KR20060081090A - New compounds and their use as flame retardants - Google Patents
New compounds and their use as flame retardants Download PDFInfo
- Publication number
- KR20060081090A KR20060081090A KR1020050001503A KR20050001503A KR20060081090A KR 20060081090 A KR20060081090 A KR 20060081090A KR 1020050001503 A KR1020050001503 A KR 1020050001503A KR 20050001503 A KR20050001503 A KR 20050001503A KR 20060081090 A KR20060081090 A KR 20060081090A
- Authority
- KR
- South Korea
- Prior art keywords
- ester
- phthalic acid
- tetrabromo
- tetrachloro
- formula
- 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.)
- Ceased
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- 239000003063 flame retardant Substances 0.000 title claims abstract description 25
- 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 abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 10
- 150000002366 halogen compounds Chemical group 0.000 claims abstract description 6
- -1 3,4,5,6-tetrabromo phthalic acid monoisopropyl ester Chemical compound 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 16
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000005580 one pot reaction Methods 0.000 claims description 12
- 238000007039 two-step reaction Methods 0.000 claims description 8
- YUOZQFFPFVKQPA-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O YUOZQFFPFVKQPA-UHFFFAOYSA-N 0.000 claims description 7
- YEFLNRQHMGSLJD-UHFFFAOYSA-N diethyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCC YEFLNRQHMGSLJD-UHFFFAOYSA-N 0.000 claims description 7
- GNBQLLNMXUOVRU-UHFFFAOYSA-N dimethyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OC GNBQLLNMXUOVRU-UHFFFAOYSA-N 0.000 claims description 7
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims description 7
- QNSMMGKTNDZTHR-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-ethoxycarbonylbenzoic acid Chemical compound CCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O QNSMMGKTNDZTHR-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- NMYAGQGGKVRMGI-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-butoxycarbonylbenzoic acid Chemical compound CCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O NMYAGQGGKVRMGI-UHFFFAOYSA-N 0.000 claims description 3
- UUVMMZYFEJKJPP-UHFFFAOYSA-N 2,3,4,5-tetrabromo-6-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O UUVMMZYFEJKJPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- OSXGYORJRMODEX-UHFFFAOYSA-N dibutyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCCC OSXGYORJRMODEX-UHFFFAOYSA-N 0.000 claims description 3
- ZMIFHTXJWUPZEF-UHFFFAOYSA-N dihexyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCCCCC ZMIFHTXJWUPZEF-UHFFFAOYSA-N 0.000 claims description 3
- HWDPPOYCVJCWQO-UHFFFAOYSA-N dipropyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCC HWDPPOYCVJCWQO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- FKNVSAZGGXCITA-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-ethoxycarbonylbenzoic acid Chemical compound CCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O FKNVSAZGGXCITA-UHFFFAOYSA-N 0.000 claims description 2
- XXXUALJFAUXZEI-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-hexoxycarbonylbenzoic acid Chemical compound CCCCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O XXXUALJFAUXZEI-UHFFFAOYSA-N 0.000 claims description 2
- HOSPDZPUWYEZHH-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O HOSPDZPUWYEZHH-UHFFFAOYSA-N 0.000 claims description 2
- MMTYGWVLDASVDN-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-pentoxycarbonylbenzoic acid Chemical compound CCCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O MMTYGWVLDASVDN-UHFFFAOYSA-N 0.000 claims description 2
- DDOHGXQMISKSCS-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-propan-2-yloxycarbonylbenzoic acid Chemical compound CC(C)OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O DDOHGXQMISKSCS-UHFFFAOYSA-N 0.000 claims description 2
- QZKHHZJSGGXTOR-UHFFFAOYSA-N 2,3,4,5-tetrachloro-6-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O QZKHHZJSGGXTOR-UHFFFAOYSA-N 0.000 claims description 2
