WO1995008589A1 - Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes - Google Patents
Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes Download PDFInfo
- Publication number
- WO1995008589A1 WO1995008589A1 PCT/EP1994/002987 EP9402987W WO9508589A1 WO 1995008589 A1 WO1995008589 A1 WO 1995008589A1 EP 9402987 W EP9402987 W EP 9402987W WO 9508589 A1 WO9508589 A1 WO 9508589A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- styrene
- weight
- sterically hindered
- expandable
- styrene polymers
- Prior art date
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229920000642 polymer Polymers 0.000 title claims abstract description 70
- 150000002989 phenols Chemical class 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 18
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- BFHPQBAXVOLJLR-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxy-2-octadecylphenyl) propanoate Chemical compound CCCCCCCCCCCCCCCCCCC1=C(OC(=O)CC)C=C(C(C)(C)C)C(O)=C1C(C)(C)C BFHPQBAXVOLJLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011324 bead Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229920006248 expandable polystyrene Polymers 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 phenol octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate Chemical compound 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000005526 organic bromine compounds Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- QFQZKISCBJKVHI-UHFFFAOYSA-N 1,2,3,4,5,6-hexabromocyclohexane Chemical compound BrC1C(Br)C(Br)C(Br)C(Br)C1Br QFQZKISCBJKVHI-UHFFFAOYSA-N 0.000 description 1
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 1
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 1
- UKFHIKGQGFCINK-UHFFFAOYSA-N 1,2,4-tribromobutane Chemical compound BrCCC(Br)CBr UKFHIKGQGFCINK-UHFFFAOYSA-N 0.000 description 1
- QWVCIORZLNBIIC-UHFFFAOYSA-N 2,3-dibromopropan-1-ol Chemical compound OCC(Br)CBr QWVCIORZLNBIIC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RYISLFWCVCPQNV-UHFFFAOYSA-N 2-(4-hydroxyphenyl)-2,3,3-trimethylbutanoic acid Chemical compound CC(C)(C)C(C)(C(O)=O)C1=CC=C(O)C=C1 RYISLFWCVCPQNV-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- VCJZTATVUDMNLU-UHFFFAOYSA-N dibromomethylbenzene Chemical compound BrC(Br)C1=CC=CC=C1 VCJZTATVUDMNLU-UHFFFAOYSA-N 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- 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
- C08J9/224—Surface treatment
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
Definitions
- the invention relates to bead-shaped, expandable styrene polymers containing sterically hindered phenols and processes for their preparation.
- EPS expandable polystyrene
- the styrene polymer can be impregnated with a blowing agent in the extruder, so that, for example, extruded styrene polymer foam can be produced.
- the melted styrene polymer can first be extruded and the granules obtained therefrom can be impregnated with a blowing agent in a subsequent step. This is generally carried out in aqueous suspension.
- the thermal treatment in this recycling of EPS foam materials basically means a thermal, but also a mechanical load on the styrene polymer, which can lead to considerable degradation of the polymer.
- the degradation of the polymer is promoted by residual initiator, heavy metals and / or atmospheric oxygen that may still be present in the foam.
- the thermal degradation can be reduced by adding stabilizers or antioxidants.
- a method for stabilizing recycled plastic mixtures is known from EP-A-0 506 614. Here, recycled plastic mixtures from household and commercial waste are stabilized against the addition of a combination of a sterically hindered phenol with a phosphite or phosphonite against thermal-oxidative degradation.
- ÜS-A-4 839 396 describes expandable and expanded alkenyl aromatic polymer particles and methods for their preparation.
- the expandable polymer particles disclosed therein can be used to produce expanded polymer particles otherwise having the same density using reduced amounts of blowing agent. This is done by using a density controller in an amount of 0.005 to 0.5% by weight based on the total weight of the Mix reached.
- a density controller z.
- B the sterically hindered phenol octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate (Irganox® 1076 from CIBA-GEIGY AG) is used.
- the particles are produced by mixing the alkenyl aromatic polymer with a blowing agent and the sterically hindered phenol in the melt and then extruding it. In this way, however, no pearl-shaped expandable styrene polymers are obtained.
- the object of the present invention was to provide bead-shaped, expandable styrene polymers which are suitable for the production of moldings which tend to reduce the decomposition reactions of the styrene polymers as little as possible during recycling in the melt.
- the invention also relates to a process for the preparation of these sterically hindered phenols-containing, expandable styrene polymers by styrene, optionally with the use of further comonomers, in aqueous suspension in the presence of suspension stabilizers and customary styrene-soluble polymerization catalysts and with Zu ⁇ set of a blowing agent or blowing agent mixture and, if appropriate, conventional additives in effective amounts and, if appropriate, up to 1.5% by weight, based on styrene and comonomers, of polymerized sterically hindered phenols, and the pearly, expandable styrene polymers obtained in this way are coated with up to 1.5% by weight, based on the blowing agent-free styrene polymer a), of sterically hindered phenols, with the proviso that the expandable styrene polymers are coated in homogeneous distribution in the styrene polymer
- the pearly, expandable styrene polymers generally contain polystyrene and / or a styrene copolymer with at least 50% by weight, preferably at least 80% by weight, of copolymerized styrene as styrene polymer a).
