EP1328530A1 - Verfahren zur herstellung von phosphorsäureestern - Google Patents
Verfahren zur herstellung von phosphorsäureesternInfo
- Publication number
- EP1328530A1 EP1328530A1 EP01987753A EP01987753A EP1328530A1 EP 1328530 A1 EP1328530 A1 EP 1328530A1 EP 01987753 A EP01987753 A EP 01987753A EP 01987753 A EP01987753 A EP 01987753A EP 1328530 A1 EP1328530 A1 EP 1328530A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphoric acid
- reaction
- monomeric
- alcohol
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000003014 phosphoric acid esters Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- -1 biaryl diphosphates Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000001177 diphosphate Substances 0.000 claims abstract description 11
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 39
- 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 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 229920005862 polyol Polymers 0.000 claims description 20
- 150000003077 polyols Chemical class 0.000 claims description 20
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 150000007517 lewis acids Chemical group 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 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 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920005669 high impact polystyrene Polymers 0.000 claims description 4
- 239000004797 high-impact polystyrene Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 239000002952 polymeric resin Substances 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 238000010626 work up procedure Methods 0.000 claims description 4
- 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 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 47
- 239000000543 intermediate Substances 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000000376 reactant Substances 0.000 description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010924 continuous production Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- TURWXBQPPKQQIC-UHFFFAOYSA-N 4-[4-(4-oxobutylamino)butylamino]butanal Chemical compound O=CCCCNCCCCNCCCC=O TURWXBQPPKQQIC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 229920002842 oligophosphate Polymers 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 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 class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
-
- 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 ner process for the production of phosphoric acid esters, in particular a ner process for the production of monomeric bridges
- Bisaryl diphosphates such as bisphenol A bis (diphenyl) phosphate and resorcinol bis (diphenyl phosphate), are known to be effective flame retardants for polymer resins
- polyphenylene oxide / high impact polystyrene PPO / HIPS
- PC / ABS polycarbonate / acrylonitrile butadiene styrene
- Resins combined with dimeric or polymeric aryl phosphates have improved impact resistance, melt flow index and tensile and flex properties.
- WO 98/47631 discloses a process for the preparation of aryl diphosphate esters, the catalyst insoluble in the reaction medium being filtered off in the third stage.
- WO 98/35970 describes a semi-continuous process for the preparation of bisaryl diphosphates with magnesium chloride as catalyst.
- EP 0 485 807 B1 describes a process for the preparation of aryl diphosphate esters in eight process steps, the catalyst being worked up or extracted in aqueous alkaline solution.
- JP-A 10/017 583 discloses a batch synthesis for the preparation of phosphate ester oligomers, the reaction being controlled via the release of HCl gas. Excess phenol is removed by distillation, the catalyst, for example magnesium chloride, is removed by washing.
- JP-A 10/007 689 discloses a process for removing the metal chloride catalyst with an acidic aqueous solution (pH ⁇ 3) and at a temperature of at least 65 ° C.
- a disadvantage of these processes is that water enters the reaction system via the raw materials used, such as bisphenol A, resorcinol and phenol. Water partially hydrolyzes the existing POCl 3 . Ultimately, this leads to non-volatile hydrolysis products which remain in the end product and damage the polymer when the phosphates are processed.
- the object of the present invention is to provide a process which provides oligophosphates with a significantly reduced proportion of hydrolysis products. Surprisingly, it has now been found that by adding a water-binding agent to the reaction solution, oligophosphates are obtained which only contain small amounts of hydrolysis products.
- the present invention therefore relates to a process for the continuous, semi-continuous or batchwise synthesis of phosphoric acid esters, characterized in that
- the polyol in step 1 is a dihydric alcohol, preferably bisphenol A or resorcinol
- the alcohol in step 2 is a monohydric alcohol, preferably phenol.
- the phosphorus oxyhalide can also first be reacted with a monohydric alcohol to form a monohalogen monophosphoric diester.
- either the reaction from step 1 or the reaction from step 2 or both together are carried out continuously. At least one step is particularly preferably carried out continuously or semi-continuously.
- the expression continuous means that the reactants are fed to the apparatus in a constant stream and the reaction mixture is also continuously removed.
