EP0401366A4 - Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyren compositions - Google Patents
Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyren compositionsInfo
- Publication number
- EP0401366A4 EP0401366A4 EP19900901968 EP90901968A EP0401366A4 EP 0401366 A4 EP0401366 A4 EP 0401366A4 EP 19900901968 EP19900901968 EP 19900901968 EP 90901968 A EP90901968 A EP 90901968A EP 0401366 A4 EP0401366 A4 EP 0401366A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame retardant
- composition
- halogen
- bis
- phosphate 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- Withdrawn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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 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 compound 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 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 11
- 229920002397 thermoplastic olefin Polymers 0.000 title description 5
- -1 bicyclic phosphate compound Chemical class 0.000 claims abstract description 55
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000004793 Polystyrene Substances 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims description 27
- 229920001155 polypropylene Polymers 0.000 claims description 27
- 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 claims description 18
- 239000000654 additive Substances 0.000 claims description 17
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- YBAIRXAJHLSFLB-UHFFFAOYSA-N BrC1(CCC(CC1)CC(Br)Br)Br Chemical compound BrC1(CCC(CC1)CC(Br)Br)Br YBAIRXAJHLSFLB-UHFFFAOYSA-N 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 4
- UZOSVZSBPTTWIG-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-chlorocyclohexane Chemical compound ClC1C(Br)C(Br)C(Br)C(Br)C1Br UZOSVZSBPTTWIG-UHFFFAOYSA-N 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- VUNCWTMEJYMOOR-UHFFFAOYSA-N hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001748 polybutylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- DHQKZHREWWXKQF-UHFFFAOYSA-I magnesium dicarbonoperoxoyloxyalumanyl hydroxy carbonate hydroxy carbonate Chemical group [Mg++].[Al+3].OOC([O-])=O.OOC([O-])=O.OOC([O-])=O.OOC([O-])=O.OOC([O-])=O DHQKZHREWWXKQF-UHFFFAOYSA-I 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims 1
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 claims 1
- CJBDUOMQLFKVQC-UHFFFAOYSA-N 3-(2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=CC=C1O CJBDUOMQLFKVQC-UHFFFAOYSA-N 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 229920005990 polystyrene resin Polymers 0.000 abstract description 8
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 229920005672 polyolefin resin Polymers 0.000 abstract description 5
- 238000010094 polymer processing Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 26
- 125000002619 bicyclic group Chemical group 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- FWKIOSWFVPOWSM-UHFFFAOYSA-N 1,1,12,12,12-pentabromododecylbenzene Chemical compound BrC(Br)(Br)CCCCCCCCCCC(Br)(Br)C1=CC=CC=C1 FWKIOSWFVPOWSM-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
- YHMOQCYOOUHZSF-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[1-(2,3,4,5,6-pentabromophenoxy)ethoxy]benzene Chemical compound BrC=1C(Br)=C(Br)C(Br)=C(Br)C=1OC(C)OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br YHMOQCYOOUHZSF-UHFFFAOYSA-N 0.000 description 1
- FIAXCDIQXHJNIX-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-ethylbenzene Chemical compound CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br FIAXCDIQXHJNIX-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
- NQKVVCRUKCIGHX-UHFFFAOYSA-N 1,2,3-tribromo-4-[1-[2-(9,9-dibromononyl)phenoxy]ethoxy]benzene Chemical compound C=1C=C(Br)C(Br)=C(Br)C=1OC(C)OC1=CC=CC=C1CCCCCCCCC(Br)Br NQKVVCRUKCIGHX-UHFFFAOYSA-N 0.000 description 1
- XNPKNHHFCKSMRV-UHFFFAOYSA-N 4-(cyclohexylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCNC1CCCCC1 XNPKNHHFCKSMRV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical group 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- UGQQAJOWXNCOPY-UHFFFAOYSA-N dechlorane plus Chemical compound C12CCC3C(C4(Cl)Cl)(Cl)C(Cl)=C(Cl)C4(Cl)C3CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl UGQQAJOWXNCOPY-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- BJOKPSIXNLQZNV-UHFFFAOYSA-N oxido-oxo-(2,6,7-trioxabicyclo[2.2.2]octan-1-yl)phosphanium Chemical compound P(=O)(=O)C12OCC(CO1)CO2 BJOKPSIXNLQZNV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Polymers C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006216 polyvinyl aromatic Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Definitions
- thermoplastic polyolefin and polystyrene compositions relate to thermal and light stable flame retardant thermoplastic polyolefin and polystyrene compositions. More particularly, this invention relates to thermoplastic compositions which are flame retardant and which resist thermal degradation or photochemically-induced degradation. These compositions comprise bicyclic phosphate compound(s); halogen-containing flame retardant( ⁇ ); and polystyrene or polyolefin resin.
