EP2601254A1 - Halogen-containing polymer mixtures - Google Patents
Halogen-containing polymer mixturesInfo
- Publication number
- EP2601254A1 EP2601254A1 EP11736113.9A EP11736113A EP2601254A1 EP 2601254 A1 EP2601254 A1 EP 2601254A1 EP 11736113 A EP11736113 A EP 11736113A EP 2601254 A1 EP2601254 A1 EP 2601254A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- polymer mixture
- polymer
- mixture according
- compound
- 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- Withdrawn
Links
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 title claims description 18
- 150000002367 halogens Chemical class 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000006641 stabilisation Effects 0.000 claims abstract description 13
- 238000011105 stabilization Methods 0.000 claims abstract description 13
- 239000003063 flame retardant Substances 0.000 claims description 41
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- -1 fatty acids polyols Chemical class 0.000 claims description 15
- 238000007127 saponification reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000000594 mannitol Substances 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 4
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004794 expanded polystyrene Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims 2
- SHRRVNVEOIKVSG-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclododecane Chemical compound BrC1(Br)CCCCCCCCCC(Br)(Br)C1(Br)Br SHRRVNVEOIKVSG-UHFFFAOYSA-N 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 73
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 239000003017 thermal stabilizer Substances 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 11
- 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 8
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229920006248 expandable polystyrene Polymers 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920006327 polystyrene foam Polymers 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004795 extruded polystyrene foam Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 4
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 150000002924 oxiranes Chemical group 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 3
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 3
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940035044 sorbitan monolaurate Drugs 0.000 description 3
- 239000001587 sorbitan monostearate Substances 0.000 description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 description 3
- 229940035048 sorbitan monostearate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000000811 xylitol Substances 0.000 description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 3
- 235000010447 xylitol Nutrition 0.000 description 3
- 229960002675 xylitol Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 2
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 235000019414 erythritol Nutrition 0.000 description 2
- 229940009714 erythritol Drugs 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 239000001570 sorbitan monopalmitate Substances 0.000 description 2
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 2
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- PLOSOTZQUBEGJE-LUAWRHEFSA-N (Z)-N-cyclopropyl-11-methyldodec-2-enamide Chemical compound CC(C)CCCCCCC\C=C/C(=O)NC1CC1 PLOSOTZQUBEGJE-LUAWRHEFSA-N 0.000 description 1
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 description 1
- AUTSLLHNWAZVLE-UHFFFAOYSA-N 1,1,2,2,3-pentabromo-3-chlorocyclohexane Chemical compound ClC1(Br)CCCC(Br)(Br)C1(Br)Br AUTSLLHNWAZVLE-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
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical group OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
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- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- WERDKABYTRBERY-UHFFFAOYSA-N C1CC(C(C(C1Br)(Br)Br)(Br)Br)(Cl)Cl Chemical compound C1CC(C(C(C1Br)(Br)Br)(Br)Br)(Cl)Cl WERDKABYTRBERY-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 235000013830 Eruca Nutrition 0.000 description 1
- 241000801434 Eruca Species 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 description 1
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- 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
Definitions
- the invention relates to polymer blends containing at least one polymer, at least one organic halogenated compound such as halogenated flame retardants, and at least one further compound for thermal stabilization of the organic halogenated compound.
- Polymers are now used in many areas as materials in which the fire behavior of the materials used is of essential importance, for example in the construction sector, in living and clothing textiles or in vehicle construction. Therefore, the polymers used must also meet the applicable fire protection requirements.
- a class of flame retardants commonly used in polymers are the halogenated organic flame retardants.
- the effect of the halogenated flame retardants is that they release halogen radicals at elevated temperatures.
- the halogen radicals interrupt the radical chain reactions that occur during combustion by trapping the radicals that support combustion. Hydrogen halides also frequently occur as intermediates.
- a problem with the use of the halogenated organic flame retardant compounds in polymers is that the polymers often have to be mixed with flame retardants at elevated temperatures in order to achieve a uniform distribution of the flame retardants in the polymer matrix.
- the polymers are often processed in forming processes that are carried out at elevated temperatures. At the temperatures required, the decomposition of a part of the halogenated flame retardants used often takes place. In particular in extrusion processes, the thermosensitive flame retardants are exposed to significant temperature loads due to the residence time and due to local, shear-induced temperature peaks. The additives can be degraded and the effective amount in the product can be reduced.
- the hydrogen halide formed during the degradation of the additives has a corrosive effect on the systems used. It has therefore begun to add a stabilizer to the polymers in addition to the halogenated organic flame retardant, which decomposition of the Flame retardant in the processing of the polymers should prevent or at least reduce.
- WO 2005/103133 A1 describes, for example, the addition of a thermally stabilizing amount of at least one acrylate or methacrylate polymer which melts in a temperature range from 50 to 150 ° C.
- US 2003/0195286 A1 discloses a flame retardant additive composition with improved thermal stability containing an alkyl tin mercaptoalkanoate and a zeolite.
- zinc compounds such as zinc stearate are used in combination with zeolites as thermal stabilizers.
- EP 0 848 727 B1 describes flame retardant compositions containing hexabromocyclododecane and at least one halogenated epoxy resin as thermal stabilizer for the hexabromocyclododecane.
- the hydrogen halides formed on decomposition of the halogenated flame retardants can be trapped by acid scavengers, as mentioned, for example, in WO 2009/065880.
- acid scavengers for example, hydroxides of magnesium, aluminum or zinc or else alkali metal carbonates or alkali metal hydrogen carbonates are used for this purpose.
- thermal stabilizers for the organic halogenated flame retardants there is a need for further thermal stabilizers which exhibit good activity on the stability of the flame retardants in the processing of the polymers and at the same time do not adversely affect the protective effect of the flame retardants.
- the halogenated flame retardant and thermal stabilizer-treated polymers should continue to show good fire performance. This object is achieved by the use of compounds having a Versei- number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated flame retardants and by polymer blends containing (a) at least one polymer .
- An object of the present invention is the use of compounds (c) having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated organic compounds, in particular halogenated organic flame retardants. These compounds are used as component (c) in the polymer mixtures according to the invention.
- (c) preferably has a saponification number of 100 to 250 mg KOH / g, particularly preferably 120 to 220 mg KOH / g. Also according to the invention preferably (c) has a hydroxyl number of 200 to 600 mg KOH / g, and more preferably from 220 to 500 mg KOH / g. Very particularly preferably, (c) has a saponification number of 100 to 220 mg KOH / g and an OH number of 200 to 600 mg KOH / g, and particularly preferably a saponification number of 120 to 200 mg KOH / g and an OH number of 220 to 500 mg KOH / g.
- the hydroxyl number is determined according to the invention according to the German DIN standard DIN 53240.
- the OH number means the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid that reacts with the acetylation of one gram of the sample substance with this.
- the saponification number is determined according to the invention according to DIN EN ISO 3681.
- the saponification is the formation of potassium salts from derivatives of organic acids. and the saponification value as the amount of potassium hydroxide (KOH) in milligrams needed to saponify one gram of the product tested.
- acid and / or epoxide groups are present in the compound to be investigated, these groups must be quantified in advance and taken into account in the determination of the hydroxyl or saponification number.
- the amount of epoxide groups can e.g. are determined according to ASTM D 1652-04, the amount of acid groups can be determined, for example, according to DIN EN 12634.
- the at least one compound used as component (c) preferably contains at most 1% by weight, preferably at most 0.5% by weight and particularly preferably at most 0.2% by weight of epoxide groups, based on the total weight of the compound according to ASTM 1652-04.
- the epoxy group is understood as meaning the entire epoxide radical of the formula -C (H) OC (H 2 ) having a molecular weight of 43 g / mol.
- the at least one compound used as component (c) has an acid number of at most 15 mg KOH / g, preferably at most 10 mg KOH / g and particularly preferably at most 5 mg KOH / g, determined according to DIN EN 12634.
- the at least one compound used as component (c) most preferably contains at most the above-stated amounts of epoxide groups and at most the acid numbers given above.
- the at least one compound used as component (c) contains carboxylic acid ester groups and free OH groups. According to a particularly preferred embodiment of the invention, the at least one compound used as component (c) contains as functional groups only OH and carboxylic ester groups. In this case, component (c) is very particularly preferably selected from polyesters which have been partially esterified with carboxylic acids.
- a polyol according to the invention is a compound having at least two OH groups.
- these include, for example, dihydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, alcohols having 3 OH groups such as trimethylolmethane and glycerol, tetrahydric alcohols such as Threit, erythritol, Sorbitan (cyclic anhydride of sorbitol) and pentaerythritol, pentahydric alcohols such as arabitol, adonitol and xylitol, hexahydric alcohols such as sorbitol, mannitol and dicitric acid and sugars such as sucrose, trehalose and maltose.
- dihydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-
- sorbitol is also called sorbitol, mannitol also mannitol, erythritol also erythrol, threitol also threitol, xylitol also xylitol, arabitol also arabitol and pentaerythritol also pentaerythritol.
- Partially esterified means that at least one OH group is esterified and at least one OH group is free.
- the carboxylic acid component of the partially esterified polyols for example, low fatty acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, crotonic acid, pentanoic acid, isovaleric acid, hexanoic acid, sorbic acid, middle fatty acids having 7 to 1 1 carbon atoms and higher fatty acids with 12 to 30 carbon atoms are used.
- low fatty acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, crotonic acid, pentanoic acid, isovaleric acid, hexanoic acid, sorbic acid, middle fatty acids having 7 to 1 1 carbon atoms and higher fatty acids with 12 to 30 carbon atoms are used.
- the medium and higher fatty acids include, for example, enanthic acid (C7), caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecanoic acid (C11), lauric acid (C12), tridecanoic acid (C13), myristic acid (C14), pentadecanoic acid (C14).
- the at least one compound used as component (c) is selected from polyesters which are partially esterified with carboxylic acids
- the partially esterified esters can be compounds of a certain carboxylic acid with a particular polyol; mixed esters of different carboxylic acids with one kind of polyols can also be mixed Esters of a carboxylic acid with different polyols and mixed esters of different carboxylic acids are used with different polyols.
- (c) is selected from glycerol partially esterified with carboxylic acids, sorbitol, mannitol, sucrose, maltose, trehalose, sorbitan and mixtures thereof.
- Component (c) is particularly preferably selected from polyesters which are partially esterified with fatty acids, particularly preferably from polyesters partially esterified with fatty acids with C 6 to C 24.
- the at least one compound used as component (c) is particularly preferably selected from the group consisting of glycerol, in each case partially esterified with carboxylic acids with C6 to C24, sorbitan, trehalose, sucrose, maltose, sorbitol, mannitol and mixtures thereof ,
- component (c) is selected from sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, Glycerol monopalmitate, glycerol monostearate, glycerol monooleate, glycerol monolaurate and mixtures thereof.
- component (c) it is possible to use one of the abovementioned compounds, but also mixtures of two or more thereof.
- the polymer mixtures according to the invention contain as component (b) at least one halogen-containing organic compound, which is preferably a halogenated organic flame retardant.
- Halogen-containing or halogenated in the context of the present invention means that the corresponding compound contains at least one substituent selected from the group consisting of F, Cl, Br and I.
- the at least one organic halogen-containing compound used as component (b) is preferably selected from the group consisting of bromine-containing compounds and compounds containing bromine and chlorine, in particular bromine-containing flame retardants and bromine- and chlorine-containing flame retardants.
