WO2001034616A1 - Procede de preparation d'esters d'acide phosphorique condenses - Google Patents
Procede de preparation d'esters d'acide phosphorique condenses Download PDFInfo
- Publication number
- WO2001034616A1 WO2001034616A1 PCT/JP2000/003481 JP0003481W WO0134616A1 WO 2001034616 A1 WO2001034616 A1 WO 2001034616A1 JP 0003481 W JP0003481 W JP 0003481W WO 0134616 A1 WO0134616 A1 WO 0134616A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bisphenol
- derivative
- reacting
- phosphorus
- hydroxy compound
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 78
- 150000003014 phosphoric acid esters Chemical class 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract 2
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 100
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011574 phosphorus Substances 0.000 claims abstract description 53
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 53
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 48
- 239000003112 inhibitor Substances 0.000 claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 claims description 79
- 239000010452 phosphate Substances 0.000 claims description 78
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 25
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 33
- 239000011347 resin Substances 0.000 abstract description 33
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 238000010186 staining Methods 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 76
- 239000000047 product Substances 0.000 description 29
- 239000003063 flame retardant Substances 0.000 description 21
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 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 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000012433 hydrogen halide Substances 0.000 description 8
- 229910000039 hydrogen halide Inorganic materials 0.000 description 8
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 8
- 150000004712 monophosphates Chemical class 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
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- 230000035484 reaction time Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 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 3
- 238000005406 washing Methods 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- AFXQOXNRTJFOJV-UHFFFAOYSA-N 2,3,4-triethylphenol Chemical compound CCC1=CC=C(O)C(CC)=C1CC AFXQOXNRTJFOJV-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- TZIPJVAKPHGVFU-UHFFFAOYSA-N 2,3,4-tripropylphenol Chemical compound CCCC1=CC=C(O)C(CCC)=C1CCC TZIPJVAKPHGVFU-UHFFFAOYSA-N 0.000 description 1
- 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
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- FHTGJZOULSYEOB-UHFFFAOYSA-N 2,6-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1O FHTGJZOULSYEOB-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
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- 235000011090 malic acid Nutrition 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- UQFOCNGSTJRLHY-UHFFFAOYSA-N trisilyl phosphate Chemical compound [SiH3]OP(=O)(O[SiH3])O[SiH3] UQFOCNGSTJRLHY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Definitions
- the present invention relates to a method for producing a condensed phosphate ester. More specifically, the present invention relates to a method for producing a condensed phosphate ester having a low content of volatile components that adversely affect the quality of a resin and being excellent as a resin additive such as a plasticizer or a flame retardant.
- a resin additive such as a plasticizer or a flame retardant.
- halogen compounds such as deca-mouth mobiphenyl ether and tetrabromobisphenol A
- low-molecular phosphorus compounds such as cresyl diphenyl phosphate and triphenyl phosphate.
- TPP triphenyl phosphate
- TCP tricresyl phosphate
- the condensed phosphate ester is obtained by reacting phosphorus oxychloride with a divalent hydroxy compound such as hydroquinone perresorcin and bisphenol A and a monovalent hydroxy compound such as phenol percresol.
- a divalent hydroxy compound such as hydroquinone perresorcin and bisphenol A
- a monovalent hydroxy compound such as phenol percresol.
- the condensed phosphate ester produced by a conventional method using a bisphenol A derivative as a divalent hydroxy compound when compounded with a resin, may cause coloring of the molded product, heat resistance and moldability. It has been pointed out that this has a negative effect on the environment.
- an object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a method for producing a condensed phosphoric acid ester using a bisphenol A derivative as a raw material, which does not cause coloring of a molded product when mixed with a resin and does not adversely affect heat resistance and moldability. Then, by using the condensed phosphate ester produced by the method of the present invention as a flame retardant, the quality of a resin molded product can be improved and contribute to society. Disclosure of the invention
- the present inventors have found that bisphenol A derivatives and oxytrihalogen When reacting phosphorus phosphide and a hydroxy compound, the bisphenol A derivative comes into contact with hydrogen halide generated by the reaction to decompose the bisphenol A derivative, and the aryl group-containing phosphate and isoprobenyl aryl group-containing
- the present inventors investigated the cause of the formation of phosphate (monomeric phosphate ester), and carried out the reaction in the presence of a decomposition inhibitor to suppress the production of monomeric phosphate ester. The inventors have found out that they can be solved, and have reached the present invention.
