EP2376562A2 - White expandable polystyrene having improved heat conductivity - Google Patents

White expandable polystyrene having improved heat conductivity

Info

Publication number
EP2376562A2
EP2376562A2 EP09768056A EP09768056A EP2376562A2 EP 2376562 A2 EP2376562 A2 EP 2376562A2 EP 09768056 A EP09768056 A EP 09768056A EP 09768056 A EP09768056 A EP 09768056A EP 2376562 A2 EP2376562 A2 EP 2376562A2
Authority
EP
European Patent Office
Prior art keywords
styrene polymer
expandable styrene
expandable
triazine derivative
foam
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Withdrawn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
EP09768056A
Other languages
German (de)
French (fr)
Inventor
Frank Braun
Ingo Bellin
Maxim Peretolchin
Maximilian Hofmann
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 EP09768056A priority Critical patent/EP2376562A2/en
Publication of EP2376562A2 publication Critical patent/EP2376562A2/en
Withdrawn legal-status Critical Current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
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • 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

Definitions

  • the present invention relates to an expandable styrene polymer containing 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expandable styrene polymer, in homogeneous distribution, a process for preparing this expandable styrene polymer by co-extruding the expandable Styrolpo- lymerisats and the at least one triazine derivative, as well as the use of at least one triazine derivative for reducing the thermal conductivity of expandable styrene polymers.
  • Expandable styrene polymers containing melamine are already known from the prior art.
  • WO 95/05414 discloses polymer beads containing a vinyl aromatic compound, a blowing agent and at least 0.2% by weight, for example 0.2 to 10% by weight, based on the uncoated bead, of a triazine derivative as a coating. The expert thus learns from WO 95/05414 that high amounts of triazine derivative of up to 10 wt .-% can be applied as a coating on polystyrene beads. That very high amounts of triazine derivatives can be homogeneously distributed in the polymer beads is not disclosed in WO 95/05414.
  • EP 3799 and EP 69364 disclose polymer beads comprising at least one styrene homopolymer, a blowing agent, a halogen-containing flame retardant and from 0.0001 to 0.1% by weight, based on the weight of the polymer, of a triazine derivative.
  • expandable styrene polymers which contain athermanous particles for lowering the thermal conductivity are known from the state of the art.
  • EP 1 448 681 B1 discloses a bright, expandable vinyl aromatic polymer and a process for the preparation thereof.
  • IR reflectors titanium dioxide or barium sulfate are used in the vinyl-aromatic polymer.
  • expandable styrene polymers are to be provided, which are characterized by a particularly uniform, ie homogeneous distribution of the triazine derivative in the polymer.
  • Another object of the present invention is to provide a process for producing the expandable styrene polymers of the present invention.
  • Another object is to use triazine derivatives for reducing the thermal conductivity of expandable styrene polymers.
  • the expandable styrene polymer of the invention containing from 0.2 to 30.0% by weight of at least one triazine derivative, based on the expandable styrene polymer, in homogeneous distribution.
  • These objects are also achieved by a process for the preparation of the styrene polymer according to the invention by coextruding the expandable styrene polymer and at least one triazine derivative, and by the use of at least one triazine derivative for reducing the thermal conductivity of expandable styrene polymers.
  • the styrenic polymer is a styrene homopolymer or a styrene copolymer having up to 40% by weight, based on the weight of the polymer, of at least one further ethylenically unsaturated monomer, in particular alkylstyrenes, for example divinylbenzene, para-methyl- ⁇ -methylstyrene, ⁇ -Methylstyrene or acrylonitrile, butadiene, acrylic acid esters or methacrylic acid esters.
  • Blends of polystyrene with other polymers, in particular with rubber, polyphenylene ethers and polyolefins such as polyethylene and polypropylene are possible.
  • the expandable styrene polymer according to the invention is selected from the group consisting of styrene polymers, impact polystyrene, anionically polymerized impact polystyrene, styrene-acrylonitrile polymers (SAN), acrylonitrile-butadiene-styrene polymers (ABS), acrylonitrile-styrene polymers.
  • Acrylic ester polymers (ASA), methyl acrylate-butadiene-styrene polymers (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymers (MABS), alpha-methylstyrene-acrylonitrile polymers (AMSAN), para-methyl-alpha-methylstyrene-acrylonitrile polymers (MAMSAN) and mixtures thereof.
  • polystyrene is used.
  • the polymers used generally have a weight average
  • Molecular weight of 50,000 to 500,000 g / mol, preferably 70,000 to 400,000 g / mol, on. This weight-average molecular weight can be determined by methods known to those skilled in the art, for example by gel permeation chromatography (GPC) and comparison with corresponding reference samples.
  • GPC gel permeation chromatography
  • the expandable styrene polymer according to the invention generally contains from 60 to 99.7% by weight, preferably from 70 to 92% by weight, particularly preferably from 70 to 90% by weight, of at least one of the stated styrene polymers.
  • the expandable styrene polymer according to the invention are from 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expandable styrene polymer, in a homogeneous distribution.
  • triazine derivatives known to those skilled in the art are suitable.
  • triazine derivatives of the general formula (I) are suitable.
  • R 1 , R 2 , R 3 independently of one another are hydrogen, alkyl radical having 1 to 20 C atoms, cycloalkyl radical having 5 to 18 C atoms, heterocycloalkyl radical having 5 to 12 C atoms and at least one heteroatom, aryl radical having 5 to 12 C atoms Atoms, heteroaryl radical having 5 to 12 C atoms and at least one heteroatom, where the cyclic radicals can be attached via C chains having 1 to 6 carbon atoms and optionally at least one heteroatom, and / or with alkyl and / or heteroalkyl radicals having 1 to 12 C atoms and optionally at least one heteroatom may be substituted, or functional groups selected from optionally substituted amino, imino, amido, imido, hydroxy or ether group,
  • heteroatoms can be selected from the group consisting of N, O, P and S.
  • R 1 , R 2 and R 3 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, heteroaryl having 1 to 18 C atoms or amino group (-NH 2 ). More preferably, at least one group of R 1 , R 2 and R 3 is an amino group (-NH 2 ), very particularly preferably at least two groups of R 1 , R 2 and R 3 are amino groups (-NH 2 ).
  • Particularly suitable further radicals R 1 , R 2 and R 3 which are preferably present in addition to at least one, more preferably at least two, amino group (s) (-NH 2 ), are for example methyl, ethyl, n-propyl, iso-propyl, nonyl , Heptadecyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl, 3-pyridyl, N-phenyl, N-dodecyl, N-octadecyl, N, N'-diphenyl, N, N'N "-triphenyl or N-cyclohexyl.
  • the present invention also relates to a styrene polymer according to the invention, wherein the triazine derivative is melamine.
  • melamine, melene and melon condensation products derived from melamine are preferably used, see, for example, Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7 th Edition, pages 1 to 18, John Wiley and Sons, Inc.
  • Triazine derivatives which can be used according to the invention are graphitic forms of carbonitride (gC 3 N 4 ), which are obtainable, for example, by further heating of the melamine condensation products.
  • Other suitable triazine derivatives are resins which are obtainable, for example, by reaction of melamine with aldehydes, such as formaldehyde. Those skilled in such resins are known.
  • the said preferred melamine derivatives or melamine are commercially available or can be prepared by methods known to those skilled in the art, see, for example, Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7 th Edition, pages 1 to 18, John Wiley and Sons, Inc.
  • the at least one triazine derivative, more preferably melamine is present in an amount of from 0.2 to 30.0 wt .-%, preferably 0.5 to 25.0 wt .-%, particularly preferably 1 to 25 wt .-%, most preferably 1 1 to 25 wt .-%, each based on the total expandable styrene polymer , in front.
  • the expandable styrene polymers according to the invention may further comprise the customary auxiliaries and additives known to the person skilled in the art, for example athermanous particles, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, coating compositions, water repellents, flame retardants and / or antioxidants.
  • auxiliaries and additives known to the person skilled in the art, for example athermanous particles, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, coating compositions, water repellents, flame retardants and / or antioxidants.
  • the present invention therefore also relates to an expandable styrene polymer according to the invention, additionally containing athermanous particles.
  • Suitable athermanous particles are, for example, selected from the group consisting of non-metal oxides, for example SiC> 2 , carbon, for example carbon black, graphite, diamond and organic dyes or dye pigments and mixtures thereof.
  • Suitable organic dyes are, in particular, those which show an absorbing and / or reflective behavior in the infrared range.
  • the abovementioned materials can be used either alone or in combination, ie in the form of a mixture of a plurality of materials.
  • the athermanous particles are graphite and / or carbon black.
  • Carbon black which can be used according to the invention preferably has a primary particle size of from 1 to 1000 nm, more preferably from 5 to 500 nm.
  • the D BP absorption of the preferably used carbon blacks measured according to ASTM D2414, is 10 to 300 ml / 100 g, more preferably 20 to 200 ml / 100 g.
  • the surface of the preferably used carbon blacks is preferably 2 to 400 m 2 / g, more preferably 5 to 200 m 2 / g, each measured according to ASTM D6556.
  • Graphite which can be used according to the invention preferably has an average particle size of from 0.1 to 50 ⁇ m, in particular from 1 to 12 ⁇ m, a bulk density of from 100 to 800 g / l and a specific surface area of from 1 to 20 m 2 / g. It can be used natural graphite, synthetic graphite or expanded graphite.
  • the preferably used graphite has an ash, determined according to DIN 51903 of generally 0 to 15 wt .-%, preferably 0.005 to 10 wt .-%, particularly preferably 0.01 to 8 wt .-%, on.
  • the athermanous particles are present in the expandable styrene polymer according to the invention in an amount of from 0.05 to 30 wt .-%, particularly preferably 0.1 to 20 wt -.%, In each case based on the expandable styrene polymer, before.
  • the optionally present athermanous particles may be regularly and / or irregularly shaped.
