WO2010076995A2 - Novel phosphonate based compound and flame retardant styrenic resin composition including the same - Google Patents
Novel phosphonate based compound and flame retardant styrenic resin composition including the same Download PDFInfo
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- WO2010076995A2 WO2010076995A2 PCT/KR2009/007631 KR2009007631W WO2010076995A2 WO 2010076995 A2 WO2010076995 A2 WO 2010076995A2 KR 2009007631 W KR2009007631 W KR 2009007631W WO 2010076995 A2 WO2010076995 A2 WO 2010076995A2
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- WIPO (PCT)
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- resin
- thermoplastic resin
- resin composition
- chemical formula
- flame resistant
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title claims description 17
- 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 description 16
- 229920001890 Novodur Polymers 0.000 title claims description 13
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 36
- -1 polypropylene Polymers 0.000 claims description 33
- 229920006026 co-polymeric resin Polymers 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229920001955 polyphenylene ether Polymers 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920013716 polyethylene resin Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 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 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- CTYOELISUWITTG-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.CCOC(=O)C=C.C=CC1=CC=CC=C1 CTYOELISUWITTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920005669 high impact polystyrene Polymers 0.000 claims description 3
- 239000004797 high-impact polystyrene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 0 *CP1(Oc(cccc2)c2-c2ccccc2O1)=O Chemical compound *CP1(Oc(cccc2)c2-c2ccccc2O1)=O 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GUDSEWUOWPVZPC-UHFFFAOYSA-N bis(2,4-ditert-butylphenyl) hydrogen phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(O)(=O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C GUDSEWUOWPVZPC-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical class C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Chemical group 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- MDJACXVQEDUUFG-UHFFFAOYSA-N bis(2,3-dimethylphenyl) hydrogen phosphate;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.CC1=CC=CC(OP(O)(=O)OC=2C(=C(C)C=CC=2)C)=C1C MDJACXVQEDUUFG-UHFFFAOYSA-N 0.000 description 1
- OJUVOJCIHNPHSA-UHFFFAOYSA-N bis(2,6-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=CC=CC(O)=C1 OJUVOJCIHNPHSA-UHFFFAOYSA-N 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- MJUJXFBTEFXVKU-UHFFFAOYSA-N diethyl phosphonate Chemical compound CCOP(=O)OCC MJUJXFBTEFXVKU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- 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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the present invention relates to novel phosphonate based compound and a flame retardant styrenic resin composition including the same.
- Styrenic resins which are used for exterior materials of electronic devices can also be used in a variety of engineering applications because of their excellent impact resistance, dimensional stability and high heat resistance.
- styrenic resins can burn easily and do not have fire resistance. Accordingly countries such as the United States, Japan and many European countries have passed laws requiring polymer resins to satisfy flame resistance standards.
- a widely used and known method for imparting good flame retardancy to styrenic resin includes adding a halogen-containing compound as a flame retardant to a rubber- modified styrenic resin and adding an antimony-containing compound as a flame retardant aid.
- halogen-containing compounds used to impart flame retardancy include polybromodiphenyl ether, tetrabromobisphenol-A, epoxy compounds substituted with bromine, chlorinated polyethylene, and the like.
- Antimony trioxide or antimony pentaoxide is commonly used as an antimony-containing compound.
- halogen- and antimony-containing compounds are widely used as the primary flame retardant for housing materials for electrical appliances and office equipment formed of ABS resins, PS resins, PBT resins, PET resins or epoxy resins.
- hydrogen halide gases released by halogen-containing compounds during processing can have fatal effects on the human body and have high environmental persistence because these compounds are not naturally degradable. Also these compounds are not soluble in water, and thus can be highly bioaccumulated.
- polybromodiphenyl ether which is widely used as a halogen-containing flame retardant, may produce toxic gases such as dioxin or furan during combustion, and is consequently harmful to humans and the environment. Accordingly, there is a need to develop flame retardancy methods that do not employ halogen-containing compounds.
- the present invention provides a novel phosphonate based compound which can be added to a resin composition to provide flame resistance.
- the present invention further provides a flame resistant thermoplastic resin composition including a novel phosphonate based compound which can have fire stability.
- the present invention further provides an environmentally-friendly thermoplastic resin composition which includes a halogen-free flame retardant and which can have excellent flame resistance as compared to a composition including a phosphate ester flame retardant.
- the present invention provides a phosphonate based compound represented by the following Chemical Formula 1.
- R 1 is Ci to C 4 alkyl, phenyl or cyano
- each R 2 and R 3 is independently H or Ci to C 4 alkyl, for example t-butyl.
- the present invention further provides a flame resistant thermoplastic resin composition
- a flame resistant thermoplastic resin composition comprising: a thermoplastic resin (A), and a phosphonate based compound (B) represented by the above Chemical Formula 1.