- WKYMTJULVAGWJM-UHFFFAOYSA-N 2-butoxycarbonyl-3,4,5,6-tetrachlorobenzoic acid Chemical compound CCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WKYMTJULVAGWJM-UHFFFAOYSA-N 0.000 claims description 2
- QCGIWDQTELRVRW-UHFFFAOYSA-N 2-o-butyl 1-o-methyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OC QCGIWDQTELRVRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- CZYWSKLOYGOGRT-UHFFFAOYSA-N dibutyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCCCC CZYWSKLOYGOGRT-UHFFFAOYSA-N 0.000 claims description 2
- IZVDQOHNHUSNIG-UHFFFAOYSA-N diethyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCC IZVDQOHNHUSNIG-UHFFFAOYSA-N 0.000 claims description 2
- GQBSGNDFFWVLJO-UHFFFAOYSA-N dihexyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCCCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCCCCCC GQBSGNDFFWVLJO-UHFFFAOYSA-N 0.000 claims description 2
- CXWWOTMXNBKMBO-UHFFFAOYSA-N dimethyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OC CXWWOTMXNBKMBO-UHFFFAOYSA-N 0.000 claims description 2
- LJWJXAUUPYVGRY-UHFFFAOYSA-N dipentyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound BrC=1C(=C(C(=C(C=1C(=O)OCCCCC)C(=O)OCCCCC)Br)Br)Br LJWJXAUUPYVGRY-UHFFFAOYSA-N 0.000 claims description 2
- AXHXVLDPQLDGRS-UHFFFAOYSA-N dipentyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCCCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCCCCC AXHXVLDPQLDGRS-UHFFFAOYSA-N 0.000 claims description 2
- OGUXNWYOZFCMFO-UHFFFAOYSA-N dipropan-2-yl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CC(C)OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OC(C)C OGUXNWYOZFCMFO-UHFFFAOYSA-N 0.000 claims description 2
- QJRSPJSHRYYBJL-UHFFFAOYSA-N dipropyl 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound CCCOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCCC QJRSPJSHRYYBJL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims 1
- 229920005990 polystyrene resin Polymers 0.000 claims 1
- 229920005749 polyurethane resin Polymers 0.000 claims 1
- 229920006337 unsaturated polyester resin Polymers 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 78
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000012153 distilled water Substances 0.000 description 16
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- HZCOFWAERKFZBU-UHFFFAOYSA-N dipropan-2-yl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound C(C)(C)OC(C=1C(C(=O)OC(C)C)=C(C(=C(C1Br)Br)Br)Br)=O HZCOFWAERKFZBU-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- UGQQAJOWXNCOPY-UHFFFAOYSA-N dechlorane plus Chemical compound C12CCC3C(C4(Cl)Cl)(Cl)C(Cl)=C(Cl)C4(Cl)C3CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl UGQQAJOWXNCOPY-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- QRBLPTJJQNRVAJ-UHFFFAOYSA-N dioctyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCCCCCCC QRBLPTJJQNRVAJ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- WOFYQUJNULCFLN-UHFFFAOYSA-N saytex bn 451 Chemical compound BrC1C(Br)C2CC1C(C1=O)C2C(=O)N1CCN(C1=O)C(=O)C2C1C1CC2C(Br)C1Br WOFYQUJNULCFLN-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
-
- 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
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Abstract
본 발명은 하기 화학식 1의 신규 화합물, 이의 제조방법 및 이의 난연제로서의 용도에 관한 것이다.The present invention relates to a novel compound of formula (1), a process for its preparation and its use as a flame retardant.
[화학식 1][Formula 1]
(상기 식에서 X는 할로겐 화합물이고 R1 및 R2는 각각 독립적으로 수소 또는 C1-C6-알킬기이다) (Wherein X is a halogen compound and R 1 and R 2 are each independently hydrogen or a C 1 -C 6 -alkyl group)
난연제Flame retardant
Description
본 발명은 신규 화합물 및 이의 난연제로서의 용도에 관한 것으로 보다 자세하게는 하기 화학식 1의 신규 화합물 및 이의 제조방법 그리고 하기 화학식 1의 화합물로 이루어진 난연제 및 이를 포함하는 수지에 관한 것이다. The present invention relates to a novel compound and its use as a flame retardant, and more particularly, to a flame retardant consisting of a novel compound of Formula 1, a method for preparing the same, and a compound comprising the compound of Formula 1, and a resin comprising the same.