- component (b) preferably has a halogen content of at least 30% by weight, more preferably at least 40% by weight and most preferably at least 50% by weight, based on the organic halogen-containing compound.
- Component (b) is preferably selected from the group consisting of bromine-containing flame retardants and bromine- and chlorine-containing flame retardants whose bromine content or bromine and chlorine content is at least 30% by weight, more preferably at least 40% by weight and very particularly preferably at least 50 wt .-%, based on the organic halogen-containing compound, is. Particularly preferred are aliphatic, cycloaliphatic and aromatic bromine-containing and chlorine and bromine-containing compounds.
- aliphatic, cycloaliphatic and aromatic bromine compounds having a bromine content of at least 30 wt .-%, more preferably at least 40 wt .-% and most preferably at least 50 wt .-%, based on the organic halogen-containing compound such as hexabromocyclodecane, Pentabrommonochlorcyclohexan , Pentabromochlorochlorocyclohexane, Pentabromphenylallylether, Tetrabrombisphenol-A and its ethers, tetrabromophthalic anhydride,
- component (b) is particularly preferably selected from hexabromocyclododecane, bromine-containing styrene-butadiene Copolymers and bromine and chlorine-containing styrene-butadiene copolymers.
- the styrene-butadiene copolymers are preferably present in the form of block polymers.
- the component (b) is usually in amounts of 0.05 to 5 wt .-%, preferably from 0, 1 to 4 wt .-% and particularly preferably from 0.5 to 2.5 wt .-%, based on the total weight of components (a), (b) and (c) used.
- the weight ratio of component (c) to at least one organic halogen-containing compound is preferably in the range of 0.1 to 10.
- Component (c) is preferably used in an amount of 0.05 to 5 wt.%, Preferably 0.1 to 1.5 4 wt .-% and particularly preferably from 0.1 to 2.5 wt .-%, based on the total weight of components (a), (b) and (c) used.
- the polymer mixture contains at least one polymer as component (a), preferably the at least one polymer used as component (a) is thermoplastic.
- thermoplastics are usually uncrosslinked linear or branched polymers, which can be repeatedly transferred by temperature change in a flowable or deformable state and solidified again.
- Thermoplastic polymers are often processed at higher temperatures in a flowable or deformable state, for example by injection molding and extrusion. Especially in these processes, the flame retardants contained in the polymers must be stabilized.
- component (a) is preferably selected from homopolymers and copolymers which contain vinylaromatic monomer units, in particular selected from homopolymers and copolymers which are composed of vinylaromatic monomer units.
- vinyl aromatic monomer units are styrene and C 1 -C 4 -alkyl-substituted styrenes, such as alphamethylstyrene, betamethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and ethylstyrene.
- Styrene homopolymers and styrene copolymers are preferably used as components (a), particularly preferably glass-clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene- ⁇ -methylstyrene copolymers, acrylonitrile-butadiene-styrene polymer ( ABS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylic ester copolymers (ASA), methacrylate-butadiene-styrene copolymers (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or mixtures thereof or Mixtures of the aforementioned styrenes and homopolymers and copolymers with polyphenylene ether (PPE
- the polymers and copolymers containing vinylaromatic monomer units mentioned can be used to improve the mechanical properties or for the temperature resistance optionally using compatibilizers with other thermoplastic polymers such as polyamine (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA ), Polycarbonate (PC), polyester esters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, usually in proportions of not more than 30% by weight in total , preferably in the range of 1 to 10 wt .-%, based on the total polymer mixture.
- PA polyamine
- PE polyolefins
- PE polypropylene
- PE polyethylene
- PMMA polyacrylates
- PC Polycarbonate
- PET polyethylene terephthalate
- PBT polybutylene
- mixtures in the stated quantitative range are also possible, for example, with hydrophobically modified or functionalized polymers or oligomers, rubbers such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
- hydrophobically modified or functionalized polymers or oligomers rubbers such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
- Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers containing epoxy groups or organosilanes.
- component (a) is selected from expandable / expanded styrene polymers.
- This may be, for example, so-called expandable polystyrene (EPS) or extruded polystyrene foam (XPS).
- Expandable / expanded styrene polymers generally contain one or more blowing agents in a homogeneous distribution in a proportion of 2 to 10% by weight, preferably 3 to 7% by weight, based on the polystyrene.
- Suitable blowing agents are the physical blowing agents commonly used in EPS or XPS, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers, carbon dioxide, water or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane for EPS and C0 2 , ethanol, water and fluorinated hydrocarbons for XPS.
- the polymer mixture according to the invention preferably contains
- component (c) 0.05 to 5 parts by weight of component (c).
- the polymer mixture contains
- component (c) 0.1 to 4 parts by weight of component (c), and most preferably
- component (c) 0.1 to 2.5 parts by weight of component (c).
- the weight percentages are based on the total weight of components (a), (b) and (c).
- the polymer mixture may comprise further additives customary in polymers, for example fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, athermanous compounds (eg graphite, carbon black, aluminum powder), UV Stabilizers and processing aids.
- Their proportion is generally 0 to 45, preferably 0 to 20, in particular 0 (when present 0.2) to 10 wt .-%, based on the total weight of components (a), (b) and (c).
- the preparation of the polymer mixtures according to the invention is carried out according to methods known per se by mixing the components. It may be advantageous to premix individual components. It is also possible to mix the components in solution or suspension while removing the solvent / suspension medium.
- the evaporation of the solvent mixtures can be carried out, for example, in evaporation extruder.
- the mixing of the components takes place in substance at temperatures in which the polymer or polymers used are meltable, for example by co-extrusion, kneading or rolling of the components.
- Expandable propellant-containing styrenic polymers can be prepared in the extruder, for example, by the process described in WO 2009/065880 A2 and subsequently granulated.
- the components (b) and (c) are preferably metered together.
- the two components can either be initially introduced with the styrene polymer, but can also be dispersed together via a side stream extruder or in the form of a suspension and metered into the mainstream stream of the blowing agent-containing styrene polymer melt and extruded together through a die plate, preferably with subsequent sub-water granulation.
- the process for the preparation of the polymer mixtures according to the invention thus comprises the steps
- component (i) providing the component (a), (ii) adding component (b) and (c) to component (a) and / or separately
- Another object of the present invention is the use of the polymer blends described above for the production of films, semi-finished products, foams, fibers and moldings.
- the novel polymer blends can be processed by the known process of thermoplastic processing, for example by extrusion, injection molding, calendering, blow molding or sintering.
- the invention also relates to the corresponding films, semi-finished products, foams, fibers and shaped articles containing a polymer mixture as described above.
- Another object of the present invention is the use of compounds (c) having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated flame retardants.
- halogenated organic flame retardant (b) and optionally thermal stabilizer were placed in a test tube, which was closed with a rubber stopper, which had two glass tubes. Nitrogen was introduced through one glass tube and discharged through the second glass tube. The exhaust gas flow was passed through distilled water and the conductivity of the water was recorded as a function of time.
- the hydrogen halide forming upon decomposition of the halo-containing flame retardants is introduced into the water by the carrier gas stream and increases its conductivity.
- the stability time t st is used, which indicates the time after which the conductivity has changed by 50 ⁇ 5 * ⁇ 1 .
- halogenated organic compounds used were the flame retardants hexabromocyclododecane (HBCD, CD 75-P from Chemtura Co.) and a brominated styrene-butadiene diblock copolymer (FR1, M w : 56000 g / mol, styrene block 37% by weight, 1, 2 - Vinyl content 72% by weight; prepared according to Example 8 of WO 2007/058736, with a Br content of about 60% by weight).
- HBCD hexabromocyclododecane
- FR1 brominated styrene-butadiene diblock copolymer
- thermal stabilizers zinc stearate (Sigma Aldrich), hydrotalcite (Kyowa Chemical Industry Co.), Al (OH) 3 (Nabaltec AG), glycerol tristearate (Sigma Aldrich), zeolite A (Sigma Aldrich), glycerol (Sigma Aldrich), glycidyl methacrylate Copolymer (Joncryl ADR-4368 BASF SE), brominated epoxy resin (F2200 HM, ICL Industrial Products), Mg (OH) 2 (Albemerle Co.), sorbitan monolaurate (Sigma Aldrich), glycerol monostearate (Evonik Goldschmidt), glycerol monolaurate (Danisco) sorbitan monostearate ( Sigma Aldrich), sorbitan monooleate (Sigma Aldrich), sorbitan monopalmitate (Sigma Aldrich) and glycerol monooleate (Sigma Aldrich).
- the corresponding expandable polystyrenes were first prepared by mixing 7% by weight of n-pentane into a polystyrene melt of PS 148G (viscosity number VZ: 83 ml / g, BASF SE). After cooling the propellant-containing polystyrene melt of originally 260 C ° to a temperature of 190 ° C, a polystyrene melt containing HBCD mixed with the respective stabilizer, mixed via a side stream extruder into the main stream. The mixture of Polystyrene melt, blowing agent, flame retardant and thermal stabilizer was conveyed at a rate of 60 kg / h through a die plate with 32 holes (nozzle diameter 0.75 mm).
- HBCD flame retardant
- the granules of expandable polystyrene were prefoamed by the action of flowing steam and, after 12 hours of storage, were sealed by further treatment with steam in a closed mold to form foam blocks with a density of 15 kg / m 3 .
- the fire behavior of the foam panels was determined after storage for 72 hours at a foam density of 15 kg / m 3 in accordance with DIN 4102.
- This test represents the stress due to a small, defined flame (match flame). Under this stress, the flammability and the flame propagation must be limited within a certain time. The test is carried out in a burner box equipped with a burner. The sample is flamed for 15 seconds and then the flame is removed. The duration between the start of the flame and the time at which the flame tip of the burning sample reaches a certain mark is measured, unless the flame goes out by itself.
- the compounds having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g are very suitable for the stabilization of organic halogenated compounds.
- the compounds to be used according to the invention show a significantly greater extension of time until the predetermined amount of halogenated compound is decomposed than the other thermal stabilizers known from the prior art.
- V5 glycerol tristearate
- V10 glycerin
- V7 equal proportions of glycerol tristearate and glycerol
- magnesium hydroxide which has proved to be the best stabilizer not according to the invention with respect to the stabilization of HBCD (see A, V11), reduces the flame resistance of expanded polystyrene foam equipped therewith to the extent that this polystyrene foam does not pass the B2 test exists (B, V12).
- B, V12 the flame resistance of expanded polystyrene foam equipped therewith to the extent that this polystyrene foam does not pass the B2 test exists (B, V12).
- B, V12 the known as a thermal stabilizer from the prior art hydrotalcite.
- Polystyrene foam finished according to the invention with glycerol monostearate shows very good stabilization (see A, Example 5) and passes the B2 test (B, Example 9).
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Abstract
The invention relates to polymer mixtures comprising at least one polymer, at least one organic halogenated compound such as halogenated flame retardant, and at least one further compound for thermal stabilization of the organic halogenated compound which has a hydrolysis number of 80 to 300 mg KOH/g and an OH number of 200 to 800 mg KOH/g.
Description
Halogenhaltige Polymermischungen Halogen-containing polymer blends
Beschreibung description
Die Erfindung betrifft Polymermischungen enthaltend mindestens ein Polymer, mindestens eine organische halogenierte Verbindung wie halogenierte Flammschutzmittel, sowie mindestens eine weitere Verbindung zur thermischen Stabilisierung der organischen halogenierten Verbindung. The invention relates to polymer blends containing at least one polymer, at least one organic halogenated compound such as halogenated flame retardants, and at least one further compound for thermal stabilization of the organic halogenated compound.