- semi-continuous means that one reactant is introduced into the apparatus, while another reactant is slowly added continuously.
- batchwise or batchwise means that the reactants are initially introduced into the apparatus, where they remain under defined reaction conditions for a defined reaction time.
- a workup step 3 can be carried out, in which the product from step 2 is worked up continuously, semi-continuously or batchwise in a phase separation apparatus at temperatures from 50 to 120 ° C.
- step 3 comprises both acidic and alkaline washing, which are also carried out continuously, semi-continuously or batchwise, preferably continuously.
- aqueous acids such as HC1 are suitable for acid washing.
- Aqueous HC1 is particularly preferred, especially in Concentration range from 0.5 to 10%. All common basic salts, for example NaOH, Na 2 CO 3 , NaHCO 3 , sodium acetate and corresponding potassium salts, are suitable for alkaline washing. Na salts are particularly preferred, in particular NaOH in the concentration range from 0.5 to 10%.
- the process according to the invention is particularly suitable for the continuous production of bisphenol A bis (diphenyl) phosphate (BDP) or resorcinol bis (diphenyl) phosphate (RDP), for which resorcinol is used as the polyol.
- BDP bisphenol A bis (diphenyl) phosphate
- RDP resorcinol bis (diphenyl) phosphate
- Another object of the present invention is to provide a process for the preparation of monomeric phosphoric acid ester products which can be used as flame retardants, for example in plastics.
- the present invention preferably relates generally to a continuous process for the preparation of phosphoric acid esters, at least one step being carried out continuously, a product with a high content of monomeric halogen phosphate intermediate compared to dimeric halogen phosphate
- Intermediate can be produced with high productivity when the reaction is carried out in a continuous reactor system, such as a continuous stirred tank reactor (CSTR) using a dehydrating agent.
- the intermediate can be used to form a desired monomeric phosphoric acid ester including BPA-bis (diphenyl) phosphate.
- the preferred reactor design ie, a continuous reactor
- the degree of oligomerization or polymerization can further be controlled in individual phases of a series of continuous, multi-phase reactors to some extent by the degree to which the reaction is allowed to proceed.
- phosphoric acid esters are continuously produced by a two-step process.
- the monomeric halogen phosphate intermediate preferably a bis (dichlorophosphate)
- an alcohol preferably a diol or other polyol.
- the monomeric halophosphate intermediate is reacted with another alcohol, preferably a monohydric alcohol, such as a phenol, to produce a desired phosphoric acid ester.
- the phosphorus oxyhalide removed for example by distillation, can be returned to the process, i.e. again to produce the
- Halogen phosphate intermediate can be used.
- the products of the step 1 reaction are predominantly monomeric, and since the monomeric product is used as the reactant in step 2, the product of the step 2 reaction is also predominantly monomeric.
- the monomeric product from step 1 can be reacted with a polyol in step 2, and the resulting product can be further processed as desired.
- the desired phosphoric acid esters are made by continuously reacting phosphorus oxyhalide with a monohydric alcohol so that at least about 60% of the monohalogenophosphoric diester intermediate is formed. The intermediate stage is then reacted with a polyol, preferably a dihydric alcohol, so that the desired phosphoric acid ester is formed.
- Step 1 of a process for the preparation of phosphoric acid esters preferably involves the continuous reaction of a suitable alcohol with
- Phosphorus oxyhalide in the presence of a Lewis acid as a catalyst.
- the phosphorus oxyhalide used in the present invention generally has the formula POX n , where X is a halide including chloride or bromide and n is preferably 3.
- Phosphorus oxychloride, POCl 3 is the most preferred phosphorus oxyhalide.
- step 1 a monomeric halophosphate intermediate is formed when a polyhydric alcohol, such as a dihydric alcohol, is used.
- a polyhydric alcohol such as a dihydric alcohol
- Unreacted POX 3 is optionally removed by distillation under reduced pressure and, as mentioned above, can be returned to the process, leaving the intermediate I from step 1.
- R is the carbon chain part (ie the aromatic, aliphatic, alicyclic part, or a combination thereof) of the alcohol
- X is a halide as mentioned above
- Compound I is the monomeric halophosphate intermediate of Step 1.