- compositions produced in accordance with this invention have a reduced tendency to develop color, to change melt viscosity, or to lose mechanical strength under conditions that are present during polymer processing or end-use. Description of the Prior Art.
- polystyrene and polyolefin ⁇ such as homopolymers and copolymers of polypropylene, polyethylene, and polybutylene, may be flame retarded with halogen-containing flame retardant ⁇ .
- flame retardant additive ⁇ are susceptible to thermal and photochemically-induced degradation during processing of the thermoplastic resin, or during polymer use conditions.
- thermoplastic composition may develop a darkened appearance during processing, indicating polymer or flame retardant chemical decomposition; or the thermoplastic composition may suffer an increase or decrease in melt viscosity, limiting, for example, the recycle of industrial scrap ("regrind") or environmental plastic waste; or the thermoplastic composition may lose mechanical strength, thus reducing the overall service life of the polymeric material.
- British Patent No. 889,338 describes the production of bicyclic phosphites, pho ⁇ phonate ⁇ , thiophosphates, and ⁇ elenophosphates. These compo ⁇ ition ⁇ are said to be stabilizer ⁇ for vinyl halide re ⁇ in ⁇ . They are alleged to be useful as heat ⁇ tabilizer ⁇ for vinyl chloride re ⁇ in, and as antioxidant ⁇ for fat ⁇ and oil ⁇ .
- the British '338 Patent does not show any examples of bicylic phosphates, nor doe ⁇ it specify the u ⁇ e of bicyclic pho ⁇ phate ⁇ , such a ⁇ pentaerythritol-ba ⁇ ed bicyclic pho ⁇ phate ⁇ of the present invention, which can be employed as a stabilizer for polystyrene or polyolefin resin. Furthermore, the British '338 Patent doe ⁇ not disclose that cyclic pho ⁇ phate ⁇ of the pre ⁇ ent invention could be used with halogen-containing flame retardant ⁇ to produce flame retardant thermoplastic compo ⁇ itions which re ⁇ i ⁇ t thermal or photochemically-induced degradation.
- British Patent No. 999,793 describes a proces ⁇ to produce organic phosphates by subjecting organic phosphites to reaction with peracetic acid.
- This patent shows a method for producing the most preferred bicyclic phosphate of the present invention, 2,6,7-trioxa-l- pho ⁇ phobicyclo[2.2.2]-octane-4-methanol-l-oxide (vide infra) _ and teaches the use of acetal ring-containing pho ⁇ phate ⁇ a ⁇ pla ⁇ ticizer ⁇ or functional fluid ⁇ .
- the British '793 Patent does not disclose the compo ⁇ itions of the present invention.
- U.S. Patent No. 4,341,694 discloses a composition comprising 2,6,7-trioxa-l-phosphobicyclo[2.2.2]octane-
- a primary object of this invention i ⁇ to provide thermal and light ⁇ table flame retardant thermoplastic polyolefin and poly ⁇ tyrene compo ⁇ itions.
- a related object is to provide compo ⁇ ition ⁇ of the character de ⁇ cribed which resist thermal degradation or photochemically induced degradation.
- a further object is to provide polystyrene or polyolefin resin compositions incorporating bicyclic phosphate compounds and halogenated flame retardant ⁇ .
- thermopla ⁇ tic polyolefin or poly ⁇ tyrene resin compo ⁇ itions incorporating an additive mixture comprising a halogen-containing flame retardant; and a bicyclic phosphate compound of the following Formula (I):
- X is OH, OR', or OC(0)R'
- R is H or a saturated or un ⁇ aturated ⁇ traight-chain or branched-chain C--C.- al yl
- R' i ⁇ a ⁇ aturated or un ⁇ aturated ⁇ traight-chain or branched chain C.-C-- alkyl.
