EP2609144A1 - Polymères thermo-isolants ignifugés et leur procédé de production - Google Patents

Polymères thermo-isolants ignifugés et leur procédé de production

Info

Publication number
EP2609144A1
EP2609144A1 EP11752455.3A EP11752455A EP2609144A1 EP 2609144 A1 EP2609144 A1 EP 2609144A1 EP 11752455 A EP11752455 A EP 11752455A EP 2609144 A1 EP2609144 A1 EP 2609144A1
Authority
EP
European Patent Office
Prior art keywords
polymer
carbon
polymers
polymers according
solid
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Withdrawn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
EP11752455.3A
Other languages
German (de)
English (en)
Inventor
Roman Eberstaller
Gerhard Hintermeier
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.)
Sunpor Kunststoff GmbH
Original Assignee
Sunpor Kunststoff GmbH
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 Sunpor Kunststoff GmbH filed Critical Sunpor Kunststoff GmbH
Publication of EP2609144A1 publication Critical patent/EP2609144A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08J9/0066—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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08K5/49—Phosphorus-containing compounds

Definitions

  • the invention relates to flame-retardant expandable polymers according to the preamble of claim 1 and the production of polymer foam insulating bodies thereof.
  • Foamed insulating materials produced from expandable polymers for example from expandable styrene polymer particles (EPS)
  • EPS expandable styrene polymer particles
  • XPS styrene polymer extruded foams
  • the expandable polymers are usually propellant-containing
  • Polymer particles e.g. from polystyrene or cellulose acetate butyrate, which can be expanded by heating with steam (VorCum perspectives) under multiplication of their volume and then by welding to arbitrarily shaped moldings, in particular to plates or blocks, can be processed.
  • expandable polymers By suspension polymerization, e.g. expandable polystyrene can be prepared by polymerization of styrene and gassing with a blowing agent.
  • expandable or expanded polymers can be mechanically processed by extrusion of polymer melts and mixing of a blowing agent in the polymer melt and subsequent promotion through a nozzle plate to extruded granules (eg EPS granules), or by foaming directly after a nozzle into foamed sheets (XPS sheets) are processed.
  • a blowing agent in the polymer melt eg EPS granules
  • XPS sheets foamed sheets
  • thermal insulation materials such as EPS, e.g. for building facades, cold stores or packaging materials.
  • EPS expandable polystyrene
  • XPS expanded polystyrene
  • Polystyrene homo- and copolymers are made predominantly with halogen-containing, in particular brominated organic compounds such as hexabromocyclododecane (HBCD) or brominated styrene copolymer, flame retardant.
  • halogen-free flame retardants need However, to achieve the same flame retardancy of the halogen-containing flame retardants usually be used in significantly higher amounts.
  • Flame-retardant styrenic polymers are usually added to support a mostly halogenated flame retardant, one or more thermal radical generators such as dicumyl or peroxides as a flame retardant synergist such as e.g. EP 0 374 812 A1 (BASF AG).
  • thermal radical generators such as dicumyl or peroxides as a flame retardant synergist such as e.g. EP 0 374 812 A1 (BASF AG).
  • thermal free-radical formers with short half-lives at temperatures of 140 to 300 ° C e.g. Dicumyl peroxide, di-t-butyl peroxide or t-butyl hydroperoxide.
  • radicals which are formed in particular from peroxides and thermal radical formers when using, for example, extruders or static mixers-in the interaction of high temperature and shear stress-lead to a particularly high degradation of the polymer chains. For this reason, the production of expandable polymer particles or extruded polymer foam boards, which contain a thermal radical generator as a synergist in addition to the actual flame retardant problematic.
  • sulfur or sulfur compounds as flame retardant synergists in halogenated or non-halogenated flame retardant systems in the processing of polymers with extruders or static mixers would be advantageous because sulfur, for example, under the usual conditions of producing expandable polystyrene granules, does not favor the degradation reactions of the polymer during extrusion.
  • the major disadvantage is that when processed with extruders or static mixers of sulfur and most sulfur compounds, small amounts of e.g. Mercaptans, sulfides, hydrogen sulfide, sulfur dioxide and similar substances that are extremely odor-intensive and smell unpleasant and / or strong pungent. These odors are also in, from the polymers thus produced molded foam bodies intense and make them virtually unsalable.
  • the object of the invention is a body, in particular a
  • Shaped body of a foamed polymer such as polystyrene or cellulose acetate butyrate, in particular made of polystyrene foam particles or an extruded polystyrene foam board, which makes use of the advantages of sulfur and is substantially free of odor.
  • the object was achieved by the use of sulfur-containing solids, consisting predominantly of atoms of the element carbon, in particular caused by natural Kohlenohlungsvone in the earth's crust and / or by artificially generated Kohlenohlungsvone natural or synthetic materials, mainly consisting of carbon atoms and a content of sulfur from 0.2 to 30 wt .-%, preferably from 0.3 to 15 wt .-%, preferably from 0.6 to 10 wt .-%, particularly preferably from 1, 2 to 7 wt .-%, based on the predominantly carbon-containing solid, in the form of sulfur and / or sulfur compounds, in, preferably halogenated or phosphate-containing, flame retardants polymers provided.
  • the sulfur and / or the sulfur compounds are contained in the solid itself or integrated or contained in the matrix of the solid or athermanic material.
  • sulfur and / or sulfur compounds are contained in the solid itself or integrated or contained in the matrix of the solid or athermanic material.
