WO2012089574A1 - Plaque de mousse à base de mélanges polymère de styrol - polyoléfine - Google Patents

Plaque de mousse à base de mélanges polymère de styrol - polyoléfine Download PDF

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Publication number
WO2012089574A1
WO2012089574A1 PCT/EP2011/073519 EP2011073519W WO2012089574A1 WO 2012089574 A1 WO2012089574 A1 WO 2012089574A1 EP 2011073519 W EP2011073519 W EP 2011073519W WO 2012089574 A1 WO2012089574 A1 WO 2012089574A1
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Prior art keywords
weight
foam sheet
polymer
component
range
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PCT/EP2011/073519
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German (de)
English (en)
Inventor
Holger RUCKDÄSCHEL
Jens Assmann
Carsten Schips
Klaus Hahn
Georg GRÄSSEL
Jürgen Lambert
Christof Zylla
Peter Merkel
Geert Janssens
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Basf Se
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Publication of WO2012089574A1 publication Critical patent/WO2012089574A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • 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
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • 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
    • 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
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Definitions

  • Foam board based on styrene polymer-polyolefin blends Description
  • the invention relates to a thermoplastic extrusion foam board based on styrene polymers, polyolefins and solubilizers, a process for their preparation and the use of the plate, for example as insulating material in the construction industry.
  • Particle foams based on polyolefin / styrene polymer mixtures are known, for example, from WO-A 2008/125250.
  • the production of particle and extrusion foams has significant process-related differences.
  • the prefoaming process is typically in the range of minutes.
  • the prefoamed granules are conditioned and finally welded in a mold by the re-entry of energy (usually water vapor) to form parts or blocks.
  • the pattern formation of multiphase systems always begins at low temperatures, which in the specific case are below the melting point of the polyolefins.
  • the material is first completely melted or plasticized and impregnated with blowing agents at elevated pressures. After a possible cooling of the melt, the foaming is usually carried out by a rapid reduction in pressure (for example, by exit of the loaded melt from a nozzle into the surrounding atmosphere). The foaming and adjustment of the morphology takes place within fractions of seconds to seconds.
  • the structure formation of multiphase systems also begins at temperatures that are in particular cases above the melting point of the polyolefins.
  • US Pat. No. 5,225,451 describes an extrusion foam of polyethylene as a continuous phase, a styrene-butadiene rubber and 1 to 15% by weight of polystyrene.
  • Japanese Patent Publication JP-A 2008-173923, JP-A 2000-204185, JP-A 2004-238413, JP-A 2003-183438, JP-A 2000-212356 disclose extruded foam films based on polystyrene / polyethylene blends Addition of a solubilizer described.
  • JP-A 2008-274072 discloses an extrusion foam sheet of polystyrene, polyethylene, polypropylene and a styrene rubber system containing block copolymers having polystyrene blocks at both ends and a polybutadiene or polyisoprene block therebetween.
  • the blowing agents used are preferably chemical blowing agents.
  • the object was therefore to develop further extruded foam boards with an improved property profile, in particular with regard to the properties mentioned.
  • the invention therefore relates to a thermoplastic extrusion foam sheet having a thickness in the range of 15 mm to 200 mm and cells having a mean cell size in the range of 20 to 2000 ⁇ , characterized in that the cell membranes have a fibrous structure with fiber diameters below 1500 nm , loading
  • the foam is formed from a polymer matrix which contains at least two incompatible thermoplastic polymers and at least one polymeric compatibilizer and which forms a continuous and a disperse phase, the continuous phase preferably containing one or more styrene polymers and the disperse phase containing at least two polyolefins, preferably in each case consists of these.
  • the foam is formed from
  • the invention further provides a process for producing the extrusion foam sheet according to the invention, comprising: a) heating a mixture of at least two incompatible thermoplastic polymers and one or more polymeric compatibilizers to form a polymer melt having a continuous and a disperse phase, b) the polymer melt with 1 to 12 parts by weight (based on the polymer in the polymer melt (P), which has 100 mass fractions) of a physical blowing agent and c) the foamable polymer melt is foamed into a region of lower pressure to a foam sheet, preferably the temperature of the die lip the slot nozzle is 120 to 170 ° C, the temperature of the polymer melt in the range of 50 to 160 ° C and the pressure in front of the nozzle is greater than 50 bar.