  • the athermanous particles can be prepared by all methods known to those skilled in the art and / or are commercially available.
  • the expandable styrene polymer according to the invention preferably contains at least one flame retardant. Therefore, the present invention also relates to a styrene polymer according to the invention, additionally containing at least one flame retardant.
  • the at least one flame retardant is selected from halogen- or phosphorus-containing compounds or substances.
  • organic bromine compounds are particularly preferably used.
  • the organic bromine compounds should have a bromine content of ⁇ 40 wt .-%.
  • Particularly suitable are aliphatic, cycloaliphatic and aromatic bromine compounds, such as hexabromocyclododecane (HBCD), Pentabrommonochlorcyclohexan, Pentabromphenyl Lallylether, 2,2 ', 6,6'-tetrabromobisphenol A-bisallyl ether, N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimid and mixtures thereof.
  • HBCD hexabromocyclododecane
  • Pentabrommonochlorcyclohexan Pentabromphenyl Lallylether
  • Suitable phosphorus-containing compounds or substances are, for example, phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, tri (dichloropropyl) phosphate, tris (chloropropyl) phosphate or tris (2,3-dibromo-propyl ) phosphate, or red phosphorus.
  • phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, tri (dichloropropyl) phosphate, tris (chloropropyl) phosphate or tris (2,
  • the at least one flame retardant is hexabromocyclododecane (HBCD).
  • bromine-containing flame retardants is significantly improved by the addition of C-C or O-O-labile organic compounds.
  • flame retardant synergists are dicumyl and dicumyl peroxide.
  • a preferred combination consists of 0.1 to 5 wt .-%, based on the expandable styrene polymer, organic bromine compounds and 0.05 to 1, 0 wt .-%, based on the expandable styrene polymer, the CC or O- 0-labile organic compounds.
  • the expandable styrene polymer according to the invention preferably contains at least one wax based on a polyolefin or a polyolefin copolymer, for example Luwax® AH3 from BASF SE.
  • the at least one wax in an amount of 0.001 to 5.0 wt .-%, particularly preferably 0.01 to 2.0 wt .-%, each based on the total expandable styrene polymer before.
  • the expandable styrene polymer according to the invention has the advantage over the melamine-containing styrene polymers known from the prior art that the at least one triazine derivative is distributed homogeneously according to the invention and is not present as a coating on the styrene polymer.
  • homogeneous means that the at least one present triazine derivative is present distributed over the entire cross-section of the expandable styrene polymer or of expanded styrene polymer and foams which can be produced therefrom.
  • expandable styrene polymer according to the invention and of expanded styrene polymerisable therefrom Styrene polymer and foams is that they are white or light, and not, as the polymers and foams according to the prior art, dark, colored.
  • At least one blowing agent is present in the expandable styrene polymer according to the invention.
  • the propellant is generally present in the usual amounts of from 1 to 10% by weight, preferably from 2 to 8% by weight, based on the total expandable styrene polymer.
  • the blowing agents used are usually aliphatic and cycloaliphatic hydrocarbons having 3 to 10, preferably 4 to 6, carbon atoms, for example n-pentane, isopentane, cyclopentane or mixtures thereof.
  • carbon dioxide, water, ethanol, methanol, acetone, methyl ethyl ketone and methyl formate are suitable.
  • the present invention also relates to a process for the preparation of the expandable styrene polymer according to the invention by coextruding the expandable styrene polymer and the at least one triazine derivative.
  • the at least one triazine derivative and, if appropriate, further components are mixed with a melt of the styrene polymer in an extruder, the melt being metered into a blowing agent at the same time. It is also possible to incorporate the at least one triazine derivative and optionally further components into a melt of propellant-containing styrene polymer, using, for example, screened edge fractions of a bead spectrum of propellant-containing polystyrene beads produced in a suspension polymerization.
  • the at least one triazine derivative in the form of particles, preferably having a particle size of less than 1200 ⁇ m, particularly preferably less than 1000 ⁇ m, very particularly preferably given less than 100 microns, especially less than 50 microns.
  • the particles preferably used have a particle size of at least 0.1 .mu.m, more preferably at least 1, 0 .mu.m.
  • the triazine derivative particles preferably used according to the invention can be regularly and / or irregularly shaped.
  • the at least one triazine derivative and optionally further components can be added directly to the polymer melt. It is also possible to add at least one triazine derivative and optionally further components in the form of a concentrate in the corresponding polystyrene of the melt. Preferably, polystyrene granules, and the at least one triazine derivative and optionally further components are added together in an extruder, the polymer is melted and mixed with the at least one triazine derivative and optionally other components.
  • the polystyrene melt containing the propellant, at least one triazine derivative and optionally further components is squeezed out and comminuted to give propellant-containing granules. Since the existing at least one triazine derivative optionally nucleating, should preferably be cooled after pressing under pressure to avoid foaming. It is therefore expedient to carry out an underwater granulation under pressure. If the polymer melt is not treated under pressure, foaming of the expandable styrene polymer occurs, forming expanded styrene polymer particles or a foam.
  • this direct foaming takes place by pressing out the blowing agent-containing melt through a corresponding nozzle, whereby it foams up, so that foam sheets of a desired size are formed directly from the expandable styrene polymer.
  • the melt is pressed through another suitable nozzle and foams up, so that expanded particles are formed from the expandable styrene polymer.
  • the present invention therefore also relates to a process for the preparation of an expanded styrene polymer according to the invention, in particular in the form of a particle, wherein an expandable styrene polymer according to the invention is foamed.
  • the present invention also relates to an expanded styrene polymer, in particular in the form of a particle, containing from 0.2 to 30.0% by weight of at least one triazine
  • the expandable styrene polymer according to the invention can be processed into foams having densities of preferably 5 to 200 g / l, particularly preferably 8 to 100 g / l and in particular from 10 to 80 g / l.
  • the present invention therefore also relates to a foam which can be produced from the expandable styrene polymer according to the invention.
  • the foam according to the invention has a density of 5 to 200 g / l, preferably 8 to 100 g / l, particularly preferably 10 to 80 g / l.
  • the foam of the invention has a density of ⁇ 35 g / l and a thermal conductivity which is lowered so far that it meets the requirements of the heat conductivity class 040 (according to DIN 18164), Part 1. Table 4.
  • the present invention also relates to a process for producing foams by preparing an expandable styrene polymer according to the invention by the process according to the invention and foaming this expandable styrene polymer.
  • the production of the foams of the invention from the blowing agent-containing expandable styrene polymers is usually also carried out by methods known in the art.
  • the expandable styrene polymers of the invention are prefoamed in a first step with steam in open or closed prefoams to form the corresponding expanded styrene polymer particles.
  • These expanded particles generally have an average particle size of 0.3 to 12 mm, in particular from 0.5 to 8 mm.
  • the prefoamed, expanded styrene polymer particles according to the invention are then welded in a second step in gas-permeable forms by means of steam to moldings or plates made of foam.
  • the foam produced from this expandable styrene polymer has a reduced thermal conductivity in comparison to products according to the prior art.
  • the thermal conductivity of the foam according to the invention can be measured according to DIN 52612.
  • the thermal conductivity of the foam according to the invention is generally less than 38 mW / (m * K), preferably less than 37 mW / (m * K), more preferably less than 36 mW / (m * K).
  • the present invention also relates to the use of the foam according to the invention for thermal insulation, for example of buildings or building parts, such. B. in the perimeter insulation.
  • the foams of the invention can be applied to the outside as well as on the inside of the parts to be insulated.
  • the present invention also relates to the use of the foam according to the invention for thermal insulation of machines and household appliances, such as ovens, refrigerators, freezers, water heaters or jugs.
  • the present invention also relates to the use of the foam according to the invention as packaging material.
  • the foam can be used particulate, so that the object to be packaged lies in a loose bed. It is also possible that a one-piece workpiece is produced from the foam according to the invention, in which the article to be packaged is embedded.
  • the present invention also relates to the use of at least one triazine derivative for reducing the thermal conductivity in foams, preferably in the foams according to the invention.
  • the triazine derivatives the foams, quantities and other characteristics, what has been said applies.
  • Example 1 (according to the invention):
  • the thermal conductivity according to DIN 52612 is 36.4 mW / (m * K) at a density of 14.4 g / l and 32.6 mW / (m * K) at a density of 24.8 g / l.
  • Example 2 The procedure is as in Example 1, except that the polymer melt contains 84.0 wt .-% polystyrene 158 K (BASF SE), 0.2 wt .-% Luwax AH3 (BASF SE), 9.3 wt .-% MeI- amine powder and 6.5% by weight of pentane.
  • BASF SE polystyrene 158 K
  • BASF SE 0.2 wt .-% Luwax AH3
  • MeI- amine powder 9.3 wt .-% MeI- amine powder and 6.5% by weight of pentane.
  • the thermal conductivity according to DIN 52612 is 35.4 mW / (m * K) at a density of 14.7 g / l and 32.2 mW / (m * K) at a density of 24.9 g / l.
  • Example 2 The procedure is as in Example 1, except that the polymer melt contains 74.6 wt .-% polystyrene 158 K (BASF SE), 0.2 wt .-% Luwax AH3 (BASF SE), 18.7 wt .-% MeI- amine powder and 6.5% by weight of pentane.
  • BASF SE polystyrene 158 K
  • BASF SE 0.2 wt .-% Luwax AH3
  • MeI- amine powder 18.7 wt .-% MeI- amine powder and 6.5% by weight of pentane.
  • the thermal conductivity according to DIN 52612 is 34.2 mW / (m * K) at a density of 14.6 g / l and 31.9 mW / (m * K) at a density of 24.8 g / l.
  • the thermal conductivity according to DIN 52612 is 37.8 mW / (m * K) at a density of 14.5 g / l and 33.8 mW / (m * K) at a density of 25.0 g / l.