Polymere werden inzwischen in sehr vielen Bereichen als Werkstoffe eingesetzt, in denen auch das Brandverhalten der verwendeten Materialien von wesentlicher Bedeutung ist, beispielsweise im Baubereich, in Wohn- und Bekleidungstextilien oder im Fahrzeugbau. Daher müssen die dabei verwendeten Polymere auch die jeweils gülti- gen Brandschutzanforderungen erfüllen. Polymers are now used in many areas as materials in which the fire behavior of the materials used is of essential importance, for example in the construction sector, in living and clothing textiles or in vehicle construction. Therefore, the polymers used must also meet the applicable fire protection requirements.
Viele Polymere wie Polyolefine, Polyamide und Polystyrol sind brandgefährdet und müssen daher für viele Anwendungen mit Flammschutzmitteln ausgerüstet werden, um ein zufriedenstellendes Brandverhalten zu zeigen. Eine bei Polymeren häufig einge- setzte Klasse von Flammschutzmitteln sind die halogenierten organischen Flammschutzmittel. Die Wirkung der halogenierten Flammschutzmittel liegt darin, dass sie bei erhöhten Temperaturen Halogenradikale freisetzen. Die Halogenradikale unterbrechen die bei der Verbrennung ablaufenden Radikalkettenreaktionen durch Abfangen der die Verbrennung unterhaltenden Radikale. Als Zwischenprodukte treten dabei häufig auch Halogenwasserstoffe auf. Many polymers such as polyolefins, polyamides and polystyrene are fire-prone and therefore need to be flame-retarded for many applications to demonstrate satisfactory fire performance. A class of flame retardants commonly used in polymers are the halogenated organic flame retardants. The effect of the halogenated flame retardants is that they release halogen radicals at elevated temperatures. The halogen radicals interrupt the radical chain reactions that occur during combustion by trapping the radicals that support combustion. Hydrogen halides also frequently occur as intermediates.
Problematisch bei der Verwendung der halogenierten organischen Flammschutzverbindungen in Polymeren ist, dass die Polymere häufig bei erhöhten Temperaturen mit Flammschutzmitteln gemischt werden müssen, um eine gleichmäßige Verteilung der Flammschutzmittel in der Polymermatrix zu erreichen. Zudem werden die Polymere häufig in Formgebungsprozessen verarbeitet, die bei erhöhten Temperaturen durchgeführt werden. Bei den dabei erforderlichen Temperaturen findet häufig schon die Zersetzung eines Teiles der eingesetzten halogenierten Flammschutzmittel statt. Insbesondere bei Extrusionsprozessen sind die thermosensiblen Flammschutzmittel auf- grund der Verweilzeit und durch lokale, scherinduzierte Temperaturspitzen deutlichen Temperaturbelastungen ausgesetzt. Die Additive können hierbei abgebaut und die effektiv wirksame Menge im Produkt verringert werden. Zudem wirkt der beim Abbau der Additive entstehende Halogenwasserstoff korrosiv auf die eingesetzten Anlagen. Man ist daher dazu übergegangen, den Polymeren neben dem halogenierte organischen Flammschutzmittel einen Stabilisator zuzusetzen, der die Zersetzung des
Flammschutzmittels bei der Verarbeitung der Polymere verhindern oder zumindest verringern soll. A problem with the use of the halogenated organic flame retardant compounds in polymers is that the polymers often have to be mixed with flame retardants at elevated temperatures in order to achieve a uniform distribution of the flame retardants in the polymer matrix. In addition, the polymers are often processed in forming processes that are carried out at elevated temperatures. At the temperatures required, the decomposition of a part of the halogenated flame retardants used often takes place. In particular in extrusion processes, the thermosensitive flame retardants are exposed to significant temperature loads due to the residence time and due to local, shear-induced temperature peaks. The additives can be degraded and the effective amount in the product can be reduced. In addition, the hydrogen halide formed during the degradation of the additives has a corrosive effect on the systems used. It has therefore begun to add a stabilizer to the polymers in addition to the halogenated organic flame retardant, which decomposition of the Flame retardant in the processing of the polymers should prevent or at least reduce.
In der WO 2005/103133 A1 wird beispielsweise der Zusatz einer thermisch stabilisie- renden Menge mindestens eines Acrylat- oder Methacrylat-Polymers, das in einem Temperaturbereich von 50 bis 150C° schmilzt, beschrieben. WO 2005/103133 A1 describes, for example, the addition of a thermally stabilizing amount of at least one acrylate or methacrylate polymer which melts in a temperature range from 50 to 150 ° C.
Aus der WO 98/16574 ist die Verwendung von Zeolith A als Wärmestabilisator für ha- logenierte Flammschutzmittel bekannt. From WO 98/16574 the use of zeolite A as a heat stabilizer for halogenated flame retardants is known.
US 2003/0195286 A1 offenbart eine Flammschutzadditivzusammensetzung mit verbesserter thermischer Stabilität, die ein Alkylzinnmerkaptoalkanoat und einen Zeolithen enthält. Gemäß WO 98/16579 werden Zinkverbindungen wie Zinkstearat in Kombination mit Zeolithen als thermische Stabilisatoren eingesetzt. US 2003/0195286 A1 discloses a flame retardant additive composition with improved thermal stability containing an alkyl tin mercaptoalkanoate and a zeolite. According to WO 98/16579, zinc compounds such as zinc stearate are used in combination with zeolites as thermal stabilizers.
EP 0 848 727 B1 beschreibt flammhemmende Zusammensetzungen, die Hexabromcyclododecan und mindestens ein halogeniertes Epoxyharz als thermischen Stabilisator für das Hexabromcyclododecan enthalten. EP 0 848 727 B1 describes flame retardant compositions containing hexabromocyclododecane and at least one halogenated epoxy resin as thermal stabilizer for the hexabromocyclododecane.
Weiterhin können die bei Zersetzung der halogenierten Flammschutzmittel entstehenden Halogenwasserstoffe durch Säurefänger abgefangen werden, wie dies beispielsweise in der WO 2009/065880 erwähnt wird. Dazu werden beispielsweise Hydroxide des Magnesiums, Aluminiums oder Zinks oder auch Alkalimetallcarbonate oder Alkali- metallhydrogencarbonate verwendet. Furthermore, the hydrogen halides formed on decomposition of the halogenated flame retardants can be trapped by acid scavengers, as mentioned, for example, in WO 2009/065880. For example, hydroxides of magnesium, aluminum or zinc or else alkali metal carbonates or alkali metal hydrogen carbonates are used for this purpose.
Trotz der bereits bekannten thermischen Stabilisatoren für die organischen halogenierten Flammschutzmittel besteht Bedarf an weiteren thermischen Stabilisatoren, die eine gute Wrksamkeit auf die Stabilität der Flammschutzmittel bei der Verarbeitung der Polymeren zeigen und gleichzeitig die schützende Wirkung der Flammschutzmittel nicht negativ beeinflussen. Die mit halogeniertem Flammschutzmittel und thermischem Stabilisator ausgerüsteten Polymere sollen weiterhin ein gutes Brandverhalten zeigen. Diese Aufgabe wird gelöst durch die Verwendung von Verbindungen mit einer Versei- fungszahl von 80 bis 300 mg KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g zur Stabilisierung von halogenierten Flammschutzmitteln sowie durch Polymermischungen enthaltend (a) mindestens ein Polymer, Despite the already known thermal stabilizers for the organic halogenated flame retardants, there is a need for further thermal stabilizers which exhibit good activity on the stability of the flame retardants in the processing of the polymers and at the same time do not adversely affect the protective effect of the flame retardants. The halogenated flame retardant and thermal stabilizer-treated polymers should continue to show good fire performance. This object is achieved by the use of compounds having a Versei- number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated flame retardants and by polymer blends containing (a) at least one polymer .
(b) mindestens eine organische halogenhaltige Verbindung und
(c) mindestens eine Verbindung mit einer Verseifungszahl von 80 bis 300 mg KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g. (B) at least one organic halogen-containing compound and (C) at least one compound having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g.
Überraschenderweise wurde gefunden, dass Verbindungen mit einer Verseifungszahl von 80 bis 300 mg/KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g halogenierte organische Verbindungen, insbesondere Flammschutzmittel deutlich besser thermisch stabilisieren als viele bekannte, zur thermischen Stabilisierung von halogenierten Flammschutzmitteln eingesetzte Verbindungen wie Zeolith A, bromiertes Epoxyharz oder Aluminiumhydroxid. Die aus dem Stand der Technik bekannten thermischen Sta- bilisatoren für halogenierte organische Flammschutzmittel können darüber hinaus das Brandverhalten der Polymere, das durch die Zugabe der halogenierten Verbindungen verbessert werden soll, derart negativ beeinflussen, dass einschlägige Brandschutztests nicht bestanden werden. Mit halogenierten organischen Flammschutzmitteln ausgerüstete Polymere, die erfindungsgemäß die Komponente (c) zur thermischen Stabili- sierung der Flammschutzmittel enthalten, erfüllen hingegen die entsprechenden Erfordernisse, wie anhand von Polystyrolschaum in den Beispielen gezeigt ist. It has surprisingly been found that compounds having a saponification number of 80 to 300 mg / KOH / g and an OH number of 200 to 800 mg KOH / g halogenated organic compounds, in particular flame retardants significantly better thermally stabilize than many known, for the thermal stabilization of halogenated Flame retardants used compounds such as zeolite A, brominated epoxy resin or aluminum hydroxide. The thermal stabilizers known from the prior art for halogenated organic flame retardants can also adversely affect the fire behavior of the polymers, which is to be improved by the addition of the halogenated compounds, so that relevant fire protection tests are not passed. On the other hand, polymers equipped with halogenated organic flame retardants, which according to the invention contain component (c) for the thermal stabilization of the flame retardants, fulfill the corresponding requirements, as shown by polystyrene foam in the examples.
Im Folgenden wird die Erfindung ausführlich erläutert. Ein Gegenstand der vorliegenden Erfindung ist die Verwendung von Verbindungen (c) mit einer Verseifungszahl von 80 bis 300 mg KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g zur Stabilisierung von halogenierten organischen Verbindungen, insbesondere von halogenierten organischen Flammschutzmitteln. Diese Verbindungen werden als Komponente (c) in den erfindungsgemäßen Polymermischungen einge- setzt. In the following the invention will be explained in detail. An object of the present invention is the use of compounds (c) having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated organic compounds, in particular halogenated organic flame retardants. These compounds are used as component (c) in the polymer mixtures according to the invention.