  • the invention likewise relates to the use of the foam sheets according to the invention as insulating material, structural foam, core material for composite applications, material for energy absorption and / or as material for packaging applications.
  • the foam sheet according to the invention usually shows a progressive pressure behavior, a good damping behavior and a good ductility. It has good insulation properties, good solvent resistance and good heat resistance. It thus combines three important properties in one material and thus makes it possible to use this material universally in a wide variety of applications where the use of different materials specially adapted to the respective application was previously necessary.
  • the foam board according to the invention is accessible without the use of blowing agents that are problematic from an environmental point of view or with respect to the fire protection regulations.
  • the foam sheet according to the invention preferably has a cuboidal basic structure, the thickness being defined as the shortest edge (height).
  • the upper limit of the thickness is preferably 200 mm.
  • the lower limit for the thickness is preferably 15 mm, particularly preferably 20 mm, in particular 25 mm.
  • the foam board according to the invention preferably has cells of average cell size in the range from 20 to 1000 ⁇ m, in particular from 50 to 500 ⁇ m, the mean cell size being defined in accordance with ASTM D3576-04.
  • the cell walls have a fibrous structure, as exemplified in FIG.
  • the figure shows an electron micrograph (REM) of Schaumsteg with cell wall.
  • An ESB (energy-selective-backscattered-electron) detector was used (high voltage 1.00 kV).
  • Bright areas are polystyrene, dark areas PE soft phase with clearly recognizable fibril structure.
  • the mean fiber diameters are below 1500 nm, preferably in the range from 10 to 1000 nm, particularly preferably 10 to 500 nm, in particular 20 to 250 nm.
  • the length of the fibrous structure is at least 5 times the average diameter, preferably at least 10 times average diameter, more preferably at least 20 times the mean diameter.
  • the average fiber diameter is determined according to the invention by evaluation of microscopic images of the foam structure (scanning electron microscopy). At least three microscopic images of the cell walls are evaluated. The fibrous appearing structures are analyzed for diameter at least four different positions and the number average is formed.
  • the foam sheet according to the invention is preferably closed-cell, which means according to the invention that the cells, measured according to DIN ISO 4590, are closed to at least 80, in particular to 90 to 100%.
  • the density of the foam board according to the invention is preferably in the range from 20 to 150 g / l, more preferably from 25 to 120 g / l, in particular from 30 to 80 g / l.
  • the cell count is preferably 0.5 to 30 cells, in particular 1 to 20 cells per mm.
  • the extrusion foam of the invention is formed from a polymer matrix containing a continuous, styrene polymer-rich phase and a discontinuous polyolefin-rich phase.
  • Form from a polymer matrix means according to the invention that the polymer matrix is the structuring element.
  • the polymer matrix preferably contains (and consists in particular of)
  • the polymer matrix preferably contains from 55.0 to 89.9% by weight of one or more styrene polymers.
  • styrene polymer comprises polymers based on styrene and further comonomers, for example, alpha-methylstyrene, acrylonitrile, methyl methacrylate; the minimum styrene content of the styrenic polymer is 90% by weight.
  • styrene polymers preference is given to glassy polystyrene (GPPS), anionically polymerized polystyrene, styrene- ⁇ -methylstyrene copolymers, styrene-acrylonitrile copolymers (SAN), acrylonitrile-alpha-methylstyrene copolymers (AMSAN) or mixtures thereof with polyphenylene ether (PPE ) used.