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

Abstract

The invention relates to an expandable styrene polymer containing 0.2 to 30.0 percent by weight of at least one homogeneously distributed triazine derivative, the percentage being relative to the expandable styrene polymer, a method for the production thereof using a coextrusion process, an expanded styrene polymer containing 0.2 to 30.0 percent by weight of at least one homogeneously distributed triazine derivative, the percentage being relative to the expanded styrene polymer, and a foam that can be made from said expandable styrene polymer.

Description

Weißes expandierbares Polystyrol mit verbesserter Wärmeleitfähigkeit White expandable polystyrene with improved thermal conductivity
Beschreibungdescription
Die vorliegende Erfindung betrifft ein expandierbares Styrolpolymerisat, enthaltend 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-Derivates, bezogen auf das expandierbare Styrolpolymerisat, in homogener Verteilung, ein Verfahren zur Herstellung dieses expandierbaren Styrolpolymerisates durch Coextrudieren des expandierbaren Styrolpo- lymerisats und des wenigstens einen Triazin-Derivates, sowie die Verwendung von wenigstens einem Triazin-Derivat zur Verminderung der Wärmeleitfähigkeit von expandierbaren Styrolpolymerisaten.The present invention relates to an expandable styrene polymer containing 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expandable styrene polymer, in homogeneous distribution, a process for preparing this expandable styrene polymer by co-extruding the expandable Styrolpo- lymerisats and the at least one triazine derivative, as well as the use of at least one triazine derivative for reducing the thermal conductivity of expandable styrene polymers.
Expandierbare Styrolpolymerisate, enthaltend Melamin, sind bereits aus dem Stand der Technik bekannt.Expandable styrene polymers containing melamine are already known from the prior art.
WO 95/05414 offenbart Polymerperlen, die eine vinylaromatische Verbindung, ein Treibmittel und wenigstens 0,2 Gew.-%, beispielsweise 0,2 bis 10 Gew.-%, bezogen auf die unbeschichtete Perle, eines Triazin-Derivates als Beschichtung enthalten. Der Fachmann erfährt somit aus WO 95/05414, dass hohe Mengen an Triazin-Derivat von bis zu 10 Gew.-% als Beschichtung auf Polystyrolperlen aufgebracht werden können. Dass sehr hohe Mengen an Triazin-Derivaten homogen verteilt in den Polymerperlen vorliegen können, wird in WO 95/05414 nicht offenbart.WO 95/05414 discloses polymer beads containing a vinyl aromatic compound, a blowing agent and at least 0.2% by weight, for example 0.2 to 10% by weight, based on the uncoated bead, of a triazine derivative as a coating. The expert thus learns from WO 95/05414 that high amounts of triazine derivative of up to 10 wt .-% can be applied as a coating on polystyrene beads. That very high amounts of triazine derivatives can be homogeneously distributed in the polymer beads is not disclosed in WO 95/05414.
EP 3799 und EP 69364 offenbaren Polymerperlen umfassend wenigstens ein Styrol- homopolymer, ein Treibmittel, ein Halogen enthaltendes Flammschutzmittel und 0,0001 bis 0,1 Gew.-%, bezogen auf das Gewicht des Polymers, eines Triazin- Derivates.EP 3799 and EP 69364 disclose polymer beads comprising at least one styrene homopolymer, a blowing agent, a halogen-containing flame retardant and from 0.0001 to 0.1% by weight, based on the weight of the polymer, of a triazine derivative.
Aus dem Stand der Technik sind des Weiteren expandierbare Styrolpolymerisate be- kannt, die zum Absenken der Wärmeleitfähigkeit athermane Partikel enthalten.Furthermore, expandable styrene polymers which contain athermanous particles for lowering the thermal conductivity are known from the state of the art.
EP 1 448 681 B1 offenbart ein helles, expandierbares vinylaromatisches Polymer und ein Verfahren zur Herstellung desselben. Als IR-Reflektoren werden in dem vinylaro- matischen Polymer Titandioxid oder Bariumsulfat eingesetzt.EP 1 448 681 B1 discloses a bright, expandable vinyl aromatic polymer and a process for the preparation thereof. As IR reflectors, titanium dioxide or barium sulfate are used in the vinyl-aromatic polymer.
Aus weiteren Dokumenten des Standes der Technik ist bekannt, Graphit und/oder Ruß als athermane Partikel in vinylaromatische expandierbare Polymerisate einzubringen. Dies weist jedoch den Nachteil auf, dass die expandierbaren Styrolpolymerisate durch das Vorliegen von Ruß bzw. Graphit dunkel gefärbt sind. Ein weiterer Nachteil ist es, dass durch das Einbringen der athermanen Partikel die mechanischen Eigenschaften der Polystyrol-Schaumstoffe leiden können. Aufgabe der vorliegenden Erfindung ist es daher, expandierbare Styrolpolymerisate bereitzustellen, die sich durch eine helle Farbe auszeichnen, die eine geringe Wärmeleitfähigkeit und zusätzlich gute mechanische Eigenschaften aufweisen. Des Weiteren sollen expandierbare Styrolpolymerisate bereitgestellt werden, welche sich durch eine besonders gleichmäßige, d. h. homogene Verteilung des Triazin-Derivates im Polymer auszeichnen. Eine weitere Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Herstellung der erfindungsgemäßen expandierbaren Styrolpolymerisate bereitzustellen. Eine weitere Aufgabe ist es, Triazin-Derivate zur Verminderung der Wärmeleit- fähigkeit von expandierbaren Styrolpolymerisaten einzusetzen.It is known from other documents of the prior art to incorporate graphite and / or carbon black as athermanous particles into vinylaromatic expandable polymers. However, this has the disadvantage that the expandable styrene polymers are colored dark by the presence of carbon black or graphite. A further disadvantage is that the mechanical properties of the polystyrene foams can suffer from the introduction of the athermanous particles. Object of the present invention is therefore to provide expandable styrene polymers, which are characterized by a light color, which have a low thermal conductivity and in addition good mechanical properties. Furthermore, expandable styrene polymers are to be provided, which are characterized by a particularly uniform, ie homogeneous distribution of the triazine derivative in the polymer. Another object of the present invention is to provide a process for producing the expandable styrene polymers of the present invention. Another object is to use triazine derivatives for reducing the thermal conductivity of expandable styrene polymers.
Diese Aufgaben werden durch das erfindungsgemäße expandierbare Styrolpolymeri- sat, enthaltend 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-Derivates, bezogen auf das expandierbare Styrolpolymerisat, in homogener Verteilung, gelöst. Diese Aufgaben werden ebenfalls durch ein Verfahren zur Herstellung des erfindungsgemäßen Styrol- polymerisats durch Coextrudieren des expandierbaren Styrolpolymerisat und wenigstens einen Triazin-Derivates, sowie durch die Verwendung von wenigstens einem Tria- zin-Derivat zur Verminderung der Wärmeleitfähigkeit von expandierbaren Styrolpolymerisaten, gelöst.These objects are achieved by the expandable styrene polymer of the invention containing from 0.2 to 30.0% by weight of at least one triazine derivative, based on the expandable styrene polymer, in homogeneous distribution. These objects are also achieved by a process for the preparation of the styrene polymer according to the invention by coextruding the expandable styrene polymer and at least one triazine derivative, and by the use of at least one triazine derivative for reducing the thermal conductivity of expandable styrene polymers.
In einer bevorzugten Ausführungsform ist das Styrolpolymerisat ein Styrolhomopolymer oder ein Styrolcopolymer mit bis zu 40 Gew.-%, bezogen auf das Gewicht des Polymers, wenigstens eines weiteren ethylenisch ungesättigten Monomers, insbesondere Alkylstyrole, beispielsweise Divinylbenzol, para-Methyl-α-methylstyrol, α-Methylstyrol oder Acrylnitril, Butadien, Acrylsäureester oder Methacrylsäureester. Auch Blends aus Polystyrol mit anderen Polymeren, insbesondere mit Kautschuk, Polyphenylenether und Polyolefinen wie Polyethylen und Polypropylen, sind möglich.In a preferred embodiment, the styrenic polymer is a styrene homopolymer or a styrene copolymer having up to 40% by weight, based on the weight of the polymer, of at least one further ethylenically unsaturated monomer, in particular alkylstyrenes, for example divinylbenzene, para-methyl-α-methylstyrene, α -Methylstyrene or acrylonitrile, butadiene, acrylic acid esters or methacrylic acid esters. Blends of polystyrene with other polymers, in particular with rubber, polyphenylene ethers and polyolefins such as polyethylene and polypropylene are possible.
In einer besonders bevorzugten Ausführungsform ist das erfindungsgemäße expan- dierbare Styrolpolymerisat ausgewählt aus der Gruppe bestehend aus Styrolpolyme- ren, Schlagzähpolystyrol, anionisch polymerisiertem Schlagzähpolystyrol, Styrol- Acrylnitrilpolymerisaten (SAN), Acrylnitril-Butadien-Styrolpolymerisaten (ABS), Acryl- nitril-Styrol-Acrylesterpolymerisaten (ASA), Methylacrylat-Butadien-Styrolpolymerisaten (MBS), Methylmethacrylat-Acrylnitril-Butadien-Styrolpolymerisaten (MABS), alpha- Methylstyrol-Acrylnitrilpolymerisaten (AMSAN), para-Methyl-alpha-methylstyrol- Acrylnitrilpolymerisaten (MAMSAN) und Mischungen davon. In einer bevorzugten Ausführungsform wird Polystyrol eingesetzt.In a particularly preferred embodiment, the expandable styrene polymer according to the invention is selected from the group consisting of styrene polymers, impact polystyrene, anionically polymerized impact polystyrene, styrene-acrylonitrile polymers (SAN), acrylonitrile-butadiene-styrene polymers (ABS), acrylonitrile-styrene polymers. Acrylic ester polymers (ASA), methyl acrylate-butadiene-styrene polymers (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymers (MABS), alpha-methylstyrene-acrylonitrile polymers (AMSAN), para-methyl-alpha-methylstyrene-acrylonitrile polymers (MAMSAN) and mixtures thereof. In a preferred embodiment, polystyrene is used.