- the thermoplastic resin may comprise polystyrene resin (PS resin), acrylonitrile- butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), acrylonitrile- styrene copolymer resin (SAN resin), methylmethacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), poly phenylene ether resin (PPE), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyamide resin (PA), or a combination thereof.
- PS resin polystyrene
- the flame resistant thermoplastic resin composition may comprise about 100 parts by weight of the thermoplastic resin (A), and about 0.5 to about 30 parts by weight of the phosphonate based compound (B) represented by the above Chemical Formula 1, based on about 100 parts by weight of the thermoplastic resin (A).
- the flame resistant thermoplastic resin composition may further comprise about 1 to about 20 parts by weight of a phosphorus flame retardant (C), based on about 100 parts by weight of the thermoplastic resin (A).
- the phosphorus flame retardant (C) may be an aromatic phosphorus ester compound (C)-I, a metal salt compound of an alkyl phosphonic acid (C)-2 which has a particle size of less than about 10 ⁇ m, or a combination thereof.
- Fig 1 is a schematic diagram representing the results of IH-NMR analysis of dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide according to an exemplary embodiment of the present invention.
- Fig 2 is a schematic diagram representing the results of IH-NMR analysis of dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide according to another exemplary embodiment of the present invention.
- the present invention provides a phosphonate based compound represented by the following Chemical Formula 1.
- R 1 is Ci to C 4 alkyl, phenyl or cyano
- each R 2 and R 3 is independently H or Ci to C 4 alkyl, for example t-butyl.
- the phosphonate based compound represented by the Chemical Formula 1 may comprise dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide, dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide, or a combination thereof.
- the compound represented by the Chemical Formula 1 according to the present invention can be prepared by preparing an intermediate which is prepared by a dechlorination reaction of phosphorus trichloride, aryl-alcohol and Ci-C 4 alkanol, such as ethanol, and reacting the intermediate and a benzylbromide or a bromo acetonitrile or a bromo Ci-C 4 alkane.
- An intermediate such as dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-Ci-C 4 alkoxy (such as dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-ethoxy) as illustrated in the Scheme 1 above can be prepared by stirring about 1 to about 3 equivalence ratio of phosphorus trichloride, for example 1 equivalence ratio, about 1 equivalence ratio of 2,2'-dihydroxy biphenyl and about 1 equivalence ratio of Ci-C 4 alkanol, for example ethanol, in the presence of nitrogen at room temperature.
- the present invention provides a flame resistant thermoplastic resin composition
- a flame resistant thermoplastic resin composition comprising a thermoplastic resin (A) and a phosphonate based compound (B) represented by the Chemical Formula 1.
- the phosphonate based compound (B) represented by the Chemical Formula 1 can provide good flame retardancy properties to the thermoplastic resin.
- the flame resistant thermoplastic resin composition may comprise about 0.5 to about
- the phosphonate based compound (B) represented by the Chemical Formula 1 based on about 100 parts by weight of the thermoplastic resin (A). If the amount of the phosphonate based compound (B) represented by the Chemical Formula 1 is less than about 0.5 parts by weight based on about 100 parts by weight of the thermoplastic resin (A), flame resistance of the thermoplastic resin composition may be reduced. If the amount of the phosphonate based compound (B) represented by the Chemical Formula 1 is more than 30 parts by weight based on about 100 parts by weight of the thermoplastic resin (A), physical properties of the resin may be reduced.
- thermoplastic resin may include without limitation styrenic resins
- polystyrene resin such as polystyrene resin (PS resin), acrylonitrile- butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), acrylonitrile- styrene copolymer resin (SAN resin), methylmethacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), and the like, polycarbonate resins (PC), polypheny lene ether resins (PPE), poly olefin resins, such as polyethylene resin (PE), polypropylene resin (PP), and the like, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like, polyvinyl
- the present invention provides a flame resistant thermoplastic resin composition
- a flame resistant thermoplastic resin composition comprising a styrenic resin (A-I), a polyphenylene ether resin (A-2) and a phosphonate based compound (B) rep- resented by the Chemical Formula 1.
- the flame resistant thermoplastic resin composition may include about 0.5 to about 30 parts by weight of the phosphonate based compound (B) represented by the Chemical Formula 1 based on about 100 parts by weight of a base resin including about 70 to about 99 % by weight of the styrenic resin (A-I) and about 1 to about 30 % by weight of the polypheny lene ether resin (A-2).
- the base resin may include about 15 to about 30 % by weight of the polyphenylene ether resin (A-2). If the amount of the polyphenylene ether resin (A-2) is less than about 1 % by weight, the flame resistance of the thermoplastic resin composition may be reduced. If the amount of the polyphenylene ether resin (A-2) is more than about 30 % by weight, moldability may be reduced.