- suitable alcohols are polyols, such as polyphenols, including dihydric alcohols, such as biphenols, bisphenol A, tetrabromobisphenol A, bisphenol S, bisphenol F, ethylene glycol, 1,4-butanediol, 1,2-hexanediol, resorcinol, pyrocatechol and hydroquinone, and trihydric alcohols, such as glycerin, and other polyols.
- the aromatic and alicyclic portions of the alcohols can be alkyl or halogen substituted.
- the aliphatic part of the alcohol can also be halogen-substituted.
- the alkyl substituent includes saturated or unsaturated aliphatic hydrocarbon groups, which can be either straight chain or branched, and have a carbon chain length of 1 to 18.
- the alkyl group includes, for example, methyl, ethyl and structural isomers of propyl, butyl,
- the halogen substituent is preferably chlorine and / or bromine.
- the catalyst can be any Lewis acid capable of promoting the reaction. Examples include A1C1 3 , ZnCl 2 , CaCl 2 , MgO or MgCl 2 , preferably MgO or MgCl 2 .
- the catalyst is used in an amount sufficient for the reaction to proceed smoothly and need not necessarily be removed from the final product. In the event that the catalyst is to be removed as completely as possible from the product, it is advisable to carry out step 3 additionally.
- the amount of catalyst used in step 1 is typically in the range from about 100 ppm to about 5000 ppm (relative to the others) Reagents added to the first reactor), preferably 100 ppm to about 1000 ppm, and most preferably about 300 ppm to about 700 ppm.
- reaction temperature in step 1 depends on the particular polyol reacted, but can generally be controlled over a wide range, from about 50 ° C to about 250 ° C, and the process can be carried out at atmospheric pressure
- the process can be operated with a sufficient excess of POX 3 so that a reaction mass which can be processed at the reaction temperature is obtained, or an unreactive solvent can be used.
- the mole ratio of phosphorus oxyhalide to polyol is typically about 2.5: 1 to about 10: 1, preferably about 3: 1 to about 6: 1, and most preferably about 4: 1 to about 5: 1.
- the residence time in each reactor can vary from 0.25 hours to about 6 hours.
- the excess POX 3 is distilled off. This can be done both in the reactor and in suitable apparatus such as falling film or thin film evaporators. The distillation takes place at a temperature of 80 to 200 ° C and a pressure of 10 to 100 mbar.
- the degree of oligomerization or polymerization may continue to be in individual phases of a series of multiple continuous reactors
- Phases are controlled to a certain extent by the degree to which the reaction is allowed to proceed.
- the degree to which the reaction is allowed to proceed is typically from about 10 to about 100% in phase 1 of step 1 and from about 20% to about 100% in subsequent phases.
- the degree to which the reaction is allowed to proceed is preferably about 30% to about 80% in phase 1 and about 50% to about 100% in subsequent phases.
- the degree to which the reaction is allowed to proceed is from about 30% to about 50% in phase 1, from about 70% to about 100% in phase 2, and from about 85% to about 100% in subsequent phases.
- the reaction of step 1 is carried out by reacting the above reactants either continuously or semi-continuously or batchwise.
- step 1 or 2 or optionally step 3 can be carried out at least in part continuously (ie the step can be divided into different phases and at least one phase is carried out continuously). , or the entire step can be carried out continuously.
- the number of phases can range from about 1 to about 5, preferably about 1 to about 3, and most preferably about 2 to about 3.
- step 1 continuously or semi-continuously and step 2 batchwise.
- step 2 can be operated continuously or semi-continuously and step 1 in batches.
- continuous reactor refers to a vessel to which raw materials or an inflow containing unreacted or partially reacted material are fed continuously or substantially continuously as material is removed from the vessel to equal the reactor volume to be kept substantially constant, and in the vessel such conditions prevail that a reaction takes place to a finite degree.
- reactor design plays an important role in determining the degree of oligomerization or polymerization and the quality of the product.
- Examples of commercially available reactors which could be used to practice the invention and with which those skilled in the art are familiar are falling film or thin film reactors.
- continuous stirred tank reactors (“CSTR"), tubular reactors and packed reactors. Although a variety of reactors can be used to practice the invention, stirred tank reactors are preferred.