Erfindungsgemäß bevorzugt weist (c) eine Verseifungszahl von 100 bis 250mg KOH/g, besonders bevorzugt von 120 bis 220 mg KOH/g auf. Ebenfalls erfindungsgemäß bevorzugt weist (c) eine Hydroxylzahl von 200 bis 600 mg KOH/g, und besonders bevor- zugt von 220 bis 500 mg KOH/g auf. Ganz besonders bevorzugt weist (c) eine Verseifungszahl von 100 bis 220 mg KOH/g und eine OH-Zahl von 200 bis 600 mg KOH/g auf und insbesondere bevorzugt eine Verseifungszahl von 120 bis 200 mg KOH/g und eine OH-Zahl von 220 bis 500 mg KOH/g. Die Hydroxylzahl wird erfindungsgemäß nach der deutschen DIN-Norm DIN 53240 bestimmt. Die OH-Zahl bedeutet dabei die Menge an Kaliumhydroxid in Milligramm, die der Menge an Essigsäure äquivalent ist, die bei der Acetylierung von einem Gramm der Probesubstanz mit dieser reagiert. Die Verseifungszahl wird erfindungsgemäß nach der DIN EN ISO 3681 bestimmt. Dabei wird als Verseifung die Bildung von Kaliumsalzen aus Derivaten organischer Säu-
ren definiert und die Verseifungszahl als Menge Kaliumhydroxid (KOH) in Milligramm, die zum Verseifen von einem Gramm des geprüften Produktes benötigt wird. According to the invention, (c) preferably has a saponification number of 100 to 250 mg KOH / g, particularly preferably 120 to 220 mg KOH / g. Also according to the invention preferably (c) has a hydroxyl number of 200 to 600 mg KOH / g, and more preferably from 220 to 500 mg KOH / g. Very particularly preferably, (c) has a saponification number of 100 to 220 mg KOH / g and an OH number of 200 to 600 mg KOH / g, and particularly preferably a saponification number of 120 to 200 mg KOH / g and an OH number of 220 to 500 mg KOH / g. The hydroxyl number is determined according to the invention according to the German DIN standard DIN 53240. The OH number means the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid that reacts with the acetylation of one gram of the sample substance with this. The saponification number is determined according to the invention according to DIN EN ISO 3681. The saponification is the formation of potassium salts from derivatives of organic acids. and the saponification value as the amount of potassium hydroxide (KOH) in milligrams needed to saponify one gram of the product tested.
Beim Vorliegen von Säure- und/oder Epoxidgruppen in der zu untersuchenden Verbin- dung müssen diese Gruppen im Vorfeld quantifiziert werden und bei der Bestimmung der Hydroxyl- bzw. der Verseifungszahl berücksichtigt werden. Die Menge an Epoxidgruppen kann z.B. nach ASTM D 1652-04 bestimmt werden, die Menge an Säuregruppen lässt sich beispielsweise nach DIN EN 12634 bestimmen. If acid and / or epoxide groups are present in the compound to be investigated, these groups must be quantified in advance and taken into account in the determination of the hydroxyl or saponification number. The amount of epoxide groups can e.g. are determined according to ASTM D 1652-04, the amount of acid groups can be determined, for example, according to DIN EN 12634.
Erfindungsgemäß bevorzugt enthält die als Komponente (c) eingesetzte mindestens eine Verbindung höchstens 1 Gew.-%, bevorzugt höchstens 0,5 Gew.-% und besonders bevorzugt höchstens 0,2 Gew.-% Epoxidgruppen, bezogen auf das Gesamtgewicht der Verbindung, bestimmt nach ASTM 1652-04. Als Epoxidgruppe wird im Rahmen der Erfindung der gesamte Epoxidrest mit der Formel -C(H)OC(H2) mit einem Molekulargewicht von 43 g/mol verstanden. According to the invention, the at least one compound used as component (c) preferably contains at most 1% by weight, preferably at most 0.5% by weight and particularly preferably at most 0.2% by weight of epoxide groups, based on the total weight of the compound according to ASTM 1652-04. Within the scope of the invention, the epoxy group is understood as meaning the entire epoxide radical of the formula -C (H) OC (H 2 ) having a molecular weight of 43 g / mol.
Ebenfalls erfindungsgemäß bevorzugt weist die als Komponente (c) eingesetzte mindestens eine Verbindung eine Säurezahl von höchstens 15 mg KOH/g, bevorzugt höchstens 10 mg KOH/g und besonders bevorzugt von höchstens 5mg KOH/g, be- stimmt nach DIN EN 12634 auf. Likewise preferred according to the invention, the at least one compound used as component (c) has an acid number of at most 15 mg KOH / g, preferably at most 10 mg KOH / g and particularly preferably at most 5 mg KOH / g, determined according to DIN EN 12634.
Erfindungsgemäß besonders bevorzugt enthält die als Komponente (c) eingesetzte mindestens eine Verbindung höchstens die vorstehend angegebenen Mengen an Epoxidgruppen und höchstens die vorstehend angegebenen Säurezahlen auf. According to the invention, the at least one compound used as component (c) most preferably contains at most the above-stated amounts of epoxide groups and at most the acid numbers given above.
Die als Komponente (c) eingesetzte mindestens eine Verbindung enthält Carbonsäureestergruppen und freie OH-Gruppen. Gemäß einer besonders bevorzugten Ausführungsform der Erfindung enthält die als Komponente (c) eingesetzte mindestens eine Verbindung als funktionelle Gruppen lediglich OH- und Carbonsäureestergruppen. Dabei wird die Komponente (c) ganz besonders bevorzugt aus mit Carbonsäuren teilveresterten Polyolen ausgewählt. The at least one compound used as component (c) contains carboxylic acid ester groups and free OH groups. According to a particularly preferred embodiment of the invention, the at least one compound used as component (c) contains as functional groups only OH and carboxylic ester groups. In this case, component (c) is very particularly preferably selected from polyesters which have been partially esterified with carboxylic acids.
Ein Polyol ist erfindungsgemäß eine Verbindung mit mindestens zwei OH-Gruppen. Dazu gehören beispielsweise zweiwertige Alkohle wie Ethylenglycol, 1 ,2- Propylenglycol, 1 ,3-Propylenglycol, 1 ,4-Butandiol, 1 ,3-Butandiol, Alkohole mit 3 OH- Gruppen wie Trimethylolmethan und Glycerin, vierwertige Alkohole wie Threit, Erythrit, Sorbitan (cyclisches Anhydrid des Sorbits) und Pentaerythrit, fünfwertige Alkohole wie Arabit, Adonit und Xylit, sechswertige Alkohole wie Sorbitol, Mannitol und Duicit und Zucker wie Saccharose, Trehalose und Maltose. Üblicherweise wird Sorbit auch Sorbitol, Mannit auch Mannitol, Erythrit auch Erythrol, Threit auch Threitol, Xylit auch Xylitol, Arabit auch Arabitol und Pentaerythrit auch Pentaerythritol genannt.
Teilverestert bedeutet, dass mindestens eine OH-Gruppe verestert vorliegt und mindestens eine OH-Gruppe frei vorliegt. Als Carbonsäurekomponente der teilveresterten Polyole können beispielsweise niedrige Fettsäuren mit 1 bis 6 C-Atomen wie Ameisensäure, Essigsäure, Propionsäure, Acrylsäure, Buttersäure, Isobuttersäure, Crotonsäure, Pentansäure, Isovaleriansäure, Hexansäure, Sorbinsäure, mittlere Fettsäuren mit 7 bis 1 1 C-Atomen und höhere Fettsäuren mit 12 bis 30 C-Atomen eingesetzt werden. Unter die mittleren und höheren Fettsäuren fallen beispielsweise Önanthsäure (C7), Caprylsäure (C8), Pelargonsäure (C9), Caprinsäure (C10), Undecansäure (C11), Laurinsäure (C12), Tridecansäure (C13), Myristinsäure (C14), Pentadecansäure (C15), Palmitinsäure (C16), Palmitoleinsäure (C16), Margarinsäure (C17), Stearinsäure (C18), Linolsäure (C18), Elaeosterarin (C18), Ölsäure (C18), Nonadecansäure (C19), Arachinsäure (C20), Arachidonsäure (C20), Behensäure (C22), Erucaöl (C22), Lignocerinsäure (C24), Cerotinsäure (C26), Melissinsäure (C30). Unter den Fettsäuren sind diejenigen mit 6 bis 24 C-Atomen bevorzugt, insbesondere Laurinsäure, Palmitinsäure, Stearinsäure und Ölsäure. Wird die als Komponente (c) eingesetzte mindestens eine Verbindung aus mit Carbonsäuren teilveresterten Polyolen ausgewählt, kann es sich bei den teilweise veresterte Estern um Verbindungen einer bestimmten Carbonsäure mit einem bestimmten Polyol handeln, es können auch gemischte Ester verschiedener Carbonsäure mit einer Sorte Polyolen, gemischte Ester einer Carbonsäure mit verschiedenen Polyolen sowie ge- mischte Ester aus verschiedenen Carbonsäuren mit verschiedenen Polyolen eingesetzt werden. A polyol according to the invention is a compound having at least two OH groups. These include, for example, dihydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, alcohols having 3 OH groups such as trimethylolmethane and glycerol, tetrahydric alcohols such as Threit, erythritol, Sorbitan (cyclic anhydride of sorbitol) and pentaerythritol, pentahydric alcohols such as arabitol, adonitol and xylitol, hexahydric alcohols such as sorbitol, mannitol and dicitric acid and sugars such as sucrose, trehalose and maltose. Usually sorbitol is also called sorbitol, mannitol also mannitol, erythritol also erythrol, threitol also threitol, xylitol also xylitol, arabitol also arabitol and pentaerythritol also pentaerythritol. Partially esterified means that at least one OH group is esterified and at least one OH group is free. As the carboxylic acid component of the partially esterified polyols, for example, low fatty acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, crotonic acid, pentanoic acid, isovaleric acid, hexanoic acid, sorbic acid, middle fatty acids having 7 to 1 1 carbon atoms and higher fatty acids with 12 to 30 carbon atoms are used. The medium and higher fatty acids include, for example, enanthic acid (C7), caprylic acid (C8), pelargonic acid (C9), capric acid (C10), undecanoic acid (C11), lauric acid (C12), tridecanoic acid (C13), myristic acid (C14), pentadecanoic acid (C14). C15), palmitic acid (C16), palmitoleic acid (C16), margarine (C17), stearic acid (C18), linoleic acid (C18), elaeosterarin (C18), oleic acid (C18), nonadecanoic acid (C19), arachidic acid (C20), arachidonic acid (C18) C20), behenic acid (C22), eruca oil (C22), lignoceric acid (C24), cerotic acid (C26), melissinic acid (C30). Among the fatty acids, those having 6 to 24 carbon atoms are preferable, especially lauric acid, palmitic acid, stearic acid and oleic acid. If the at least one compound used as component (c) is selected from polyesters which are partially esterified with carboxylic acids, the partially esterified esters can be compounds of a certain carboxylic acid with a particular polyol; mixed esters of different carboxylic acids with one kind of polyols can also be mixed Esters of a carboxylic acid with different polyols and mixed esters of different carboxylic acids are used with different polyols.
Bevorzugt wird (c) aus jeweils mit Carbonsäuren teilverestertem Glycerin, Sorbitol, Mannitol, Saccharose, Maltose, Trehalose, Sorbitan und Mischungen davon ausge- wählt. Preferably, (c) is selected from glycerol partially esterified with carboxylic acids, sorbitol, mannitol, sucrose, maltose, trehalose, sorbitan and mixtures thereof.