  • solids consisting predominantly of carbon atoms are preferably particles having a particle size in the range of 0.5 or 1 to 50 ⁇ ⁇ , preferably from 1 to 30 ⁇ , more preferably from 1 to 10 ⁇ . Both isotropic and anisotropic solids are suitable. Platelet-shaped particles having a high aspect ratio are particularly preferred. These can preferably be produced in delaminating mills, for example in ball mills or air jet mills.
  • the preferred amounts used are between 0.5 and 10 wt .-%, based on the weight of the polymer granules produced.
  • the athermanous particles or solids are homogeneously and evenly distributed in the polymer.
  • the expandable polymers of the present invention include all thermoplastic, expandable thermoplastics, e.g. Polystyrene, cellulose acetobutyrate, polyethylene, polypropylene, polyethylene terephthalate, polylactic acid, and mixtures of various thermoplastics.
  • thermoplastic expandable thermoplastics
  • expandable thermoplastics e.g. Polystyrene, cellulose acetobutyrate, polyethylene, polypropylene, polyethylene terephthalate, polylactic acid, and mixtures of various thermoplastics.
  • the expandable polymers according to the invention are preferably expandable styrene polymers (EPS) or expandable styrene polymer granules (EPS) which are in particular homopolymers and copolymers of styrene, preferably glass-clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A).
  • EPS expandable styrene polymers
  • EPS expandable styrene polymer granules
  • GPPS glass-clear polystyrene
  • HIPS impact polystyrene
  • A anionically polymerized polystyrene or impact polystyrene
  • IPS styrene-alpha-methylstyrene copolymers
  • ABS acrylonitrile-butadiene-styrene polymers
  • SAN styrene-acrylonitrile
  • ASA acrylonitrile-styrene-acrylic ester
  • MVS methyl acrylate-butadiene-styrene
  • MABS methyl methacrylate-acrylonitrile-butadiene- Styrene
  • PPE polyphenylene ether
  • thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyether sulfones (PES), polyether ketones or polyether sulfides (PES), or mixtures thereof in U.S. Pat Generally in proportions of up to a maximum of 30 wt .-%, preferably in the range of 1 to 10 wt .-%, each based on the amount of polymer melt, blended.
  • PA polyamides
  • PE polyolefins
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PES polyether sulfones
  • PES polyether ketones or polyether sul
  • Suitable propellants under normal conditions are gaseous or liquid hydrocarbons which have a boiling point below the softening point of the polymer. Typical representatives of these compounds are propane, butane, pentane, hexane and the isomers of these compounds. Also, water, nitrogen, halogenated blowing agents or carbon dioxide are useful as blowing agents. Furthermore, chemical blowing agents and blowing agents which - thermally or radiation-induced - release volatile components can be used.
  • mixtures in the above amounts ranges with z.
  • rubbers such as polyacrylates or polydienes, z.
  • styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters possible.
  • Suitable compatibilizers are e.g. Maleic anhydride-modified
  • Styrene copolymers polymers containing epoxy groups or organosilanes.
  • halogenated organic compounds having a bromine content greater than 50% by weight are used.
  • Known examples thereof are hexabromocyclododecane, brominated styrene copolymers (for example styrene-butadiene copolymers) or pentabromo- nonchlorocyclohexane.
  • all other halogenated, but also halogen-free flame retardants can be used. Possible representatives of these substances are, for example, red phosphorus, organic phosphorus compounds, e.g.
  • DOP (9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide); DOPS-SH (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-thione or -10-sulfide), organic and inorganic N-compounds (e.g., ammonium polyphosphate), inorganic compounds, e.g. Magnesium hydroxide, aluminum hydroxide, water glass or expanded graphite.
  • DOPS-SH 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-thione or -10-sulfide
  • organic and inorganic N-compounds e.g., ammonium polyphosphate
  • inorganic compounds e.g. Magnesium hydroxide, aluminum hydroxide, water glass or expanded graphite.
  • the polymer melt thus obtained was conveyed through a die plate at a rate of 20 kg / h and granulated with a pressurized underwater granulator to form compact EPS granules.
  • the resulting granules were coated with customary for this purpose coating materials (glycerol or zinc stearates) to prevent sticking during the foaming and then prefoamed in a batch prefoamer to a density of about 15 kg / m 3 .
  • the cell structure of the foam beads thus obtained was homogeneous. After an intermediate storage of 24 hours, blocks were made. From these blocks molded parts for a fire test according to DIN 4102 were produced.
  • the moldings produced in this way had a density of 15 kg / m 3 and the class B1 according to DIN 4102 could be achieved.
  • Example 2 The preparation of the granules and the processing into moldings was carried out analogously to Example 1 with the difference that 4 wt .-% petroleum coke (with a content of 1, 2 wt .-% sulfur), and 1, 2 wt.% HBCD were used.
  • the plates thus produced had a density of 15 kg / m 3 and class B1 according to DIN 4102 could be achieved.
  • Example 2 The preparation of the granules and the processing into moldings was carried out analogously to Example 1 with the difference that 4 wt .-% coal dust (with a content of 4.0 wt .-% sulfur), and 1, 2 wt.% HBCD were used.
  • the plates thus produced had a density of 15 kg / m 3 and class B1 according to DIN 4102 could be achieved.
  • Example 2 The preparation of the granules and the processing into moldings was carried out analogously to Example 1 with the difference that 4 wt .-% large-crystalline natural graphite (with a content of 0 wt .-% sulfur), and 1, 4 wt .-% HBCD were used.
  • the plates thus produced had a density of 15 kg / m 3 and class B1 according to DIN 4102 could not be achieved.
  • the carbon solids used in Examples 1 to 4 had a particle size with a d 50 less than 10 pm.
  • the moldings produced according to Examples 1 to 3 could reach the thermal conductivity group (WLG) according to DIN 18164 and thus showed in comparison to EPS without these solids (WLG 040) a significantly improved thermal insulation property.
  • WLG thermal conductivity group

