EP2475710A1 - Mousse extrudée - Google Patents

Mousse extrudée

Info

Publication number
EP2475710A1
EP2475710A1 EP10752335A EP10752335A EP2475710A1 EP 2475710 A1 EP2475710 A1 EP 2475710A1 EP 10752335 A EP10752335 A EP 10752335A EP 10752335 A EP10752335 A EP 10752335A EP 2475710 A1 EP2475710 A1 EP 2475710A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
blowing agent
carbon dioxide
copolymerized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10752335A
Other languages
German (de)
English (en)
Inventor
Klaus Hahn
Holger Ruckdaeschel
Ingo Bellin
Peter Merkel
Markus Hartenstein
Manfred Pawlowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10752335A priority Critical patent/EP2475710A1/fr
Publication of EP2475710A1 publication Critical patent/EP2475710A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2325/08—Copolymers of styrene
    • C08J2325/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • 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

Definitions

  • the invention relates to an extrusion foam obtainable by heating an alpha-methylstyrene-acrylonitrile copolymer (AMSAN) to form a polymer melt, introducing a blowing agent component into the polymer melt, optionally adding auxiliaries and additives and foaming the polymer melt. Furthermore, the invention relates to a method for producing the extrusion die foam and its use as an insulating material and as a structural foam.
  • AMSAN alpha-methylstyrene-acrylonitrile copolymer
  • Polystyrene-based extrusion foams are widely used in the construction industry to insulate building parts such as foundations, walls, floors and roofs.
  • extrusion foams are needed, which have the lowest possible thermal conductivity and thus a high insulation capacity.
  • closed-cell extruded foams In order to achieve good insulation properties, it is preferred to use closed-cell extruded foams, since these have significantly better insulating properties compared to open-celled extrusion foams.
  • good heat resistance at low density is expected of them.
  • the heat resistance is very important, otherwise it can lead to deformation of the extrusion foams and thus to damage the insulation. Components in which a good heat resistance plays a special role, for example, roof insulation and wall insulation, which are exposed to direct sunlight.
  • extrusion foams should also have good resistance to solvents, especially to oil and mineral oil. This is especially necessary for components used in the lower wall, foundation and floor areas.
  • EP-A 1 661 939 describes extruded foam boards based on styrene polymers which have a reduced thermal conductivity.
  • polystyrene polymers in addition to polystyrene and copolymers are disclosed in addition to at least 50 wt .-% of copolymerized styrene other comonomers from the group o methylstyrene, ring halogenated styrenes, nuclear alkylated styrenes, acrylonitrile, esters of (meth) acrylic acid of alcohols having 1 to 8 carbon atoms , N-vinyl compounds, maleic anhydride, and small amounts of compounds having two polymerizable double bonds.
  • the blowing agent used is preferably a blowing agent mixture from 95 to 20 wt .-% carbon dioxide, 5 to 80 wt .-% water and 0 to 75 wt .-% of an alcohol, ketone or ester used.
  • pure polystyrene is extruded with a 1: 1 mixture of carbon dioxide and ethanol.
  • the foam boards according to the teaching of DE 10 2004 057 602 show good insulation properties. However, there is room for improvement in terms of heat distortion resistance and solvent resistance.
  • EP-A 1 479 717 discloses a process for the production of foam boards based on styrene-acrylonitrile copolymers which have improved solvent resistance.
  • the blowing agent or blowing agent component used is water, if appropriate in combination with CO 2 and / or further organic blowing agents.
  • the foam boards obtainable by this process have good solvent resistance. However, there is room for improvement in terms of heat distortion resistance and insulation properties.
  • the object of the invention is accordingly to provide extruded foams which have good insulating properties, good solvent resistance and good heat resistance.
  • the extrusion foams should have a homogeneous cell structure and be accessible without the use of environmentally harmful blowing agents such as CFCs or easily combustible blowing agents such as alkanes.