Besonders bevorzugt wird die Komponente (c) aus mit Fettsäuren teilveresterten Polyolen, besonders bevorzugt aus mit Fettsäuren mit C6 bis C24 teilveresterten Polyolen ausgewählt. Dabei ist die als Komponente (c) eingesetzte mindestens eine Verbindung besonders bevorzugt ausgewählt aus der Gruppe bestehend aus jeweils mit Carbonsäuren, insbesondere aus jeweils mit Fettsäuren mit C6 bis C24 teilverestertem Glycerin, Sorbitan, Trehalose, Saccharose, Maltose, Sorbitol, Mannitol und Mischungen davon. Erfindungsgemäß insbesondere bevorzugt wird die Komponente (c) ausgewählt aus Sorbitanmonopalmitat, Sorbitanmonostearat, Sorbitanmonooleat, Sorbitanmonolaurat,
Glycerinmonopalmitat, Glycerinmonostearat, Glycerinmonooleat, Glycerinmonolaurat und Mischungen davon. Component (c) is particularly preferably selected from polyesters which are partially esterified with fatty acids, particularly preferably from polyesters partially esterified with fatty acids with C 6 to C 24. The at least one compound used as component (c) is particularly preferably selected from the group consisting of glycerol, in each case partially esterified with carboxylic acids with C6 to C24, sorbitan, trehalose, sucrose, maltose, sorbitol, mannitol and mixtures thereof , Particularly preferred according to the invention, component (c) is selected from sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, Glycerol monopalmitate, glycerol monostearate, glycerol monooleate, glycerol monolaurate and mixtures thereof.
Als Komponente (c) kann eine der vorstehend genannten Verbindungen eingesetzt werden, aber auch Mischungen aus zwei oder mehreren davon. As component (c) it is possible to use one of the abovementioned compounds, but also mixtures of two or more thereof.
Die erfindungsgemäßen Polymermischungen enthalten als Komponente (b) mindestens eine halogenhaltige organische Verbindung, bei der es sich vorzugsweise um ein halogeniertes organisches Flammschutzmittel handelt. Halogenhaltig bzw. haloge- niert bedeutet im Rahmen der vorliegenden Erfindung, dass die entsprechende Verbindung mindestens einen Substituenten ausgewählt aus der Gruppe F, Cl, Br und I enthält. Bevorzugt ist die als Komponente (b) eingesetzte mindestens eine organische halogenhaltige Verbindung ausgewählt aus der Gruppe bestehend aus bromhaltigen Verbindungen und aus brom- und chlorhaltigen Verbindungen, insbesondere aus bromhaltigen Flammschutzmitteln und aus brom- und chlorhaltigen Flammschutzmitteln. The polymer mixtures according to the invention contain as component (b) at least one halogen-containing organic compound, which is preferably a halogenated organic flame retardant. Halogen-containing or halogenated in the context of the present invention means that the corresponding compound contains at least one substituent selected from the group consisting of F, Cl, Br and I. The at least one organic halogen-containing compound used as component (b) is preferably selected from the group consisting of bromine-containing compounds and compounds containing bromine and chlorine, in particular bromine-containing flame retardants and bromine- and chlorine-containing flame retardants.
Erfindungsgemäß bevorzugt weist die Komponente (b) einen Halogengehalt von mindestens 30 Gew.-%, mehr bevorzugt mindestens 40 Gew.-% und ganz besonders bevorzugt mindestens 50 Gew.-%, bezogen auf die organische halogenhaltige Verbindung, auf. According to the invention, component (b) preferably has a halogen content of at least 30% by weight, more preferably at least 40% by weight and most preferably at least 50% by weight, based on the organic halogen-containing compound.
Bevorzugt wird die Komponente (b) aus der Gruppe bestehend aus bromhaltigen Flammschutzmitteln und brom- und chlorhaltigen Flammschutzmitteln ausgewählt, de- ren Bromgehalt beziehungsweise Brom- und Chlorgehalt bei mindestens 30 Gew.-%, mehr bevorzugt mindestens 40 Gew.-% und ganz besonders bevorzugt mindestens 50 Gew.-%, bezogen auf die organische halogenhaltige Verbindung, liegt. Besonders bevorzugt sind aliphatische, cycloaliphatische und aromatische bromhaltige und chlor- und bromhaltige Verbindungen. Besonders bevorzugt sind aliphatische, cycloaliphatische und aromatische Bromverbindungen mit einem Bromgehalt von mindestens 30 Gew.-%, insbesondere bevorzugt mindestens 40 Gew.-% und ganz besonders bevorzugt mindestens 50 Gew.-%, bezogen auf die organische halogenhaltige Verbindung, wie Hexabromcyclodecan, Pentabrommonochlorcyclohexan, Pentabrommonochlorcyclohexan, Pentabromphenylallylether, Tetrabrombisphenol-A und dessen Ether, Tetrabromphtalsäureanhydrid,Component (b) is preferably selected from the group consisting of bromine-containing flame retardants and bromine- and chlorine-containing flame retardants whose bromine content or bromine and chlorine content is at least 30% by weight, more preferably at least 40% by weight and very particularly preferably at least 50 wt .-%, based on the organic halogen-containing compound, is. Particularly preferred are aliphatic, cycloaliphatic and aromatic bromine-containing and chlorine and bromine-containing compounds. Particularly preferred are aliphatic, cycloaliphatic and aromatic bromine compounds having a bromine content of at least 30 wt .-%, more preferably at least 40 wt .-% and most preferably at least 50 wt .-%, based on the organic halogen-containing compound such as hexabromocyclodecane, Pentabrommonochlorcyclohexan , Pentabromochlorochlorocyclohexane, Pentabromphenylallylether, Tetrabrombisphenol-A and its ethers, tetrabromophthalic anhydride,
Dodecanchlorpentacyclooctadecadien (Dechlorane), Chlorparaffine, bromierte Diphenylether wie Pentabromdiphenylether, Octabromdiphenylether und Decabromdiphenylether sowie bromhaltige und brom- und chlorhaltige Styrol-Butadien- Copolymere eingesetzt. Erfindungsgemäß besonders bevorzugt wird die Komponente (b) ausgewählt aus Hexabromcyclododecan, bromhaltigen Styrol-Butadien-
Copolymeren und brom- und chlorhaltigen Styrol-Butadien-Copolymeren. Die Styrol- Butadien-Copolymere liegen dabei bevorzugt in Form von Blockpolymeren vor. Dodecanchlorpentacyclooctadecadiene (dechloro), chlorinated paraffins, brominated diphenyl ethers such as pentabromodiphenyl ether, octabromodiphenyl ether and decabromodiphenyl ether and bromine-containing and bromine and chlorine-containing styrene-butadiene copolymers used. According to the invention, component (b) is particularly preferably selected from hexabromocyclododecane, bromine-containing styrene-butadiene Copolymers and bromine and chlorine-containing styrene-butadiene copolymers. The styrene-butadiene copolymers are preferably present in the form of block polymers.
Die Komponente (b) wird in der Regel in Mengen von 0,05 bis 5 Gew.-%, bevorzugt von 0, 1 bis 4 Gew.-% und besonders bevorzugt von 0,5 bis 2,5 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten (a), (b) und (c), eingesetzt. Das Gewichtsverhältnis von Komponente (c) zur mindestens einen organischen halogenhaltigen Verbindungen liegt bevorzugt im Bereich von 0,1 bis 10. Die Komponente (c) wird bevorzugt in einer Menge von 0,05 bis 5 Gew.-% bevorzugt von 0, 1 bis 4 Gew.-% und besonders bevorzugt von 0,1 bis 2,5 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten (a), (b) und (c), eingesetzt. The component (b) is usually in amounts of 0.05 to 5 wt .-%, preferably from 0, 1 to 4 wt .-% and particularly preferably from 0.5 to 2.5 wt .-%, based on the total weight of components (a), (b) and (c) used. The weight ratio of component (c) to at least one organic halogen-containing compound is preferably in the range of 0.1 to 10. Component (c) is preferably used in an amount of 0.05 to 5 wt.%, Preferably 0.1 to 1.5 4 wt .-% and particularly preferably from 0.1 to 2.5 wt .-%, based on the total weight of components (a), (b) and (c) used.
Weiterhin enthält die Polymermischung als Komponente (a) mindestens ein Polymer, bevorzugt ist das als Komponente (a) eingesetzte mindestens eine Polymer thermoplastisch. Als Thermoplasten werden üblicherweise unvernetzte lineare oder verzweigte Polymere, die wiederholt durch Temperaturänderung in einen fließfähigen beziehungsweise verformbaren Zustand überführt und wieder verfestigt werden können, bezeichnet. Thermoplastische Polymere werden häufig bei höheren Temperaturen in einem fließfähigen beziehungsweise verformbaren Zustand verarbeitet, beispielsweise durch Spritzgießen und Extrusion. Gerade bei diesen Prozessen müssen die in den Polymeren enthaltenen Flammschutzmittel stabilisiert werden. Furthermore, the polymer mixture contains at least one polymer as component (a), preferably the at least one polymer used as component (a) is thermoplastic. As thermoplastics are usually uncrosslinked linear or branched polymers, which can be repeatedly transferred by temperature change in a flowable or deformable state and solidified again. Thermoplastic polymers are often processed at higher temperatures in a flowable or deformable state, for example by injection molding and extrusion. Especially in these processes, the flame retardants contained in the polymers must be stabilized.
Erfindungsgemäß bevorzugt wird die Komponente (a) aus Homopolymeren und Copolymeren ausgewählt, die vinylaromatische Monomereinheiten enthalten, insbesondere aus Homopolymeren und Copolymeren ausgewählt, die aus vinylaromati- schen Monomereinheiten aufgebaut sind. Vinylromatische Monomereinheiten sind beispielsweise Styrol und C1- bis C4-Alkyl substituierte Styrole wie Alphamethylstyrol, Betamethylstyrol, o-Methylstyrol, m-Methylstyrol, p-Methylstyrol und Ethylstyrol. According to the invention, component (a) is preferably selected from homopolymers and copolymers which contain vinylaromatic monomer units, in particular selected from homopolymers and copolymers which are composed of vinylaromatic monomer units. Examples of vinyl aromatic monomer units are styrene and C 1 -C 4 -alkyl-substituted styrenes, such as alphamethylstyrene, betamethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and ethylstyrene.
Bevorzugt werden als Komponenten (a) Styrolhomopolymere und Styrolcopolymere eingesetzt, besonders bevorzugt glasklares Polystyrol (GPPS), Schlagzähpolystyrol (HIPS), anionisch polymerisiertes Poylstyrol oder Schlagzähpolystyrol (A-IPS), Styrol- α-Methylstyrol-Copolymere, Acrylnitril-Butadien-Styrolpolymer (ABS), Styrol-Acrylnitril- Copolymere (SAN), Acrylnitril-Styrol-Acrylester-Copolymere (ASA), Methacrylat- Butadien-Styrol-Copolymere (MBS), Methylmethacrylat-Acrylnitril-Butadien-Styrol- Copolymere (MABS) oder Mischungen davon oder Mischungen der vorgenannten Styrole und Homopolymere und Copolymere mit Polyphenylenether (PPE).