- thermoplastic polyolefin and polystyrene resin compo ⁇ ition ⁇ which are flame retardant and which re ⁇ ist thermal degradation or photochemically induced degradation and which incorporate an additive mixture compri ⁇ ing one or more bicyclic phosphate compounds and one or more halogen-containing flame retardant ⁇ .
- Compo ⁇ ition ⁇ produced in accordance with thi ⁇ invention have a reduced tendency to develop color, to change melt vi ⁇ co ⁇ ity, or to lose mechanical strength under conditions pre ⁇ ent during polymer proces ⁇ ing or in u ⁇ e.
- Preferred bicyclic pho ⁇ phate ⁇ in accordance with this invention are compounds of Formula (I) where X i ⁇ OH or OC(0)R' .
- the most preferred bicyclic compounds are 2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-l- oxide (Compound BCP, that i ⁇ , Formula [I] when R i ⁇ H and X i ⁇ OH), and 2,6,7-trioxa-l-pho ⁇ phobicyclo[2.2.2]- octane-4-methanol, acetate, 1-oxide (Compound BCP-A, that i ⁇ , when R i ⁇ H and X i ⁇ OC(O)CH-).
- the halogen-containing flame retardant compound may be any brominated or chlorinated aliphatic or aromatic organic compound that can be used in thermoplastic compo ⁇ ition ⁇ .
- Preferred halogen-containing compounds are hexabromocyclododecane, tetrabromobi ⁇ phenol A, tetrabromobi ⁇ phenol A bi ⁇ -(dibromopropylether), dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, bi ⁇ -(dibromonorbornane dicarboximido)ethane, bi ⁇ -(tetrabromophthalimido)ethane, Diel ⁇ -Alder adduct of chlorinated cyclopentadiene and unsaturated cycloaliphatic compound, bi ⁇ -(tribromophenoxy- ethyl)tetrabromobisphenol A ether, pentabromodiphenyl
- Re ⁇ ins which may be treated in accordance with the invention include thermopla ⁇ tic ⁇ ⁇ uch a ⁇ poly ⁇ tyrene and copolymers of ⁇ tyrene with butadiene and acrylonitrile ("ABS copolymer ⁇ ") and homopolymer ⁇ and copolymers of polyolefin ⁇ ⁇ uch a ⁇ polypropylene, polyethylene, and polybutylene.
- ABS copolymer ⁇ thermopla ⁇ tic ⁇ ⁇ uch a ⁇ poly ⁇ tyrene and copolymers of ⁇ tyrene with butadiene and acrylonitrile
- Polystyrene and polypropylene are preferred thermoplastics in accordance with this invention.
- the poly ⁇ tyrene may be any thermoplastic poly ⁇ tyrene, especially impact modified grades, as described in Modern Plastics Encyclopedia. Vol. 63, No. 10A, 74 (1986), or grades suitable for making foamed products.
- the additives of the invention are used with impact grades classified by notched impact values between
- the polypropylene may be any thermoplastic polypropylene, especially homopolymer type, as described in Modern Pla ⁇ tics Encyclopedia. Vol. 63, No. 10A, 12 (1986), or grade ⁇ suitable for making foamed product ⁇ .
- the additive ⁇ of thi ⁇ invention are u ⁇ ed with grades cla ⁇ ified by melt flows between 2 and 30 g/10 min. , and most preferably between 4 and 10 g/10 min.
- Enhancing agent ⁇ u ⁇ eful in accordance with thi ⁇ invention comprise the oxide ⁇ and halide ⁇ of group ⁇ IV-A and V-A of the periodic table; organic or inorganic compound ⁇ of phosphorus, nitrogen, boron or sulfur; and oxide ⁇ and halide ⁇ of, for example, zinc, magnesium and titanium, all a ⁇ di ⁇ clo ⁇ ed in U.S. Patent No. 4,016,139.
- Preferred enhancing agent ⁇ in accordance with thi ⁇ invention are the oxide ⁇ of antimony, ar ⁇ enic and bismuth, with the oxides of antimony being especially preferred.