- IPP isoprobenyl aryl group-containing phosphate
- the method for producing a condensed phosphate according to the present invention includes a process of reacting a bisphenol A derivative, a phosphorus oxytrihalide, and a hydroxy compound in the presence of a decomposition inhibitor.
- the decomposition inhibitor is an organic carboxylic acid compound.
- the organic carboxylic compound is ascorbic acid and / or adipic acid.
- the decomposition inhibitor is tin, copper, iron oxide and Z or chloride.
- the tin, copper, iron oxide and Z or chloride are stannic oxide, ferric chloride, or cupric chloride.
- the amount of the decomposition inhibitor used is 0.01 to 5 parts by weight based on 100 parts by weight of the bisphenol A derivative.
- the process of reacting the bisphenol A derivative, phosphorus oxytrihalide, and a hydroxy compound comprises:
- the process of reacting the bisphenol A derivative, phosphorus oxytrihalide, and a hydroxy compound comprises:
- the amount of the hydroxy compound used is 2 mol% or less in excess of the theoretical amount required to convert all of the phosphorohalide into a condensed phosphate ester.
- the process of reacting the bisphenol A derivative, phosphorus oxytrihalide, and a hydroxy compound comprises:
- the reaction product obtained in the first step is reacted with a monophenolic compound at a temperature of 120 or less, and then the temperature is raised and the phosphorohalidate is reacted with the hydroxy compound at a temperature of 120 ° C or more. 2 steps
- the process of reacting the bisphenol A derivative, phosphorus oxytrihalide, and a hydroxy compound comprises:
- the reaction product obtained in the first step is reacted with a monophenolic compound at a temperature of 12 (TC or lower), and then the temperature is raised to cause the phosphorohalidate to react with the hydroxy compound at 120 ° C or higher.
- Second stage Is included.
- the condensed phosphate ester is 2,2-bis ⁇ 4-1 [bis (phenoxy) phosphoryl] oxyphenyl ⁇ propane.
- the above process includes the first and second steps described below.
- the bisphenol A derivative is reacted with phosphorus oxytrihalide in the presence of a decomposition inhibitor to obtain phosphorohalidate.
- the term "decomposition inhibitor” means a compound which has an action of suppressing the decomposition of a bisphenol A derivative by hydrogen halide.
- Preferred examples of such a compound include an organic carboxylic acid-based compound and a compound containing any of tin, copper, and iron.
- the organic carboxylic acid compound means an organic carboxylic acid and a salt thereof.
- Organic carboxylic acids are preferred. Specific examples include ascorbic acid, terephthalic acid, malic acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, cunic acid, magnesium stearate, and magnesium stearate. Preferred are ascorbic acid and adipic acid.
- the compound containing any of tin, copper, and iron preferably means oxides and chlorides of tin, copper, or iron, and specifically includes stannic oxide, cupric chloride, and chloride. Ferric and the like are more preferable, and stannic oxide is more preferable.
- decomposition inhibitors suppress the reaction of bisphenol A derivatives being decomposed by hydrogen halide. For this reason, in the production of the condensed phosphate ester, it is possible to suppress the by-product of the monomer phosphate ester.
- the decomposition inhibitor may be used alone, or two or more decomposition inhibitors may be used in combination.
- the amount of the decomposition inhibitor to be used is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the bisphenol A derivative. More preferably, the amount is 0.15 to 1.5 parts by weight.
- the amount of the decomposition inhibitor is too small, the effect of suppressing the decomposition is reduced, and it is difficult to obtain a sufficient effect of suppressing the decomposition. If there are too many decomposition inhibitors, the decomposition inhibitors are likely to remain in the product as impurities.
- the decomposition inhibitor can be added at an arbitrary timing when producing the condensed phosphate ester.
- the decomposition inhibitor suppresses the reaction between the bisphenol A derivative and hydrogen halide, it is preferable to add the decomposition inhibitor before reacting the bisphenol A derivative with phosphorus oxytrihalide. .
- the decomposition inhibitor may be allowed to remain in the condensed phosphate product without being removed after the production of the condensed phosphate ester.
- a process for removing the decomposition inhibitor should be provided. Is also good. In this case, any method can be used to remove the decomposition inhibitor, for example, filtration or decantation.
- the timing for removing the decomposition inhibitor is preferably after the reaction between the phosphorohalidate and the hydroxy compound is completed.
- Examples of the phosphorus oxytrihalide include phosphorus oxychloride, phosphorus oxybromide and the like.