  • the object is achieved by a closed-cell extrusion foam with a density in the range of 20 to 150 g / l and a cell number in the range of 1 to 30 cells per mm, available through
  • P1 from 5 to 100% by weight (based on P) of one or more alpha-methylstyrene-acrylonitrile copolymers (AMSAN) containing
  • AMSAN alpha-methylstyrene-acrylonitrile copolymers
  • P1 1) from 18 to 40% by weight (based on AMSAN) of copolymerized acrylonitrile
  • P12 from 60 to 82% by weight (based on AMSAN) of copolymerized ⁇ -methylstyrene (P121) or of a copolymerized mixture of ⁇ -methylstyrene and styrene (P122),
  • P13 0 to 22 wt .-% (based on AMSAN) of at least one copolymerized monomer selected from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimides.
  • P2) 95 to 0 wt .-% (based on P) of one or more styrene-acrylonitrile copolymers (SAN), comprising, preferably consisting of,
  • P23 0 to 22 wt .-% (based on SAN) of at least one copolymerized monomer selected from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimide.
  • thermoplastic polymers selected from the group consisting of styrene polymers and copolymers; polyolefins; polyacrylates; Polycarbonates (PC); polyesters; polyamides; Polyether sulfones (PES); Polyether ketones (PEK) and polyether sulfides (PES), to form a polymer melt,
  • blowing agent component T which preferably contains less than 0.2% by weight of water (based on P), containing b1) from 15 to 95% by weight (based on T) carbon dioxide and b2) from 5 to 85% by weight (based on T) of one or more co-blowing agents selected from the group consisting of C 1 -C 4 alcohols and CC 4 carbonyl compounds; in the polymer melt to form a foamable melt,
  • the invention further relates to the described process for producing the extruded foam according to the invention and to the use of this foam as insulating material and as structural foam.
  • the extruded foam according to the invention has good insulation properties, good solvent resistance and in particular 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 it was previously necessary to use different and specially adapted materials for the respective application.
  • the extrusion foam 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. In addition, in spite of its low density compared to the prior art extruded foams, it offers good insulating properties and mechanical properties with simultaneously high solvent and heat resistance.
  • the extrusion foam according to the invention has a cell count in the range of 1 to 30 cells per mm, preferably 3 to 20 cells per mm, in particular 3 to 25 cells per mm.
  • the density of the extrusion foam according to the invention is in the range of 20 to 150 g / l.
  • the extrusion foam has a density in the range of 50 to 130 g / l, more preferably 60 to 120 g / l.
  • the extrusion foam has a density in the range from 20 to 60 g / l, particularly preferably from 20 to 50 g / l and particularly preferably from 25 to 45 g / l.
  • closed-cell extruded foam means that the cells, measured in accordance with DIN ISO 4590, are closed to at least 90%, in particular to 95-100%.
  • the AMSAN (P1), SAN (P2) and the thermoplastic polymers (P3) used according to the invention as polymer component P can be prepared by processes known to those skilled in the art, for example by free-radical, anionic or cationic polymerization in bulk, solution, dispersion or emulsion. In the case of SAN and AMSAN, preference is given to preparation by free-radical polymerization.
  • Component P1 consists of one or more alpha-methylstyrene-acrylonitrile copolymers (AMSAN) containing, preferably consisting of,
  • P13 0 to 30 wt .-%, preferably less than 20 wt .-%, more preferably less than 5 wt .-% (based on AMSAN) of at least one polymerized monomer selected from the group consisting of alkyl (meth) acrylates, (Meth ) acrylic acid, maleic anhydride and maleimides.
  • Alylk (meth) acrylates in the context of the invention are to be understood as meaning both alkyl acrylates and alkyl methacrylates.
  • (meth) acrylic acid is meant both acrylic acid and methacrylic acid.
  • Preferred alkyl (meth) acrylates are formed from (meth) acrylic acid and CrC 6 - alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1 Pentanol and its isomers, 1-hexanol and its isomers and cyclohexanol.
  • Preferred maleimides are maleimide itself, N-alkyl-substituted maleimides (preferably with C 1 -C 6 -alklyne) and N-phenyl-substituted maleimides.