- the compo ⁇ ition ⁇ of thi ⁇ invention may additionally incorporate one or more antioxidant ⁇ , hindered amine light ⁇ tabilizer ⁇ , or acid ⁇ cavenger ⁇ .
- antioxidant i ⁇ 2,2-bi ⁇ [ [3-[3,5-bi ⁇ (l,l-dimethylethyl)- 4-hydroxypheny1]-1- oxopropoxy]methyl]1,3-propanediy1 3,5,-bi ⁇ (1,l-dimethylethyl)-4-hydroxybenzenepropanoate; especially preferred hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebecate; and especially preferred acid scavenger is magnesium aluminum hydroxy carbonate g 4 5 A1 2 (0H) 13 C0 3 .
- the scope of the present invention includes the incorporation of other additives in the composition so far as to produce a particular end result.
- additive ⁇ include, without limitation, blowing agent ⁇ , heat stabilizers, light stabilizers, pla ⁇ ticizer ⁇ , pigments, pre ⁇ ervative ⁇ , ultraviolet light ⁇ tabilizer ⁇ , fillers, antioxidant ⁇ , antistatic agent ⁇ and other materials well known to those skilled in the art, for example, a ⁇ de ⁇ cribed in Modern Plastics Encyclopedia, Vol. 63, No. 10A, McGraw-Hill, Inc. (1986).
- the bicyclic phosphate ⁇ of the present invention may be used alone or as mixture ⁇ of any ⁇ uch compound ⁇ . When mixture ⁇ of bicyclic pho ⁇ phate ⁇ are employed, substantially any combinations of amounts and proportions of the individual compound ⁇ may be used.
- the u ⁇ e of Compound BCP and Compound BCP-A i ⁇ especially preferred in accordance with thi ⁇ invention.
- the halogen-containing flame retardant ⁇ of the pre ⁇ ent invention may be used alone or as mixture ⁇ of any such compound ⁇ .
- substantially any combinations of amounts and proportions of the individual compound ⁇ may be used.
- the bicyclic pho ⁇ phate compound and halogen-containing flame retardant are provided a ⁇ a mixture u ⁇ eful as an additive which may be added to poly ⁇ tyrene or polyolefin re ⁇ in compo ⁇ ition ⁇ .
- the additive mixture utilize ⁇ bicyclic pho ⁇ phate in halogen-containing flame retardant in a weight ratio lying in the range of about 0.001 to 0.200, most preferably, about 0.005 to 0.050.
- poly ⁇ tyrene refer ⁇ to poly ⁇ tyrene available from Huntsman Chemical Corporation a ⁇ PS 3037; the term polypropylene refer ⁇ to polypropylene available from Hi ont Chemical Company a ⁇ Profax 6301; and the term acrylonitrile- butadiene- ⁇ tyrene refer ⁇ to acrylonitrile-butadiene- ⁇ tyrene available from Borg Warner Corporation a ⁇ Cycolac GSM 1000.
- thermoplastic compo ⁇ ition ⁇ were compounded in a 3/4" eingle screw extruder (L D 25:1) at 430 °F. The extrudate wa ⁇ pelletized and re-extruded ten times. The melt vi ⁇ co ⁇ ity of the final extrudate wa ⁇ ea ⁇ ured by a melt flow technique.
- Examples 1-2 are flame retardant polypropylene compositions containing 4.0% hexabromocyclododecane (Flame Retardant HBCD), available under the trademark CD-75P from Great Lakes Chemical Corporation, and, re ⁇ pectively, 0.1% and 0.2% 2,6,7-trioxa-l-pho ⁇ phobicyclo[2.2.2] octane-4-methanol-l-oxide (Compound BCP).
- Flame Retardant HBCD hexabromocyclododecane
- CD-75P from Great Lakes Chemical Corporation
- Comparative Example 1 ⁇ how ⁇ the inherent melt vi ⁇ co ⁇ ity of a non-flame retardant polypropylene compo ⁇ ition which ha ⁇ been subjected to multiple extrusions. Comparative Example 2 shows that Flame
- Retardant HBCD has a detrimental effect on polymer melt viscosity, as evidenced by an increase in melt flow from 29.3 g/10 min (Comparative Example 1) to 77.1 g/10 min (Comparative Example 2).