Die genannten vinylaromtische Monomereinheiten enthaltenden Polymere und Copolymere können zur Verbesserung der mechanischen Eigenschaften oder für die Temperaturbeständigkeit gegebenenfalls unter Verwendung von Verträglichkeitsvermittlern mit weiteren thermoplastischen Polymeren wie Polyamin (PA), Polyolefinen wie Polypropylen (PP) oder Polyethylen (PE), Polyacrylaten wie Polymethylmethacrylat (PMMA), Polycarbonat (PC), Poylestern wie Polyethylenterephthalat (PET) oder Polybutylenterephthalat (PBT), Polyethersulfonen (PES), Polyetherketonen oder Polyethersulfiden (PES) oder Mischungen davon abgemischt werden, in der Regel in Anteilen von insgesamt bis maximal 30 Gew.-%, bevorzugt im Bereich von 1 bis 10 Gew.-%, bezogen auf die gesamt Polymermischung. Des weiteren sind Mischungen in dem genannten Mengenbereich auch beispielsweise mit hydrophob modifizierten oder funktionalisierten Polymeren oder Oligomeren, Kautschuken wie Polyacrylaten oder Polydienen, z.B. Styrol-Butadien-Blockcopolymeren oder biologisch abbaubaren aliphatischen oder aliphatisch/aromatischen Copolyestern möglich. Styrene homopolymers and styrene copolymers are preferably used as components (a), particularly preferably glass-clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene-α-methylstyrene copolymers, acrylonitrile-butadiene-styrene polymer ( ABS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylic ester copolymers (ASA), methacrylate-butadiene-styrene copolymers (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS) or mixtures thereof or Mixtures of the aforementioned styrenes and homopolymers and copolymers with polyphenylene ether (PPE). The polymers and copolymers containing vinylaromatic monomer units mentioned can be used to improve the mechanical properties or for the temperature resistance optionally using compatibilizers with other thermoplastic polymers such as polyamine (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA ), Polycarbonate (PC), polyester esters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, usually in proportions of not more than 30% by weight in total , preferably in the range of 1 to 10 wt .-%, based on the total polymer mixture. Furthermore, mixtures in the stated quantitative range are also possible, for example, with hydrophobically modified or functionalized polymers or oligomers, rubbers such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
Als Verträglichkeitsvermittler eigenen sich z.B. Maleinsäureanhydrid-modifizierte Sty- rol-Copolymere, Epoxidgruppen enthaltende Polymere oder Organosilane. Suitable compatibilizers are e.g. Maleic anhydride-modified styrene copolymers, polymers containing epoxy groups or organosilanes.
Besonders bevorzugt wird als Komponente (a) aus expandierbaren/expandierten Styrolpolymeren ausgewählt. Dabei kann es sich beispielsweise um so genanntes expandierbares Polystyrol (EPS) oder um extrudierten Polystyrolschaum (XPS) handeln. Expandierbare/expandierte Styrolpolymere enthalten in der Regel ein oder mehrere Treibmittel in homogener Verteilung in einem Anteil von insgesamt 2 bis 10 Gew.- %, bevorzugt 3 bis 7 Gew.-% bezogen auf das Polystyrol. Als Treibmittel eignen sich die üblicherweise in EPS bzw. XPS eingesetzten physikalischen Treibmittel wie aliphatische Kohlenwasserstoffe mit 2 bis 7 Kohlenstoffatomen, Alkohole, Ketone, Ether, Kohlenstoffdioxid, Wasser oder halogenierte Kohlenwasserstoffe. Bevorzugt werden iso-Butan, n-Butan, iso-Pentan, n-Pentan für EPS und C02, Ethanol, Wasser und fluorierte Kohlenwasserstoffe für XPS eingesetzt. Particularly preferred as component (a) is selected from expandable / expanded styrene polymers. This may be, for example, so-called expandable polystyrene (EPS) or extruded polystyrene foam (XPS). Expandable / expanded styrene polymers generally contain one or more blowing agents in a homogeneous distribution in a proportion of 2 to 10% by weight, preferably 3 to 7% by weight, based on the polystyrene. Suitable blowing agents are the physical blowing agents commonly used in EPS or XPS, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers, carbon dioxide, water or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane for EPS and C0 2 , ethanol, water and fluorinated hydrocarbons for XPS.
Die erfindungsgemäße Polymermischung enthält bevorzugt The polymer mixture according to the invention preferably contains
90 bis 99,9 Gew.-% Komponente (a), From 90 to 99.9% by weight of component (a),
0,05 bis 5 Gew.-% Komponente (b) und 0.05 to 5 wt .-% of component (b) and
0,05 bis 5 Gew.- Komponente (c). 0.05 to 5 parts by weight of component (c).
Erfindungsgemäß mehr bevorzugt enthält die Polymermischung More preferably, according to the invention, the polymer mixture contains
92 bis 99,8 Gew.-% Komponente (a), From 92 to 99.8% by weight of component (a),
0,1 bis 4 Gew.-% Komponente (b) und 0.1 to 4 wt .-% of component (b) and
0,1 bis 4 Gew.- Komponente (c),
und ganz besonders bevorzugt 0.1 to 4 parts by weight of component (c), and most preferably
95 bis 99,4 Gew.-% Komponente (a), From 95 to 99.4% by weight of component (a),
0,5 bis 2,5 Gew.-% Komponente (b) und 0.5 to 2.5 wt .-% of component (b) and
0, 1 bis 2,5 Gew.- Komponente (c). 0.1 to 2.5 parts by weight of component (c).
Die Gew.-% beziehen sich jeweils auf das Gesamtgewicht der Komponenten (a), (b) und (c). The weight percentages are based on the total weight of components (a), (b) and (c).
Die Polymermischung kann neben den Komponenten (a) bis (c) weitere, in Polymeren übliche Additive enthalten, beispielsweise Füllstoffe, Weichmacher, lösliche und unlöslich anorganische und/oder organische Farbstoffe und Pigmente, athermane Verbindungen (z.B. Graphit, Ruß, Aluminiumpulver), UV-Stabilisatoren und Verarbeitungs- hilfsmittel. Deren Anteil beträgt im Allgemeinen 0 bis 45, vorzugsweise 0 bis 20, insbesondere 0 (bei Vorliegen 0,2) bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten (a), (b) und (c). In addition to the components (a) to (c), the polymer mixture may comprise further additives customary in polymers, for example fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments, athermanous compounds (eg graphite, carbon black, aluminum powder), UV Stabilizers and processing aids. Their proportion is generally 0 to 45, preferably 0 to 20, in particular 0 (when present 0.2) to 10 wt .-%, based on the total weight of components (a), (b) and (c).
Die Herstellung der erfindungsgemäßen Polymermischungen erfolgt nach an sich be- kannten Verfahren durch Mischen der Komponenten. Es kann vorteilhaft sein, einzelne Komponenten vorzumischen. Auch das Mischen der Komponenten in Lösung oder Suspension unter Entfernen der Lösungsmittel/Suspensionsmedium ist möglich. Das Eindampfen der Lösungsmittelgemische kann beispielsweise in Eindampfextruder erfolgen. Vorzugsweise geschieht das Mischen der Komponenten in Substanz bei Tem- peraturen, in denen das oder die eingesetzten Polymere schmelzfähig sind, beispielsweise durch gemeinsames Extrudieren, Kneten oder Verwalzen der Komponenten. The preparation of the polymer mixtures according to the invention is carried out according to methods known per se by mixing the components. It may be advantageous to premix individual components. It is also possible to mix the components in solution or suspension while removing the solvent / suspension medium. The evaporation of the solvent mixtures can be carried out, for example, in evaporation extruder. Preferably, the mixing of the components takes place in substance at temperatures in which the polymer or polymers used are meltable, for example by co-extrusion, kneading or rolling of the components.
Expandierbare, treibmittelhaltige Styrolpolymere können beispielsweise nach dem in der WO 2009/065880 A2 beschriebenen Verfahren im Extruder hergestellt und an- schließend granuliert werden. Dabei werden die Komponenten (b) und (c) bevorzugt gemeinsam dosiert. Die beiden Komponenten können entweder mit dem Styrolpolymer vorgelegt werden, können jedoch auch gemeinsam über einen Seitenstromextruder oder in Form einer Suspension dispergiert und der treibmittelhaltigen Styrolpolymerschmelze im Hauptstrom zu dosiert und gemeinsam durch eine Düsen- platte, bevorzugt mit anschießender Unter-Wasser Granulation extrudiert werden. Expandable propellant-containing styrenic polymers can be prepared in the extruder, for example, by the process described in WO 2009/065880 A2 and subsequently granulated. The components (b) and (c) are preferably metered together. The two components can either be initially introduced with the styrene polymer, but can also be dispersed together via a side stream extruder or in the form of a suspension and metered into the mainstream stream of the blowing agent-containing styrene polymer melt and extruded together through a die plate, preferably with subsequent sub-water granulation.
Das Verfahren zur Herstellung der erfindungsgemäßen Polymermischungen umfasst somit die Schritte The process for the preparation of the polymer mixtures according to the invention thus comprises the steps
(i) Bereitstellen der Komponente (a),
(ii) Gemeinsame oder getrennte Zugabe von Komponente (b) und (c) zu Komponente (a) und (i) providing the component (a), (ii) adding component (b) and (c) to component (a) and / or separately
(iii) Mischen der Komponenten. Weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der vorstehend beschriebenen Polymermischungen zur Herstellung von Folien, Halbzeugen, Schäumen, Fasern und Formkörpern. Die erfindungsgemäßen Polymermischungen können nach dem bekannten Verfahren der Thermoplastverarbeitung verarbeitet werden, beispielsweise durch Extrudieren, Spritzgießen, Kalandrieren, Hohlkörperblasen oder Sin- tern. (iii) mixing the components. Another object of the present invention is the use of the polymer blends described above for the production of films, semi-finished products, foams, fibers and moldings. The novel polymer blends can be processed by the known process of thermoplastic processing, for example by extrusion, injection molding, calendering, blow molding or sintering.
Die Erfindung betrifft auch die entsprechenden Folien, Halbzeuge, Schäume, Fasern und Formkörper enthaltend eine Polymermischung wie vorstehend beschrieben. Weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der Verbindungen (c) mit einer Verseifungszahl von 80 bis 300 mg KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g zur Stabilisierung von halogenierten Flammschutzmitteln. The invention also relates to the corresponding films, semi-finished products, foams, fibers and shaped articles containing a polymer mixture as described above. Another object of the present invention is the use of compounds (c) having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of halogenated flame retardants.
Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert. The invention is explained in more detail by the following examples.
A) Thermostabilität (erfindungsgemäße Beispiele 1 bis 8, Vergleichsbeispiele V1 bis V11 ) A) Thermostability (Inventive Examples 1 to 8, Comparative Examples V1 to V11)
Zunächst wurde die Eignung verschiedener Verbindungen als thermische Stabilisato- ren für organische, bromhaltige Flammschutzmittel getestet, indem die HBr- Freisetzung bei 200 °C in Analogie zur Bestimmung der Thermostabilität von PVC (HCI-Freisetzung gemäß DIN 53381 , Verfahren B) bestimmt wurde. Dazu wurde eine kleine Menge der zu untersuchenden Probe (halogeniertes organisches Flammschutzmittel (b) und ggf. thermischer Stabilisator) in ein Reagenzglas eingefüllt, das mit einem Gummistopfer verschlossen wurde, der zwei Glasrohre aufwies. Durch das eine Glasrohr wurde Stickstoff eingeleitet und durch das zweite Glasrohr wieder abgeleitet. Der Abgasstrom wurde durch destilliertes Wasser geführt und die Leitfähigkeit des Wassers in Abhängigkeit von der Zeit aufgezeichnet. Der sich bei Zersetzung der halo- genhaltigen Flammschutzmittel bildende Halogenwasserstoff wird durch den Träger- gasstrom in das Wasser eingeleitet und erhöht dessen Leitfähigkeit. Als Maß für die Stabilisierung wird die Stabilitätszeit tst herangezogen, die die Zeit angibt, nach der sich die Leitfähigkeit um 50 μ5*οηΤ1 geändert hat. First, the suitability of various compounds as thermal stabilizers for organic, bromine-containing flame retardants was tested by the HBr release at 200 ° C in analogy to the determination of the thermal stability of PVC (HCI release according to DIN 53381, method B) was determined. For this purpose, a small amount of the sample to be examined (halogenated organic flame retardant (b) and optionally thermal stabilizer) was placed in a test tube, which was closed with a rubber stopper, which had two glass tubes. Nitrogen was introduced through one glass tube and discharged through the second glass tube. The exhaust gas flow was passed through distilled water and the conductivity of the water was recorded as a function of time. The hydrogen halide forming upon decomposition of the halo-containing flame retardants is introduced into the water by the carrier gas stream and increases its conductivity. As a measure of the stabilization, the stability time t st is used, which indicates the time after which the conductivity has changed by 50 μ 5 * ηηΤ 1 .