- a number of continuous reactors can always be the same, or different types of reactors can be used.
- a CSTR is preferably used in phase 1 of a step, and then either another CSTR can be used or a batch reactor can be used. Most preferably, a series of CSTRs are used, or alternatively, a series of CSTRs are used, the last phase being carried out in a batch reactor.
- step 1 Compound I can react with reactants from step 1 (i.e. with the dihydric alcohol and with POX) to produce the following dimeric component:
- the above dimeric component can also result from the reaction of step 1 by reacting the following reactants and intermediates:
- a suitable method for determining the relative amounts of monomer, dimer and other homologues from step 1 is liquid chromatography (GPC) using an RI detector.
- the reaction from step 1 preferably results in at least about 60% content of monomeric halogen phosphate intermediate. Furthermore, the reaction of step 1 preferably forms at least about 70% and particularly preferably at least about 80% content of monomeric halogen phosphate intermediate.
- step 2 of the procedure.
- the product of step 1 is similarly reacted with an alcohol such as a monohydric alcohol including phenol under Lewis acid catalysis.
- an alcohol such as a monohydric alcohol including phenol under Lewis acid catalysis.
- Step 2 are shown schematically as follows:
- X and R are as defined for Step 1 above, and X 2 OP-ORO-POX 2 is a monomeric halophosphate intermediate.
- ROH is the monohydric alcohol, where R 'is the carbon chain part (ie the aromatic, aliphatic, alicyclic part, or a combination thereof) of the alcohol, and (R'O) 2 OP-ORO-PO (OR') 2 is the desired phosphoric acid ester product , If ROH contains an aromatic or alicyclic ring, the aromatic or alicyclic ring may be alkyl or halogen substituted, as discussed for the dihydric alcohol in step 1 above. The aliphatic portion of the alcohol can also be halogen substituted, as discussed above.
- Step 2 is preferably carried out by reacting the halophosphate intermediate from step 1 with phenol, using magnesium chloride as catalyst.
- the phenol (or other alcohol) and the product from step 1 in step 2 can be continuously fed to a CSTR.
- the phenol (or other alcohol) can be added as a single batch to the product from step 1 and the resulting mixture can be added continuously to the reactor.
- the effluent from the first continuous reactor can be fed to a second continuous reactor where the material is held at 125-250 ° C for a dwell time of about 0.25-6 hours.
- the entire batch of phenol can be added to the first reactor, or it can be divided so that a portion of the total batch of phenol is added to the first reactor and the remainder is added to the second reactor.
- the effluent from the second reactor is fed to a buffer tank.
- the buffer tank is used to supply a continuous or discontinuous vacuum stripper that is designed to remove excess alcohol from step 2, such as phenol.
- the removed excess alcohol, e.g. B. phenol can be recycled into the process, i.e. H. used again to perform step 2.
- a catalyst is used as in the step 1 reaction.
- the reaction of step 2 is typically carried out at a temperature sufficient to convert the halophosphate intermediate to the desired phosphoric acid ester product.
- this temperature may vary depending on the reagents used and the desired product, the temperature of the material in the reactor is advantageously in the range of 50 ° C to about 250 ° C, but preferably about 125 ° C to about 250 ° C.
- the volume of the reactor is preferably set so that the residence time is in the range of about 0.25-6 hours.
- the molar ratio of alcohol to monomeric halogen phosphate intermediate is typically about 4: 1 to about 5: 1, but preferably about 4.04: 1 to about 4.40: 1 and most preferably about 4.04: 1 to about 4.12: 1st
- an excess of the alcohol can be used to improve the ease of processing, or an unreactive solvent can be used.
- An excess of alcohol is removed in a vacuum after step 2, which can also be carried out continuously or in batches.
- BPA is continuously added to magnesium chloride and phosphorus oxychloride at about 50 ° C. in a dissolving container.
- the relative feed rates are so great that the molar ratio of phosphorus oxychloride to BPA is about 5: 1.
- the reaction mixture is then fed to a first CSTR at a temperature of about 90 ° C.
- the volume of the reactor is maintained so that a residence time of about 1 hour is obtained.
- the contents of the first reactor are continuously removed and transferred to further CSTRs connected in series.