- Compound BCP i ⁇ added to the composition the damaging effects of Flame Retardant HBCD on the melt vi ⁇ co ⁇ ity of polypropylene re ⁇ in are reduced.
- Example 1 and Example 2 show less change in melt flow than Comparative Example 2.
- Example ⁇ 3-4 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.1% hindered phenolic antioxidant (Compound AO), which i ⁇ available from Ciba-Geigy Corporation a ⁇ Irganox 1010, and 0.1% acid ⁇ cavenger (Compound AS), which i ⁇ available from Kyowa Chemical Indu ⁇ try a ⁇ DHT-4A, respectively.
- Compound AO hindered phenolic antioxidant
- Compound AS 0.1% acid ⁇ cavenger
- Example 3 ⁇ how ⁇ the effectivene ⁇ of Compound BCP in the pre ⁇ ence of a hindered phenolic antioxidant
- Example 4 ⁇ how ⁇ the effectivene ⁇ of Compound BCP in the pre ⁇ ence of an acid ⁇ cavenger.
- TABLE II contains examples which illustrate the effectiveness of the preferred bicyclic phosphate compound and HBCD in poly ⁇ tyrene re ⁇ in to minimize a change in polymer melt vi ⁇ cosity during proces ⁇ ing.
- EXAMPLE 5 i ⁇ a flame retardant poly ⁇ tyrene formulation in accordance with thi ⁇ invention containing 0.1% Compound BCP and 2.0% Flame Retardant HBCD.
- Example 5 illustrates an improvement in melt flow over Comparative Example 5 and Comparative Example 6. Thu ⁇ , Compound BCP is effective in polystyrene when no additional additives are pre ⁇ ent (Comparative Example 5) or when an acid ⁇ cavenger i ⁇ present (Comparative Example 6).
- the polymer melt was sampled at three minute intervals, and visual in ⁇ pection ⁇ of the appearance of the polymer compo ⁇ ition were made.
- the color and description of the formulated compo ⁇ ition ⁇ are listed in Table III, and reflect the appearance of the compo ⁇ ition when either the material showed total degradation (that is, developed a black or dark red color or showed signs of decomposition, such a ⁇ off-ga ⁇ ing), or when the 21 minute interval of the te ⁇ t wa ⁇ attained.
- EXAMPLES 6-10 and COMPARATIVE EXAMPLES 7-12 are flame retardant poly ⁇ tyrene compo ⁇ ition ⁇ containing 0.2% Compound BCP and 4.0%, re ⁇ pectively, Flame Retardant HBCD; dibromo(dibromoethyl) cyclohexane (Flame Retardant TBCH), available from Ethyl Corporation a ⁇ BCL-462; Diele-Alder adduct of hexachlorocyclopentadiene and cyclooctadiene (Flame Retardant CBCO) , available from Occidental Corporation as Dechlorane Plus; and monochloropentabromocyclohexane (Flame Retardant CBCH), available from Dow Chemical Corporation as FR-651.
- Flame Retardant HBCD flame retardant poly ⁇ tyrene compo ⁇ ition ⁇ containing 0.2% Compound BCP and 4.0%, re ⁇ pectively, Flame Re
- Example 10 i ⁇ a flame retardant poly ⁇ tyrene compo ⁇ ition containing 0.8% Compound BCP and 16.0% tetrabromobi ⁇ phenol A (Flame Retardant TBBP), available from Great Lake ⁇ Chemical Corporation a ⁇ BA-59P.
- Example ⁇ 6-10 a ⁇ ⁇ upported by compari ⁇ on ⁇ to Comparative Example ⁇ 8-12 (specified in Table III) illustrate poly ⁇ tyrene compo ⁇ ition ⁇ which re ⁇ i ⁇ t thermal degradation and have le ⁇ tendency to develop color under proce ⁇ ing condition ⁇ .
- Comparative Example 7 shows the inherent color development of non-flame retardant polystyrene resin which has been subjected to the test procedures.
- Examples 6-10 illustrate al ⁇ o that Compound BCP is effective in the presence of variou ⁇ halogen-containing flame retardant additives.
- Example 11 i ⁇ a flame retardant poly ⁇ tyrene compo- ⁇ ition containing 0.2% acetate derivative of Compound BCP (designated Compound BCP-A) and 4.0% Flame Retardant HBCD.