  • GPPS glassy polystyrene
  • anionically polymerized polystyrene styrene- ⁇ -methylstyrene copolymers
  • SAN styrene-acrylonitrile copolymers
  • AMSAN acrylonitrile-alpha-methylstyrene copolymers
  • PPE polyphenylene ether
  • impact modified varieties can thereof, for example, high-impact polystyrene (HIPS), impact polystyrene (A-IPS), acrylonitrile-butadiene-styrene polymers (ABS), methyl acrylate-butadiene-styrene (MBS), acrylonitrile-styrene-acrylic ester (ASA), methyl methacrylate-acrylonitrile Butadiene-styrene (MABS) polymers or mixtures thereof with polyphenylene ether (PPE).
  • HIPS high-impact polystyrene
  • A-IPS impact polystyrene
  • ABS acrylonitrile-butadiene-styrene polymers
  • MVS methyl acrylate-butadiene-styrene
  • ASA acrylonitrile-styrene-acrylic ester
  • MABS methyl methacrylate-acrylonitrile Butadiene-styrene
  • thermoplastic polymers in particular styrene polymers and expandable styrene polymers (EPS), in amounts which do not substantially impair their properties, as a rule in amounts of not more than 50% by weight, in particular in amounts of from 1 to 20% by weight .-% (based on the component A).
  • EPS expandable styrene polymers
  • polystyrene Preference is given to polystyrene.
  • Standard polystyrene types are particularly preferred having weight average molecular weights ranging from 120,000 to 300,000 g / mol and a melt volume rate MVR (200 ° C / 5 kg) according to ISO 1 13 in the range of 1 to 10 cm 3/10 min. for example PS 158 K, 168 N or 148 G of Styrolution GmbH.
  • the polymer matrix generally contains a polyolefin component B consisting of one or more thermoplastic polyolefins which are incompatible with component A.
  • the polyolefin component B is made
  • the polymer B1) used is preferably a homo- or copolymer of ethene, in particular in combination with propene.
  • Homopolymers used are commercially available polyethylenes, such as PE-LD, PE-LLD, PE-HD.
  • Suitable copolymers include the following systems are suitable: copolymers of ethene and propene (for example Moplen ® RP220 and RP320 Moplen ® Basell), copolymers of ethene and vinyl acetate (EVA), copolymers of ethylene and acrylates (EA, such as Surlyn ® grades 1901 and 2601 (from DuPont) or copolymers of ethylene, butene and acrylates EBA, including Lucofin ® 1400 HN, 1400 HM from the Lucobit AG).
  • the melt volume index MVI (190 ° C / 2.6 kg) of the polyethylenes is usually in the range of 0.5 to 40 g / 10 min, the density in the range of 0.86 to 0.97 g / cm 3 , preferably in the range from 0.91 to 0.95 g / cm 3 .
  • mixtures with polyisobutylene (OIB) eg Oppanol B150 ® of BASF SE
  • the polymer B2) used is preferably a copolymer of ethene, for example ethene and octene (EOC, eg Engage® , Dow).
  • the proportion of component B1) in the polymer matrix is preferably 2 to 25% by weight, particularly preferably 5 to 20% by weight.
  • the proportion of component B2) is from 2 to 25 wt .-%, particularly preferably 5 to 20 wt .-%.
  • compatibilizers for targeted adjustment of the desired morphology usually at least two different compatibilizers (component C) in amounts of from 0.2 to 35 wt .-%, preferably 0.2 to 5 wt .-%, based on the polymer matrix used.
  • the compatibilizers lead to improved adhesion between the polyolefin-rich and the polystyrene-rich phase and improve the elasticity of the foam even in small quantities compared to conventional EPS foams.
  • the component C) preferably consists of
  • butadiene-, isoprene-, ethylene-, butylene- or propylene-containing styrene block copolymer means a polymer obtainable by polymerization of these monomers, the polymer then having the corresponding saturated or partially unsaturated structures.
  • Suitable components (C1) are, for example, unhydrogenated or partially hydrogenated styrene-butadiene or styrene-isoprene block copolymers.
  • the total styrene content is preferably in the range of 40 to 80 wt .-%, particularly preferably in the range of 50 to 70 wt .-% (based on C1).