  • component P1 contains no further (0 wt .-%) comonomers P13.
  • the component P1 contains 0.1 to 22 wt .-%, preferably 1 to 20 wt .-% of one or more comonomers (P13), preferably from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimides.
  • P13 comonomers
  • the component P12 is alpha-methylstyrene (P121). In a further preferred embodiment, the component P12 consists of a mixture of styrene and alpha-methylstyrene (P122). In a particularly preferred embodiment, component P1 contains no comonomer P13 and component P12 consists of alpha-methylstyrene (P121).
  • P1 consists of one or more, preferably one, copolymer with the component P121. In a further embodiment, P1 consists of one or more, preferably one, copolymer with the component P122.
  • P1 consists of one or more, preferably one, copolymer with component P121 and one or more, preferably one, copolymer with component P122.
  • AMSAN (P1) with the component (P121) AMSAN types are available from
  • (P1 1) 18 to 35 wt .-%, preferably 27 to 33 wt .-% (based on (P1)) of acrylonitrile and
  • AMSAN (P1) with the component (P122) are polymers obtainable from
  • the SAN component (P2) if present, generally contains from 18 to 40% by weight, preferably from 25 to 35% by weight and in particular from 30 to 35% by weight, of copolymerized acrylonitrile and generally from 60 to 82% by weight. -%, preferably 65 to 75 wt .-% and particularly preferably 65 to 75 wt .-% of copolymerized styrene (in each case based on SAN).
  • the SAN consists of the components P21 and P22 and optionally P23.
  • the SAN (P2) may optionally contain 0 to 22% by weight of at least one copolymerized monomer from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimides (component P23). In a preferred embodiment, the SAN (P2) contains no monomer of the component (P23).
  • the SAN used in the invention (P2) generally have a melt volume rate MVR (220 ° C / 10 kg) according to ISO 1 13 in the range of 5 to 20 cm 3/10 min.
  • Suitable SAN types are, for example, polymers from BASF SE such as Luran 3380, Luran 33100 and Luran 2580.
  • the component (P) contains no (0 wt .-%) styrene-acrylonitrile copolymer (P2).
  • component (P) contains a (1) styrene-acrylonitrile copolymer (P2). In another embodiment, component (P) contains two to four, preferably two, styrene-acrylonitrile copolymers (P2).
  • component (P) contains no (0 wt.%) Thermoplastic polymer (P3).
  • the polymer component P (and thus also the extrusion foam) contains 0.1 to 15 wt .-%, particularly preferably 0.5 to 5 wt .-% of a thermoplastic polymer P3 (each based on P).
  • thermoplastic polymers (P3) of the polymer component P styrene polymers and copolymers are optionally used; polyolefins; polyacrylates; Polycarbonates (PC); Polyester; polyamides; Polyethersulfones (PES); Polyether ketones (PEK); Polyether sulfides (PES) or mixtures thereof used.
  • Suitable styrene copolymers are, for example, acrylonitrile-butadiene-styrene (ABS), styrene-maleic anhydride (SMA), acrylonitrile-styrene-acrylic ester (ASA) and styrene-methacrylic acid.
  • ABS acrylonitrile-butadiene-styrene
  • SMA styrene-maleic anhydride
  • ASA acrylonitrile-styrene-acrylic ester
  • ASA acrylonitrile-styrene-methacrylic acid
  • component P3 and polystyrene can be used. However, this is not preferred.
  • Suitable polyolefins (as component P3) are, for example, polypropylene (PP) polyethylene (PE) and polybutadiene.
  • a suitable polyacrylate (as component P3) is, for example, polymethyl methacrylate (PMMA).
  • Suitable polyesters are, for example, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
  • Suitable polyamides are, for example, polyamide 6 (PA6), polyamide 6,6, polyamide 6, 1 and polyamide 6 / 6,6.
  • the polymer component P contains no (0% by weight) styrene copolymer (as component P3).
  • the polymer component P contains no (0 wt .-%) thermoplastic polymer P3.
  • the components (P3) preferably contain no polystyrene.