- the temperature is gradually increased to approx. 100 ° C and finally 120 ° C.
- the feed rates of the inflow and outflow of the reactor are so great that the residence time is about 1 hour each.
- the effluent from the last reactor is fed to a buffer tank which is kept at about 90 ° C while being filled.
- the filled buffer tank is used to provide continuous distillation to remove the excess POCl 3 from the product from step 1.
- the product from step 1 is reacted with phenol, using magnesium chloride as a catalyst.
- the continuous process of the invention can be operated so that part of the first step or the second step is carried out in a continuous reactor while the rest of the reaction is terminated in one or more batch reactors.
- one step can be carried out entirely in a continuous reactor or a series of continuous reactors, while the other step is carried out in batch reactors.
- the steps can be carried out in such a way that the production of monomeric halogen phosphate intermediate and consequently also of monomeric phosphoric acid ester product is maximized.
- the monomer content of the reaction product from step 2 depends on the presence of a high percentage of monomeric halophosphate intermediate which acts as a reactant in step 2. Thus, if a large amount of monomeric halophosphate intermediate is generated in step 1 compared to the dimeric component, the monomer content of the step 2 reaction will also be relatively large. That is, compared to dimeric, oligomeric, or polymeric phosphoric ester product, relatively large amounts of the monomeric phosphoric ester product from step 2 are formed.
- the parameters that can affect the properties and quality of the products from step 1 and step 2 include the choice and the amount of the
- step 1 or step 2 is carried out in a series of reactors, at least one of which is a continuous reactor, the raw materials, such as solvent, catalyst, phosphorus oxyhalide and alcohol (ie phenol or polyol, such as a diol) can be used only in the first Reactor in the row or in addition to the first also in subsequent reactors. This can be done to improve the ease of processing, to control the product quality and / or to obtain the desired product or product mixture.
- the raw materials such as solvent, catalyst, phosphorus oxyhalide and alcohol (ie phenol or polyol, such as a diol) can be used only in the first Reactor in the row or in addition to the first also in subsequent reactors. This can be done to improve the ease of processing, to control the product quality and / or to obtain the desired product or product mixture.
- both physically and chemically active agents can be used, such as, for example, zeolites, PCI5, P 4 O 10 , silica gel, water-binding salts, magnesium alkyls and other organometallic compounds or other substances which are known to those skilled in the art as water-binding.
- These agents are used in an amount which is sufficient to eliminate the water introduced via the starting materials. The amount required depends on the type of water-binding agent used. The typical application range is 0.1 to 5% (based on the sum of the educts).
- These water-binding agents can be added in step 1 and / or step 2 of the reaction.
- in-situ production of the water-binding agent in one of the reactants is also possible, for example PC1 3 can
- Chlorination can be transferred to PC1 5 .
- a method for producing phosphoric acid residues is provided, which is characterized in that
- step 2 can also be followed by an additional work-up step in which the product from step 2 is worked up continuously, semi-continuously or batchwise in a phase separation apparatus at temperatures of 50 to 120 ° C., preferably 70 to 90 ° C.
- the products from this step are then reacted with the selected alcohol selected from the alcohols described above, preferably with a polyol, such as a diol, which gives the desired phosphoric acid ester.
- a polyol such as a diol
- This route also uses the above-mentioned Lewis acid catalysts and water-binding agents, and preferably the continuous addition of the reactants, as is the case for the others
- composition and properties of the product from step 2 are similar to those obtained from the route described above.
- the continuous process of the invention can be operated in a manner similar to that described above.
- the reaction of the intermediate with the polyol can also be carried out in a continuous reactor.
- the first reaction can be carried out in a batch reactor and the second reaction can be carried out continuously.
- step 1 of the monohydric alcohol Reaction of step 1 of the monohydric alcohol with the phosphorus oxyhalide can be shown schematically as follows:
- the reaction temperature in step 1 of the alternative embodiment can also be controlled over a wide range, from about 50 ° C to about 250 ° C, and the process can similarly be operated at different pressures.
- a temperature from 50 ° C to about 200 ° C is preferred and a temperature from about 90 ° C to about 140 ° C is particularly preferred.
- residence times are typically from about 0.25 hours to about 6 hours.
