JP5416395B2 - 対称性環状リン系化合物、その製造方法、およびこれを含む難燃性スチレン系樹脂組成物 - Google Patents
対称性環状リン系化合物、その製造方法、およびこれを含む難燃性スチレン系樹脂組成物 Download PDFInfo
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- JP5416395B2 JP5416395B2 JP2008322822A JP2008322822A JP5416395B2 JP 5416395 B2 JP5416395 B2 JP 5416395B2 JP 2008322822 A JP2008322822 A JP 2008322822A JP 2008322822 A JP2008322822 A JP 2008322822A JP 5416395 B2 JP5416395 B2 JP 5416395B2
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- -1 cyclic phosphorus compound Chemical class 0.000 title claims description 98
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 82
- 239000003063 flame retardant Substances 0.000 title claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 36
- 239000011574 phosphorus Substances 0.000 title claims description 36
- 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 34
- 239000011342 resin composition Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 239000000126 substance Substances 0.000 claims description 37
- 229910019142 PO4 Inorganic materials 0.000 claims description 27
- 239000010452 phosphate Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 229920001955 polyphenylene ether Polymers 0.000 claims description 14
- 229920001890 Novodur Polymers 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 3
- NJLHHACGWKAWKL-UHFFFAOYSA-N ClP(Cl)=O Chemical compound ClP(Cl)=O NJLHHACGWKAWKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000000178 monomer Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WUEAMTVQNGYLRI-UHFFFAOYSA-N 2-dichlorophosphoryl-1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=C(P(Cl)(Cl)=O)C(C(C)C)=C1 WUEAMTVQNGYLRI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OQUGNSMOWJIYMO-UHFFFAOYSA-N 2-dichlorophosphoryl-2-methylpropane Chemical compound CC(C)(C)P(Cl)(Cl)=O OQUGNSMOWJIYMO-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 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 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004724 Iupiace Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SOENTGYTFPUWKK-UHFFFAOYSA-N OC1=CC=C(O)C=C1.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 Chemical compound OC1=CC=C(O)C=C1.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 SOENTGYTFPUWKK-UHFFFAOYSA-N 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- PRLOUQPPIDTCKH-UHFFFAOYSA-N benzene-1,4-diol;bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound OC1=CC=C(O)C=C1.CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C PRLOUQPPIDTCKH-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- WZZNZLTYLRKPII-UHFFFAOYSA-N bis(2,4-ditert-butylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=CC(O)=C1 WZZNZLTYLRKPII-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
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005548 pyrenylene group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 238000012719 thermal polymerization Methods 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