  • the component P consists of the component P1, this component P1 preferably contains the component P121 and also preferably no component P13, more preferably the component P121 and no component P13.
  • the component P consists of the component P1 and the component P2, wherein preferably the component P1 contains the component P121 and / or no component P13, and / or the component P2 contains no component P23 and where particularly preferred the component P1 contains the component P121 and no component P13 and the component P2 contains no component P23.
  • the two components P1 and P2 each consist of one (1) copolymer. It is furthermore particularly preferred in this embodiment if component P consists of from 20 to 98% by weight and preferably from 50 to 97% by weight of P1, and the amount of P2 complementary to 100% by weight.
  • component P consists of component P1 and component P3, component P1 preferably containing component P121 and / or no component P13 and / or component P3 containing styrene-maleic anhydride (SMA) and / or acrylonitrile.
  • Styrene acrylic ester ASA
  • the components P1 and P3 each consist of one (1) copolymer or polymer.
  • the component P consists of the components P1, P2 and P3, wherein the component P1 preferably contains the component P121 and / or no component P13 and / or wherein the component P2 preferably contains no component P23 and / or the component P3 is preferably styrene-maleic anhydride (SMA) and / or acrylonitrile-styrene-acrylic ester (ASA), and most preferably component P1 contains component P121 and no component P13, component P2 contains no component P23 and component P3 is styrene-maleic anhydride (SMA) and / or acrylonitrile-styrene-acrylic ester (ASA).
  • the components P1, P2 and P3 each consist of a copolymer or polymer.
  • the invention further provides a process for producing a closed-cell extrusion foam having a density in the range from 20 to 150 g / l and a cell count in the range from 1 to 30 cells per mm
  • AMSAN alpha-methylstyrene acrylonitrile copolymers
  • P1 1) from 18 to 40% by weight (based on AMSAN) of copolymerized acrylonitrile
  • P12 from 60 to 82% by weight (based on AMSAN) of copolymerized ⁇ -methylstyrene (P121) or of a copolymerized mixture of ⁇ -methylstyrene and styrene (P122),
  • P13 0 to 22% by weight (based on AMSAN) of at least one copolymerized monomer selected from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimides;
  • SAN styrene-acrylonitrile copolymers
  • P23 0 to 22% by weight (based on SAN) of at least one copolymerized monomer from the group consisting of alkyl (meth) acrylates, (meth) acrylic acid, maleic anhydride and maleimides.
  • thermoplastic polymers selected from the group consisting of styrene polymers and copolymers; polyolefins; polyacrylates; Polycarbonates (PC); polyesters; polyamides; Polyether sulfones (PES); Polyether ketones (PEK) and polyether sulfides (PES); to form a polymer melt,
  • blowing agent component T which preferably contains less than 0.2% by weight of water (based on P), containing b1) from 15 to 95% by weight (based on T) carbon dioxide and b2) from 5 to 85% by weight (based on T) of one or more co-blowing agents selected from the group consisting of C 1 -C 4 alcohols and CC 4 carbonyl compounds in the polymer melt to form a foamable melt,
  • step (a) of the process the polymer component P is heated to obtain a polymer melt.
  • a polymer melt is meant in the context of the invention, a plasticization of the polymer component P in a broad 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 150 ° C, preferably 160 to 290 ° C, more preferably 180 to 250 ° C.
  • step (a) of the process according to the invention can be carried out by means of any means known in the art, such as by means of an extruder, a mixer (for example a kneader). Preference is given to the use of Aufschmelzextrudern (primary extruders). Step (a) of the process according to the invention can be carried out continuously or batchwise, a continuous procedure being preferred.
  • Step (b) of the process according to the invention comprises introducing a blowing agent component T into the polymer melt produced in step (a) to form a foamable melt.
  • the blowing agent component (T) comprises (and preferably consists of)
  • Wt .-% particularly preferably 0 to 0.08 and most preferably 0 to 0.05 wt .-% water (in each case based on P).
  • One or two, more preferably one co-propellant (b2) is preferably used.