  • Suitable styrene-butadiene block copolymers which consist of at least two polystyrene blocks S and at least one styrene-butadiene copolymer block S / B are, for example, star-branched block copolymers, as described in EP-A 0 654 488.
  • the block copolymers used are characterized in that they have at least one hard block having a glass transition temperature of at least 80 ° C. and at least one soft block having a glass transition temperature of at most -20 ° C.
  • the glass transition temperatures of the different blocks are determined according to ASTM D 5026-01 at a frequency of 1 Hz as the maximum of the loss modulus.
  • block copolymers having at least two hard blocks Si and S 2 of vinylaromatic monomers having at least one intermediate random soft block B / S of vinylaromatic monomers and diene are suitable, the proportion of hard blocks being more than 40% by weight, based on the total block copolymer and the 1,2-vinyl content in soft block B / S is below 20%, as described in WO 00/58380.
  • compatibilizer (C1) are linear styrene-butadiene block copolymers of the general structure S (S / B) -S with one or more blocks which are located between the two S blocks and have a static styrene / butadiene distribution (S. / B) r on d om suitable.
  • Such block copolymers are obtainable by anionic polymerization in a nonpolar solvent with the addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 and WO 97/40079.
  • the vinyl content is understood to be the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages.
  • the 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
  • Preferred compatibilizers (C1) are styrene-butadiene-styrene (SBS) triblock copolymers having a butadiene content of from 20 to 60% by weight, preferably from 30 to 50% by weight, which may be hydrogenated or unhydrogenated.
  • SBS styrene-butadiene-styrene
  • These are for example under the name Styroflex ® 2G66, Styrolux ® 3G55, Styroclear ® GH62, Kraton ® D 1 101, Kraton ® G 1650, Kraton ® D 1 155, Tuftec ® H 1043 or Europren ® SOL 6414 commercially.
  • SBS styrene-butadiene-styrene
  • butadiene such as Kraton ® G types.
  • component (C2) is styrene-ethylene-butylene block copolymers, for example, linear triblock copolymers / butylene blocks are based on styrene and ethylene (SE / BS), as, under the designation Kraton ® G1654 from Kraton Polymers GmbH, Eschborn Germany are available. Also suitable are styrene-ethylene / propylene-styrene block copolymers (SEPS), as sold for example under the name Septon ® 2063 from Kuraray Co. Ltd., Tokyo, Japan.
  • SEPS styrene-ethylene / propylene-styrene block copolymers
  • components A) to C) of the polymer matrix are the following materials:
  • component A is polystyrene.
  • component B1 is polyethylene.
  • component B2 is an ethylene-octene copolymer.
  • component C1 is a styrene-butadiene block copolymer.
  • component C2 is a styrene-ethylene / butylene block copolymer.
  • the polymer matrix particularly preferably consists of the particularly preferred components.
  • the polymer matrix preferably contains the stated components in the following proportions: 75 to 95% by weight of component A);
  • the sum of components B1) and B2) is> 15% by weight, wherein the proportion of component B1) must be greater than the proportion of component B2).
  • the extruded foam sheet according to the invention contains, in addition to the polymer matrix, a blowing agent component (T).
  • the blowing agent component (T) comprises (and preferably consists of (b1) 100-15% by weight, preferably 85-15% by weight, particularly preferably 75-15% by weight, (based on (T)) C0 2 ,
  • C 4 -carbonyl compounds preferably C 2 -C 4 -carbonyl compounds, in particular C 3 -C 4 -ketones and formates, and
  • the blowing agent component (T) used is preferably mixtures of CO 2 and one or two co-blowing agents. Particularly preferred are binary mixtures.
  • Preferred alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol and tert-butanol. Particularly preferred is ethanol.
  • CrC 4 -Carbonyl compounds are ketones, aldehydes, carboxylic esters carboxylic acid amides having 1 to 4 carbon atoms.
  • Suitable ketones are acetone and methyl ethyl ketone, preferred formates are methyl formate, ethyl formate, n-propyl formate and i-propyl formate. Preference is given to acetone.