- Comonomers such. B. in question ⁇ -methyl styrene, nuclear halogenated styrenes, nuclear alkylated styrenes, acrylonitrile, esters of acrylic or methacrylic acid of alcohols with 1 to 8 carbon atoms, N-vinyl carbazole and maleic acid (anhydride).
- Sterically hindered phenols b) according to the invention are, for example, 3,5-dialkyl-4-hydroxyphenyl compounds.
- octa-decyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-phenyl-propionate is used very particularly preferably.
- the bead-like, expandable styrene polymers contain a blowing agent or blowing agent mixture c) which is generally used in an amount of 2 to 10% by weight, preferably 3 to 8% by weight, based on the sum of a) and b) becomes.
- the blowing agents should not dissolve the styrene polymer, but should be soluble in the styrene polymer.
- the boiling point should be below the softening point of the styrene polymer.
- Suitable blowing agents are, for example, propane, butane, pentane, hexane, cyclohexane and octane. Pentane is preferably used.
- the expandable styrene polymers can furthermore contain customary additives d) in effective amounts, such as flame retardants, dyes, fillers, stabilizers, synergists, nucleating agents, lubricants, antistatic agents, substances which have an anti-adhesive action when foaming and agents for reducing the mold release time when foaming .
- customary additives d) such as flame retardants, dyes, fillers, stabilizers, synergists, nucleating agents, lubricants, antistatic agents, substances which have an anti-adhesive action when foaming and agents for reducing the mold release time when foaming .
- Organic bromine and / or chlorine compounds are generally used as flame retardants.
- the organic bromine compounds used are the bromine compounds usually used as flame retardants, which generally contain at least 2 bromine atoms and have a bromine content of at least 40% by weight.
- Suitable bromine compounds are 1,2,3,4-tetrabromobutane, 1,2,4-tribromobutane, tetrabromopentane, bromine-substituted cycloalkanes, such as l-chloro-2,3,4,4,5,6-pentabromocyclohexane, 1,2,3 , 4,5, 6-hexabromocyclohexane, 1,2,5, 6, 9, 10-hexabromocyclododecane, octabromocyclohexadecane, dibromomethylbenzene, pentabromodiphenyl ether, esters and acetals of dibromopropanol, such as tris (2, 3-d
- the bead-like, expandable styrene polymers additionally contain 0.05 to 1.0, preferably 0.1 to 0.8, particularly preferably 0.2 to 0.6% by weight, based on a), of phosphites e).
- phosphites e preferably triaryl phosphites, particularly preferably trisnonylphenyl phosphite, are preferably used as phosphites.
- the pearl-shaped, expandable styrene polymers generally have a diameter of 0.1 to 6 mm, in particular 0.4 to 3 mm.
- the bead-like, expandable styrene polymers according to the invention are generally prepared by polymerizing styrene and, if appropriate, further comonomers in aqueous suspension.
- the sterically hindered phenol b) is added to the suspension before or during the polymerization and / or applied to the beads as a coating component, with the proviso that the expandable styrene polymers are obtained in homogeneous distribution in the styrene polymer and / or as a surface coating on the styrene polymer a), 0.03 to 1.5, preferably 0.05 to 1.2 and particularly preferably 0.1 to 1.0% by weight of sterically hindered phenols b).
- the blowing agent can be included in the polymerization or added in the course of the polymerization. It can also be added to the batch only after the polymerization has ended.
- the bead-like, expandable styrene polymers obtained in the suspension polymerization are separated from the aqueous phase, washed and dried.
- the surface coating of the expandable styrene polymers can be carried out in a conventional manner.
- 0.05 to 1.2% by weight, particularly preferably 0.1 to 1.0% by weight, in each case based on styrene and comonomers are sterically hindered in the suspension polymerization Phenols and up to 1.15% by weight, particularly preferably up to 0.9% by weight, in each case based on the styrene polymer a), as surface coating on the beads obtained in the suspension polymerization, sterically hindered phenols applied.
- the sterically hindered phenol is added to the suspension before or during the polymerization, it is particularly surprising that the sterically hindered phenols used according to the invention as free radical scavengers do not impair the suspension polymerization which proceeds via free radicals.
- the expandable styrene polymers are expanded in a known manner by heating to temperatures above their softening point, for example using hot air or preferably using steam.
- the foam particles obtained can be foamed further by cooling and, if appropriate, intermediate storage by heating again. They can then be welded in a known manner into moldings in non-gastight forms.