  • Preferred alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol and tert-butanol. Particularly preferred are 2-propanol and ethanol. Particularly preferred is ethanol.
  • Ci-C 4- carbonyl compounds are ketones, aldehydes, carboxamides and Carbonklareester 1 - 4 carbon atoms.
  • Suitable ketones are acetone and methyl ethyl ketone, preferred formates being methyl formate, ethyl formate, n-propyl formate and i-propyl formate. Preference is given to methyl formate and acetone. Especially preferred is acetone. Also preferred is a mixture of ethanol and acetone, in particular with an acetone content of at least 50 wt .-% (based on acetone and ethanol).
  • water b3 may be contained in the co-propellant b2 and in the carbon dioxide b1. Water enters the blowing agent component T, especially by the use of technical alcohols and / or ketones. The water concentration is in the above ranges.
  • the blowing agent component is substantially anhydrous. Particularly preferred are mixtures of carbon dioxide and ethanol, carbon dioxide and acetone, carbon dioxide and methyl formate, carbon dioxide and mixtures of ethanol and acetone in the above mixing ratios.
  • the blowing agent component T is added to the polymer melt in a proportion of in total 1 to 12% by weight, preferably 1 to 8 and particularly preferably 1 to 5% by weight (in each case based on P). In a preferred embodiment, the blowing agent component T is added to the polymer melt in a proportion of from 1 to 4.5% by weight (based on P).
  • the blowing agent component T is added to the polymer melt in a proportion of 2.5 to 8% by weight (based on P).
  • a suitable composition of the blowing agent component T contains from 15 to 95% by weight of the component b1) and from 5 to 85% by weight of the component b2).
  • the proportion of component b1) based on P is at most 6 wt .-% and the proportion of component b2) based on P at most 5 wt .-%, and the total amount of components b1) and b2) based on P maximum 8 wt .-%.
  • the proportion of component b1) with respect to P is particularly preferably at most 4.5% by weight and the proportion of component b2) relative to P is at most 4% by weight.
  • the blowing agent component T is added to the polymer melt in a proportion of 1 to 4.5% by weight, based on P, and the blowing agent component contains 15 to 40% by weight (based on T) of carbon dioxide (component b1).
  • the blowing agent component T is added to the polymer melt in a proportion of from 1 to 4.5% by weight, based on P, and the blowing agent component contains from 15 to 40% by weight (based on T) of carbon dioxide (Component b1), and the extrusion foam has a density in the range of 50 to 130 g / l, preferably from 60 to 120 g / l.
  • the blowing agent component T is added to the polymer melt in a proportion of 2.5 to 8 wt .-% (based on P), and the blowing agent component contains 55 to 75 wt .-%, (based on T) carbon dioxide (Component b1).
  • the blowing agent component T is added to the polymer melt in an amount of from 2.5 to 8% by weight (based on P), the blowing agent component contains from 55 to 75% by weight, based on T of carbon dioxide ( Component b1), and the extrusion foam has a density in the range of 20 to 60 g / l, preferably 20 to 50 g / l and particularly preferably 25 to 45 g / l.
  • the blowing agent component T can be introduced into a molten polymer component P by any method known to those skilled in the art. For example, extruders or mixers (for example, kneaders) are suitable.
  • 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).
  • the temperature in 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 150 ° C, preferably 160 to 290 ° C, more preferably 180 to 250 ° C. Step (b) may be carried out continuously or batchwise, preferably step (b) is carried out continuously.
  • the blowing agent can be added in the melt extruder (primary extruder) or in a downstream step.
  • 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 discontinuously, 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 50-180 ° C, preferably to a temperature of 80-160 ° C.
  • the polymer component P before carrying out the process and / or in at least one of the steps a), b) and / or c), contains additives, i. Auxiliaries and / or additives, added. Suitable auxiliaries and additives are known to the person skilled in the art.
  • At least one nucleating agent is added to the polymer component P.