  • water b3) may be contained in the co-propellants b2) and in the carbon dioxide b1).
  • a blowing agent component T which has a water content b3) of not more than 10% by weight, preferably not more than 5% by weight, more preferably not more than 4% by weight and especially preferably not more than 2% by weight (in each case based on (T).
  • the blowing agent component is substantially anhydrous.
  • Particular preference is given to mixtures of carbon dioxide and ethanol, carbon dioxide and acetone, carbon dioxide and methyl formate, and also carbon dioxide and mixtures of ethanol and acetone in the abovementioned mixing ratios.
  • the blowing agent component T is added to the polymer melt in a proportion of a total of 1 to 12 parts by mass, preferably 1 to 8 and particularly preferably 1 to 5 parts by mass (in each case based on the polymer matrix P, which has 100 parts by mass).
  • a suitable composition of the blowing agent component T contains from 15 to 100% by weight of component b1) and from 0 to 85% by weight of component b2).
  • Propellant levels based on the polymer matrix are the initial levels achieved in the production of the extrusion foam panels. It is known to the person skilled in the art that these values decrease due to outdiffusion of the blowing agent from the finished foam board.
  • the polymer matrix P contains additives, ie auxiliaries and / or additives. Suitable auxiliaries and additives are known to the person skilled in the art.
  • At least one nucleating agent is added to the polymer matrix P.
  • nucleating agents finely divided, inorganic solids such as talc, metal oxides, silicates or polyethylene waxes in amounts of generally 0.1 to 10 parts by mass, preferably 0.1 to 3 parts by mass, particularly preferably 1 to 1.5 mass parts, based on 100 parts by mass P, be used.
  • the mean particle diameter of the nucleating agent is generally in the range from 0.01 to 100 ⁇ m, preferably from 1 to 60 ⁇ m.
  • a particularly preferred nucleating agent is talc, for example from Luzenac Pharma.
  • the nucleating agent may be added by methods known to those skilled in the art.
  • one or more additives such as nucleating agents, fillers (for example mineral fillers such as glass fibers), plasticizers, flame retardants, IR absorbers such as carbon black or graphite, aluminum powder and titanium dioxide, soluble and insoluble dyes and pigments may be added.
  • Preferred additives are graphite and carbon black.
  • graphite is added in amounts of generally 0.05 to 25 parts by mass, more preferably in amounts of 2 to 8 parts by mass, based on 100 parts by mass of P.
  • Suitable particle sizes for the graphite used are in the range of 1 to 50 ⁇ , preferably in the range of 2 to 10 ⁇ . Due to fire safety regulations in the construction industry and other industries, one or more flame retardants are preferably added.
  • Suitable flame retardants are, for example, bromine and / or phosphorus compounds such as tetrabromobisphenol A, brominated polystyrene oligomers, brominated styrene-butadiene copolymers, tetrabromobisphenol A diallyl ether, expandable graphite, red phosphorus, triphenyl phosphate and 9,10-dihydro-9-oxa-10. phosphaphenanthrene-10-oxide.
  • HBCD hexabromocyclododecane
  • industrial products which essentially contain the ⁇ , ⁇ and ⁇ isomers and preferably an addition of dicumyl (2,3-dimethyl-2,3-diphenylbutane) as synergists contain.
  • thermal insulation is the addition of graphite, carbon black, aluminum powder or an IR dye (e.g., indoaniline dyes, oxonol dyes or anthraquinone dyes).
  • an IR dye e.g., indoaniline dyes, oxonol dyes or anthraquinone dyes.
  • the dyes and pigments are added in amounts ranging from 0.01 to 30 parts by mass, preferably in the range from 1 to 5 parts by mass, based on 100 parts by mass (P).
  • a dispersing aid e.g. Organosilane, epoxy group-containing polymers or maleic anhydride-grafted styrenic polymers to use.
  • the total amount of additives is generally 0 to 30 parts by mass, preferably 0 to 20 parts by mass, based on the polymers (P), which have 100 parts by mass.