Es ist möglich, dass Mischungen von zwei oder mehr der genannten Styrolpolymerisa- te vorliegen. Die eingesetzten Polymere weisen im Allgemeinen ein gewichtsmittleresIt is possible that mixtures of two or more of said styrene polymers are present. The polymers used generally have a weight average
Molekulargewicht von 50.000 bis 500.000 g/mol, bevorzugt 70.000 bis 400.000 g/mol, auf. Dieses gewichtsmittlere Molekulargewicht kann durch dem Fachmann bekannte Verfahren bestimmt werden, beispielsweise durch Gel-Permeations-Chromatographie (GPC) und Vergleich mit entsprechenden Referenzproben.Molecular weight of 50,000 to 500,000 g / mol, preferably 70,000 to 400,000 g / mol, on. This weight-average molecular weight can be determined by methods known to those skilled in the art, for example by gel permeation chromatography (GPC) and comparison with corresponding reference samples.
Das erfindungsgemäße expandierbare Styrolpolymerisat enthält im Allgemeinen 60 bis 99,7 Gew.-%, bevorzugt 70 bis 92 Gew.-%, besonders bevorzugt 70 bis 90 Gew.-%, wenigstens eines der genannten Styrolpolymerisate.The expandable styrene polymer according to the invention generally contains from 60 to 99.7% by weight, preferably from 70 to 92% by weight, particularly preferably from 70 to 90% by weight, of at least one of the stated styrene polymers.
In dem erfindungsgemäßen expandierbaren Styrolpolymerisat liegen 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-Derivates, bezogen auf das expandierbare Styrolpolymerisat, in homogener Verteilung vor.In the expandable styrene polymer according to the invention are from 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expandable styrene polymer, in a homogeneous distribution.
Erfindungsgemäß sind alle dem Fachmann bekannten Triazin-Derivate geeignet. In einer bevorzugten Ausführungsform werden Triazin-Derivate der allgemeinen For- mel (l)According to the invention, all triazine derivatives known to those skilled in the art are suitable. In a preferred embodiment, triazine derivatives of the general formula (I)
(I) worin (I) wherein
R1, R2, R3 unabhängig voneinander Wasserstoff, Alkylrest mit 1 bis 20 C- Atomen, Cycloalkylrest mit 5 bis 18 C-Atomen, Heterocycloalkylrest mit 5 bis 12 C-Atomen und wenigstens einem Heteroatom, Arylrest mit 5 bis 12 C-Atomen, Heteroarylrest mit 5 bis 12 C-Atomen und wenigstens einem Heteroatom, wobei die cyclischen Reste über C- Ketten mit 1 bis 6 Kohlenstoffatomen und gegebenenfalls wenigstens einem Heteroatom angebunden sein können, und/oder mit Alkyl- und/oder Heteroalkylresten mit 1 bis 12 C-Atomen und gegebenenfalls wenigstens einem Heteroatom substituiert sein können, oder funktionelle Gruppen ausgewählt aus gegebenenfalls substituierter Amino-, Imino-, Amido-, Imido, Hydroxy- oder Ether-Gruppe,R 1 , R 2 , R 3 independently of one another are hydrogen, alkyl radical having 1 to 20 C atoms, cycloalkyl radical having 5 to 18 C atoms, heterocycloalkyl radical having 5 to 12 C atoms and at least one heteroatom, aryl radical having 5 to 12 C atoms Atoms, heteroaryl radical having 5 to 12 C atoms and at least one heteroatom, where the cyclic radicals can be attached via C chains having 1 to 6 carbon atoms and optionally at least one heteroatom, and / or with alkyl and / or heteroalkyl radicals having 1 to 12 C atoms and optionally at least one heteroatom may be substituted, or functional groups selected from optionally substituted amino, imino, amido, imido, hydroxy or ether group,
bedeuten.mean.
Erfindungsgemäß können Heteroatome aus der Gruppe bestehend aus N, O, P und S ausgewählt werden. In einer bevorzugten Ausführungsform bedeuten R1, R2 und R3 unabhängig voneinander Wasserstoff, Alkyl-, Cycloalkyl-, Aryl-, Heteroaryl- mit 1 bis 18 C-Atomen oder Ami- nogruppe (-NH2). Besonders bevorzugt ist mindestens eine Gruppe aus R1, R2 und R3 eine Aminogruppe (-NH2), ganz besonders bevorzugt sind mindestens zwei Gruppen aus R1, R2 und R3 Aminogruppen (-NH2).According to the invention, heteroatoms can be selected from the group consisting of N, O, P and S. In a preferred embodiment, R 1 , R 2 and R 3 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, heteroaryl having 1 to 18 C atoms or amino group (-NH 2 ). More preferably, at least one group of R 1 , R 2 and R 3 is an amino group (-NH 2 ), very particularly preferably at least two groups of R 1 , R 2 and R 3 are amino groups (-NH 2 ).
Besonders geeignete weitere Reste R1, R2 und R3, die bevorzugt neben mindestens einer, besonders bevorzugt mindestens zwei, Aminogruppe(n) (-NH2) vorliegen, sind beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, Nonyl, Heptadecyl, Cyclopentyl, Cyclohexyl, Cyclohexylmethyl, Phenyl, 3-Pyridyl-, N-Phenyl, N-Dodecyl, N-Octadecyl, N,N'-Diphenyl, N,N'N"-Triphenyl oder N-Cyclohexyl.Particularly suitable further radicals R 1 , R 2 and R 3 , which are preferably present in addition to at least one, more preferably at least two, amino group (s) (-NH 2 ), are for example methyl, ethyl, n-propyl, iso-propyl, nonyl , Heptadecyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl, 3-pyridyl, N-phenyl, N-dodecyl, N-octadecyl, N, N'-diphenyl, N, N'N "-triphenyl or N-cyclohexyl.
Ganz besonders bevorzugt wird Melamin (2,4,6-Triamino-1 ,3,5-triazin) der folgenden Formel (II) als Triazin-Derivat verwendetVery particular preference is given to using melamine (2,4,6-triamino-1,3,5-triazine) of the following formula (II) as the triazine derivative
H 2N^ /N^ /NH2 H 2 N ^ / N ^ / NH 2
N NN N
NH '2,NH '2,
(H)(H)
Somit betrifft die vorliegende Erfindung auch ein erfindungsgemäßes Styrolpolymerisat, wobei das Triazin-Derivat Melamin ist.Thus, the present invention also relates to a styrene polymer according to the invention, wherein the triazine derivative is melamine.
Des Weiteren werden bevorzugt die aus Melamin durch Erwärmen entstehenden Kondensationsprodukte Melam, Melen und Melon verwendet, siehe beispielsweise Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7th Edition, Seiten 1 bis 18, John Wiley und Sons, Inc. Weitere erfindungsgemäß einsetzbare Triazin-Derivat sind graphitische Formen von Carbonitrid (g-C3N4), die bei- spielsweise durch weiteres Erhitzen der Melamin-Kondensationsprodukte erhältlich sind. Weitere geeignete Triazin-Derivate sind Harze, welche beispielsweise durch Umsetzung von Melamin mit Aldehyden wie Formaldehyd erhältlich sind. Dem Fachmann sind solche Harze bekannt.Furthermore, melamine, melene and melon condensation products derived from melamine are preferably used, see, for example, Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7 th Edition, pages 1 to 18, John Wiley and Sons, Inc. Others Triazine derivatives which can be used according to the invention are graphitic forms of carbonitride (gC 3 N 4 ), which are obtainable, for example, by further heating of the melamine condensation products. Other suitable triazine derivatives are resins which are obtainable, for example, by reaction of melamine with aldehydes, such as formaldehyde. Those skilled in such resins are known.
Die genannten bevorzugten Melamin-Derivate bzw. Melamin sind kommerziell erhältlich, bzw. können durch den Fachmann bekannte Verfahren hergestellt werden, siehe beispielsweise Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7th Edition, Seiten 1 bis 18, John Wiley und Sons, Inc.The said preferred melamine derivatives or melamine are commercially available or can be prepared by methods known to those skilled in the art, see, for example, Melamine and Guanamines, Ullmann's Encyclopedia of Industrial Chemistry, Release 2008, 7 th Edition, pages 1 to 18, John Wiley and Sons, Inc.
In dem erfindungsgemäßen expandierbaren Styrolpolymerisat liegt das wenigstens eine Triazin-Derivat, insbesondere bevorzugt Melamin, in einer Menge von 0,2 bis 30,0 Gew.-%, bevorzugt 0,5 bis 25,0 Gew.-%, besonders bevorzugt 1 bis 25 Gew.-%, ganz besonders bevorzugt 1 1 bis 25 Gew.-%, jeweils bezogen auf das gesamte expandierbare Styrolpolymerisat, vor.In the expandable styrene polymer according to the invention, the at least one triazine derivative, more preferably melamine, is present in an amount of from 0.2 to 30.0 wt .-%, preferably 0.5 to 25.0 wt .-%, particularly preferably 1 to 25 wt .-%, most preferably 1 1 to 25 wt .-%, each based on the total expandable styrene polymer , in front.
Die erfindungsgemäßen expandierbaren Styrolpolymerisate können des Weiteren die üblichen dem Fachmann bekannten Hilfsmittel und Zusatzstoffe enthalten, beispielsweise athermane Partikel, Keimbildner, UV-Stabilisatoren, Kettenüberträger, Treibmittel, Weichmacher, Beschichtungsmittel, Hydrophobierungsmittel, Flammschutzmittel und/oder Antioxidantien.The expandable styrene polymers according to the invention may further comprise the customary auxiliaries and additives known to the person skilled in the art, for example athermanous particles, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, coating compositions, water repellents, flame retardants and / or antioxidants.
Die vorliegende Erfindung betrifft daher auch ein erfindungsgemäßes expandierbares Styrolpolymerisat, zusätzlich enthaltend athermane Partikel.The present invention therefore also relates to an expandable styrene polymer according to the invention, additionally containing athermanous particles.