  • nucleating agents finely divided inorganic solids such as talc, metal oxides, silicates or polyethylene waxes in amounts of in Generally 0.1 to 10 wt .-%, preferably 0.1 to 3 wt .-%, particularly preferably 1 to 1, 5 wt .-%, based on P, are used.
  • the average 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 talc from Luzenac Pharma.
  • the nucleating agent may be added by methods known to those skilled in the art. The addition may be carried out before carrying out the process and / or in step a) and / or b) and / or c).
  • 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 from 0.05 to 25% by weight, particularly preferably in amounts of from 2 to 8% by weight, based on P.
  • Suitable particle sizes for the graphite used are in the range from 1 to 50 ⁇ m, preferably in the range from 2 to 10 ⁇ m. 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, tetrabromobisphenol A, brominated polystyrene oligomers, 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 o, ß and v isomers and preferably an addition of dicumyl (2,3-dimethyl-2,3-diphenylbutane) as synergists
  • brominated aromatic compounds such as tetrabromobisphenol A and brominated polystyrene oligomers.
  • the addition of graphite, carbon black, aluminum powder or an IR dye is preferred for thermal insulation.
  • the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 wt .-% (based on P).
  • a dispersing aid for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
  • Preferred plasticizers are fatty acid esters, Fatty acid amides and phthalates, which can be used in amounts of 0.05 to 10 wt .-%, based on the polymer component P.
  • the total amount of additives is generally 0 to 30 wt .-%, preferably 0 to 20 wt .-%, based on the total weight of the extrusion foam.
  • the total amount of additives is 0.5 to 30 wt .-%, particularly preferably 0.5 to 20 wt .-% (based on the total weight of the extrusion foam).
  • the extrusion foam contains no additives.
  • 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.
  • 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 60 to 210 ° C.
  • the temperature of the nozzle plate is 1 10 to 190 ° 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.
  • a temperature at which the polymeric material to be foamed is in a molten state.
  • temperatures of 170 ° C preferably at 90 to 160 ° C, more preferably at 1 10 to 150 ° C.
  • 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.
  • the geometric shape of the cross section of the extruded foams obtainable by the process according to the invention is essentially determined by the choice of the nozzle plate and, if appropriate, by suitable downstream devices such as plate calibrations, roller conveyors or strip drawers and is freely selectable.
  • the extruded foams 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 Dusenplattenschlitzes.
  • the width of the extrusion foams is determined by the width of the Dusenplattenschlitzes.
  • 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. Particularly preferred are extruded foam parts with a plate-shaped geometry. Plate-shaped means that the dimension of the thickness (height) is small in comparison with the dimension of the width and the dimension of the length of the molding.
  • the extruded foam parts obtainable by the process according to the invention generally have a compressive strength, measured in accordance with DIN EN 826, in the range from 0.15 to 6 N / mm 2 , preferably in the range from 0.3 to 2 N / mm 2 .
  • the invention also relates to the use of the extruded foams according to the invention and the moldings obtainable therefrom.
  • the use as insulating material especially in the construction industry, underground and above ground, for example, for foundations, walls, floors and roofs.
  • Luran 3380 SAN with an acrylonitrile content of 33% by weight and a viscosity number of 80 ml / g (commercial product of BASF SE)
  • Luran 2580 SAN with an acrylonitrile content of 25% by weight and a viscosity number of 80 ml / g commercial product of BASF SE
  • the copolymers used were continuously fed together with talc to a melt-down extruder.
  • the total throughput of the polymers was 7 kg / h.
  • the propellants (C0 2 , ethanol, acetone, methyl formate) were fed continuously through an injection opening introduced into the melting extruder.
  • the blowing agent-containing melt was cooled in a subsequent cooling extruder and extruded through a slot die.
  • the intumescent melt was withdrawn without calibration via a roller belt.
  • Comparative Examples V1 and V2 have high densities or an inhomogeneous cell structure which are unacceptable for extrusion foams for use in the construction industry. Comparative Examples V3 and V4 show no satisfactory blowing agent and / or UV resistance.
  • Table 2 shows the influence of nucleating agent on extrudates according to the invention.