- the molar ratio of alcohol to phosphorus oxyhalide is advantageously about 1.5: 1 to about 3: 1 and particularly preferably about 1.75: 1 to about 2.25: 1.
- Compound LU is a dihalogen monophosphoric acid monoester intermediate
- Compound TV is a phosphoric acid triester.
- Compound IN is undesirable because in step 2 this compound can no longer react with a polyol to form a desired phosphoric ester product.
- Compound III is undesirable because it has the potential to be generated in the reaction of step 2
- Reactants and intermediates to react, and therefore to form dimers, oligomeric or polymeric products in step 2 can lead.
- Those skilled in the art are aware of the particular undesirable reactions that can occur and the products that can arise, so it is not necessary to describe them here.
- the reaction between phosphorus oxyhalide and the monohydric alcohol typically results in at least about 60% content of monohalogen monophosphoric diester. Furthermore, at least about 70% and particularly preferably at least about 80% of the monohalomonophosphoric acid diester are preferably formed.
- Step 2 of the alternative embodiment can be represented schematically as follows:
- step 2 gives the desired monomeric phosphoric acid ester product (RO) 2 OP-ORO-PO (OR ') 2 .
- the reaction temperature in step 2 of the alternative embodiment can also be controlled over a wide range, from about 50 ° C to about 250 ° C, and the process can be operated in a similar manner at different pressures. However, a temperature of about 125 ° C to about 250 ° C is preferred.
- residence times are typically from about 0.25 hours to about 6
- the molar ratio of polyol to monohalogenophosphoric diester intermediate is advantageously about 0.3: 1 to about 0.8: 1 and particularly preferably about 0.4: 1 to about 0.6: 1.
- the preferred levels to which the reaction proceeds in step 1 are similar to those described above.
- the phosphoric acid esters made by the methods of the present invention can be used as flame retardants in resin compositions.
- the resin may be a polymer and may include polyphenylene oxide, high impact polystyrene, polycarbonate, polyurethane, polyvinyl chloride, acrylonitrile butadiene styrene, polybutylene terephthalate, and mixtures thereof. A host of others
- Polymer resins can also be used.
- the bisaryl phosphate obtained is characterized with regard to its hydrolysis products.
- the hydrolysis products are determined by means of liquid chromatography (reverse phase HPLC) and UV detector at 254 nm.
- the hydrolysis products are stated as the sum of the individual products.
- HCl amount approx. 73 g.
- the apparatus is then provided with a distillation bridge and distilled
- reaction mixture is cooled to about 100 ° C. under normal pressure, then 370 g (3.94 mol) of phenol are added and the mixture is then heated again.
- HCl development starts again between 120 and 130 ° C. In about 4 hours the internal temperature is raised to 200 ° C in several stages.
- the hydrochloric acid is also absorbed in water. After reaching the final temperature, you conduct for 1 hour
- a boiler cascade consisting of 4 one-liter reactors equipped with a stirrer, reflux condenser, thermocouple and a heating jacket was set up for the following experiments.
- the reaction volume is kept constant at 1 1 by means of an overflow.
- the reaction temperature is set for each reactor using a separate thermostat.
- the hydrochloric acid released during the reaction is drained off and absorbed in water.
- the following temperature profile is set for the cascade: 82/86/105/120 ° C.
- the flow rate is 1.5 to 2.0 1 h. This results in an average residence time of 2 to 2.5 hours.
- the excess POCI3 is continuously distilled off and returned to the reaction.
- the intermediate product from the 1st stage is mixed with the desired amount of phenol in the initial charge at 50 ° C. (excess 8 mol% with respect to the Cl content of the intermediate product).
- the reaction mixture is transferred to the first reactor using a pump.
- the following temperature profile is set: 135/160/190/210 ° C.
- the flow rate is 1.0 to 1.3 l / h.
- the average residence time is 3 to 4 hours.