Geeignete athermane Partikel sind beispielsweise ausgewählt aus der Gruppe beste- hend aus Nichtmetalloxiden, zum Beispiel SiC>2, Kohlenstoff, zum Beispiel Ruß, Graphit, Diamant und organischen Farbstoffe bzw. Farbstoffpigmenten und Mischungen davon. Als organische Farbstoffe kommen insbesondere solche in Betracht, die im Infrarotbereich ein absorbierendes und/oder reflektierendes Verhalten zeigen. Die vorstehend genannten Materialien können sowohl jeweils allein als auch in Kombination, d. h. in Form einer Mischung aus mehreren Materialien, Verwendung finden. In einer bevorzugten Ausführungsform sind in dem erfindungsgemäßen Styrolpolymerisat die athermanen Partikel Graphit und/oder Ruß.Suitable athermanous particles are, for example, selected from the group consisting of non-metal oxides, for example SiC> 2 , carbon, for example carbon black, graphite, diamond and organic dyes or dye pigments and mixtures thereof. Suitable organic dyes are, in particular, those which show an absorbing and / or reflective behavior in the infrared range. The abovementioned materials can be used either alone or in combination, ie in the form of a mixture of a plurality of materials. In a preferred embodiment, in the styrene polymer according to the invention the athermanous particles are graphite and / or carbon black.
Erfindungsgemäß einsetzbarer Ruß weist bevorzugt eine Primärpartikelgröße von 1 bis 1000 nm, besonders bevorzugt 5 bis 500 nm auf. Die D BP-Absorption der bevorzugt eingesetzten Ruße, gemessen nach ASTM D2414, beträgt 10 bis 300 mL/100 g, besonders bevorzugt 20 bis 200 mL/100 g. Die Oberfläche der bevorzugt eingesetzten Ruße beträgt bevorzugt 2 bis 400 m2/g, besonders bevorzugt 5 bis 200 m2/g, jeweils gemessen nach ASTM D6556.Carbon black which can be used according to the invention preferably has a primary particle size of from 1 to 1000 nm, more preferably from 5 to 500 nm. The D BP absorption of the preferably used carbon blacks, measured according to ASTM D2414, is 10 to 300 ml / 100 g, more preferably 20 to 200 ml / 100 g. The surface of the preferably used carbon blacks is preferably 2 to 400 m 2 / g, more preferably 5 to 200 m 2 / g, each measured according to ASTM D6556.
Erfindungsgemäß einsetzbarer Graphit hat vorzugsweise eine mittlere Partikelgröße von 0,1 bis 50 μm, insbesondere von 1 bis 12 μm, eine Schüttdichte von 100 bis 800 g/l und eine spezifische Oberfläche von 1 bis 20 m2/g. Es kann Naturgraphit, synthetischer Graphit oder Blähgraphit eingesetzt werden. Das bevorzugt eingesetzte Graphit weist eine Asche, bestimmt nach DIN 51903 von im Allgemeinen 0 bis 15 Gew.-%, bevorzugt 0,005 bis 10 Gew.-%, besonders bevorzugt 0,01 bis 8 Gew.-%, auf.Graphite which can be used according to the invention preferably has an average particle size of from 0.1 to 50 μm, in particular from 1 to 12 μm, a bulk density of from 100 to 800 g / l and a specific surface area of from 1 to 20 m 2 / g. It can be used natural graphite, synthetic graphite or expanded graphite. The preferably used graphite has an ash, determined according to DIN 51903 of generally 0 to 15 wt .-%, preferably 0.005 to 10 wt .-%, particularly preferably 0.01 to 8 wt .-%, on.
Die athermanen Partikel liegen in einer bevorzugten Ausführungsform in dem erfin- dungsgemäßen expandierbaren Styrolpolymerisat in einer Menge von 0,05 bis 30 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew. -%, jeweils bezogen auf das expandierbare Styrolpolymerisat, vor.In a preferred embodiment, the athermanous particles are present in the expandable styrene polymer according to the invention in an amount of from 0.05 to 30 wt .-%, particularly preferably 0.1 to 20 wt -.%, In each case based on the expandable styrene polymer, before.
Die gegebenenfalls vorliegenden athermanen Partikel können regelmäßig und/oder unregelmäßig geformt sein. Die athermanen Partikel können nach allen dem Fachmann bekannten Verfahren hergestellt werden und/oder sind kommerziell erhältlich.The optionally present athermanous particles may be regularly and / or irregularly shaped. The athermanous particles can be prepared by all methods known to those skilled in the art and / or are commercially available.
Das erfindungsgemäße expandierbare Styrolpolymerisat enthält bevorzugt wenigstens ein Flammschutzmittel. Daher betrifft die vorliegende Erfindung auch ein erfindungs- gemäßes Styrolpolymerisat, zusätzlich enthaltend wenigstens ein Flammschutzmittel.The expandable styrene polymer according to the invention preferably contains at least one flame retardant. Therefore, the present invention also relates to a styrene polymer according to the invention, additionally containing at least one flame retardant.
Bevorzugt ist das wenigstens eine Flammschutzmittel ausgewählt aus halogen- oder phosphorhaltigen Verbindungen oder Substanzen. Als Flammschutzmittel werden besonders bevorzugt organische Bromverbindungen eingesetzt. Die organischen Brom- Verbindungen sollen einen Bromgehalt von ≥ 40 Gew.-% aufweisen. Insbesondere geeignet sind aliphatische, cycloaliphatische und aromatische Bromverbindungen, wie Hexabromcyclododecan (HBCD), Pentabrommonochlorcyclohexan, Pentabrompheny- lallylether, 2,2',6,6'-Tetrabrombisphenol A-bisallylether, N-2,3-dibromopropyl-4,5- dibromohexahydrophthalimid und Mischungen davon.Preferably, the at least one flame retardant is selected from halogen- or phosphorus-containing compounds or substances. As flame retardants, organic bromine compounds are particularly preferably used. The organic bromine compounds should have a bromine content of ≥ 40 wt .-%. Particularly suitable are aliphatic, cycloaliphatic and aromatic bromine compounds, such as hexabromocyclododecane (HBCD), Pentabrommonochlorcyclohexan, Pentabromphenyl Lallylether, 2,2 ', 6,6'-tetrabromobisphenol A-bisallyl ether, N-2,3-dibromopropyl-4,5-dibromohexahydrophthalimid and mixtures thereof.
Geeignete phosphorhaltige Verbindungen oder Substanzen sind beispielsweise Phosphate wie Trimethylphosphat, Triethylphosphat, Tributylphosphat, Tributoxye- thylphosphat, Triphenylphosphat, Tricresylphosphat, Tris(chloroethyl)phosphat, Tri(dichloropropyl)phosphat, Tris(chloropropyl)phosphat oder Tris(2,3-dibromo- propyl)phosphat, oder roter Phosphor.Suitable phosphorus-containing compounds or substances are, for example, phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, tri (dichloropropyl) phosphate, tris (chloropropyl) phosphate or tris (2,3-dibromo-propyl ) phosphate, or red phosphorus.
Erfindungsgemäß können auch Mischungen der genannten Flammschutzmittel eingesetzt werden. In einer besonders bevorzugten Ausführungsform ist das wenigstens eine Flammschutzmittel Hexabromcyclododecan (HBCD).According to the invention, it is also possible to use mixtures of the abovementioned flame retardants. In a particularly preferred embodiment, the at least one flame retardant is hexabromocyclododecane (HBCD).
Die Wirkung der bromhaltigen Flammschutzmittel wird durch Zusatz von C-C- oder O- O-Iabilen organischen Verbindungen erheblich verbessert. Beispiele solcher Flammschutzsynergisten sind Dicumyl und Dicumylperoxid. Eine bevorzugte Kombination besteht aus 0,1 bis 5 Gew.-%, bezogen auf das expandierbare Styrolpolymerisat, or- ganischer Bromverbindungen und 0,05 bis 1 ,0 Gew.-%, bezogen auf das expandierbare Styrolpolymerisat, der C-C- oder O-0-labilen organischen Verbindungen.The effect of bromine-containing flame retardants is significantly improved by the addition of C-C or O-O-labile organic compounds. Examples of such flame retardant synergists are dicumyl and dicumyl peroxide. A preferred combination consists of 0.1 to 5 wt .-%, based on the expandable styrene polymer, organic bromine compounds and 0.05 to 1, 0 wt .-%, based on the expandable styrene polymer, the CC or O- 0-labile organic compounds.
In dem erfindungsgemäßen expandierbaren Styrolpolymerisat liegt bevorzugt wenigstens ein Wachs auf Basis einen Polyolefins oder eines Polyolefin-Copolymeren vor, beispielsweise Luwax® AH3 der BASF SE. Bevorzugt liegt der wenigstens eine Wachs in einer Menge von 0,001 bis 5,0 Gew.-%, besonders bevorzugt 0,01 bis 2,0 Gew.-%, jeweils bezogen auf das gesamte expandierbare Styrolpolymerisat, vor.The expandable styrene polymer according to the invention preferably contains at least one wax based on a polyolefin or a polyolefin copolymer, for example Luwax® AH3 from BASF SE. Preferably, the at least one wax in an amount of 0.001 to 5.0 wt .-%, particularly preferably 0.01 to 2.0 wt .-%, each based on the total expandable styrene polymer before.
Das erfindungsgemäße expandierbare Styrolpolymerisat weist gegenüber den aus dem Stand der Technik bekannten Melamin enthaltenden Styrolpolymerisaten den Vorteil auf, dass das wenigstens eine Triazin-Derivat erfindungsgemäß homogen verteilt und nicht als Beschichtung auf dem Styrolpolymerisat vorliegt. Im Rahmen der vorliegenden Erfindung bedeutet „homogen", dass die das wenigstens eine vorliegende Triazin-Derivat über den gesamten Querschnitt des expandierbaren Styrolpolymerisates bzw. von daraus herstellbaren expandierten Styrolpolymerisat und Schaumstoffen verteilt vorliegt. Ein weiterer Vorteil des erfindungsgemäßen expandierbaren Styrolpolymerisates, sowie daraus herstellbarem expandiertem Styrolpolymerisat und Schaumstoffen, ist, dass diese weiß bzw. hell, und nicht, wie die Polymerisate und Schaumstoffe gemäß Stand der Technik, dunkel, gefärbt sind.The expandable styrene polymer according to the invention has the advantage over the melamine-containing styrene polymers known from the prior art that the at least one triazine derivative is distributed homogeneously according to the invention and is not present as a coating on the styrene polymer. In the context of the present invention, "homogeneous" means that the at least one present triazine derivative is present distributed over the entire cross-section of the expandable styrene polymer or of expanded styrene polymer and foams which can be produced therefrom.Another advantage of the expandable styrene polymer according to the invention and of expanded styrene polymerisable therefrom Styrene polymer and foams, is that they are white or light, and not, as the polymers and foams according to the prior art, dark, colored.
