequently extruded, cooled and further reduced to particles.
• a blowing agent brominated SBS (styrene-butadiene-styrene)
• carbon source styrene-butadiene-styrene
• auxiliaries as referred to in the enclosed subclaims
• the present invention further relates to a method for producing a particulate, expandable polymer in which a monomer, brominated SBS (styrene-butadiene-styrene), a blowing agent, an agent for increasing the thermal insulation value and one or more other auxiliaries as referred to in the enclosed subclaims are subjected to a polymerisation reaction in a reactor.
• a monomer, brominated SBS (styrene-butadiene-styrene), a blowing agent, an agent for increasing the thermal insulation value and one or more other auxiliaries as referred to in the enclosed subclaims are subjected to a polymerisation reaction in a reactor.
• EPS styrene-butadiene-styrene
• a preferable blowing agent is (iso)pentane. It is desirable to exclude hydrocarbon compounds containing fluorine as a blowing agent.
• a particulate expandable polymer in which the amount of hydrocarbon compounds containing fluorine is minimised, preferably less than 2.0 wt.%, in particular less than 1 .0 wt.%, more specifically less than 0.5 wt.%, based on the amount of particulate expandable polymer.
• the foamed product ultimately obtained is essentially free of hydrocarbon compounds containing fluorine.
• the present invention further relates to a polymer foam material based on a particulate, expandable polymer as described above, the polymer foam material preferably being used for thermal insulation purposes, for example in the building industry, but also as packaging material in the food and non-food industries.
• Figure 1 shows the measurement results of various carbon sources.
• Figure 2 is a graphical representation of the density vs the lambda value of various EPS materials.
• the D50 value is at most 1 ⁇ m, more specifically at most 0.8 ⁇ m.
• FR122P (commercially introduced by ICI) as a flame retardant
• XP-7720 FR122P (commercially introduced by Albemarle) as a flame retardant.
• the extruder's temperature is preferably between 150°C and 230°C; in this embodiment 0.8% extra pentane was also added as a blowing agent.
• the mixture was fed to a cooling extruder with temperatures between 60°C and 150°C, with which a grey XPS plate was produced.
• the obtained foam had a density of 35 kg/m3.
• the foam's insulation value was found to be 31 .1 mW/mK in the case of the master batch and 30.9 mw/mK in the case of the concentrate, and both products passed the flammability test DI N4102 B2.
• the enclosed figure 2 is a graphic representation of a number of measurements, with the horizontal axis representing the density and the vertical axis the lambda (W/mK). From this representation it can be clearly inferred that a higher lambda value is obtained for the commercially available Neopor, containing 4 wt.% graphite (predominantly with a particle size of > 1 ⁇ m, in particular 1-50 ⁇ m), at the same density as for EPS to which exfoliated graphite (particle size between 0.1 and 0.8 ⁇ m) has been added in a certain weight percentage.
• Zetasizer GMA is a so-called Dynamic Light Scattering instrument with the following specifications: Correlator: ALV5000/60X0 External Goniometer Correlator: ALV-125 Detector: ALV / SO SIPD Single Photon Detector with Static and Dynamic Enhancer ALV Laser Fiber optics: Cobolt Samba 300 DPSS Laser, Wavelength: 532 nm, 300 mW Power Temperature Control: Static Thermal Bath: Haake F8-C35. No special standards were used; the instrument measures the Brownian motion of the particles and the measured values are converted into particle sizes via the Einstein-Stokes equation under the assumptions that the solvent is water and that the particles are approximately spherical. The radius was measured.

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