[화학식 1][Formula 1]
(상기 식에서 X는 할로겐 화합물이고 R1 및 R2는 각각 독립적으로 수소 또는 C1-C6-알킬기이다)(Wherein X is a halogen compound and R 1 and R 2 are each independently hydrogen or a C 1 -C 6 -alkyl group)
난연제는 플라스틱과 같이 연소하기 쉬운 성질을 갖고 있는 유기 물질의 성질을 물리 · 화학적으로 변형시켜 잘 타지 못하게 유도하는 물질을 의미한다. 당 업계에 공지된 난연제의 종류는 할로겐계, 인계, 멜라민계 등의 유기계 난연제와 수산화알루미늄, 산화안티몬, 수산화마그네슘 등의 무기계 난연제 등이 있다. 또한, 각 종류에 따른 다양한 난연제가 알려져 있다.Flame retardant refers to a material that induces poor burning by physically and chemically modifying the properties of organic materials, such as plastics, that are easily burned. Kinds of flame retardants known in the art include organic flame retardants such as halogen-based, phosphorus-based, melamine-based and inorganic flame retardants such as aluminum hydroxide, antimony oxide, magnesium hydroxide, and the like. In addition, various flame retardants according to each type are known.
대한민국 특허공개 1991-0006459호는 함인 난연제로 유용한 신규한 9,10-디히드로-9-옥사-10-포스포페난트렌-10-옥사이드 유도체 화합물과 이의 제조방법을 개시하고 있다.Korean Patent Publication No. 1991-0006459 discloses a novel 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide derivative compound useful as a flame retardant and a method for preparing the same.
대한민국 특허공개 2000-0027195호는 인산, 피로인산, 폴리인산 또는 오산화인을 함질소 화합물과 화학반응시키거나 이러한 화학반응의 결과물을 카르보닐 기능기를 가진 화합물과 반응시켜 얻은 함질소 인산에스테르계 균일 혼합물로 폴리에스테르, 커튼, 레이온 등의 소재로 만들어진 각종 섬유직물에 처리하여 섬유직물에 난연성을 부여할 수 있는 함질소 인산에스테르계 난연제 및 이의 제조방법을 개시하고 있다.Korean Patent Publication No. 2000-0027195 discloses a nitrogen-containing phosphate ester-based homogeneous mixture obtained by chemically reacting phosphoric acid, pyrophosphoric acid, polyphosphoric acid or phosphorus pentoxide with a nitrogen compound or by reacting the result of such chemical reaction with a compound having a carbonyl functional group. A nitrogen-containing phosphate ester flame retardant which can impart flame retardancy to a textile fabric by treating it with various textile fabrics made of a material such as polyester, curtain, rayon, and the like, and a method of manufacturing the same.
이상과 같이 다양한 난연제가 개발 및 이용되고 있지만 난연화 효과가 미흡하고 제조방법이 복잡하며 적용 대상이 제한적인 문제점을 보이고 있다. 이에 비하여 할로겐 난연제는 난연화 효과가 뛰어나고 비용대비 성능 면에서 우수한 난연제로 인정받고 있으며 각종 전자기기, ABS 수지, PS, PBT, PET, 에폭시 수지 등의 난연제로 이용되고 있다.Various flame retardants have been developed and used as described above, but the flame retardant effect is insufficient, the manufacturing method is complicated, and the application target is limited. On the other hand, halogen flame retardants are recognized as flame retardants having excellent flame retardant effect and excellent cost performance, and are used as flame retardants for various electronic devices, ABS resin, PS, PBT, PET, epoxy resin, and the like.