- the bisphenol A derivative is bisphenol A or a derivative thereof, and means a compound represented by the following formula (A).
- R 5 and R 6 are the same or different and represent an alkyl group having 1 to 3 carbon atoms.
- n1 and n2 show the integer of 0-4.
- phosphorohalidate means a compound represented by the following formula (I).
- X represents a halogen atom
- n represents an integer of 1 to 10.
- R 5 , R 6 , n 1 and n 2 are as defined above.
- the amount of phosphorus trihalide and bisphenol A derivative used is calculated based on the stoichiometric amount calculated from the amount of bisphenol compound used. As the amount exceeds the reaction amount (that is, 2 mol times of the bisphenol compound), the amount of the remaining unreacted oxytrihalogenide necessarily increases, and the unreacted oxytrioctaphosphorus genide is recovered. The operation was complicated, which was not preferred. However, if the amount of phosphorus trioxyhalide used is an excess of 4.5 mol times or more, more preferably 5 mols or more, and still more preferably 5.4 mol times or more of the bisphenol A derivative. However, the advantage that decomposition of bisphenol A derivative is suppressed is expected.
- the amount of the phosphorus trihalide and the bisphenol A derivative used is not particularly limited, but for the above-mentioned reasons, the amount of the phosphorus trioxyhalide is set to 4.5 relative to the amount of the bisphenol A derivative.
- the molar amount is preferably at least 5 times, more preferably at least 5 times, even more preferably at least 5.4 times.
- molar times refers to a compounding ratio based on the number of moles.
- the upper limit of the amount of oxytrihalogenated phosphorus is not particularly limited, but if it is used too much, the efficiency of the kettle tends to decrease, and the productivity tends to decrease. Preferably, it is used in an amount of 6 mole times or less. More preferably, the amounts of the phosphorus oxytrihalide and the bisphenol A derivative are adjusted so that the hydrogen halide concentration in the reaction solution is 5% by weight or less within the above range.
- a catalyst may be used.
- Lewis acid catalysts such as aluminum chloride, magnesium chloride, titanium tetrachloride and the like can be mentioned.
- Other reaction conditions for example, reaction temperature, reaction time, degree of reduced pressure, and the like can be appropriately selected depending on the type and degree of condensation of the desired condensed phosphate ester, and the type and scale of the equipment to be used.
- the temperature condition in the first stage of the process 1 is preferably 80 to 130 ° C.
- the temperature may be started at a temperature lower than 80 ° C., and then the temperature may be raised to 80 to 130.
- the time of the first stage of the process 1 is preferably 3 hours to 20 hours.
- the hydrogen halide gas generated during the reaction is collected by water.
- an organic solvent can be used if necessary.
- aromatic organic solvents such as toluene, xylene and dichlorobenzene, and aliphatic organic solvents such as hexane and heptane can be used.
- phosphorus-based compounds such as triphenylphosphite and tri (2,6-di-t-butyl) phosphite, 2,6-di-t-butyl- Hindered phenolic compounds such as p-cresol (BHT) and 2-methyl-6-t-butyl-P-cresol can be added as coloring inhibitors.
- the first step of the above process it is preferable to further carry out an operation of removing the phosphorus oxytrihalide remaining unreacted after the reaction of the bisphenol A derivative with the oxytrihalide.
- the removal of the phosphorus oxyhalide can be performed using any conventionally known method.
- the operation of removing unreacted oxytrihalide is usually performed under normal pressure or reduced pressure.
- the conditions for removing and recovering the phosphorous trihalide are, for example, preferably reduced to 200 mmHg or less, more preferably 100 mmHg or less, and still more preferably 50 mmHg or less with a vacuum pump.
- the recovery temperature is preferably from 100 to 200, more preferably from 100 to L70. More preferably, it is 100 to 150.
- the second stage of the process 1 is intended to produce a condensed phosphate by reacting the phosphorohalide obtained as described above with a hydroxy compound.
- the condensed phosphate ester is defined as a compound obtained by reacting a phosphorus oxylogenogenated compound having two phosphorus atoms in its molecule, a hydroxy compound, and a bisphenol A derivative. Means the phosphoric acid ester obtained by the reaction.
- Preferred condensed phosphate esters include compounds of formula (II):
- 0 f C CH is 3 3 ⁇ (R " n20 ⁇
- R 1 , R 2 , R 3 and R 4 represent the same or different aryl groups having 6 to 15 carbon atoms.