Landscapes

  • 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des polymères expansibles ignifugés, contenant au moins un produit ignifuge, renfermant un ou plusieurs solides, notamment présent(s) sous la forme de particules athermanes, constitué(s) de plus de 70% en poids d'atomes de carbone. Selon l'invention, ce ou ces solides présente(nt) une teneur en soufre de 0,2 à 30 % en poids, de préférence de 0,3 à 15 % en poids, de préférence de 0,6 à 10 % en poids, de préférence encore de 1,2 à 7 % en poids, sous forme de soufre et/ou de composés sulfurés.
EP11752455.3A 2010-08-27 2011-08-17 Polymères thermo-isolants ignifugés et leur procédé de production Withdrawn EP2609144A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ATA1442/2010A AT510311B1 (de) 2010-08-27 2010-08-27 Flammgeschützte, wärmedämmende polymerisate und verfahren zu deren herstellung
DE202010013851U DE202010013851U1 (de) 2010-08-27 2010-10-01 Flammgeschützte, expandierbare Polymerisate
FR1058322A FR2964113B3 (fr) 2010-08-27 2010-10-13 Polymeres expansibles ignifuges et leurs procedes de production
PCT/AT2011/000347 WO2012024709A1 (fr) 2010-08-27 2011-08-17 Polymères thermo-isolants ignifugés et leur procédé de production

Publications (1)