- 239000008096 xylene Substances 0.000 description 1
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
- C07F9/657181—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, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Description
本発明に係る対称性環状リン系化合物は、下記化学式1で表される。
本発明は、前記対称性環状リン系化合物の製造方法を提供する。前記対称性環状リン系化合物は、下記化学式2で表されるホスホン酸ジクロライドと、下記化学式3で表されるポリオールとを、塩基の存在下で反応させて製造することができる。
本発明は、前記対称性環状リン系化合物を難燃剤として適用した難燃性スチレン系樹脂組成物を提供する。
本発明の難燃性スチレン系樹脂組成物に用いることができるスチレン系樹脂(A)の具体的な例としては、例えば、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂(ABS樹脂)、アクリロニトリル−スチレン共重合体樹脂(AS樹脂)、ゴム変性耐衝撃性ポリスチレン樹脂(HIPS)などが挙げられるが、これらに限定されるものではない。なお、前記スチレン系樹脂(A)は、単独で使用してもよいし2種以上組み合わせて用いてもよい。
本発明に係る難燃性スチレン系樹脂組成物は、前記スチレン系樹脂(A)の不十分な難燃性と耐熱性とを向上させるために、ポリフェニレンエーテル樹脂(B)をベース樹脂の成分として用いる。このようなポリフェニレンエーテル樹脂(B)の具体的な例としては、例えば、ポリ(2,6−ジメチル−1,4−フェニレン)エーテル、ポリ(2,6−ジエチル−1,4−フェニレン)エーテル、ポリ(2,6−ジプロピル−1,4−フェニレン)エーテル、ポリ(2−メチル−6−エチル−1,4−フェニレン)エーテル、ポリ(2−メチル−6−プロピル−1,4−フェニレン)エーテル、ポリ(2−エチル−6−プロピル−1,4−フェニレン)エーテル、ポリ(2,6−ジフェニル−1,4−フェニレン)エーテル、ポリ(2,6−ジメチル−1,4−フェニレン)エーテルと、ポリ(2,3,6−トリメチル−1,4−フェニレン)エーテルとの共重合体、およびポリ(2,6−ジメチル−1,4−フェニレン)エーテルとポリ(2,3,5−トリエチル−1,4−フェニレン)エーテルなど挙げられるが、これらに限定されるものではない。これらは、単独でもまたは2種以上組み合わせても用いることができる。好ましくは、ポリ(2,6−ジメチル−1,4−フェニレン)エーテルとポリ(2,3,6−トリメチル−1,4−フェニレン)エーテルとの共重合体、またはポリ(2,6−ジメチル−1,4−フェニレン)エーテルが挙げられ、ポリ(2,6−ジメチル−1,4−フェニレン)エーテルがさらに好ましい。
本発明の難燃性スチレン系樹脂組成物に用いられる対称性環状リン系化合物は、下記化学式1で表される化合物である。
本発明で用いる芳香族リン酸エステル化合物は、下記化学式4で表される構造を有する化合物であることが好ましい。
本発明で用いられるリン酸塩化合物は、アルキルホスフィン酸金属塩化合物が好ましく、下記化学式5で表される構造を有する。
t−ブチルホスホン酸ジクロライド(IV)2当量、テトラオール(V)1当量、およびトリエチルアミン4当量を、トルエン溶媒中で、130℃で約10時間還流反応させた。反応終了後、水を入れて固体がなくなるまで攪拌し、その後有機層を取り出して減圧蒸留し、純度99%以上、収率約50%で対称性環状リン系化合物(I−1)を得た(下記反応式1参照)。
実施例および比較例で用いた各成分の詳細は、次の通りである。
第一毛織株式会社製のゴム変性耐衝撃性スチレン系樹脂 HG−1760S(ゴムの平均粒径:0.4μm)を用いた。
三菱エンジニアリングプラスチックス株式会社製のポリ(2,6−ジメチル−1,4−フェニレン)エーテル(商品名:ユピエース(登録商標)PX−100F、固有粘度:0.5dl/g)を用いた。粒子の大きさは数十μmの平均粒子径を有し、粉末形態である。
前記実施例1で製造された対称性環状リン系化合物(I−1)を用いた。
大八化学工業株式会社製のビスフェノールAビス(ジフェニル)ホスフェート(商品名:CR−741S)を用いた。
クラリアント(Clariant)社製のジエチルホスフィン酸アルミニウム塩(商品名:Exolit(登録商標) OP930)を用いた。
前記各成分を下記表1に記載された含有量で混合した後、通常の二軸押出機で200〜280℃の温度範囲で押出してペレットを製造した。製造されたペレットを約80℃で約2時間乾燥した後、6オンス射出成形機で成形温度180〜280℃、金型温度40〜80℃の条件で射出して試験片を製造した。
下記表1の記載のように、各成分の含有量を調節したことを除いては、実施例2〜7と同様にして試験片を製造し、各物性を測定した。測定結果を下記表1に示す。
Claims (8)
- 下記化学式1で表される、対称性環状リン系化合物:
- 下記化学式2で表されるホスホン酸ジクロライドと、下記化学式3で表されるポリオールとを塩基の存在下で反応させる、下記化学式1で表される対称性環状リン系化合物の製造方法:
- (A)スチレン系樹脂と、(B)ポリフェニレンエーテル樹脂とからなるベース樹脂100質量部、および
(C)下記化学式1で表される対称性環状リン系化合物0.5〜50質量部、
を含む、難燃性スチレン系樹脂組成物:
- 前記ベース樹脂は、スチレン系樹脂(A)99〜60質量%とポリフェニレンエーテル樹脂(B)1〜40質量%とからなる(ただし、(A)と(B)との合計量は100質量%)、請求項3に記載の難燃性スチレン系樹脂組成物。
- 前記ベース樹脂100質量部に対して、(D)芳香族リン酸エステル化合物および(E)リン酸塩化合物の少なくとも一方を0.1〜40質量部をさらに含む、請求項3または4に記載の難燃性スチレン系樹脂組成物。
- 前記芳香族リン酸エステル化合物(D)は、下記化学式4で表される構造を有する、請求項5に記載の難燃性スチレン系樹脂組成物:
- 前記リン酸塩化合物(E)は、下記化学式5で表される構造を有する、請求項5または6に記載の難燃性スチレン系樹脂組成物:
- 前記ベース樹脂100質量部に対して、熱安定剤、滴下防止剤、酸化防止剤、相溶化剤、光安定剤、可塑剤、顔料、染料、および無機添加剤からなる群より選択される添加剤を30質量部以下でさらに含む、請求項3〜7のいずれか1項に記載の難燃性スチレン系樹脂組成物。
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