- the flame resistant thermoplastic resin composition may further comprise a phosphorus flame retardant (C).
- the phosphorus flame retardant (C) may be an aromatic phosphorus ester compound (C)-I or a metal salt compound of an alkyl phosphonic acid (C)-2 which has a particle size less than about 10 ⁇ m, or a combination thereof.
- the phosphorus flame retardant (C) may be used in an amount of about 1 to about 20 parts by weight, based on about 100 parts by weight of the thermoplastic resin (A).
- the flame resistant thermoplastic resin composition according to the present invention further comprises the phosphorus flame retardant (C)
- the phosphonate based compound (B) may be used in amount of about 1 to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin (A).
- aromatic phosphorus ester compound (C)-I may be represented by the following
- each R 3 , R 4 , R 5 , R 3 ', R 4 ', R 5 ', R 3 ", R 4 ", R 5 ", R 3 '", R 4 '" and R 5 '” is independently H or Ci to C 4 alkyl
- X is C 6 to C 2 o aryl or C 6 to C 2 o aryl substituted with Ci to C 4 alkyl
- n is an integer ranging from 0 to 4.
- X may be resorcinol, hydroquinol or dialcohol derived from bisphenol-
- examples of the compound represented by the Chemical Formula 2 may include triphenyl phosphate, tri(2,6-dimethyl)phosphate and the like, and combinations thereof.
- examples of the compound represented by the Chemical Formula 2 may include triphenyl phosphate, tri(2,6-dimethyl)phosphate and the like, and combinations thereof.
- the metal salt compound of an alkyl phosphonic acid (C)-2 may be represented by the following Chemical Formula 3, and can have a particle size of less than about 10 ⁇ m, for example, about 1 to about 10 ⁇ m.
- C alkyl phosphonic acid
- R is Ci to C 6 alkyl, Ci to C 6 cycloalkyl or C 6 to Ci 0 aryl
- M is a metal such as
- Al, Zn, Ca, and n is an integer of 2 or 3.
- R may be methyl, ethyl, propyl, butyl or phenyl
- M may be Al or
- the flame resistant thermoplastic resin composition according to the present invention may further include one or more additives selected without limitation from plasticizers, heat stabilizers, antioxidants, compatibilizers, light- stabilizers, inorganic additives, pigments, dyes and the like, and combinations thereof.
- the inorganic additives may include asbestos, glass fiber, talc, ceramic, sulfate and the like, and combinations thereof.
- the one or more additives may be used in an amount of less than about 30 parts by weight based on the total weight of the resin composition.
- the flame resistant thermoplastic resin composition of the present invention can be prepared by known methods.
- the components and optionally the additives can be mixed simultaneously, and the mixture can be extruded through an extruder to prepare pellets.
- the present invention provides a molded article prepared from the flame resistant thermoplastic resin composition of the present invention.
- the molded article may have excellent flame resistance and can be environmentally-friendly.
- the molded article can be prepared using any suitable molding technique, such as but not limited to melt extrusion, injection molding, and the like. The skilled artisan will understand how to prepare a molded article using the flame resistant thermoplastic resin composition of the invention without undue experimentation.
- Styrenic resin Rubber-reinforced styrenic resin made by Cheil Industries, Inc. of South Korea (product name: HG- 1760S) is used.
- PET resin made by SK Chemical of South Korea (BB-8055) is used, with an intrinsic viscosity [ ⁇ ] of about 0.8, and a melting point of 254 0 C.
- ABS resin ABS resin made by Cheil Industries, Inc. of South Korea (product name: SD-0150) is used.
- (C)-I aromatic phosphorus ester compound (C)-I Bis(dimethylphenyl)phosphate bis-phenol A made by DAIHACHI Chemical Industry Co., Ltd. (product name: CR741S) is used.
- (C)-2 metal salt compound of alkyl phosphonic acid (C)-2: Aluminum salt of diethyl phosphonic acid made by Clariant Corporation (product name: Exolit OP930) is used.
- Fig 1 represents the results of IH-NMR analysis of dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide prepared by the above method.
- Fig 2 represents the results of IH-NMR analysis of dibenzo ⁇ d,f>[l,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide prepared by above method.
- Comparative Examples are prepared in the same manner as the Examples above except the Comparative Examples include the components in the amounts shown in the following Table 2. The results are shown in the following Table 2.
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Abstract
The present invention provides a phosphonate based compound and a flame resistant thermoplastic resin composition including a thermoplastic resin (A) and the phosphonate based compound (B).
Description
The present invention relates to novel phosphonate based compound and a flame retardant styrenic resin composition including the same.