In einer bevorzugten Ausführungsform liegt in dem erfindungsgemäßen expandierbaren Styrolpolymerisat wenigstens ein Treibmittel vor. Das Treibmittel liegt im Allgemeinen in den üblichen Mengen von 1 bis 10 Gew.-%, bevorzugt 2 bis 8 Gew.-%, bezogen auf das gesamte expandierbare Styrolpolymerisat, vor. Als Treibmittel werden übli- cherweise aliphatische und cycloaliphatische Kohlenwasserstoffe mit 3 bis 10, vorzugsweise 4 bis 6 Kohlenstoffatomen, beispielsweise n-Pentan, iso-Pentan, Cyclopen- tan oder Mischungen davon, eingesetzt. Weiterhin sind Kohlendioxid, Wasser, Ethanol, Methanol, Aceton, Methylethylketon und Methylformiat geeignet.In a preferred embodiment, at least one blowing agent is present in the expandable styrene polymer according to the invention. The propellant is generally present in the usual amounts of from 1 to 10% by weight, preferably from 2 to 8% by weight, based on the total expandable styrene polymer. The blowing agents used are usually aliphatic and cycloaliphatic hydrocarbons having 3 to 10, preferably 4 to 6, carbon atoms, for example n-pentane, isopentane, cyclopentane or mixtures thereof. Furthermore, carbon dioxide, water, ethanol, methanol, acetone, methyl ethyl ketone and methyl formate are suitable.
Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung des erfindungsgemäßen expandierbaren Styrolpolymerisats durch Coextrudieren des expandierbaren Styrolpolymerisats und des wenigstens einen Triazin-Derivates.The present invention also relates to a process for the preparation of the expandable styrene polymer according to the invention by coextruding the expandable styrene polymer and the at least one triazine derivative.
In einer bevorzugten Ausführungsform vermischt man das wenigstens eine Triazin- Derivat und gegebenenfalls weitere Komponenten mit einer Schmelze des Styrolpolymerisats in einem Extruder, wobei der Schmelze gleichzeitig ein Treibmittel zudosiert wird. Man kann das wenigstens eine Triazin-Derivat und gegebenenfalls weitere Komponenten auch in eine Schmelze von treibmittelhaltigem Styrolpolymerisat einarbeiten, wobei beispielsweise ausgesiebte Randfraktionen eines Perlspektrums von in einer Suspensionspolymerisation entstandenen treibmittelhaltigen Polystyrolperlen eingesetzt werden.In a preferred embodiment, the at least one triazine derivative and, if appropriate, further components are mixed with a melt of the styrene polymer in an extruder, the melt being metered into a blowing agent at the same time. It is also possible to incorporate the at least one triazine derivative and optionally further components into a melt of propellant-containing styrene polymer, using, for example, screened edge fractions of a bead spectrum of propellant-containing polystyrene beads produced in a suspension polymerization.
In einer bevorzugten Ausführungsform wird in dem Verfahren zur Herstellung des erfindungsgemäßen expandierbaren Styrolpolymerisates das wenigstens eine Triazin- Derivat in Form von Partikeln eingesetzt, bevorzugt mit einer Partikelgröße von weniger als 1200 μm, besonders bevorzugt weniger als 1000 μm, ganz besonders bevor- zugt weniger als 100 μm, insbesondere weniger als 50 μm. Die bevorzugt eingesetzten Partikel weisen eine Partikelgröße von mindestens 0,1 μm, besonders bevorzugt mindestens 1 ,0 μm, auf. Die erfindungsgemäß bevorzugt eingesetzten Triazin-Derivat- Partikel können regelmäßig und/oder unregelmäßig geformt sein.In a preferred embodiment, in the process for producing the expandable styrene polymer according to the invention, the at least one triazine derivative is used in the form of particles, preferably having a particle size of less than 1200 μm, particularly preferably less than 1000 μm, very particularly preferably given less than 100 microns, especially less than 50 microns. The particles preferably used have a particle size of at least 0.1 .mu.m, more preferably at least 1, 0 .mu.m. The triazine derivative particles preferably used according to the invention can be regularly and / or irregularly shaped.
Das wenigstens eine Triazin-Derivat und gegebenenfalls weitere Komponenten können der Polymerschmelze direkt zugesetzt werden. Man kann das wenigstens eine Triazin- Derivat und gegebenenfalls weitere Komponenten auch in Form eines Konzentrats in dem entsprechenden Polystyrol der Schmelze zusetzen. Bevorzugt werden auch Po- lystyrolgranulat, und das wenigstens eine Triazin-Derivat und gegebenenfalls weitere Komponenten zusammen in einen Extruder gegeben, das Polymer aufgeschmolzen und mit dem wenigstens einen Triazin-Derivat und gegebenenfalls weiteren Komponenten vermischt.The at least one triazine derivative and optionally further components can be added directly to the polymer melt. It is also possible to add at least one triazine derivative and optionally further components in the form of a concentrate in the corresponding polystyrene of the melt. Preferably, polystyrene granules, and the at least one triazine derivative and optionally further components are added together in an extruder, the polymer is melted and mixed with the at least one triazine derivative and optionally other components.
Die das Treibmittel, wenigstens ein Triazin-Derivat und gegebenenfalls weitere Komponenten enthaltende Polystyrolschmelze wird ausgepresst und zu einem treibmittel- haltigen Granulat zerkleinert. Da das vorhandene wenigstens eine Triazin-Derivat gegebenenfalls nukleierend wirkt, sollte bevorzugt nach dem Auspressen unter Druck abgekühlt werden, um ein Aufschäumen zu vermeiden. Man führt daher zweckmäßi- gerweise eine Unterwassergranulierung unter Druck durch. Wird die Polymerschmelze nicht unter Druck behandelt, so kommt es zu einem Aufschäumen des expandierbaren Styrolpolymerisats, wobei expandierte Styrolpolymerisat-Partikel oder ein Schaumstoff gebildet werden.The polystyrene melt containing the propellant, at least one triazine derivative and optionally further components is squeezed out and comminuted to give propellant-containing granules. Since the existing at least one triazine derivative optionally nucleating, should preferably be cooled after pressing under pressure to avoid foaming. It is therefore expedient to carry out an underwater granulation under pressure. If the polymer melt is not treated under pressure, foaming of the expandable styrene polymer occurs, forming expanded styrene polymer particles or a foam.
In einer bevorzugten Ausführungsform geschieht dieses direkte Aufschäumen durch Auspressen der treibmittelhaltigen Schmelze durch eine entsprechende Düse, wobei diese aufschäumt, so dass direkt Schaumstoff-Platten in einer gewünschten Größe aus dem expandierbaren Styrolpolymerisat gebildet werden.In a preferred embodiment, this direct foaming takes place by pressing out the blowing agent-containing melt through a corresponding nozzle, whereby it foams up, so that foam sheets of a desired size are formed directly from the expandable styrene polymer.
In einer weiteren Ausführungsform wird die Schmelze durch eine andere geeignete Düse gepresst und schäumt dabei auf, so dass expandierte Partikel aus dem expandierbaren Styrolpolymerisat gebildet werden.In a further embodiment, the melt is pressed through another suitable nozzle and foams up, so that expanded particles are formed from the expandable styrene polymer.
Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung eines erfin- dungsgemäßen expandierten Styrolpolymerisates, insbesondere in Form eines Partikels, wobei ein erfindungsgemäßes expandierbares Styrolpolymerisat aufgeschäumt wird.The present invention therefore also relates to a process for the preparation of an expanded styrene polymer according to the invention, in particular in the form of a particle, wherein an expandable styrene polymer according to the invention is foamed.
Die vorliegende Erfindung betrifft auch ein expandiertes Styrolpolymerisat, insbesonde- re in Form eines Partikels, enthaltend 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-The present invention also relates to an expanded styrene polymer, in particular in the form of a particle, containing from 0.2 to 30.0% by weight of at least one triazine
Derivates, bezogen auf das expandierte Styrolpolymerisat, in homogener Verteilung, bevorzugt herstellbar nach dem erfindungsgemäßen Verfahren. Bezüglich der einzelnen Merkmale und der bevorzugten Ausführungsformen des erfindungsgemäßen expandierten Styrolpolymerisates, insbesondere in Form eines Partikels, gilt das bezüglich des expandierbaren Styrolpolymerisates, insbesondere in Form eines Partikels, Gesagte.Derivatives, based on the expanded styrene polymer, in homogeneous distribution, preferably produced by the process according to the invention. With regard to the individual features and the preferred embodiments of the expanded styrene polymer according to the invention, in particular in the form of a particle, what has been said with respect to the expandable styrene polymer, in particular in the form of a particle, applies.
Das erfindungsgemäße expandierbare Styrolpolymerisat kann zu Schaumstoffen mit Dichten von bevorzugt 5 bis 200 g/l, besonders bevorzugt von 8 bis 100 g/l und insbesondere von 10 bis 80 g/l, verarbeitet werden. Die vorliegende Erfindung betrifft daher auch einen Schaumstoff, herstellbar aus dem erfindungsgemäßen expandierbaren Styrolpolymerisat. In einer bevorzugten Ausführungsform weist der erfindungsgemäße Schaumstoff eine Dichte von 5 bis 200 g/l, bevorzugt 8 bis 100 g/l, besonders bevorzugt 10 bis 80 g/l, auf.The expandable styrene polymer according to the invention can be processed into foams having densities of preferably 5 to 200 g / l, particularly preferably 8 to 100 g / l and in particular from 10 to 80 g / l. The present invention therefore also relates to a foam which can be produced from the expandable styrene polymer according to the invention. In a preferred embodiment, the foam according to the invention has a density of 5 to 200 g / l, preferably 8 to 100 g / l, particularly preferably 10 to 80 g / l.