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Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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DE10051189 | 2000-10-16 | ||
DE10051189 | 2000-10-16 | ||
DE10060754 | 2000-12-07 | ||
DE10060754A DE10060754A1 (de) | 2000-10-16 | 2000-12-07 | Verfahren zur Herstellung von Phosphorsäureestern |
PCT/EP2001/011438 WO2002032910A1 (de) | 2000-10-16 | 2001-10-04 | Verfahren zur herstellung von phosphorsäureestern |
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EP01987753A Withdrawn EP1328530A1 (de) | 2000-10-16 | 2001-10-04 | Verfahren zur herstellung von phosphorsäureestern |
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US (1) | US6489502B2 (de) |
EP (1) | EP1328530A1 (de) |
JP (1) | JP2004511563A (de) |
AU (1) | AU2002215920A1 (de) |
WO (1) | WO2002032910A1 (de) |
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DE10223649C1 (de) * | 2002-05-28 | 2003-08-14 | Bayer Ag | Verfahren zur Herstellung von Phosphorsäuretriester |
CN100427494C (zh) * | 2006-06-05 | 2008-10-22 | 南京师范大学 | 阻燃剂间苯二酚四苯基二磷酸酯的制备方法 |
US9371437B2 (en) | 2009-11-05 | 2016-06-21 | Covestro Deutschland Ag | Polycarbonate plates with improved flame resistance |
US20120308829A1 (en) | 2010-01-22 | 2012-12-06 | Bayer Intellectual Property Gmbh | Flame-protected article having a high level of transmission |
EP2543695A1 (de) | 2011-07-08 | 2013-01-09 | Bayer MaterialScience AG | Matte, flammgeschützte Artikel mit hoher Transmission |
CN106699805B (zh) * | 2016-12-15 | 2019-02-01 | 衢州普信新材料有限公司 | 一种双酚a双(二苯基磷酸酯)的制备方法 |
CN112142779B (zh) * | 2020-10-13 | 2023-01-13 | 中国科学院宁波材料技术与工程研究所 | 一种双酚a双(磷酸二芳酯)的快速制备方法 |
CN113206294B (zh) * | 2021-04-15 | 2022-09-02 | 湖州永兴新能源有限公司 | 一种磷酸酯及其制备方法和应用 |
CN114181247B (zh) * | 2022-02-17 | 2022-07-01 | 山东旭锐新材股份有限公司 | 一种聚非卤型阻燃剂微反应连续合成方法 |
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US1960184A (en) * | 1932-05-14 | 1934-05-22 | Hoffmann La Roche | Derivatives of the di-hydroxy-benzenes and process for manufacture of same |
US3174931A (en) * | 1961-12-05 | 1965-03-23 | Sinclair Research Inc | Grease compositions |
US5281741A (en) | 1990-11-13 | 1994-01-25 | Fmc Corporation | Process for preparing aryldiphosphate esters |
US5756798A (en) * | 1996-06-13 | 1998-05-26 | Great Lakes Chemical Corporation | Process to prepare aryldiphosphoric esters |
JP3558450B2 (ja) | 1996-06-18 | 2004-08-25 | 旭化成ケミカルズ株式会社 | 触媒の除去方法 |
JP3558457B2 (ja) | 1996-07-04 | 2004-08-25 | 旭化成ケミカルズ株式会社 | 燐酸エステルオリゴマーの製造方法 |
BR9808644A (pt) | 1997-02-14 | 2000-05-23 | Great Lakes Chemical Corp | Processo para a fabricação e uso de bisaril difosfatos |
US5958511A (en) | 1997-04-18 | 1999-09-28 | Henkel Corporation | Process for touching up pretreated metal surfaces |
US6031035A (en) * | 1998-02-13 | 2000-02-29 | Great Lakes Chemical Corporation | Process for making and using bisaryl diphosphates |
WO1999055771A1 (en) | 1998-04-29 | 1999-11-04 | Great Lakes Chemical Corporation | Continuous process for the manufacture of phosphoric acid esters |
-
2000
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2001
- 2001-10-04 AU AU2002215920A patent/AU2002215920A1/en not_active Abandoned
- 2001-10-04 WO PCT/EP2001/011438 patent/WO2002032910A1/de not_active Application Discontinuation
- 2001-10-04 JP JP2002536291A patent/JP2004511563A/ja active Pending
- 2001-10-04 EP EP01987753A patent/EP1328530A1/de not_active Withdrawn
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US6489502B2 (en) | 2002-12-03 |
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