Styrenic resins which are used for exterior materials of electronic devices can also be used in a variety of engineering applications because of their excellent impact resistance, dimensional stability and high heat resistance. However, styrenic resins can burn easily and do not have fire resistance. Accordingly countries such as the United States, Japan and many European countries have passed laws requiring polymer resins to satisfy flame resistance standards.
A widely used and known method for imparting good flame retardancy to styrenic resin includes adding a halogen-containing compound as a flame retardant to a rubber-modified styrenic resin and adding an antimony-containing compound as a flame retardant aid. Examples of halogen-containing compounds used to impart flame retardancy include polybromodiphenyl ether, tetrabromobisphenol-A, epoxy compounds substituted with bromine, chlorinated polyethylene, and the like. Antimony trioxide or antimony pentaoxide is commonly used as an antimony-containing compound.
When a halogen- and antimony-containing compound is used to improve flame retardancy of resins, a desired degree of flame retardancy can readily be imparted to the resulting products without significantly degrading the physical properties thereof. Therefore, the halogen- and antimony-containing compounds are widely used as the primary flame retardant for housing materials for electrical appliances and office equipment formed of ABS resins, PS resins, PBT resins, PET resins or epoxy resins. However, hydrogen halide gases released by halogen-containing compounds during processing can have fatal effects on the human body and have high environmental persistence because these compounds are not naturally degradable. Also these compounds are not soluble in water, and thus can be highly bioaccumulated. Particularly, polybromodiphenyl ether, which is widely used as a halogen-containing flame retardant, may produce toxic gases such as dioxin or furan during combustion, and is consequently harmful to humans and the environment. Accordingly, there is a need to develop flame retardancy methods that do not employ halogen-containing compounds.
The present invention provides a novel phosphonate based compound which can be added to a resin composition to provide flame resistance.
The present invention further provides a flame resistant thermoplastic resin composition including a novel phosphonate based compound which can have fire stability.
The present invention further provides an environmentally-friendly thermoplastic resin composition which includes a halogen-free flame retardant and which can have excellent flame resistance as compared to a composition including a phosphate ester flame retardant.
Other aspects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
The present invention provides a phosphonate based compound represented by the following Chemical Formula 1.
[Chemical Formula 1]
wherein in the above Chemical Formula 1:
R1 is C1 to C4 alkyl, phenyl or cyano, and each R2 and R3 is independently H or C1 to C4 alkyl, for example t-butyl.
The present invention further provides a flame resistant thermoplastic resin composition comprising: a thermoplastic resin (A), and a phosphonate based compound (B) represented by the above Chemical Formula 1.
The thermoplastic resin may comprise polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), acrylonitrile-styrene copolymer resin (SAN resin), methylmethacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), poly phenylene ether resin (PPE), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyamide resin (PA), or a combination thereof.
In an exemplary embodiment of the present invention, the flame resistant thermoplastic resin composition may comprise about 100 parts by weight of the thermoplastic resin (A), and about 0.5 to about 30 parts by weight of the phosphonate based compound (B) represented by the above Chemical Formula 1, based on about 100 parts by weight of the thermoplastic resin (A).
In an exemplary embodiment of the present invention, the flame resistant thermoplastic resin composition may further comprise about 1 to about 20 parts by weight of a phosphorus flame retardant (C), based on about 100 parts by weight of the thermoplastic resin (A). The phosphorus flame retardant (C) may be an aromatic phosphorus ester compound (C)-1, a metal salt compound of an alkyl phosphonic acid (C)-2 which has a particle size of less than about 10 μm, or a combination thereof.
Fig 1 is a schematic diagram representing the results of 1H-NMR analysis of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide according to an exemplary embodiment of the present invention.
Fig 2 is a schematic diagram representing the results of 1H-NMR analysis of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide according to another exemplary embodiment of the present invention.
The present invention now will be described more fully hereinafter in the following detailed description of the invention, in which some, but not all embodiments of the invention are described. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
In one exemplary embodiment of the present invention, the present invention provides a phosphonate based compound represented by the following Chemical Formula 1.
[Chemical Formula 1]
wherein in the above Chemical Formula 1:
R1 is C1 to C4 alkyl, phenyl or cyano, and each R2 and R3 is independently H or C1 to C4 alkyl, for example t-butyl.
For example, the phosphonate based compound represented by the Chemical Formula 1 may comprise dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide, dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide, or a combination thereof.
The phosphonate based compound represented by the Chemical Formula 1 can be synthesized according to Scheme 1.
[Scheme 1]
wherein in the above Scheme 1, R4 is C1 to C4 alkyl, and R1, R2 and R3 is the same as described above.