Als halogenierte organische Verbindung wurden die Flammschutzmittel Hexabromcyclododecan (HBCD; CD 75-P von Chemtura Co.) und ein bromiertes Sty- rol-Butadien-Diblockcopolymer (FR1 ; Mw: 56000g/mol, Styrolblock 37 Gew.-%, 1 ,2-
Vinylanteil 72 Gew.-%; hergestellt nach Beispiel 8 der WO 2007/058736, mit einem Br- Gehalt von etwa 60 Gew.-%) eingesetzt. The halogenated organic compounds used were the flame retardants hexabromocyclododecane (HBCD, CD 75-P from Chemtura Co.) and a brominated styrene-butadiene diblock copolymer (FR1, M w : 56000 g / mol, styrene block 37% by weight, 1, 2 - Vinyl content 72% by weight; prepared according to Example 8 of WO 2007/058736, with a Br content of about 60% by weight).
Als thermische Stabilisatoren wurden Zinkstearat (Sigma Aldrich), Hydrotalcit (Kyowa Chemical Industry Co.), AI(OH)3 (Nabaltec AG), Glycerintristearat (Sigma Aldrich), Zeolith A (Sigma Aldrich), Glycerin (Sigma Aldrich), Glycidylmethacrylat-Copolymer (Joncryl ADR-4368 BASF SE), bromiertes Epoxidharz (F2200 HM, ICL Industrial Products), Mg (OH)2 (Albemerle Co.), Sorbitanmonolaurat (Sigma Aldrich), Glycerinmonostearat (Evonik Goldschmidt), Glycerinmonolaurat (Danisco) Sorbitanmonostearat (Sigma Aldrich), Sorbitanmonooleat (Sigma Aldrich), Sorbitanmonopalmitat (Sigma Aldrich) und Glycerinmonooleat (Sigma Aldrich) verwendet. As thermal stabilizers, zinc stearate (Sigma Aldrich), hydrotalcite (Kyowa Chemical Industry Co.), Al (OH) 3 (Nabaltec AG), glycerol tristearate (Sigma Aldrich), zeolite A (Sigma Aldrich), glycerol (Sigma Aldrich), glycidyl methacrylate Copolymer (Joncryl ADR-4368 BASF SE), brominated epoxy resin (F2200 HM, ICL Industrial Products), Mg (OH) 2 (Albemerle Co.), sorbitan monolaurate (Sigma Aldrich), glycerol monostearate (Evonik Goldschmidt), glycerol monolaurate (Danisco) sorbitan monostearate ( Sigma Aldrich), sorbitan monooleate (Sigma Aldrich), sorbitan monopalmitate (Sigma Aldrich) and glycerol monooleate (Sigma Aldrich).
Die Verseifungszahl und die Hydroxidzahl von Glycerinmonostearat, Sorbitanmonostearat und Sorbitanmonolaurat wurden wie in der Beschreibung dargestellt bestimmt. Die Ergebnisse sind in Tabelle 1 zu sehen. The saponification number and the hydroxide number of glycerol monostearate, sorbitan monostearate and sorbitan monolaurate were determined as shown in the description. The results are shown in Table 1.
Tabelle 1 Table 1
Es wurden jeweils 0,2 Gramm thermischer Stabilisator auf ein Gramm halogeniertes organisches Flammschutzmittel eingesetzt. Die Ergebnisse der Stabilitätstests sind in Tabelle 2 zusammengefasst.
0.2 grams of thermal stabilizer per one gram of halogenated organic flame retardant were used. The results of the stability tests are summarized in Table 2.
Tabelle 2: Einfluss unterschiedlicher Stabilisatoren auf die Stabilität von bromierten organischen Flammschutzmitteln Table 2: Influence of different stabilizers on the stability of brominated organic flame retardants
B) Brandverhalten (erfindungsgemäßes Beispiel 9, Vergleichsbeispiele V12 und V13) B) Fire Behavior (Inventive Example 9, Comparative Examples V12 and V13)
Weiterhin wurde für verschiedene thermische Stabilisatoren in mit HBCD ausgerüste- tem Polystyrolschaumstoff der Brandschutztest B2 nach DIN 4102 durchgeführt. Furthermore, the fire protection test B2 according to DIN 4102 was carried out for various thermal stabilizers in HBCD-finished polystyrene foam.
Dazu wurden zunächst die entsprechenden expandierbaren Polystyrole hergestellt, indem 7 Gew.-% n-Pentan in eine Polystyrolschmelze aus PS 148G (Viskositätszahl VZ: 83 ml/ g, BASF SE) eingemischt wurden. Nach Abkühlen der treibmittelhaltigen Polystyrolschmelze von ursprünglich 260 C° auf eine Temperatur von 190 °C wurde eine Polystyrolschmelze, die HBCD gemischt mit dem jeweiligen Stabilisator enthielt, über einen Seitenstromextruder in den Hauptstrom eingemischt. Das Gemisch aus
Polystyrolschmelze, Treibmittel, Flammschutzmittel und thermischem Stabilisator wurde mit einer Förderrate von 60 kg/h durch eine Düsenplatte mit 32 Bohrungen (Durchmesser der Düsen 0,75 mm) gefördert. Mit Hilfe einer druckbeaufschlagten Unterwas- sergranulierung wurden kompakte Granulate aus expandierbarem Polystyrol mit enger Größenverteilung erhalten. Die Polystyrole enthielten jeweils 2 Gew.-% Flammschutzmittel (HBCD) und 0,2 Gew.-% des zu testenden thermischen Stabilisators. For this purpose, the corresponding expandable polystyrenes were first prepared by mixing 7% by weight of n-pentane into a polystyrene melt of PS 148G (viscosity number VZ: 83 ml / g, BASF SE). After cooling the propellant-containing polystyrene melt of originally 260 C ° to a temperature of 190 ° C, a polystyrene melt containing HBCD mixed with the respective stabilizer, mixed via a side stream extruder into the main stream. The mixture of Polystyrene melt, blowing agent, flame retardant and thermal stabilizer was conveyed at a rate of 60 kg / h through a die plate with 32 holes (nozzle diameter 0.75 mm). By means of a pressurized underwater granulation, compact granules of expandable polystyrene having a narrow size distribution were obtained. The polystyrenes each contained 2% by weight of flame retardant (HBCD) and 0.2% by weight of the thermal stabilizer to be tested.
Durch Einwirkung von strömendem Wasserdampf wurden die Granulate aus expandierbarem Polystyrol vorgeschäumt und nach 12-stündiger Lagerung durch wei- tere Behandlung mit Wasserdampf in einer geschlossenen Form zu Schaumstoffblöcken mit einer Dichte von 15 kg/m3 verschweißt. The granules of expandable polystyrene were prefoamed by the action of flowing steam and, after 12 hours of storage, were sealed by further treatment with steam in a closed mold to form foam blocks with a density of 15 kg / m 3 .
Die Ermittlung des Brandverhaltens der Schaumstoffplatten erfolgte nach 72-stündiger Lagerung bei einer Schaumstoffdichte von 15 kg/m3 gemäß DIN 4102. Diese Prüfung stellt die Beanspruchung durch eine kleine, definierte Flamme (Streichholzflamme) dar. Unter dieser Beanspruchung müssen die Entzündbarkeit und die Flammenausbreitung innerhalb einer bestimmten Zeit begrenzt sein. Die Prüfung wird in einem mit einem Brenner ausgerüsteten Brennkasten durchgeführt. Dabei wird die Probe 15 Sekunden beflammt und anschließend die Flamme entfernt. Die Dauer zwischen Beginn der Beflammung und dem Zeitpunkt, an der die Flammenspitze der brennenden Probe eine bestimmte Messmarke erreicht, wird gemessen sofern die Flamme nicht von selbst erlischt. The fire behavior of the foam panels was determined after storage for 72 hours at a foam density of 15 kg / m 3 in accordance with DIN 4102. This test represents the stress due to a small, defined flame (match flame). Under this stress, the flammability and the flame propagation must be limited within a certain time. The test is carried out in a burner box equipped with a burner. The sample is flamed for 15 seconds and then the flame is removed. The duration between the start of the flame and the time at which the flame tip of the burning sample reaches a certain mark is measured, unless the flame goes out by itself.
Die Ergebnisse sind in Tabelle 3 wiedergegeben. The results are shown in Table 3.
Tabelle 3: Brandtest B2 Table 3: Fire test B2
Aus Tabelle 2 geht deutlich hervor, dass sich die Verbindungen mit einer Verseifungs- zahl von 80 bis 300 mg KOH/g und einer OH-Zahl von 200 bis 800 mg KOH/g sehr gut zur Stabilisierung von organischen halogenierten Verbindungen eignen. Abgesehen von Magnesiumhydroxid zeigen die erfindungsgemäß zu verwendenden Verbindungen eine deutlich größere Verlängerung der Zeit, bis die vorgegebene Menge der haloge- nierten Verbindung zersetzt wird, als die weiteren aus dem Stand der Technik bekannten thermischen Stabilisatoren. Insbesondere der Vergleich von V5 (Glycerintristearat),
V10 (Glycerin) und V7 (gleiche Anteile an Glycerintristearat und Glycerin) zeigt, dass es sich nicht einfach um einen Effekt handelt, der durch die Gegenwart von freien OH- Gruppen und Carbonsäureestergruppen hervorgerufen wird, sondern dass beide funktionelle Gruppen gemeinsam in einer Verbindung vorhanden sein müssen, um die thermische Stabilisierung der halogenhaltigen Verbindungen zu erreichen. It is clear from Table 2 that the compounds having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g are very suitable for the stabilization of organic halogenated compounds. Apart from magnesium hydroxide, the compounds to be used according to the invention show a significantly greater extension of time until the predetermined amount of halogenated compound is decomposed than the other thermal stabilizers known from the prior art. In particular, the comparison of V5 (glycerol tristearate), V10 (glycerin) and V7 (equal proportions of glycerol tristearate and glycerol) show that it is not simply an effect caused by the presence of free OH groups and carboxylic acid ester groups, but that both functional groups coexist in a compound must be in order to achieve the thermal stabilization of the halogen-containing compounds.