현재 당업계에서 이용되고 있는 대표적인 할로겐 난연제로는 클로로알킬 포스페이트 에스테르(ANTIBLAZE AB-100, Albright amp; Wilson 제조; FYROL FR2, Akzo Nobel 제조), 폴리브롬화된 디페닐 옥사이드(DE-60F, Great Lakes Corp.), 데 카브로모디페닐 옥사이드(DBDPO; SAYTEX 102E), 트리스[3-브로모-2,2-비스(브로모메틸)프로필]포스페이트(PB370, FMC Corp. 제조), 에틸렌-비스(테트라브로모프탈이미드)(SAYTEX BT-93), 비스(헥사클로로시클로펜타디에노)시클로옥탄(DECLORANE PLUS) 및 에틸렌 비스-(디브로모-노르보르난디카르복시미드)(SAYTEX BN-451) 등이 있다.Representative halogen flame retardants currently used in the art include chloroalkyl phosphate esters (ANTIBLAZE AB-100, Albright amp; Wilson; FYROL FR2, Akzo Nobel), polybrominated diphenyl oxide (DE-60F, Great Lakes Corp .), Decarbromodiphenyl oxide (DBDPO; SAYTEX 102E), tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate (PB370, manufactured by FMC Corp.), ethylene-bis (tetra Bromophthalimide) (SAYTEX BT-93), bis (hexachlorocyclopentadieno) cyclooctane (DECLORANE PLUS) and ethylene bis- (dibromo-norbornanedicarboximide) (SAYTEX BN-451) There is this.
일례로 3,4,5,6-테트라브로모프탈산 디옥 틸에스테르는 할로겐계 난연제 중에서도 특히 우수한 난연성으로 광범위하게 이용되고 있지만 투명한 수지에 혼합되었을 때 상기 수지의 색상을 뿌옇게 만들어 그 사용에 많은 제약이 따르고 있다.For example, 3,4,5,6-tetrabromophthalic acid dioctyl ester is widely used in halogen-based flame retardants, especially because of its excellent flame retardancy, but when mixed with a transparent resin, the color of the resin becomes cloudy, which causes many restrictions on its use. Following.
이러한 문제점을 해결하기 위하여 본 발명자들은 프탈산 유도체와 함수산기 화합물을 반응시켜 신규 화합물을 제조하였고 이러한 화합물을 수지에 첨가한 결과 난연성 뿐만 아니라 수지의 투명성을 유지할 수 있음을 확인하고 본 발명을 완성하기에 이르렀다. In order to solve this problem, the present inventors prepared a novel compound by reacting a phthalic acid derivative and a hydrous acid group compound, and it was confirmed that the addition of such a compound to the resin can maintain the transparency of the resin as well as the flame retardancy. Reached.
따라서 본 발명은 한 관점으로 하기 화학식 1의 화합물을 제공한다. Accordingly, the present invention provides, in one aspect, a compound of formula (I).
[화학식 1][Formula 1]
(상기 식에서 X는 할로겐 화합물이고 R1 및 R2는 각각 독립적으로 수소 또는 C1-C6-알킬기이다)(Wherein X is a halogen compound and R 1 and R 2 are each independently hydrogen or a C 1 -C 6 -alkyl group)
다른 관점으로 상기 화학식 1에 따른 화합물의 제조방법을 제공한다.In another aspect, there is provided a method of preparing a compound according to Chemical Formula 1.
또 다른 관점으로 상기 화학식 1의 화합물로 이루어진 난연제 및 이를 포함하는 수지를 제공한다.In another aspect, a flame retardant consisting of the compound of Chemical Formula 1 and a resin including the same are provided.
본 발명은 하기 화학식 1을 갖는 신규 화합물에 관한 것으로 The present invention relates to a novel compound having the formula
상기 식에서 X는 할로겐 화합물이고, R1 및 R2는 각각 독립적으로 수소 또는 C1-C6-알킬기이다.Wherein X is a halogen compound, and R 1 and R 2 are each independently hydrogen or a C 1 -C 6 -alkyl group.