- R 5 , R s , nl, n 2 and n are as defined above]
- Examples of the aryl group having 6 to 15 carbon atoms include phenyl, (o—, m—, P-) methylphenyl, (o—, m—, p—) ethylphenyl, (o—, m—, p—) n— Propylphenyl, (o—, m—, p-) isopropylphenyl, (o—, m—, p—) n-butylphenyl, (o—, m—, p—) sec—butylphenyl, (o —, M—, p-) tert-butylphenyl, (2,3—, 2,4-1, 2,5—, 2,6—, 3,4—, 3,5—) dimethylphenyl, (2, 3-, 2, 4--1, 2, 5-, 2, 6-, 3, 4-, 3, 5--) Jethylphenyl, 2-methyl, 3-ethylphenyl, 2-methyl, 4-methylphenyl, 2-methyl, 5-eth
- condensed phosphate represented by the formula (II) include 2,2-bis ⁇ 4- [bis (phenoxy) phosphoryl] oxyphenyl ⁇ propane using bisphenol A as a raw material. —Bis ⁇ 4— [bis (methylphenoxy) phosphoryl] oxyphenyl ⁇ propane, 2,2-bis ⁇ 4— [bis (dimethylphenoxy) phosphoryl] oxyphenyl ⁇ propane, 2-bis ⁇ 4_ [bis ( Methylethyl phenoxy) phosphoryl] oxyphenyl ⁇ propane.
- Examples of the hydroxy compound include phenol, (0—, m—, P—) methylphenol, (o—, m—, p—) ethylphenol, (0—, m—, p—) n—propylphenol, (o —, M—, P-) isopropylphenol, (o—, m—, p-) n-butylphenol, (o—, m—, p—) sec—butylphenol J, ( ⁇ -1, m—, p—) tert—butyl J rephenone J, (o— , M—, p-) methylphenol, (2,3—, 2,4_, 2,5—, 2,6—, 3,4—, 3, ⁇ -) dimethylphenol, (2,3—, 2 , 4, 1, 2, 5—, 2, 6—, 3, 4—, 3, 5—) Jethyl phenol, 2-methyl, 3-ethyl phenol,
- Triethylphenol (2, 3, 6—, 2, 3, 5—, 2, 3, 4—, 2, 4, 5—, 2, 4, 6—, 3, 4 , 5-—) tripropyl phenol, naphthol and the like, with phenol being particularly preferred.
- the hydroxy compounds may be used alone or in combination of two or more.
- the monomer phosphate is a phosphate having 1% of phosphorus atoms in the molecule
- Triester of phosphoric acid generated by the reaction of a decomposition product of bisphenol A derivative with phosphorus oxyphosphorus Triester of phosphoric acid generated by the reaction of the residual phosphorus trioxyhalide without reacting with the bisphenol A derivative and the hydroxy compound
- the bisphenol A derivative is bisphenol A and the hydroxy compound is phenol
- the hydroxy compound are cresol [( o—, m—, p—) methylphenol] in the case of tricresyl phosphate, phenyl dicresyl phosphate, isopropenylphenyl digresyl phosphate
- the hydroxy compound is xylenol [(2,3-— 2,5-—, 2,6_, 3,4 -—, 3,5-) dimethylphenol] includes trisilyl phosphate, phenyldixylenyl phosphate, and isopropenylphenyldixylenyl phosphate. .
- the temperature at which the second stage of the process 1 is performed is preferably from 60 to 170, more preferably from 80 to 170, further preferably from 120 to 170, and particularly preferably from 140 to 160.
- the time of the second stage of the process 1 is preferably 1 hour 30 minutes to 21 hours, more preferably 3 hours to 15 hours.
- the amount of the hydroxy compound used is an excess of 2 mol% or less based on the theoretical amount required to convert all of the phosphorohalidate contained in the reaction mixture into a condensed phosphate ester. . Details of this excess ratio will be described later. Other reaction conditions are appropriately selected as desired. In addition, it is preferable that hydrogen octogenogen generated during the reaction and remaining after the reaction is recovered under normal pressure or reduced pressure.
- the reaction product obtained in the first stage is reacted with the monophenolic compound at 120 in the following, The temperature is raised and the phosphorohalidate is further reacted with the hydroxy compound at 120 or more.
- the reaction product obtained in the first step of the process 1 is reacted with a monophenolic compound at 120 ° C. or lower.