Aus Tabelle 3 wird deutlich, dass Magnesiumhydroxid, das sich hinsichtlich der Stabilisierung von HBCD (siehe A, V11)) als der beste nicht erfindungsgemäße Stabilisator erwiesen hat, den Flammwiderstand von damit ausgerüstetem expandierten Polystyrolschaumstoff soweit herabsetzt, dass dieser Polystyrolschaumstoff den B2- Test nicht besteht (B, V12). Gleiches gilt für das als thermischer Stabilisator aus dem Stand der Technik bekannte Hydrotalcit. Erfindungsgemäß mit Glycerinmonostearat ausgerüsteter Polystyrolschaumstoff zeigt eine sehr gute Stabilisierung (siehe A, Beispiel 5) und besteht den B2-Test (B, Beispiel 9).
It is clear from Table 3 that magnesium hydroxide, which has proved to be the best stabilizer not according to the invention with respect to the stabilization of HBCD (see A, V11), reduces the flame resistance of expanded polystyrene foam equipped therewith to the extent that this polystyrene foam does not pass the B2 test exists (B, V12). The same applies to the known as a thermal stabilizer from the prior art hydrotalcite. Polystyrene foam finished according to the invention with glycerol monostearate shows very good stabilization (see A, Example 5) and passes the B2 test (B, Example 9).
Claims
Polymermischung enthaltend Containing polymer mixture
(a) mindestens ein Polymer, (a) at least one polymer,
(b) mindestens eine organische halogenhaltige Verbindung und (B) at least one organic halogen-containing compound and
(c) mindestens eine Verbindung mit einer Verseifungszahl von 80 bis 300 mg KOH /g und einer OH-Zahl von 200 bis 800 mg KOH/g. (C) at least one compound having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g.
Polymermischung nach Anspruch 1 dadurch gekennzeichnet, dass die als Komponente (b) eingesetzte mindestens eine organische halogenhaltige Verbindung ein Flammschutzmittel ist. Polymer mixture according to claim 1, characterized in that the component (b) used at least one organic halogen-containing compound is a flame retardant.
Polymermischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Polymermischung Polymer mixture according to claim 1 or 2, characterized in that the polymer mixture
90 bis 99,9 Gew.- % (a), From 90 to 99.9% by weight (a),
0,05 bis 5 Gew.- % (b) und 0.05 to 5% by weight (b) and
0,05 bis 5 Gew.- % (c) enthält, bezogen auf das Gesamtgewicht der Komponenten (a), (b) und (c). 0.05 to 5% by weight (c), based on the total weight of components (a), (b) and (c).
Polymermischung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die als Komponente (c) eingesetzte mindestens eine Verbindung Carbonsäureestergruppen und freie OH-Gruppen enthält. Polymer mixture according to one of claims 1 to 3, characterized in that the at least one compound used as component (c) contains carboxylic acid ester groups and free OH groups.
Polymermischung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die als Komponente (c) eingesetzte mindestens eine Verbindung ausgewählt ist aus mit Carbonsäuren teilveresterten Polyolen. Polymer mixture according to one of claims 1 to 4, characterized in that the at least one compound used as component (c) is selected from partially esterified polyols with carboxylic acids.
Polymermischung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die als Komponente (c) eingesetzte mindestens eine Verbindung ausgewählt ist aus mit Fettsäuren teilveresterten Polyolen. Polymer mixture according to one of claims 1 to 5, characterized in that the at least one compound used as component (c) is selected from partially esterified with fatty acids polyols.
Polymermischung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die als Komponente (c) eingesetzte mindestens eine Verbindung ausgewählt ist aus der Gruppe bestehend aus jeweils mit Carbonsäuren teilverestertem Glycerin, Sorbitan, Trehalose, Saccharose, Maltose, Sorbitol, Mannitol und Mischungen davon. Polymer mixture according to one of claims 1 to 5, characterized in that the at least one compound used as component (c) is selected from the group consisting of each partially esterified with carboxylic acids glycerol, sorbitan, trehalose, sucrose, maltose, sorbitol, mannitol and mixtures thereof ,
8. Polymermischung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die als Komponente (b) eingesetzte mindestens eine organische halogen- haltige Verbindung ausgewählt ist aus der Gruppe bestehend aus bromhaltigen Verbindungen und aus brom- und chlorhaltigen Verbindungen. 8. Polymer mixture according to one of claims 1 to 7, characterized in that the component (b) used at least one organic halogen-containing compound is selected from the group consisting of bromine-containing compounds and of bromine and chlorine-containing compounds.
9. Polymermischung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die die als Komponente (b) eingesetzte mindestens eine organische halo- genhaltige Verbindung ausgewählt ist aus der Gruppe bestehend aus bromhalti- gen aliphatischen, cycloaliphatischen und aromatischen Verbindungen und brom- und chlorhaltigen aliphatischen, cycloaliphatischen und aromatischen Verbindungen. 9. Polymer mixture according to one of claims 1 to 8, characterized in that the at least one organic halo-containing compound used as component (b) is selected from the group consisting of bromine-containing aliphatic, cycloaliphatic and aromatic compounds and bromo and chlorine-containing aliphatic, cycloaliphatic and aromatic compounds.
10. Polymermischung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die als Komponente (b) eingesetzte mindestens eine organische halogen- haltige Verbindung ausgewählt ist aus der Gruppe bestehend aus Hexabromcyclododecan, bromhaltigen Styrol-Butadien-Copolymeren und brom- und chlorhaltigen Styrol-Butadien-Copolymeren. 10. Polymer mixture according to one of claims 1 to 9, characterized in that as component (b) used at least one organic halogen-containing compound is selected from the group consisting of Hexabromcyclododecan, bromine-containing styrene-butadiene copolymers and bromine and chlorine-containing styrene butadiene copolymers.
1 1. Polymermischung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das als Komponente (a) eingesetzte mindestens eine Polymer thermoplastisch ist. 1 1. A polymer mixture according to any one of claims 1 to 10, characterized in that the component (a) used at least one polymer is thermoplastic.
12. Polymermischung nach einem der Ansprüche 1 bis 1 1 , dadurch gekennzeichnet, dass das als Komponente (a) eingesetzte mindestens eine Polymer ausgewählt ist aus Homopolymeren und Copolymeren enthaltend vinylaromatische Monomereinheiten. 12. Polymer mixture according to one of claims 1 to 1 1, characterized in that the at least one polymer used as component (a) is selected from homopolymers and copolymers containing vinyl aromatic monomer units.
13. Polymermischung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass das als Komponente (a) eingesetzte mindestens eine Polymer ausgewählt ist aus Homopolymeren und Copolymeren aufgebaut aus vinylaromatische Monomereinheiten. 13. Polymer mixture according to one of claims 1 to 12, characterized in that the at least one polymer used as component (a) is selected from homopolymers and copolymers composed of vinylaromatic monomer units.
14. Polymermischung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass das als Komponente (a) eingesetzte mindestens eine Polymer expandierbares/expandiertes Polystyrol ist. 14. Polymer mixture according to one of claims 1 to 13, characterized in that the at least one polymer used as component (a) is expandable / expanded polystyrene.
15. Verwendung von Verbindungen mit einer Verseifungszahl von 80 bis 300 mg KOH /g und einer OH-Zahl von 200 bis 800 mg KOH/g zur Stabilisierung von or- ganischen halogenierten Flammschutzmitteln. 15. Use of compounds having a saponification number of 80 to 300 mg KOH / g and an OH number of 200 to 800 mg KOH / g for the stabilization of organic halogenated flame retardants.
16. Verfahren zur Herstellung von Polymermischungen nach einem der Ansprüche 1 bis 14 umfassend die Schritte (i) Bereitstellen der Komponente (a), 16. A process for the preparation of polymer blends according to any one of claims 1 to 14 comprising the steps of (i) providing the component (a),
(ii) Gemeinsame oder getrennte Zugabe der Komponenten (b) und (c) zu (ii) adding components (b) and (c) together or separately
Komponente (a) und Component (a) and
(iii) Mischen der Komponenten. (iii) mixing the components.
17. Verwendung von Polymermischungen nach einem der Ansprüche 1 bis 14 zur Herstellung von Folien, Halbzeugen, Schäumen, Fasern und Formkörpern. 17. Use of polymer blends according to one of claims 1 to 14 for the production of films, semi-finished products, foams, fibers and moldings.
18. Folien, Halbzeuge, Schäume, Fasern und Formkörper enthaltend eine Polymermischung nach einem der Ansprüche 1 bis 14. 18. Films, semi-finished products, foams, fibers and shaped bodies containing a polymer mixture according to one of claims 1 to 14.
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EP (1) | EP2601254A1 (en) |
RU (1) | RU2013109371A (en) |
WO (1) | WO2012016906A1 (en) |
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WO2014014648A2 (en) * | 2012-07-18 | 2014-01-23 | Rohm And Haas Company | Textiles with brominated polymer flame retardant |
WO2014066089A1 (en) * | 2012-10-24 | 2014-05-01 | Dow Global Technologies Llc | Glycerol ester and brominated polymer in styrenic polymer |
EP2789651A1 (en) | 2013-04-11 | 2014-10-15 | Basf Se | Fire retardant composition for use in styrene polymer foam materials |
EP2957413A1 (en) | 2014-06-18 | 2015-12-23 | Basf Se | Process for degassing flame retardant polymer granules containing a blowing agent or flame retardant foam recyclates |
EP2957595A1 (en) | 2014-06-18 | 2015-12-23 | Basf Se | Fire retardant composition for use in styrene polymer foam materials |
MX2022015715A (en) | 2020-06-10 | 2023-01-24 | Basf Se | Flame retardant styrene polymer composition and process for recycling styrene polymercontaining scrap. |
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ES2142606T3 (en) | 1995-09-07 | 2000-04-16 | Bromine Compounds Ltd | FIREPROOF MATERIALS OF HEXABROMOCICLODODECAN WITH THERMAL STABILITY. |
WO1998016579A1 (en) | 1996-10-15 | 1998-04-23 | Albemarle Corporation | Heat stabilized, flame retardant thermoplastic polymer compositions |
US5639799A (en) * | 1996-10-15 | 1997-06-17 | Albemarle Corporation | Heat stabilized flame retardant styrenic polymer foam compositions |
US6376584B1 (en) * | 1999-02-25 | 2002-04-23 | Ciba Specialty Chemicals Corporation | Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith |
BR0003178B1 (en) * | 1999-10-07 | 2011-10-04 | polymer composition based on crosslinkable polyolefins with high thermal coefficient of working in automotive cable, and process of preparation of a polymer composition. | |
EP1092748A1 (en) | 1999-10-15 | 2001-04-18 | Albemarle Corporation | Stabilized flame retardant additives and their use |
DE10333892A1 (en) * | 2003-07-22 | 2005-02-10 | Ami-Agrolinz Melamine International Gmbh | Plastic product of high strength and flexibility |
US20050215695A1 (en) | 2004-03-29 | 2005-09-29 | Goossens Danielle F | Stabilized flame retardant additives and their use |
DE102004061985A1 (en) * | 2004-12-23 | 2006-07-06 | Rehau Ag + Co | TPV Alternative |
CA2627253C (en) | 2005-11-12 | 2013-11-19 | Dow Global Technologies Inc. | Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends |
EP2212377B1 (en) | 2007-11-21 | 2012-02-08 | Basf Se | Flameproof expandable styrene polymers, and method for the production thereof |
EP2123659A1 (en) * | 2008-05-15 | 2009-11-25 | Arkema France | High purity monoalkyltin compounds and uses thereof |
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2011
- 2011-07-28 WO PCT/EP2011/063012 patent/WO2012016906A1/en active Application Filing
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RU2013109371A (en) | 2014-09-10 |
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