본 발명에 따른 화학식 1의 화합물은 이에 제한되는 것은 아니지만 예를 들면 다음과 같다: 3,4,5,6-테트라브로모 프탈산 모노메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 모노에틸 에스테르; 3,4,5,6-테트라브로모 프탈산 모노프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 모노이소프로필 에스테르; 3,4,5,6-테트라브로 모 프탈산 모노부틸 에스테르; 3,4,5,6-테트라브로모 프탈산 모노펜틸 에스테르; 3,4,5,6-테트라브로모 프탈산 모노헥실 에스테르; 3,4,5,6-테트라브로모 프탈산 디메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 디에틸 에스테르; 3,4,5,6-테트라브로모 프탈산 디프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 디이소프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 디부틸 에스테르; 3,4,5,6-테트라브로모 프탈산 디펜틸 에스테르; 3,4,5,6-테트라브로모 프탈산 디헥실 에스테르; 3,4,5,6-테트라브로모 1-에틸 에스테르 2-메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-메틸 에스테르 2-프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 1-이소프로필 에스테르 2-메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-부틸 에스테르 2-메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-메틸 에스테르 2-펜틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-헥실 에스테르 2-메틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-에틸 에스테르 2-프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 1-에틸 에스테르 2-이소프로필 에스테르; 3,4,5,6-테트라브로모 프탈산 1-부틸 에스테르 2-에틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-에틸 에스테르 2-펜틸 에스테르; 3,4,5,6-테트라브로모 프탈산 1-에틸 에스테르 2-헥실 에스테르; 3,4,5,6-테트라클로로 프탈산 모노메틸 에스테르; 3,4,5,6-테트라클로로 프탈산 모노에틸 에스테르; 3,4,5,6-테트라클로로 프탈산 모노프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 모노이소프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 모노부틸 에스테르; 3,4,5,6-테트라클로로 프탈산 모노펜틸 에스테르; 3,4,5,6-테트라클로로 프탈산 모노헥실 에스테르; 3,4,5,6-테트라클로로 프탈산 디메틸 에스테르; 3,4,5,6-테트라클로로 프탈 산 디에틸 에스테르; 3,4,5,6-테트라클로로 프탈산 디프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 디이소프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 디부틸 에스테르; 3,4,5,6-테트라클로로 프탈산 디펜틸 에스테르; 3,4,5,6-테트라클로로 프탈산 디헥실 에스테르; 3,4,5,6-테트라클로로 1-에틸 에스테르 2-메틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-메틸 에스테르 2-프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 1-이소프로필 에스테르 2-메틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-부틸 에스테르 2-메틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-메틸 에스테르 2-펜틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-헥실 에스테르 2-메틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-에틸 에스테르 2-프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 1-에틸 에스테르 2-이소프로필 에스테르; 3,4,5,6-테트라클로로 프탈산 1-부틸 에스테르 2-에틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-에틸 에스테르 2-펜틸 에스테르; 3,4,5,6-테트라클로로 프탈산 1-에틸 에스테르 2-헥실 에스테르.Compounds of formula (I) according to the present invention include, but are not limited to, for example: 3,4,5,6-tetrabromo phthalic acid monomethyl ester; 3,4,5,6-tetrabromo phthalic acid monoethyl ester; 3,4,5,6-tetrabromo phthalic acid monopropyl ester; 3,4,5,6-tetrabromo phthalic acid monoisopropyl ester; 3,4,5,6-tetrabromo phthalic acid