The compound represented by the Chemical Formula 1 according to the present invention can be prepared by preparing an intermediate which is prepared by a dechlorination reaction of phosphorus trichloride, aryl-alcohol and C1-C4 alkanol, such as ethanol, and reacting the intermediate and a benzylbromide or a bromo acetonitrile or a bromo C1-C4 alkane.
Preparations of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide are described below.
The dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide may prepared as follows. An intermediate such as dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-C1-C4 alkoxy (such as dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-ethoxy) as illustrated in the Scheme 1 above can be prepared by stirring about 1 to about 3 equivalence ratio of phosphorus trichloride, for example 1 equivalence ratio, about 1 equivalence ratio of 2,2’-dihydroxy biphenyl and about 1 equivalence ratio of C1-C4 alkanol, for example ethanol, in the presence of nitrogen at room temperature. Then about 1 to about 2 equivalence ratio of benzylbromide or bromo acetonitrile or bromo C1-C4 alkane, for example 1 equivalence ratio, is added to the resultant intermediate and the mixture is stirred at about 100 to about 150 ℃.
In another exemplary embodiment of the present invention, the present invention provides a flame resistant thermoplastic resin composition comprising a thermoplastic resin (A) and a phosphonate based compound (B) represented by the Chemical Formula 1. The phosphonate based compound (B) represented by the Chemical Formula 1 can provide good flame retardancy properties to the thermoplastic resin.
The flame resistant thermoplastic resin composition may comprise about 0.5 to about 30 parts by weight, for example about 5 to about 25 parts by weight, of the phosphonate based compound (B) represented by the Chemical Formula 1 based on about 100 parts by weight of the thermoplastic resin (A). If the amount of the phosphonate based compound (B) represented by the Chemical Formula 1 is less than about 0.5 parts by weight based on about 100 parts by weight of the thermoplastic resin (A), flame resistance of the thermoplastic resin composition may be reduced. If the amount of the phosphonate based compound (B) represented by the Chemical Formula 1 is more than 30 parts by weight based on about 100 parts by weight of the thermoplastic resin (A), physical properties of the resin may be reduced.
Examples of the thermoplastic resin may include without limitation styrenic resins (resins including styrene), such as polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), acrylonitrile-styrene copolymer resin (SAN resin), methylmethacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), and the like, polycarbonate resins (PC), polyphenylene ether resins (PPE), polyolefin resins, such as polyethylene resin (PE), polypropylene resin (PP), and the like, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like, polyvinyl chloride (PVC), acrylic resins such as polymethyl methacrylate (PMMA), polyamide resins (PA) and the like, and copolymers and combinations thereof. Accordingly, the resins can include a homopolymer, a copolymer, an alloy and/or a combination thereof.
In one exemplary embodiment of the present invention, the present invention provides a flame resistant thermoplastic resin composition comprising a styrenic resin (A-1), a polyphenylene ether resin (A-2) and a phosphonate based compound (B) represented by the Chemical Formula 1. For example, the flame resistant thermoplastic resin composition may include about 0.5 to about 30 parts by weight of the phosphonate based compound (B) represented by the Chemical Formula 1 based on about 100 parts by weight of a base resin including about 70 to about 99 % by weight of the styrenic resin (A-1) and about 1 to about 30 % by weight of the polyphenylene ether resin (A-2). As another example, the base resin may include about 15 to about 30 % by weight of the polyphenylene ether resin (A-2). If the amount of the polyphenylene ether resin (A-2) is less than about 1 % by weight, the flame resistance of the thermoplastic resin composition may be reduced. If the amount of the polyphenylene ether resin (A-2) is more than about 30 % by weight, moldability may be reduced.
The flame resistant thermoplastic resin composition may further comprise a phosphorus flame retardant (C). The phosphorus flame retardant (C) may be an aromatic phosphorus ester compound (C)-1 or a metal salt compound of an alkyl phosphonic acid (C)-2 which has a particle size less than about 10 μm, or a combination thereof. The phosphorus flame retardant (C) may be used in an amount of about 1 to about 20 parts by weight, based on about 100 parts by weight of the thermoplastic resin (A). When the flame resistant thermoplastic resin composition according to the present invention further comprises the phosphorus flame retardant (C), the phosphonate based compound (B) may be used in amount of about 1 to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin (A).
The aromatic phosphorus ester compound (C)-1 may be represented by the following Chemical Formula 2.
[Chemical Formula 2]
wherein each R3, R4, R5, R3’, R4’, R5’, R3”, R4”, R5”, R3’”, R4’” and R5’” is independently H or C1 to C4 alkyl, X is C6 to C20 aryl or C6 to C20 aryl substituted with C1 to C4 alkyl, and n is an integer ranging from 0 to 4.