- Example 11 i ⁇ an illustration of a bicyclic phos ⁇ phate other than Compound BCP which is within the scope of thi ⁇ invention.
- Example 12 i ⁇ a flame retardant acrylonitrile-butadiene- ⁇ tyrene CABS") compo ⁇ ition containing 0.5% Compound BCP, 4.0% Sb 2 0 3 , and 16.0% Flame Retardant TBBP.
- Example 12 a ⁇ ⁇ upported by compari ⁇ on to Comparative Example ⁇ 14 ( ⁇ pecified in Table III), i ⁇ an illustration of utility of the pre ⁇ ent invention in ABS re ⁇ in.
- Comparative Example 13 ⁇ how ⁇ the inherent color develop ⁇ ment of non-flame retardant ABS re ⁇ in which ha ⁇ been ⁇ ubjected to the te ⁇ t procedure ⁇ .
- Examples 13-14 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.5% Compound BCP, 1.0% Sb.O.., and, re ⁇ pectively, 3.0% tetrabromobi ⁇ phenol A bis(dibromo- propylether) (Flame Retardant TBPE) and 5.0% Flame Retardant HBCD.
- Example ⁇ 13-14 a ⁇ supported by comparison to Comparative Example ⁇ 16-17 ( ⁇ pecified in Table III), illustrate the effectivenes ⁇ of the pre ⁇ ent invention to reduce the tendency for diecoloration in flame retardant polypropylene compo ⁇ ition ⁇ .
- Comparative Example 15 ⁇ how ⁇ the inherent color development of non-flame retardant polypropylene re ⁇ in which ha ⁇ been ⁇ ubjected to the te ⁇ t procedure ⁇ . TABLE III
- the ends of the te ⁇ t specimens were clamped together, placed in an Xenon Arc Weatherometer (Atlas Model Ci-35), and irradiated according to ASTM D-4459 procedure ⁇ for 3000 hour ⁇ .
- the te ⁇ t specimen ⁇ were observed periodically for ⁇ ign ⁇ of crack ⁇ or crazing. The time at which failure occured wa ⁇ noted.
- Example ⁇ 15-16 are flame retardant polypropylene compo ⁇ ition ⁇ containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, 3.3% Sb-O-, and, re ⁇ pectively, 0.5% hindered amine light stabilizer (Compound HALS), available from Ciba-Geigy Corporation a ⁇ TINUVIN 770, and 0.5% Compound AS.
- Compound HALS hindered amine light stabilizer
- Example ⁇ 15-16 a ⁇ supported by comparison to Comparative Example ⁇ 18-19 (specified in Table IV), illustrate the effectiveness of the present invention to reduce the tendency for photochemically-induced mechanical failure in flame retardant polypropylene compo ⁇ ition ⁇ .
- Thermoplastics compo ⁇ ition ⁇ were compounded, injection molded into 3.0" x 1.0" x 0.125" te ⁇ t specimen ⁇ , and irradiated in a Xenon Arc Weatherometer (Atla ⁇ Model Ci-35), according to ASTM D-4459 procedure ⁇ for 2000 hour ⁇ . Change ⁇ in color were mea ⁇ ured a ⁇ Delta E values, accord ⁇ ing to ASTM-2244 procedure ⁇ .
- Example ⁇ 17-18 are flame retardant polypropylene compo ⁇ ition ⁇ containing 3.3% Sb ⁇ O-, 10.0% Flame Retardant TBPE, and, re ⁇ pectively, 1.0% BCP Compound and 0.5% Compound BCP.
- Example ⁇ 19-20 are flame retardant polypropylene composition ⁇ containing 0.5% Compound BCP, 10.0% Flame Retardant TBPE, and, re ⁇ pectively, 0.5% hindered amine light ⁇ tabilizer Compound HALS and 0.5% alkytin-containing ⁇ tabilizer (Compound TLS), available from Witco Chemical Company a ⁇ Mark 1413.
- Example ⁇ 17-20 a ⁇ supported by comparison to Comparative Example ⁇ 20-22 (specified in Table V), illu ⁇ trate the effectiveness of the present invention to reduce the tendency for photochemically-induced di ⁇ coloration in flame retardant polypropylene compo ⁇ i ⁇ tion ⁇ .