- the temperature at this time is preferably 110 or less, more preferably 105 or less, and even more preferably 100 or less.
- reaction temperature is too high, the reaction between the monophenolic compound and IPP is difficult to proceed sufficiently because the monophenolic compound and the phosphorohalidate react preferentially. As a result, the amount of IPP is not sufficiently reduced.
- the lower limit of the reaction temperature in the second step of the process 1 in this embodiment is not particularly limited.
- the temperature be such that the IPP and the monophenol-based compound can be efficiently contacted without causing a dehydrohalogenation reaction. It can be appropriately determined from the combination of the type, amount and rate of addition of the monophenolic compound, the reaction scale, and other reaction conditions (reaction time, degree of decompression, use of a solvent). For example, it is preferably 40 or more, more preferably 60 * or more, further preferably 70 or more, and particularly preferably 80 or more.
- the period during which the reaction temperature of the second step of the process 1 in this embodiment is 120 at 120 or less is preferably 30 minutes to 8 hours, more preferably 1 to 6 hours.
- the reactant after the first stage of the process of step 1 contains a phosphate containing an isoprobenylaryl group
- the isoprobenylaryl group-containing phosphate is removed. Can be removed.
- the temperature is raised to a temperature exceeding 120 and the phosphorohalidate is reacted with the hydroxy compound to produce a condensed phosphate ester. .
- the temperature is raised from the following reaction temperature at 120 to the reaction temperature exceeding 120 ⁇ , preferably over 30 minutes to 8 hours, more preferably over 1 hour to 6 hours.
- the temperature is raised to 120 to 170 "C. More preferably, the temperature is raised to 140 to 160. After the temperature is further raised, preferably 30 minutes to 5 hours. More preferably, the temperature is maintained above 120 ° C. for 1-3 hours, preferably between 140 ° C. and 160 ° C.
- the total amount of materials used in the second stage of the process of step 1 is preferably added before the start of the second stage of the process of step 1. However, if desired, some of it may be added during the second stage of the process of 1. For example, a part of the material may be added when the reaction is performed at the above 12 OX: below, and the temperature is increased from the following reaction temperature at the above 120 to the reaction temperature above the above 120. May be added when reacting at a reaction temperature exceeding the above-mentioned 120.
- the amount of the reaction material used in the second step of the process 1 described in the present specification refers to the total amount of the material added until the completion of the second step of the process 1.
- Other reaction conditions are appropriately selected as desired.
- the hydrogen halide generated during the reaction and remaining after the reaction is preferably recovered at normal pressure or under reduced pressure.
- the amount of the hydroxy compound used is an excess of 2 mol% or less based on the theoretical amount required to convert all of the phosphorohalide contained in the reaction mixture into a condensed phosphate ester.
- this embodiment it is possible to suppress the by-product of a monomeric phosphate ester caused by the transesterification reaction between the condensed phosphate ester once produced and the hydroxy compound without lowering the yield and quality. Can be. Especially on an industrial scale In large-scale production, since the reaction time is long, it is very advantageous to use the hydroxy compound in the above excess ratio in view of the fact that the transesterification reaction between the condensed phosphate ester and the hydroxy compound is likely to occur.
- the industrial scale means that the total amount of the monophenolic compound and the phosphorohalidate when the monophenolic compound and the phosphorohalidate are reacted is a scale in normal industrial production.
- the industrial scale is preferably at least 5 liters, more preferably at least 30 liters, still more preferably at least 100 liters, particularly preferably at least 300 liters.
- the total amount of the hydroxy compound and the phosphorohalidate when the hydroxy compound and the phosphorohalidate are reacted is preferably, specifically, 200 liters or less due to the limitation of the reaction apparatus. More preferably, it is 100 liters or less.
- the amount of the hydroxy compound used is a stoichiometrically calculated stoichiometric amount, the reaction is liable to be incomplete, so that unreacted phosphorohalidate remains and remains in the product as impurities, Problems such as complicated purification and post-treatment steps are likely to occur.
- the excess of the monophenolic compound is preferably 2.0 mol% or less. It is more preferably at most 1.8 mol%, still more preferably at most 1.6 mol%, particularly preferably at most 1.5 mol%.
- the stoichiometric amount required to convert all of the phosphorohalidate into a condensed phosphate ester means that all the halogen atoms contained in the phosphorohalidate are all Refers to the amount required for substitution to the ester group.