In einer besonders bevorzugten Ausführungsform weist der erfindungsgemäße Schaumstoff eine Dichte von < 35 g/l und eine Wärmeleitfähigkeit auf, die soweit erniedrigt ist, dass sie den Anforderungen der Wärmeleitklasse 040 (nach DIN 18164), Teil 1. Tabelle 4 genügt.In a particularly preferred embodiment, the foam of the invention has a density of <35 g / l and a thermal conductivity which is lowered so far that it meets the requirements of the heat conductivity class 040 (according to DIN 18164), Part 1. Table 4.
Die vorliegende Erfindung betrifft auch ein Verfahren zur Herstellung von Schaumstoffen durch Herstellen eines erfindungsgemäßen expandierbaren Styrolpolymerisats durch das erfindungsgemäße Verfahren und Aufschäumen dieses expandierbaren Styrolpolymerisats.The present invention also relates to a process for producing foams by preparing an expandable styrene polymer according to the invention by the process according to the invention and foaming this expandable styrene polymer.
Die Herstellung der erfindungsgemäßen Schaumstoffe aus den Treibmittel enthaltenden expandierbaren Styrolpolymerisaten erfolgt üblicherweise ebenfalls nach aus dem Stand der Technik bekannten Verfahren. Beispielsweise werden die erfindungsgemäßen expandierbaren Styrolpolymerisate in einem ersten Schritt mit Wasserdampf in offenen oder geschlossenen Vorschäumern zu den entsprechenden expandierten Sty- rolpolymerisat-Partikeln vorgeschäumt. Diese expandierten Partikel weisen im Allgemeinen eine mittlere Partikelgröße von 0,3 bis 12 mm, insbesondere von 0,5 bis 8 mm auf. Die erfindungsgemäßen vorgeschäumten, expandierten Styrolpolymerisat-Partikel werden anschließend in einem zweiten Schritt in gasdurchlässigen Formen mittels Wasserdampf zu Formteilen oder Platten aus Schaumstoff verschweißt.The production of the foams of the invention from the blowing agent-containing expandable styrene polymers is usually also carried out by methods known in the art. For example, the expandable styrene polymers of the invention are prefoamed in a first step with steam in open or closed prefoams to form the corresponding expanded styrene polymer particles. These expanded particles generally have an average particle size of 0.3 to 12 mm, in particular from 0.5 to 8 mm. The prefoamed, expanded styrene polymer particles according to the invention are then welded in a second step in gas-permeable forms by means of steam to moldings or plates made of foam.
Durch das Vorliegen des wenigstens einen Triazin-Derivates in dem erfindungsgemäßen expandierbaren Styrolpolymerisat weist der aus diesem expandierbaren Styrolpolymerisat hergestellte Schaumstoff eine im Vergleich zu Produkten gemäß Stand der Technik reduzierte Wärmeleitfähigkeit auf. Die Wärmeleitfähigkeit des erfindungsge- mäßen Schaumstoffes kann gemäß DIN 52612 gemessen werden. Die Wärmeleitfähigkeit des erfindungsgemäßen Schaumstoffes beträgt im Allgemeinen weniger als 38 mW/(m*K), bevorzugt weniger als 37 mW/(m*K), besonders bevorzugt weniger als 36 mW/(m*K).By virtue of the presence of the at least one triazine derivative in the expandable styrene polymer according to the invention, the foam produced from this expandable styrene polymer has a reduced thermal conductivity in comparison to products according to the prior art. The thermal conductivity of the foam according to the invention can be measured according to DIN 52612. The thermal conductivity of the foam according to the invention is generally less than 38 mW / (m * K), preferably less than 37 mW / (m * K), more preferably less than 36 mW / (m * K).
Die vorliegende Erfindung betrifft auch die Verwendung des erfindungsgemäßen Schaumstoffes zur Wärmedämmung, beispielsweise von Gebäuden oder Gebäudeteilen, wie z. B. in der Perimeterdämmung. Dabei können die erfindungsgemäßen Schaumstoffe auf der Außen- als auch auf der Innenseite der zu dämmenden Teile aufgebracht werden.The present invention also relates to the use of the foam according to the invention for thermal insulation, for example of buildings or building parts, such. B. in the perimeter insulation. The foams of the invention can be applied to the outside as well as on the inside of the parts to be insulated.
Die vorliegende Erfindung betrifft auch die Verwendung des erfindungsgemäßen Schaumstoffes zur thermischen Isolierung von Maschinen und Haushaltsgeräten, beispielsweise Backöfen, Kühlschränken, Gefriertruhen, Warmwasserbereitern oder Isolierkannen.The present invention also relates to the use of the foam according to the invention for thermal insulation of machines and household appliances, such as ovens, refrigerators, freezers, water heaters or jugs.
Die vorliegende Erfindung betrifft auch die Verwendung des erfindungsgemäßen Schaumstoffes als Verpackungsmaterial. Dabei kann der Schaumstoff teilchenförmig verwendet werden, so dass der zu verpackende Gegenstand in einer losen Schüttung liegt. Es ist auch möglich, dass aus dem erfindungsgemäßen Schaumstoff ein einteili- ges Werkstück hergestellt wird, in das der zu verpackende Gegenstand eingebettet wird.The present invention also relates to the use of the foam according to the invention as packaging material. In this case, the foam can be used particulate, so that the object to be packaged lies in a loose bed. It is also possible that a one-piece workpiece is produced from the foam according to the invention, in which the article to be packaged is embedded.
Die vorliegende Erfindung betrifft auch die Verwendung wenigstens eines Triazin- Derivates zur Verminderung der Wärmeleitfähigkeit in Schaumstoffen, bevorzugt in den erfindungsgemäßen Schaumstoffen. Bezüglich der Triazin-Derivate, der Schaumstoffe, Mengen und weiteren Merkmalen gilt das Gesagte.The present invention also relates to the use of at least one triazine derivative for reducing the thermal conductivity in foams, preferably in the foams according to the invention. With respect to the triazine derivatives, the foams, quantities and other characteristics, what has been said applies.
BeispieleExamples
Beispiel 1 (erfindungsgemäß):Example 1 (according to the invention):
88,6 Gew.-% Polystyrol 158 K (BASF SE), 0,2 Gew.-% Luwax AH3 (BASF SE) und 4,7 Gew.-% Melaminpulver werden zusammen in einen Extruder gegeben, und die Mischung wird aufgeschmolzen. Zu dieser Schmelze werden 6,5 Gew.-% Pentan als Treibmittel gegeben. Die resultierende Polymerschmelze wird durch eine Düsenplatte gefördert und mit Hilfe einer druckbeaufschlagten Unterwassergranulierung zu expandierbaren Partikeln mit einem mittleren Durchmesser von 1 ,0 mm granuliert. Die expandierbaren Partikel werden mit Wasserdampf zu expandierten Partikeln vorgeschäumt und nach eintägiger Lagerung durch weitere Behandlung durch Wasserdampf in einer geschlossenen Form zu Schaumstoffblöcken verschweißt.88.6% by weight of polystyrene 158 K (BASF SE), 0.2% by weight of Luwax AH3 (BASF SE) and 4.7% by weight of melamine powder are added together to an extruder, and the mixture is melted. 6.5% by weight of pentane as blowing agent are added to this melt. The resulting polymer melt is conveyed through a die plate and granulated by means of a pressurized underwater granulation to expandable particles with a mean diameter of 1, 0 mm. The expandable particles are prefoamed with steam to expandable particles and welded after one day storage by further treatment by steam in a closed mold into foam blocks.
Die Wärmeleitfähigkeit nach DIN 52612 beträgt 36,4 mW/(m*K) bei einer Dichte von 14,4 g/l und 32,6 mW/(m*K) bei einer Dichte von 24,8 g/l.The thermal conductivity according to DIN 52612 is 36.4 mW / (m * K) at a density of 14.4 g / l and 32.6 mW / (m * K) at a density of 24.8 g / l.
Beispiel 2 (erfindungsgemäß):Example 2 (according to the invention):
Es wird verfahren wie in Beispiel 1 , jedoch enthält die Polymerschmelze 84,0 Gew.-% Polystyrol 158 K (BASF SE), 0,2 Gew.-% Luwax AH3 (BASF SE), 9,3 Gew.-% MeI- aminpulver und 6,5 Gew.-% Pentan.The procedure is as in Example 1, except that the polymer melt contains 84.0 wt .-% polystyrene 158 K (BASF SE), 0.2 wt .-% Luwax AH3 (BASF SE), 9.3 wt .-% MeI- amine powder and 6.5% by weight of pentane.
Die Wärmeleitfähigkeit nach DIN 52612 beträgt 35,4 mW/(m*K) bei einer Dichte von 14,7 g/l und 32,2 mW/(m*K) bei einer Dichte von 24,9 g/l.The thermal conductivity according to DIN 52612 is 35.4 mW / (m * K) at a density of 14.7 g / l and 32.2 mW / (m * K) at a density of 24.9 g / l.
Beispiel 3 (erfindungsgemäß):Example 3 (according to the invention):
Es wird verfahren wie in Beispiel 1 , jedoch enthält die Polymerschmelze 74,6 Gew.-% Polystyrol 158 K (BASF SE), 0,2 Gew.-% Luwax AH3 (BASF SE), 18,7 Gew.-% MeI- aminpulver und 6,5 Gew.-% Pentan.The procedure is as in Example 1, except that the polymer melt contains 74.6 wt .-% polystyrene 158 K (BASF SE), 0.2 wt .-% Luwax AH3 (BASF SE), 18.7 wt .-% MeI- amine powder and 6.5% by weight of pentane.
Die Wärmeleitfähigkeit nach DIN 52612 beträgt 34,2 mW/(m*K) bei einer Dichte von 14,6 g/l und 31 ,9 mW/(m*K) bei einer Dichte von 24,8 g/l.The thermal conductivity according to DIN 52612 is 34.2 mW / (m * K) at a density of 14.6 g / l and 31.9 mW / (m * K) at a density of 24.8 g / l.
VergleichsbeispielComparative example
Es wird verfahren wie in Beispiel 1 , aber auf die Zugabe von Melamin wird verzichtet.The procedure is as in Example 1, but the addition of melamine is omitted.
Die Wärmeleitfähigkeit nach DIN 52612 beträgt 37,8 mW/(m*K) bei einer Dichte von 14,5 g/l und 33,8 mW/(m*K) bei einer Dichte von 25,0 g/l. The thermal conductivity according to DIN 52612 is 37.8 mW / (m * K) at a density of 14.5 g / l and 33.8 mW / (m * K) at a density of 25.0 g / l.