For example, X may be resorcinol, hydroquinol or dialcohol derived from bisphenol-A, or a combination thereof.
When n is 0, examples of the compound represented by the Chemical Formula 2 may include triphenyl phosphate, tri(2,6-dimethyl)phosphate and the like, and combinations thereof. When n is 2, examples of the compound represented by the Chemical Formula 2 may include resorcinol bis(diphenyl)phosphate, resorcinol bis(2,6-dimethylphenyl)phosphate, resorcinol bis(2,4-ditert-butylphenyl)phosphate, hydroquinol bis(2,6-dimethylphenyl)phosphate, hydroquinol bis(2,4-ditert-butylphenyl)phosphate and the like, and combinations thereof.
The metal salt compound of an alkyl phosphonic acid (C)-2 may be represented by the following Chemical Formula 3, and can have a particle size of less than about 10 μm, for example, about 1 to about 10 μm.
[Chemical Formula 3]
wherein R is C1 to C6 alkyl, C1 to C6 cycloalkyl or C6 to C10 aryl, M is a metal such as Al, Zn, Ca, and n is an integer of 2 or 3.
For example, R may be methyl, ethyl, propyl, butyl or phenyl, and M may be Al or Zn.
The flame resistant thermoplastic resin composition according to the present invention may further include one or more additives selected without limitation from plasticizers, heat stabilizers, antioxidants, compatibilizers, light-stabilizers, inorganic additives, pigments, dyes and the like, and combinations thereof. Examples of the inorganic additives may include asbestos, glass fiber, talc, ceramic, sulfate and the like, and combinations thereof. The one or more additives may be used in an amount of less than about 30 parts by weight based on the total weight of the resin composition.
The flame resistant thermoplastic resin composition of the present invention can be prepared by known methods. For example, the components and optionally the additives can be mixed simultaneously, and the mixture can be extruded through an extruder to prepare pellets.
In another embodiment of the present invention, the present invention provides a molded article prepared from the flame resistant thermoplastic resin composition of the present invention. The molded article may have excellent flame resistance and can be environmentally-friendly. The molded article can be prepared using any suitable molding technique, such as but not limited to melt extrusion, injection molding, and the like. The skilled artisan will understand how to prepare a molded article using the flame resistant thermoplastic resin composition of the invention without undue experimentation.
The invention may be better understood by reference to the following examples which are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
Examples and Comparative Examples
Components used in the following examples and comparative examples are as follows.
(A-1) Styrenic resin: Rubber-reinforced styrenic resin made by Cheil Industries, Inc. of South Korea (product name: HG-1760S) is used.
(A-2) Polyphenylene ether (PPE) resin: Poly(2,6-dimethyl-phenylether) made by Mitsubishi Engineering Plastic Corporation of Japan (product name: PX-100F) is used, and the particle size is several tens of μm in the form of a powder.
(A-3) PET resin: PET resin made by SK Chemical of South Korea (BB-8055) is used, with an intrinsic viscosity [η] of about 0.8, and a melting point of 254 ℃.
(A-4) ABS resin: ABS resin made by Cheil Industries, Inc. of South Korea (product name: SD-0150) is used.
(B) Phosphonate based compound (B) represented by the Chemical Formula 1: dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide prepared in Preparation Example 1 and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide prepared in Preparation Example 2 are used.
(C)-1 aromatic phosphorus ester compound (C)-1: Bis(dimethylphenyl)phosphate bis-phenol A made by DAIHACHI Chemical Industry Co., Ltd. (product name: CR741S) is used.
(C)-2 metal salt compound of alkyl phosphonic acid (C)-2: Aluminum salt of diethyl phosphonic acid made by Clariant Corporation (product name: Exolit OP930) is used.
Preparation Example 1
Preparation of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide: After injecting phosphorus tri-chloride(137.3 g, 1.0 mol), 2,2’-dihydroxy biphenyl(186.2 g, 1 mol) and ethanol(46.1 g, 1.0 mol) into a receptacle, the mixture is stirred for 3 hours in the presence of nitrogen at room temperature. After adding benzyl bromide(171.0 g, 1 mol), the temperature of the receptacle is raised to 150 ℃ and the mixture is stirred for 12 hours in the presence of nitrogen. Then, the temperature of the receptacle is lowered to room temperature and the contents are washed with dimethyl ether, and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide which has a degree of purity of more than about 98 % and a yield rate of about 95 % is recovered. Fig 1 represents the results of 1H-NMR analysis of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide prepared by the above method.