- 1 mo 1 of phosphorohalidate is 5 mo 1 of a monophenolic compound
- 1 mo 1 of phosphorohalidate is 6 mo 1 of a monophenolic compound.
- the excess ratio is defined as the stoichiometric number of moles subtracted from the number of moles of the monophenolic compound used, and divided by the stoichiometric number of moles to obtain the ratio. And then multiply by 100 to express the value in%.
- the lower limit of the amount of the monophenolic compound cannot be determined because it varies depending on the type of the condensed phosphate ester and the reaction conditions, but is preferably at least 0.2 mol%. It is more preferably at least 0.3 mol%, particularly preferably at least 0.4 mol%, and still more preferably at least 0.5 mol%.
- reaction conditions for example, the degree of reduced pressure and the additional time of the hydroxy compound.
- the hydrogen halide generated during the reaction and remaining after the reaction is preferably recovered under normal pressure or reduced pressure.
- it can be collected by collecting it in water.
- the condensed phosphate ester produced in this manner contains a large amount of impurities such as partial reactants, unreacted raw materials, and catalyst residues, and is therefore known in the art such as neutralization, washing with water, and steam distillation.
- the impurities are removed from the crude condensed phosphate ester by the purification method described above.
- the epoxy compound can be added to the 10H group of the partial reactant and then selectively hydrolyzed to convert to phosphoric acid. Then, by washing with hot water, the phosphoric acid content can be removed and the acid value of the product can be reduced.
- the product obtained in this way has a very low content of monomeric phosphate It is a high quality condensed phosphate ester.
- the bisphenol A derivative in the first step of the process of step 1, is reacted with the phosphorus oxytrihalide to produce phosphorohalide, and the unreacted carboxylic acid is further reacted from the reaction product.
- the phosphorus trihalide is removed, and in the second step, the reaction product obtained in the first step is reacted with the monophenol-based compound at 120 or less, and then the temperature is raised to 120 or more.
- Such a high-quality condensed phosphate ester can be used as a flame retardant in various resins.
- polyethylene resin polypropylene resin, polybutadiene resin, polystyrene resin, polyphenylene ether resin, polycarbonate resin, ABS (acrylonitrile butadiene styrene).
- Thermoplastics such as resin, impact-resistant styrene resin, SAN (styrene acrylonitrile) resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polyacryl resin, and polymethacryl resin Resins and thermosetting resins such as epoxy resins, polyurethane resins, polyimide resins, phenolic resins, novolak resins, polyetherimide resins, melamine resins, and urea resins.
- a resin having a high molding temperature for example, in one embodiment, a resin molded at 160 ° C. or higher, in a more preferred embodiment, a resin molded at 180 ° C. or higher, particularly preferred embodiment
- a resin molded at 200 ° C. or higher the condensed phosphate obtained by the method of the present invention can be advantageously used.
- the condensed phosphate obtained by the method of the present invention is added to a resin and molded to provide any desired, flame-retardant molded article.
- any known method can be adopted.
- each component for example, resin, flame retardant, plasticizer, flame retardant aid, release agent, UV absorber, antioxidant, light shielding agent, weather resistance improver, inorganic filler, etc.
- a general-purpose kneading device such as an extruder, twin-screw extruder, Banbury mixer, kneader, mixer, roll, etc. and compounded into the resin.
- a general-purpose kneading device such as an extruder, twin-screw extruder, Banbury mixer, kneader, mixer, roll, etc.
- compounded into the resin can be formed into a plate, sheet, or film by using the molding machine, and a desired molded product can be obtained.
- the second step of reacting the obtained reaction product with a bisphenol A derivative is performed.
- a step for distilling diphenylphosphorochloride may be provided between the first and second steps of the process of 2.
- the conditions employed in a conventionally known method for producing a condensed phosphate ester can be employed. Preferably, it is performed at a temperature of 40 to 130 ° C. As conditions other than the temperature, for example, conditions substantially equivalent to the second stage of the above-described process 1 can be used.
- the conditions employed in the conventionally known method for producing a condensed phosphate ester can be employed. Preferably, it is carried out at a temperature of 12 Ot: ⁇ 150. For conditions other than temperature, for example, the process described in 1. Substantially the same conditions as in the first stage can be used.
- a material that can be used in this process a material that is used in a conventionally known method for producing a condensed phosphate ester can be used.
- a material similar to the material used in the process 1 described above may be used.
- the decomposition inhibitor may be left in the condensed phosphate ester product without being removed after the production of the condensed phosphate ester.