Claims

Patentansprüche claims
1. Expandierbares Styrolpolymerisat, enthaltend 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-Derivates, bezogen auf das expandierbare Styrolpolymerisat, in homogener Verteilung.1. Expandable styrene polymer containing 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expandable styrene polymer, in a homogeneous distribution.
2. Styrolpolymerisat nach Anspruch 1 , dadurch gekennzeichnet, dass es ein Styrol- homopolymer oder ein Styrolcopolymer mit bis zu 40 Gew.-% bezogen auf das Gewicht des Polymers, wenigstens eines weiteren ethylenisch ungesättigten Mo- nomers ist.2. Styrene polymer according to claim 1, characterized in that it is a styrene homopolymer or a styrene copolymer with up to 40 wt .-% based on the weight of the polymer, at least one further ethylenically unsaturated monomer is.
3. Styrolpolymerisat nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es 0,5 bis 25,0 Gew.-% wenigstens eines Triazin-Derivates enthält.3. Styrene polymer according to claim 1 or 2, characterized in that it contains 0.5 to 25.0 wt .-% of at least one triazine derivative.
4. Styrolpolymerisat nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Triazin-Derivat Melamin ist.4. styrene polymer according to one of claims 1 to 3, characterized in that the triazine derivative is melamine.
5. Styrolpolymerisat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass zusätzlich wenigstens ein Treibmittel vorliegt.5. Styrene polymer according to one of claims 1 to 4, characterized in that additionally at least one blowing agent is present.
6. Styrolpolymerisat nach einem der Ansprüche 1 bis 5, zusätzlich enthaltend a- thermane Partikel.6. Styrene polymer according to one of claims 1 to 5, additionally containing a- thermane particles.
7. Styrolpolymerisat nach einem der Ansprüche 1 bis 6, zusätzlich enthaltend we- nigstens ein Flammschutzmittel.7. Styrene polymer according to one of claims 1 to 6, additionally containing at least one flame retardant.
8. Verfahren zur Herstellung eines expandierbaren Styrolpolymerisates nach einem der Ansprüche 1 bis 7 durch Coextrudieren des expandierbaren Styrolpolymerisates und des wenigstens einen Triazin-Derivates.8. A process for preparing an expandable styrene polymer according to any one of claims 1 to 7 by coextruding the expandable styrene polymer and the at least one triazine derivative.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das wenigstens eine Triazin-Derivat mit einer Partikelgröße von weniger als 1200 μm eingesetzt wird.9. The method according to claim 8, characterized in that the at least one triazine derivative having a particle size of less than 1200 microns is used.
10. Verfahren zur Herstellung eines expandierten Styrolpolymerisates, dadurch ge- kennzeichnet, dass ein expandierbares Styrolpolymerisat nach einem der Ansprüche 1 bis 7 aufgeschäumt wird.10. A process for preparing an expanded styrene polymer, character- ized in that an expandable styrene polymer according to any one of claims 1 to 7 is foamed.
1 1. Expandiertes Styrolpolymerisat, enthaltend 0,2 bis 30,0 Gew.-% wenigstens eines Triazin-Derivates, bezogen auf das expandierte Styrolpolymerisat, in homo- gener Verteilung. 1 1. Expanded styrene polymer containing 0.2 to 30.0 wt .-% of at least one triazine derivative, based on the expanded styrene polymer, in homogeneous distribution.
12. Verfahren zur Herstellung von Schaumstoffen durch Herstellen eines expandierbaren Styrolpolymerisates nach einem der Ansprüche 1 bis 7 durch ein Verfahren nach Anspruch 8 oder 9 und Aufschäumen dieses expandierbaren Styrolpolymerisates.12. A process for producing foams by preparing an expandable styrene polymer according to any one of claims 1 to 7 by a process according to claim 8 or 9 and foaming of this expandable styrene polymer.
13. Schaumstoff, herstellbar aus dem expandierbaren Styrolpolymerisat nach einem der Ansprüche 1 bis 7.13. Foam, producible from the expandable styrene polymer according to one of claims 1 to 7.
14. Schaumstoff nach Anspruch 13, dadurch gekennzeichnet, dass er eine Dichte von 5 bis 200 g/l aufweist.14. Foam according to claim 13, characterized in that it has a density of 5 to 200 g / l.
15. Schaumstoff nach Anspruch 13 oder 14, dadurch gekennzeichnet, dass dieser eine Dichte von < 35 g/l und eine Wärmeleitfähigkeit aufweist, die so weit erniedrigt ist, dass sie den Anforderungen der Wärmeleitklasse 040 (nach DIN 18164), Teil 1. Tab. 4, genügt.15. Foam according to claim 13 or 14, characterized in that it has a density of <35 g / l and a thermal conductivity which is so low that it meets the requirements of the heat conductivity 040 (according to DIN 18164), Part 1. Tab 4, is enough.
16. Verfahren zur Herstellung eines Schaumstoffs nach einem der Ansprüche 13 bis 15 durch Herstellen eines expandierbaren Styrolpolymerisates nach einem der Ansprüche 1 bis 6 durch ein Verfahren nach Anspruch 8 oder 9 und Aufschäu- men dieses expandierbaren Styrolpolymerisates.16. A method for producing a foam according to any one of claims 13 to 15 by preparing an expandable styrene polymer according to any one of claims 1 to 6 by a method according to claim 8 or 9 and foaming of this expandable styrene polymer.
17. Verwendung eines Schaumstoffes nach einem der Ansprüche 13 bis 15 zur Wärmedämmung, zur thermischen Isolierung von Maschinen und Haushaltsgeräten und als Verpackungsmaterial.17. Use of a foam according to any one of claims 13 to 15 for thermal insulation, for the thermal insulation of machinery and household appliances and as packaging material.
18. Verwendung wenigstens eines Triazin-Derivates zur Verminderung der Wärmeleitfähigkeit in Schaumstoffen. 18. Use of at least one triazine derivative for reducing the thermal conductivity in foams.
EP09768056A 2008-12-11 2009-12-09 White expandable polystyrene having improved heat conductivity Withdrawn EP2376562A2 (en)

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EP09768056A EP2376562A2 (en) 2008-12-11 2009-12-09 White expandable polystyrene having improved heat conductivity
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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
EP2420531A1 (en) * 2010-08-18 2012-02-22 Basf Se Extrusion foams with improved rigidity

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JPS53106799A (en) 1977-03-02 1978-09-18 Bridgestone Corp Synthetic resin form and its preparation
DE2807710A1 (en) 1978-02-23 1979-09-06 Hoechst Ag FINE PARTICLE EXPANDABLE STYRENE POLYMERISATE
IT1137191B (en) 1981-07-03 1986-09-03 Montedison Spa SELF-EXTINGUISHING EXPANDABLE POLYSTYRENE PARTICLES HAVING IMPROVED PROCESSABILITY
WO1995005414A1 (en) 1993-08-16 1995-02-23 Shell Internationale Research Maatschappij B.V. Beads of a polymer of a vinylaromatic compound
US6262161B1 (en) * 1997-06-26 2001-07-17 The Dow Chemical Company Compositions having improved ignition resistance
ITMI20012168A1 (en) 2001-10-18 2003-04-18 Enichem Spa EXPANDABLE VINYLAROMATIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION

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