  • the total amount of additives is 0.5 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on the polymers (P), which have 100 parts by mass.
  • the foam sheet according to the invention contains no additives.
  • extrusion foam sheet according to the invention is obtainable by
  • a polymer component P which is formed from a mixture of at least two incompatible thermoplastic polymers and one or more polymeric compatibilizers, preferably a mixture of one or more styrene polymers, one or more polyolefins and one or more polymeric compatibilizers, more preferably A) from 45 to 97.8% by weight of one or more styrene polymers,
  • step (a) of the process the polymer component P is heated to obtain a polymer melt.
  • the formation of a polymer melt is understood to mean a plasticization of the polymer component P in a broader sense, i. the conversion of the solid components of the polymer component P into a deformable or flowable state.
  • the polymer component P is heated to a temperature above the melting or glass transition temperature. Suitable temperatures are generally at least 140.degree. C., preferably 150 to 260.degree. C., particularly preferably 160 to 220.degree.
  • step (a) of the process of the invention may be accomplished by any means known in the art, such as by means of an extruder or a mixer (eg, a kneader). Preference is given to the use of Aufschmelzextrudern (primary extruders). Step (a) of the invention
  • the process according to the invention can be carried out continuously or batchwise, with a continuous procedure being preferred.
  • Step (b) of the process according to the invention comprises introducing the above-described blowing agent component T into the polymer melt prepared in step (a) to form a foamable melt.
  • the blowing agent component T can be introduced into a molten polymer component P by any method known to those skilled in the art.
  • extruders or mixers e.g., kneaders
  • the propellant is mixed with the molten polymer component P under elevated pressure.
  • the pressure must be so high that substantially prevents foaming of the molten polymer material and a homogeneous distribution of the blowing agent component T in the molten polymer component P is achieved.
  • Suitable pressures are 50 to 500 bar (absolute), preferably 100 to 300 bar (absolute), more preferably 150 to 250 bar (absolute).
  • step (b) of the process according to the invention must be selected such that the polymeric material is in the molten state. For this it is necessary that the polymer component P is heated to a temperature above the melting or glass transition temperature. Suitable temperatures are generally at least 140 ° C, preferably 150 to 260 ° C, particularly preferably 160 to 220 ° C.
  • the blowing agent can be added in the melt extruder (primary extruder) or in a downstream step.
  • the production of the foamable polymer melt is carried out in XPS extruders known to the person skilled in the art, for example via a tandem structure consisting of a melting extruder (primary extruder) and a cooling extruder (secondary extruder).
  • the process can be carried out continuously and batchwise, wherein the polymer component P is melted in the primary extruder (step (a)) and the addition of the blowing agent (step (b)) to form a foamable melt also takes place in the primary extruder.
  • the foamable melt provided with blowing agent in the secondary extruder is cooled to a suitable temperature for foaming of 50 to 160 ° C, preferably to a temperature of 80 to 140 ° C.
  • Step (c) of the process of the invention comprises foaming the foamable melt to obtain an extrusion foam.
  • the melt is to promote by a suitable device, such as a nozzle plate.
  • the nozzle plate is heated at least to the temperature of the blowing agent-containing polymer melt.
  • the temperature of the nozzle plate is 50 to 180 ° C. More preferably, the temperature of the nozzle plate is 120 to 170 ° C.
  • the blowing agent-containing polymer melt is transferred through the nozzle plate in a region in which a lower pressure prevails than in the region in which the foamable melt is held prior to extrusion through the nozzle plate.
  • the lower pressure may be superatmospheric or subatmospheric.
  • the extrusion is in a region of atmospheric pressure.
  • Step (c) is also conducted at a temperature at which the polymeric material to be foamed is in a molten state, generally at temperatures of 50 to 160 ° C, preferably 80 to 140 ° C, more preferably 110 to 140 ° C , Characterized in that the blowing agent-containing polymer melt is transferred in step (c) in a region in which a lower pressure prevails, the blowing agent is converted into the gaseous state. Due to the large volume increase, the polymer melt is expanded and foamed.