- the stirred kettle was closed, a nitrogen pressure of 1 bar was set, and the temperature was raised from 25 to 100 ° C. in 2 hours. The mixture was then heated to 130 ° C. in 5 hours and left at this temperature for 3 hours. 55 minutes after the start of heating, 478 g of polyvinylpyrrolidone and 3 hours after the start of heating, 1300 g of pentane were added.
- the bead polymer obtained was separated from the aqueous phase, washed, dried and coated with 0.1% by weight, based on the bead polymer, of ethylene-bis-stearic acid amide.
- the viscosity number VZ (0.5% by weight at 25 ° C. in toluene) was determined in accordance with DIN 53 726 on part of the beads obtained.
- Example 2 The procedure was as in Example 1. However, the sterically hindered phenol was not initially introduced into the suspension polymerization, but only in an amount of 0.5% by weight, based on the bead polymer, in a mixture with ethylene bis-stearic acid amide applied as a coating to the beads obtained in suspension polymerization.
- Example 2 The procedure was as in Example 2, with an additional 0.5% by weight, based on the bead polymer, of tris-nonylphenyl phosphite being used in the coating mixture.
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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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94927578A EP0719298A1 (fr) | 1993-09-18 | 1994-09-07 | Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes |
AU76949/94A AU7694994A (en) | 1993-09-18 | 1994-09-07 | Pearl-shaped, expandable styrene polymers containing sterically hinhibited phenols |
KR1019960701394A KR960704968A (ko) | 1993-09-18 | 1994-09-07 | 입체장애된 페놀을 포함하는 발포성 스티렌 중합체 비이드 및 이것의 제조 방법(peral-shaped, expandable styrene polymers containing sterically inhibited phenols) |
JP7509528A JPH09504814A (ja) | 1993-09-18 | 1994-09-07 | 立体障害フェノールを含有するパール状の発泡性スチレン重合体 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4331808.8 | 1993-09-18 | ||
DE4331808A DE4331808A1 (de) | 1993-09-18 | 1993-09-18 | Perlförmige, expandierbare Styrolpolymerisate, enthaltend sterisch gehinderte Phenole und Verfahren zu ihrer Herstellung |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995008589A1 true WO1995008589A1 (fr) | 1995-03-30 |
Family
ID=6498059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/002987 WO1995008589A1 (fr) | 1993-09-18 | 1994-09-07 | Polymeres expansibles de styrene en perles contenant des phenols steriquement inhibes |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0719298A1 (fr) |
JP (1) | JPH09504814A (fr) |
KR (1) | KR960704968A (fr) |
AU (1) | AU7694994A (fr) |
CA (1) | CA2171867A1 (fr) |
DE (1) | DE4331808A1 (fr) |
WO (1) | WO1995008589A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6588245B2 (ja) * | 2015-06-15 | 2019-10-09 | 株式会社ジェイエスピー | ポリスチレン系樹脂発泡体の製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2352858A1 (fr) * | 1976-05-24 | 1977-12-23 | Arco Polymers Inc | Anti-oxydants phenoliques pour composes halogenes non-polymeres durant l'impregnation de particules de polymeres de styrene |
GB2137213A (en) * | 1983-03-23 | 1984-10-03 | Polysar Ltd | Process for producing stabilized polystyrene compositions |
US4839396A (en) * | 1988-08-22 | 1989-06-13 | The Dow Chemical Company | Expandable and expanded alkenyl aromatic polymer particles and methods of making the same |
-
1993
- 1993-09-18 DE DE4331808A patent/DE4331808A1/de not_active Withdrawn
-
1994
- 1994-09-07 JP JP7509528A patent/JPH09504814A/ja active Pending
- 1994-09-07 CA CA002171867A patent/CA2171867A1/fr not_active Abandoned
- 1994-09-07 AU AU76949/94A patent/AU7694994A/en not_active Abandoned
- 1994-09-07 WO PCT/EP1994/002987 patent/WO1995008589A1/fr not_active Application Discontinuation
- 1994-09-07 EP EP94927578A patent/EP0719298A1/fr not_active Withdrawn
- 1994-09-07 KR KR1019960701394A patent/KR960704968A/ko not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2352858A1 (fr) * | 1976-05-24 | 1977-12-23 | Arco Polymers Inc | Anti-oxydants phenoliques pour composes halogenes non-polymeres durant l'impregnation de particules de polymeres de styrene |
GB2137213A (en) * | 1983-03-23 | 1984-10-03 | Polysar Ltd | Process for producing stabilized polystyrene compositions |
US4839396A (en) * | 1988-08-22 | 1989-06-13 | The Dow Chemical Company | Expandable and expanded alkenyl aromatic polymer particles and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
JPH09504814A (ja) | 1997-05-13 |
AU7694994A (en) | 1995-04-10 |
DE4331808A1 (de) | 1995-03-23 |
EP0719298A1 (fr) | 1996-07-03 |
CA2171867A1 (fr) | 1995-03-30 |
KR960704968A (ko) | 1996-10-09 |
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