Publication Number Publication Date
EP2609144A1 true EP2609144A1 (fr) 2013-07-03

Family

ID=43383189

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11752455.3A Withdrawn EP2609144A1 (fr) 2010-08-27 2011-08-17 Polymères thermo-isolants ignifugés et leur procédé de production

Country Status (5)

Country Link
EP (1) EP2609144A1 (fr)
AT (1) AT510311B1 (fr)
DE (1) DE202010013851U1 (fr)
FR (1) FR2964113B3 (fr)
WO (1) WO2012024709A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106033845A (zh) * 2015-03-20 2016-10-19 深圳光启高等理工研究院 超材料及超材料的导电微结构制作方法

Families Citing this family (9)

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AT510311B1 (de) * 2010-08-27 2013-02-15 Sunpor Kunststoff Gmbh Flammgeschützte, wärmedämmende polymerisate und verfahren zu deren herstellung
AT511509A1 (de) * 2011-04-18 2012-12-15 Sunpor Kunststoff Gmbh Expandierbare polymerisate aus celluloseacetatbutyrat und styrolpolymerisat
EP2733165A1 (fr) 2012-11-20 2014-05-21 Basf Se Procédé pour la préparation de mousses de polystyrène retardateurs de flamme et libre d'halogène
KR101782702B1 (ko) 2013-02-05 2017-09-27 에스지엘 카본 에스이 경성 발포 폴리스티렌
DE102014213685A1 (de) 2014-07-15 2016-01-21 Sgl Carbon Se Neuartige Polystyrolhartschaumstoffe
MA41344B1 (fr) 2015-01-14 2019-01-31 Synthos Sa Combinaison de silice et de graphite et son utilisation pour réduire la conductivité thermique d'une mousse de polymère aromatique vinylique
MA41342A (fr) 2015-01-14 2017-11-21 Synthos Sa Procédé pour la production de granulés de polymère vinylique aromatique expansible ayant une conductivité thermique réduite
LT3245242T (lt) 2015-01-14 2018-12-10 Synthos S.A. Mineralo, turinčio perovskito sandarą, panaudojimas aromatinio vinilo polimero putose
PT3245172T (pt) 2015-01-14 2019-04-23 Synthos Sa Granulado de polímero vinílico aromático expansível e espuma de polímero vinílico aromático expandida compreendendo compósito geopolimérico e a sua utilização aí

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ES2157245T3 (es) 1994-02-21 2001-08-16 Sulzer Chemtech Ag Procedimiento para la preparacion de granulados plasticos expandibles.
DE102004034516A1 (de) 2004-07-15 2006-02-16 Basf Ag Verfahren zur Herstellung von flammgeschütztem, expandierbarem Polystyrol
AT505735A1 (de) 2007-09-14 2009-03-15 Sunpor Kunststoff Gmbh Verfahren zur herstellung von expandierbaren styroloplymerisaten
DE102007053652A1 (de) * 2007-11-08 2009-05-14 BAM Bundesanstalt für Materialforschung und -prüfung Expandierter Graphit und Verfahren zu seiner Herstellung
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DE102008033280A1 (de) * 2008-07-11 2010-01-14 BAM Bundesanstalt für Materialforschung und -prüfung Verfahren zur Modifizierung von expandiertem Graphit und Verwendung des modifizierten expandierten Graphits
DE102008047594A1 (de) * 2008-09-17 2010-04-15 H.C. Carbon Gmbh Infrarotblocker enthaltende Formkörper aus Polystyrolhartschaum oder Polystyrolpartikelschaum
AT510311B1 (de) * 2010-08-27 2013-02-15 Sunpor Kunststoff Gmbh Flammgeschützte, wärmedämmende polymerisate und verfahren zu deren herstellung

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106033845A (zh) * 2015-03-20 2016-10-19 深圳光启高等理工研究院 超材料及超材料的导电微结构制作方法
CN106033845B (zh) * 2015-03-20 2021-06-04 深圳光启高等理工研究院 超材料及超材料的导电微结构制作方法

Also Published As

Publication number Publication date
AT510311B1 (de) 2013-02-15
DE202010013851U1 (de) 2010-12-16
FR2964113B3 (fr) 2012-08-24
FR2964113A3 (fr) 2012-03-02
WO2012024709A1 (fr) 2012-03-01
AT510311A1 (de) 2012-03-15

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