- a process for removing the decomposition inhibitor may be provided. Good.
- any method can be used to remove the decomposition inhibitor, such as filtration or decantation.
- the timing of removing the decomposition inhibitor is preferably after the second stage of the process of 2.
- the conditions used in a conventionally known method for producing a condensed phosphate ester may be employed.
- a material that can be used in this process a material that is used in a conventionally known method for producing a condensed phosphate ester can be used.
- a material similar to the material used in the process 1 described above may be used.
- the decomposition inhibitor may be left in the condensed phosphate ester product without being removed after the production of the condensed phosphate ester.
- a step of removing the decomposition inhibitor may be provided.
- any method can be used for removing the decomposition inhibitor, for example, filtration or decantation.
- the timing of removing the decomposition inhibitor is preferably after the reaction of the bisphenol A derivative, the phosphorus oxyhalogenated compound, and the hydroxy compound is completed.
- % indicates “% by weight” unless otherwise specified.
- Example 2 The same operation as in Example 1 was performed, except that 0.5 g of ascorbic acid was used instead of stannic oxide.
- the obtained product had a monomeric phosphate content of 2.0% and an acid value (KOHZmg) of 0.06.
- Example 3 The same operation as in Example 1 was performed except that stannic oxide was not used.
- the obtained product had a monophosphate content of 4.2% and an acid value (KOHZmg) of 0.04. (Example 3)
- Example 2 The same operation as in Example 1 was performed except that cupric chloride was used instead of stannic oxide.
- the obtained product had a monophosphate content of 2.9% and an acid value (KOHXmg) of 0.06.
- Example 2 The same operation as in Example 1 was performed except that ferric chloride was used instead of stannic oxide.
- the obtained product had a monophosphate content of 2.4% and an acid value (KOHZmg) of 0.07.
- Example 2 The same operation as in Example 1 was performed except that adipic acid was used instead of stannic oxide.
- the obtained product had a monophosphate content of 2.0% and an acid value (KOH / mg) of 0.09.
- Example 2 The same operation as in Example 1 was performed except that oxalic acid was used instead of stannic oxide.
- the obtained product had a monophosphate type ester content of 2.% and an acid value (KOHZmg) of 0.06.
- Example 2 The same operation as in Example 1 was performed except that cunic acid was used instead of stannic oxide.
- the obtained product had a monophosphate content of 2.4% and an acid value (KOHZmg) of 0.05.
- the condensed phosphate ester obtained by the present invention can reduce the content of the monophosphate ester resulting from the decomposition of the bisphenol A derivative without lowering the yield of the product. Further, by setting the conditions, it is possible to obtain a condensed phosphate ester substantially free of a monomeric phosphate ester. Therefore, the condensed phosphate ester produced by the method of the present invention is excellent in heat resistance, volatility and coloring resistance, and when used as a plasticizer or flame retardant for resins, it is harmful during molding. It has the advantage of not causing problems such as generation of gas, contamination of the mold, and reduced heat resistance of the molded product. Among them, the improvement of the effect of preventing contamination of the mold in particular leads to an increase in the number of continuous shots, which is a very industrial advantage because the cost of the product is reduced.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Fireproofing Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00931613A EP1227101B1 (en) | 1999-11-05 | 2000-05-30 | Process for the preparation of condensed phosphoric acid esters |