Preparation Example 2
Preparation of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide: After injecting phosphorus tri-chloride(137.3 g, 1.0 mol), 2,2’-dihydroxy biphenyl(186.2 g, 1 mol) and ethanol(46.1 g, 1.0 mol) into a receptacle, the mixture is stirred for 3 hours in the presence of nitrogen at room temperature. After adding bromo-acetonitrile(119.9 g, 1 mol), the temperature of the receptacle is raised to 150 ℃ and the mixture is stirred for 12 hours in the presence of nitrogen. Then, the temperature of the receptacle is lowered to room temperature and the contents are washed with dimethyl ether, and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide which has a degree of purity of more than about 98 % and a yield rate of about 95 % is recovered. Fig 2 represents the results of 1H-NMR analysis of dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide prepared by above method.
Examples 1 to 12
The components in amounts shown in the following Table 1 are extruded through a conventional extruder at about 240 ℃ to prepare pellets. After the prepared pellets are dried, the pellets are injected under conditions of a molding temperature of 230 ℃ and a tool temperature of 50 ℃. Then, flame resistant samples are prepared. The flame resistance of prepared samples is measured according to UL 94 VB with a thickness of 1/8” and the impact strength is measured according to ASTM D256.
Comparative Examples 1 to 8
Comparative Examples are prepared in the same manner as the Examples above except the Comparative Examples include the components in the amounts shown in the following Table 2. The results are shown in the following Table 2.
Table 1 
Table 2 
As illustrated by the results set forth in Tables 1 and 2, when the dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide and dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide are used, flame resistance and impact strength are excellent compared to an aromatic phosphorus ester compound.
Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being defined in the claims.
Claims (16)
- A phosphonate based compound represented by the following Chemical Formula 1:[Chemical Formula 1]
wherein R1 is C1 to C4 alkyl, phenyl or cyano, and each R2 and R3 is independently H or C1 to C4 alkyl. - The phosphonate based compound of Claim 1, wherein said R1 is phenyl or cyano.
- A flame resistant thermoplastic resin composition comprising a thermoplastic resin (A) and a phosphonate based compound (B) represented by the Chemical Formula 1:[Chemical Formula 1]
wherein R1 is C1 to C4 alkyl, phenyl or cyano, and each R2 and R3 is independently H or C1 to C4 alkyl. - The flame resistant thermoplastic resin composition of Claim 3, wherein said thermoplastic resin comprises styrenic resin, polycarbonate resin (PC), polyphenylene ether resin (PPE), polyolefin resin, polyester resin, polyvinyl chloride (PVC), acrylic resin, polyamide resin (PA) or a combination thereof.
- The flame resistant thermoplastic resin composition of Claim 4, wherein said thermoplastic resin comprises polystyrene resin (PS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), acrylonitrile-styrene copolymer resin (SAN resin), methylmethacrylate-butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), polyphenylene ether resin (PPE), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyamide resin (PA) or a combination thereof.
- The flame resistant thermoplastic resin composition of Claim 3, comprising about 0.5 to about 30 parts by weight of the phosphonate based compound represented by the Chemical Formula 1 based on about 100 parts by weight of the thermoplastic resin (A).
- The flame resistant thermoplastic resin composition of Claim 6, further comprising about 1 to about 20 parts by weight of a phosphorus flame retardant (C) based on about 100 parts by weight of the thermoplastic resin (A).
- The flame resistant thermoplastic resin composition of Claim 7, wherein said phosphorus flame retardant (C) comprises an aromatic phosphorus ester compound (C)-1, a metal salt compound of an alkyl phosphonic acid (C)-2 which has a particle size of less than about 10 μm, or a combination thereof.
- The flame resistant thermoplastic resin composition of Claim 8, wherein said aromatic phosphorus ester compound (C)-1 is represented by the following Chemical Formula 2:[Chemical Formula 2]
wherein each R3, R4, R5, R3’, R4’, R5’, R3”, R4”, R5”, R3’”, R4’” and R5’” is independently H or C1 to C4 alkyl, X is C6 to C20 aryl or C6 to C20 aryl substituted with C1 to C4 alkyl, and n is an integer ranging from 0 to 4. - The flame resistant thermoplastic resin composition of Claim 8, wherein said metal salt compound of alkyl phosphonic acid (C)-2 is represented by the following Chemical Formula 3:[Chemical Formula 3]
wherein R is C1 to C6 alkyl, C1 to C6 cycloalkyl or C6 to C10 aryl, M is Al, Zn, or Ca, and n is an integer of 2 or 3. - The flame resistant thermoplastic resin composition of Claim 6, further comprising less than about 30 parts by weight of a plasticizer, heat stabilizer, antioxidant, compatibilizer, light-stabilizer, inorganic additive, pigment, dye or a combination thereof based on about 100 parts by weight of the thermoplastic resin (A).
- A molded article prepared from the flame resistant thermoplastic resin composition of Claim 3.