  • a masterbatch of the components A, B, C and, if appropriate, auxiliaries and additives is prepared, which is mixed with further styrene polymer before or during step a) of the process.
  • the geometric shape of the cross section of the extruded foam sheet obtainable by the process according to the invention is essentially determined by the choice of the nozzle plate and, if necessary, by suitable downstream devices such as plate calibrations, roller conveyors or strip drawers and is freely selectable.
  • the extrusion foam sheets obtainable by the process according to the invention preferably have a rectangular cross section. The thickness of the extrusion foams is determined by the height of the Düsenplattenschlit- zes.
  • the width of the extrusion foams is determined by the width of the nozzle plate slot.
  • the length of the extruded foam parts is determined in a subsequent step by known to those skilled in the art such as bonding, welding, sawing and cutting.
  • Preferred are extrusion foam sheet having a geometry in which the dimension of the thickness (height) is small compared with the dimension of the width and the dimension of the length of the molding.
  • the invention also provides the use of the extrusion foam sheets according to the invention as insulating material in particular in the construction industry, underground and above ground, eg for foundations, walls, floors and roofs. Preference is likewise given to use as structural foam, in particular for lightweight construction applications and as core material for composite applications.
  • the invention further relates to the use of the material for energy absorption, for example in the automotive industry for automotive applications, and in the packaging industry for packaging applications, such as electronic goods or food.
  • the foam boards according to the invention were produced on a tandem extrusion line.
  • the polymers used were continuously fed together with talc to a melt-down extruder.
  • the total throughput of the polymers was 12 kg / h.
  • the propellants (C0 2 , ethanol) were fed continuously through an injection opening introduced into the melting extruder.
  • the propellant-containing melt was cooled in a subsequent cooling extruder and extruded through a slot die (width 25 mm, height 0.8 mm).
  • the intumescent melt was withdrawn without calibration via a roller belt.
  • the extruded cross sections had a height of about 15 mm and a width of about 80 mm at a typical density of 45 g / l.
  • Polystyrene 158K (Styrolution GmbH) was used as the reference polymer in the production of the foam board and was usually processed to densities of approx. 45 g / l on the tandem extrusion line. The processing-related density range extended over 25 to 150 g / l.
  • Styroflex® 2G66 thermoplastic elastic styrene-butadiene block copolymer (S-TPE) from Styrolution GmbH
  • a pentane-containing masterbatch was first degassed and subsequently foamed on the tandem foam extrusion plant with and without the addition of PS.
  • the material composition is given in Table 1.
  • the composition is given in parts by weight, all polymers add up to 100 parts by weight, the blowing agent and the nucleating agent (component D.1) behave additively. In all cases, 35 parts by weight of C0 2 and 2.5 parts by weight of ethanol were used for the foam processing.
  • Table 1 Composition of the degassed masterbatch No. 1
  • Component A1) (parts by weight) 77.0
  • Component B1) (parts by weight) 10.2
  • Component B2) (parts by weight) 9.4
  • Component C1) (parts by weight) 1, 7
  • Component C2) (parts by weight) 1, 7
  • a masterbatch was first prepared, which was subsequently foamed on the tandem foam extrusion plant.
  • the material composition is given in Table 6.
  • the composition is given in parts by weight, all polymers add up to 100 parts by weight, the blowing agent and the nucleating agent (component D.1) behave additively.
  • 3.5 parts by weight of C0 2 and 2.5 weight portions of ethanol (Table 7) were used for foam processing.
  • Table 6 Composition of Masterbatches Nos. 2 to 4
  • Component A1) (parts by weight) 76.8
  • Component B1) (parts by weight) 5.0
  • Component B2) (parts by weight) 14.6
  • Component C1) (parts by weight) 1, 8
  • Component C2) (parts by weight) 1, 8

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

Abstract

L'invention concerne une plaque de mousse d'extrusion thermoplastique présentant une épaisseur comprise entre 15 mm et 200 mm et des cellules présentant une taille moyenne de cellule comprise entre 20 et 2 000 μm. La plaque est caractérisée en ce que les membranes cellulaires présentent une structure fibreuse ayant des diamètres de fibres inférieurs à 1 500 nm, qui convient par exemple en tant que matériau isolant, en particulier dans l'industrie de la construction.