  • nucleating agent improves the mechanical properties of inventive extrusion foams.
  • Example B3 the closed cell content of Example B3 is compared with Comparative Examples V5-V7.
  • Table 3 AMSAN with C0 2 + ethanol, addition of polystyrene (PS)
  • Open-cell degree was determined according to DIN ISO 4590 Although the addition of polystyrene can bring slight advantages in density, it does not unacceptably reduce the closed cell content.
  • Table 4 compares the properties, in particular the UV stability, of various extruded foams according to the invention (AMSAN / SAN mixtures) with a pure SAN extrusion foam.
  • Open-cell degree was determined according to DIN ISO 4590.
  • extruded foams according to the invention having a high proportion of AMSAN have excellent UV resistance.
  • the replacement of AMSAN by PS leads to a deterioration of foam structure and UV resistance even at low levels.
  • Table 5 shows the effect of different blowing agent components T, especially acetone, and different blowing agent concentrations for the same polymer composition of SAN / AMSAN 50/50 blends.
  • Examples B7 to B1 1 show that acetone can be used analogously to ethanol as a suitable co-blowing agent.
  • Table 6 shows the influence of different blowing agent components T, especially methyl formate, and different blowing agent concentrations with the same polymer composition SAN / AMSAN 50/50 blends.
  • Examples B13 and B14 show that methyl formate can be used analogously to ethanol as a suitable co-propellant.

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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)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une mousse extrudée à cellules fermées obtenue par (a) chauffage d'un constituant polymère P formé d'un ou plusieurs copolymères d'alpha-méthylstyrène et d'acrylonitrile (AMSAN), éventuellement d'un ou plusieurs copolymères de styrène et d'acrylonitrile (SAN) et éventuellement d'un ou plusieurs polymères thermoplastiques du groupe composé de polymères et copolymères de styrène, polyacrylates, polycarbonates, polyesters, polyamides, polyéthersulfones, polyéthercétones et polyéthersulfures pour former un polymère en fusion, (b) introduction dans le polymère en fusion de 1 à 12 % en poids (par rapport à P) d'un constituant agent moussant T contenant b1) 15 à 95 % en poids (par rapport à T) de dioxyde de carbone et b2) 5 à 85 % en poids (par rapport à T) d'un ou plusieurs co-agents moussants sélectionnés dans le groupe composé d'alcools C1-C4 et de composés carbonyle C1-C4 pour former une matière en fusion expansible, (c) extrusion de la matière en fusion expansible dans une zone de moindre pression avec moussage en mousse extrudée, (d) ajout éventuel d'additifs au constituant polymère P dans au moins l'une des étapes a), b) et/ou c). La mousse ainsi obtenue convient comme matériau isolant et mousse structurelle.
EP10752335A 2009-09-07 2010-09-06 Mousse extrudée Withdrawn EP2475710A1 (fr)

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EP10752335A EP2475710A1 (fr) 2009-09-07 2010-09-06 Mousse extrudée
PCT/EP2010/063045 WO2011026978A1 (fr) 2009-09-07 2010-09-06 Mousse extrudée

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US8636929B2 (en) 2010-05-21 2014-01-28 Basf Se Nanoporous foamed active compound-containing preparations based on pharmaceutically acceptable thermoplastically workable polymers
EP2520610A1 (fr) * 2011-05-05 2012-11-07 Basf Se Mousse d'extrusion thermorésistante et ignifuge en copolymères du styrène
WO2014049061A1 (fr) * 2012-09-27 2014-04-03 Basf Se Particules expansibles en polymère

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DE10321787A1 (de) 2003-05-14 2004-12-09 Basf Ag Schaumstoffplatten mit verbesserter Lösungsmittelbeständigkeit
DE102004057602A1 (de) 2004-11-29 2006-06-01 Basf Ag Schaumstoffplatten mit verminderter Wärmeleitfähigkeit
EP2162269B1 (fr) * 2007-06-28 2012-08-15 Basf Se Granules expansibles à base de copolymères d'acrylonitrile

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