- The phosphonate based compound of Claim 1, wherein the compound is dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide.
- The phosphonate based compound of Claim 1, wherein the compound is dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide.
- The flame resistant thermoplastic resin composition of Claim 3, wherein the phosphonate based compound (B) is dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-phenylmethyl-, 6-oxide.
- The flame resistant thermoplastic resin composition of Claim 3, wherein the phosphonate based compound (B) is dibenzo<d,f>[1,3,2]dioxaphos-phepin, 6-cyanomethyl-, 6-oxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200980152776.2A CN102264749B (en) | 2008-12-29 | 2009-12-21 | Novel phosphonate based compound and flame retardant styrenic resin composition including same |
| US13/166,203 US8846789B2 (en) | 2008-12-29 | 2011-06-22 | Phosphonate based compound and flame retardant styrenic resin composition including the same |
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| KR20080135866 | 2008-12-29 | ||
| KR10-2008-0135866 | 2008-12-29 | ||
| KR1020090104023A KR101219556B1 (en) | 2008-12-29 | 2009-10-30 | Novel phosphoanate based compound and flame retardant thermoplastic resin composition including the same |
| KR10-2009-0104023 | 2009-10-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/166,203 Continuation-In-Part US8846789B2 (en) | 2008-12-29 | 2011-06-22 | Phosphonate based compound and flame retardant styrenic resin composition including the same |
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| Publication Number | Publication Date |
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| WO2010076995A2 true WO2010076995A2 (en) | 2010-07-08 |
| WO2010076995A3 WO2010076995A3 (en) | 2010-09-10 |
| WO2010076995A9 WO2010076995A9 (en) | 2010-10-28 |
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| PCT/KR2009/007631 WO2010076995A2 (en) | 2008-12-29 | 2009-12-21 | Novel phosphonate based compound and flame retardant styrenic resin composition including the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846789B2 (en) | 2008-12-29 | 2014-09-30 | Cheil Industries Inc. | Phosphonate based compound and flame retardant styrenic resin composition including the same |
| WO2014197462A1 (en) * | 2013-06-03 | 2014-12-11 | Polyone Corporation | Flame retardant high temperature nylon |
| TWI498334B (en) * | 2012-01-16 | 2015-09-01 | Univ Nat Chunghsing | Phosphorous-containing compounds, blends thereof and preparing method for the same |
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| WO2007081904A1 (en) * | 2006-01-06 | 2007-07-19 | Supresta Llc | Halogen-free flame retardant compositions, thermoplastic compositions comprising the same and methods of producing the compositions |
| WO2008119693A1 (en) * | 2007-04-03 | 2008-10-09 | Basf Se | Dopo flame retardant compositions |
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| WO2007081904A1 (en) * | 2006-01-06 | 2007-07-19 | Supresta Llc | Halogen-free flame retardant compositions, thermoplastic compositions comprising the same and methods of producing the compositions |
| WO2008119693A1 (en) * | 2007-04-03 | 2008-10-09 | Basf Se | Dopo flame retardant compositions |
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| ALYSSA H. ET AL.: 'THE CONFORMATION OF MEDIUM-SIZED HETEROCYCLES:SYNTHESIS AND SOLID-STATE CONFORMATION OF A 6-ARYLTHIO-SUBSTITUTED DIBENZO-[d,f][1,3,2] DIOXAPHOSPHEPIN' PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS vol. 82, no. 1-4, 1989, pages 1 - 6 * |
| M. KASTHURAIAH ET AL.: 'Syntheses, Spectral Property, and Antimicrobial Activities of 6-a-Amino Dibenzo[d,f ][1,3,2]Dioxaphosphepin 6-Oxides' HETEROATOM CHEMISTRY vol. 18, no. 1, 2007, pages 2 - 8 * |
| P.HARANATH ET AL.: 'Syntheses and Antimicrobial Activity of Some Novel 6-Substituted Dibenzo[d,f][1,3,2]dioxaphosphepin-6-oxides , sulfides, and Selenides' SYNTHETIC COMMUNICATIONS vol. 37, 2007, pages 1697 - 1708 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846789B2 (en) | 2008-12-29 | 2014-09-30 | Cheil Industries Inc. | Phosphonate based compound and flame retardant styrenic resin composition including the same |
| TWI498334B (en) * | 2012-01-16 | 2015-09-01 | Univ Nat Chunghsing | Phosphorous-containing compounds, blends thereof and preparing method for the same |
| WO2014197462A1 (en) * | 2013-06-03 | 2014-12-11 | Polyone Corporation | Flame retardant high temperature nylon |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010076995A9 (en) | 2010-10-28 |
| WO2010076995A3 (en) | 2010-09-10 |
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