PCT/EP2011/073519 2010-12-28 2011-12-21 Plaque de mousse à base de mélanges polymère de styrol - polyoléfine WO2012089574A1 (fr)

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EP10197113 2010-12-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253610A (zh) * 2020-01-21 2020-06-09 翁秋梅 一种动态聚合物泡沫复合材料

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US4847150A (en) * 1987-05-14 1989-07-11 Asahi Kasei Kogyo Kabushiki Kaisha Foams of polyolefin/polystyrene resin mixture
US5225451A (en) 1992-08-27 1993-07-06 Astro-Valcour, Inc. Ultra low density polyolefin foam, foamable polyolefin compositions and process for making same
EP0654488A1 (fr) 1993-11-15 1995-05-24 Phillips Petroleum Company Copolymères à base de diènes conjugués et de monovinylarènes comprenant des blocs à séquences progressives
WO1995035335A1 (fr) 1994-06-17 1995-12-28 Basf Aktiengesellschaft Elastomere thermoplastique
WO1997040079A1 (fr) 1996-04-19 1997-10-30 Basf Aktiengesellschaft Matiere de moulage thermoplastique
WO1998058991A1 (fr) 1997-06-23 1998-12-30 The Dow Chemical Company Procede de production de mousses polymeres aromatiques alcenyle a alveoles ouvertes
US6093752A (en) 1998-03-16 2000-07-25 The Dow Chemical Company Open-cell foam and method of making
JP2000204185A (ja) 1999-01-12 2000-07-25 Daicel Chem Ind Ltd 易引裂き性発泡シ―トおよびその製造方法
JP2000212356A (ja) 1999-01-28 2000-08-02 Idemitsu Petrochem Co Ltd 芳香族ビニル重合体樹脂組成物、樹脂発泡シ―ト、樹脂発泡シ―トの製造方法及び容器
WO2000058380A1 (fr) 1999-03-27 2000-10-05 Basf Aktiengesellschaft Polystyrene transparent et resistant aux chocs a base de copolymeres blocs styrene-butadiene
JP2001310968A (ja) 2000-04-28 2001-11-06 Asahi Kasei Corp ポリエチレン−ポリスチレン系混合樹脂押出発泡体及びその製造方法
JP2003183438A (ja) 2001-12-25 2003-07-03 Jsp Corp 熱成形用発泡シート及び果菜容器
JP2004238413A (ja) 2003-02-03 2004-08-26 Sekisui Plastics Co Ltd 押出発泡シート、押出発泡シートの製造方法、押出発泡シート成形品及び青果用トレー
JP2008173923A (ja) 2007-01-22 2008-07-31 Sekisui Plastics Co Ltd 積層発泡シートとその製造方法及び青果用トレー
WO2008125250A1 (fr) 2007-04-11 2008-10-23 Basf Se Mousse particulaire élastique à base de mélanges de polyoléfines/polymères styréniques
JP2008274072A (ja) 2007-04-27 2008-11-13 Fukuvi Chem Ind Co Ltd 桟木用樹脂組成物及び桟木
US20090197983A1 (en) * 2008-02-06 2009-08-06 Dow Global Technologies Inc. Article and method of producing a low density foam blend of styrenic polymer and polyolefin
WO2009112549A1 (fr) * 2008-03-13 2009-09-17 Basf Se Mousse particulaire élastique à base de mélanges polymère styrénique/polyoléfine
WO2010076184A1 (fr) * 2008-12-30 2010-07-08 Basf Se Mousse particulaire élastique à base de mélanges de polyoléfine et de polymère styrène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253610A (zh) * 2020-01-21 2020-06-09 翁秋梅 一种动态聚合物泡沫复合材料

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