US10/129,204 US6605737B1 (en) | 1999-11-05 | 2000-05-30 | Process for the preparation of condensed phosphoric acid esters |
DE60027454T DE60027454T2 (de) | 1999-11-05 | 2000-05-30 | Verfahren zur herstellung kondensierter phosphorsäureester |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/316022 | 1999-11-05 | ||
JP31602299A JP4536185B2 (ja) | 1999-11-05 | 1999-11-05 | 縮合燐酸エステルの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001034616A1 true WO2001034616A1 (fr) | 2001-05-17 |
Family
ID=18072388
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/003481 WO2001034616A1 (fr) | 1999-11-05 | 2000-05-30 | Procede de preparation d'esters d'acide phosphorique condenses |
Country Status (7)
Country | Link |
---|---|
US (1) | US6605737B1 (ja) |
EP (1) | EP1227101B1 (ja) |
JP (1) | JP4536185B2 (ja) |
KR (1) | KR100483652B1 (ja) |
CN (1) | CN1169815C (ja) |
DE (1) | DE60027454T2 (ja) |
WO (1) | WO2001034616A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101043794B1 (ko) * | 2009-04-13 | 2011-06-27 | 청우산업 주식회사 | 황토판재로 제공되는 기능성 황토방 |
TWI382988B (zh) * | 2009-12-25 | 2013-01-21 | Grand Tek Advance Material Science Co Ltd | 有機矽磷酸酯及其製作方法 |
KR200451887Y1 (ko) * | 2010-04-05 | 2011-01-17 | 주식회사 좋은아침 | 쿠션력을 배가시킨 침대용 온열보료 |
TWI410446B (zh) | 2011-01-05 | 2013-10-01 | Grand Tek Advance Material Science Co Ltd | 含磷酚醛樹脂與其形成方法及含磷配方 |
CN112409404B (zh) | 2020-12-07 | 2022-08-09 | 浙江万盛股份有限公司 | 一种高纯双酚a-双(二苯基磷酸酯)的连续工业化生产方法 |
CN114907400B (zh) * | 2022-05-07 | 2023-12-19 | 万华化学集团股份有限公司 | 一种bdp中间体的制备工艺 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0912587A (ja) * | 1995-06-26 | 1997-01-14 | Asahi Chem Ind Co Ltd | 縮合燐酸エステルの製造方法 |
JPH107689A (ja) * | 1996-06-18 | 1998-01-13 | Asahi Chem Ind Co Ltd | 触媒の除去方法 |
JPH1171488A (ja) * | 1997-08-28 | 1999-03-16 | Asahi Chem Ind Co Ltd | 耐光変色性の優れたポリフェニレンエーテル系樹脂組成物 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0918780A4 (en) * | 1996-06-13 | 1999-07-21 | Great Lakes Chemical Corp | METHOD FOR PRODUCING ESTERS OF ARYLPHOSPHORIC ACID |
JP3558454B2 (ja) * | 1996-06-28 | 2004-08-25 | 旭化成ケミカルズ株式会社 | 燐酸エステルの製造方法 |
BR9808644A (pt) * | 1997-02-14 | 2000-05-23 | Great Lakes Chemical Corp | Processo para a fabricação e uso de bisaril difosfatos |
US6388120B1 (en) * | 1998-02-13 | 2002-05-14 | Pabu Services, Inc. | Continuous process for the manufacture of phosphoric acid esters |
JP2000239285A (ja) * | 1998-12-14 | 2000-09-05 | Asahi Chem Ind Co Ltd | 燐酸エステルの製造方法 |
-
1999
- 1999-11-05 JP JP31602299A patent/JP4536185B2/ja not_active Expired - Fee Related
-
2000
- 2000-05-30 US US10/129,204 patent/US6605737B1/en not_active Expired - Fee Related
- 2000-05-30 DE DE60027454T patent/DE60027454T2/de not_active Expired - Lifetime
- 2000-05-30 WO PCT/JP2000/003481 patent/WO2001034616A1/ja active IP Right Grant
- 2000-05-30 CN CNB008179891A patent/CN1169815C/zh not_active Expired - Fee Related
- 2000-05-30 KR KR10-2002-7005674A patent/KR100483652B1/ko not_active IP Right Cessation
- 2000-05-30 EP EP00931613A patent/EP1227101B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0912587A (ja) * | 1995-06-26 | 1997-01-14 | Asahi Chem Ind Co Ltd | 縮合燐酸エステルの製造方法 |
JPH107689A (ja) * | 1996-06-18 | 1998-01-13 | Asahi Chem Ind Co Ltd | 触媒の除去方法 |
JPH1171488A (ja) * | 1997-08-28 | 1999-03-16 | Asahi Chem Ind Co Ltd | 耐光変色性の優れたポリフェニレンエーテル系樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1227101A4 * |
Also Published As
Publication number | Publication date |
---|---|
CN1414968A (zh) | 2003-04-30 |
KR20020047324A (ko) | 2002-06-21 |
CN1169815C (zh) | 2004-10-06 |
DE60027454T2 (de) | 2006-09-21 |
US6605737B1 (en) | 2003-08-12 |
EP1227101B1 (en) | 2006-04-19 |
JP4536185B2 (ja) | 2010-09-01 |
EP1227101A4 (en) | 2004-04-21 |
EP1227101A1 (en) | 2002-07-31 |
KR100483652B1 (ko) | 2005-04-18 |
DE60027454D1 (de) | 2006-05-24 |
JP2001131191A (ja) | 2001-05-15 |
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