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Abstract
Description
Claims
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US28997388A | 1988-12-22 | 1988-12-22 | |
US289973 | 1988-12-22 |
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EP0401366A1 EP0401366A1 (en) | 1990-12-12 |
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EP19900901968 Withdrawn EP0401366A4 (en) | 1988-12-22 | 1989-12-15 | Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyren compositions |
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EP (1) | EP0401366A4 (en) |
JP (1) | JPH03502820A (en) |
KR (1) | KR910700007A (en) |
CA (1) | CA2006134A1 (en) |
WO (1) | WO1990006691A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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AU6625390A (en) * | 1989-09-15 | 1991-04-18 | Great Lakes Chemical Corporation | Smoke suppressed flame retardant thermoplastic resin compositions |
US5627915A (en) * | 1995-01-31 | 1997-05-06 | Princeton Video Image, Inc. | Pattern recognition system employing unlike templates to detect objects having distinctive features in a video field |
CN1091453C (en) | 1995-08-29 | 2002-09-25 | 埃克森美孚化学专利公司 | Radiation tolerant polypropylene and its useful articles |
US6472456B1 (en) | 1997-06-30 | 2002-10-29 | Ciba Specialty Chemicals Corp. | Flame retardant compositions |
US6599963B2 (en) | 1997-06-30 | 2003-07-29 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
CA2477884A1 (en) * | 2002-03-01 | 2003-09-12 | Dow Global Technologies Inc. | Dimensionally-stable propylene polymer foam with improved thermal aging. |
MY139230A (en) * | 2002-10-17 | 2009-08-28 | Ciba Holding Inc | Flame retardant polymeric electrical parts |
US7109260B2 (en) * | 2002-10-17 | 2006-09-19 | Ciba Specialty Chemicals Corporation | Flame retardant compositions |
JP4937610B2 (en) * | 2005-04-12 | 2012-05-23 | 第一工業製薬株式会社 | Flame-retardant foamed polystyrene resin and molded article thereof |
CN102369243B (en) * | 2009-03-19 | 2014-11-05 | 界面解决方案Ip有限责任公司 | Biobased polymer compositions |
KR102423979B1 (en) * | 2016-07-29 | 2022-07-22 | 가부시키가이샤 아데카 | Flame retardant composition and flame retardant synthetic resin composition |
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US3293327A (en) * | 1958-07-21 | 1966-12-20 | Hooker Chemical Corp | Cyclic phosphites and phosphates |
NL154241C (en) * | 1971-01-29 | 1900-01-01 | ||
US4016139A (en) * | 1973-02-08 | 1977-04-05 | Michigan Chemical Corporation | Plastic composition comprising acrylonitrile-butadiene-styrene polymer, a bis-phenoxy flame retardant and a flame retardant enhancing agent |
DE2621323A1 (en) * | 1976-05-13 | 1977-12-01 | Hoechst Ag | NEW ORGANIC PHOSPHITES, PROCESSES FOR THEIR PRODUCTION AND THEIR USE AS STABILIZERS |
GB2075989B (en) * | 1980-05-13 | 1984-04-26 | Kyowa Chem Ind Co Ltd | Stabilized thermoplastic resin compositions |
JPS59138260A (en) * | 1983-01-28 | 1984-08-08 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether resin composition |
JPH07788B2 (en) * | 1984-10-30 | 1995-01-11 | 丸菱油化工業株式会社 | Flame retardant composition |
-
1989
- 1989-12-15 WO PCT/US1989/005627 patent/WO1990006691A1/en not_active Application Discontinuation
- 1989-12-15 JP JP90502089A patent/JPH03502820A/en active Pending
- 1989-12-15 KR KR1019900701817A patent/KR910700007A/en not_active Application Discontinuation
- 1989-12-15 EP EP19900901968 patent/EP0401366A4/en not_active Withdrawn
- 1989-12-20 CA CA002006134A patent/CA2006134A1/en not_active Abandoned
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CA2006134A1 (en) | 1990-06-20 |
JPH03502820A (en) | 1991-06-27 |
WO1990006691A1 (en) | 1990-06-28 |
KR910700007A (en) | 1991-03-13 |
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