monobutyl ester; 3,4,5,6-tetrabromo phthalic acid monopentyl ester; 3,4,5,6-tetrabromo phthalic acid monohexyl ester; 3,4,5,6-tetrabromo phthalic acid dimethyl ester; 3,4,5,6-tetrabromo phthalic acid diethyl ester; 3,4,5,6-tetrabromo phthalic acid dipropyl ester; 3,4,5,6-tetrabromo phthalic acid diisopropyl ester; 3,4,5,6-tetrabromo phthalic acid dibutyl ester; 3,4,5,6-tetrabromo phthalic acid dipentyl ester; 3,4,5,6-tetrabromo phthalic acid dihexyl ester; 3,4,5,6-tetrabromo 1-ethyl ester 2-methyl ester; 3,4,5,6-tetrabromo phthalic acid 1-methyl ester 2-propyl ester; 3,4,5,6-tetrabromo phthalic acid 1-isopropyl ester 2-methyl ester; 3,4,5,6-tetrabromo phthalic acid 1-butyl ester 2-methyl ester; 3,4,5,6-tetrabromo phthalic acid 1-methyl ester 2-pentyl ester; 3,4,5,6-tetrabromo phthalic acid 1-hexyl ester 2-methyl ester; 3,4,5,6-tetrabromo phthalic acid 1-ethyl ester 2-propyl ester; 3,4,5,6-tetrabromo phthalic acid 1-ethyl ester 2-isopropyl ester; 3,4,5,6-tetrabromo phthalic acid 1-butyl ester 2-ethyl ester; 3,4,5,6-tetrabromo phthalic acid 1-ethyl ester 2-pentyl ester; 3,4,5,6-tetrabromo phthalic acid 1-ethyl ester 2-hexyl ester; 3,4,5,6-tetrachloro phthalic acid monomethyl ester; 3,4,5,6-tetrachloro phthalic acid monoethyl ester; 3,4,5,6-tetrachloro phthalic acid monopropyl ester; 3,4,5,6-tetrachloro phthalic acid monoisopropyl ester; 3,4,5,6-tetrachloro phthalic acid monobutyl ester; 3,4,5,6-tetrachloro phthalic acid monopentyl ester; 3,4,5,6-tetrachloro phthalic acid monohexyl ester; 3,4,5,6-tetrachloro phthalic acid dimethyl ester; 3,4,5,6-tetrachlorophthalic acid diethyl ester; 3,4,5,6-tetrachloro phthalic acid dipropyl ester; 3,4,5,6-tetrachloro phthalic acid diisopropyl ester; 3,4,5,6-tetrachloro phthalic acid dibutyl ester; 3,4,5,6-tetrachloro phthalic acid dipentyl ester; 3,4,5,6-tetrachloro phthalic acid dihexyl ester; 3,4,5,6-tetrachloro 1-ethyl ester 2-methyl ester; 3,4,5,6-tetrachloro phthalic acid 1-methyl ester 2-propyl ester; 3,4,5,6-tetrachloro phthalic acid 1-isopropyl ester 2-methyl ester; 3,4,5,6-tetrachloro phthalic acid 1-butyl ester 2-methyl ester; 3,4,5,6-tetrachloro phthalic acid 1-methyl ester 2-pentyl ester; 3,4,5,6-tetrachloro phthalic acid 1-hexyl ester 2-methyl ester; 3,4,5,6-tetrachloro phthalic acid 1-ethyl ester 2-propyl ester; 3,4,5,6-tetrachloro phthalic acid 1-ethyl ester 2-isopropyl ester; 3,4,5,6-tetrachloro phthalic acid 1-butyl ester 2-ethyl ester; 3,4,5,6-tetrachloro phthalic acid 1-ethyl ester 2-pentyl ester; 3,4,5,6-tetrachloro phthalic acid 1-ethyl ester 2-hexyl ester.
본 발명에 따른 보다 바람직한 화학식 1의 화합물은 다음과 같다: 3,4,5,6-테트라브로모 프탈산 모노메틸 에스테르, 3,4,5,6-테트라브로모 프탈산 모노에틸 에스테르, 3,4,5,6-테트라브로모 프탈산 디메틸 에스테르, 3,4,5,6-테트라브로모 프탈산 디에틸 에스테르.More preferred compounds of formula 1 according to the invention are: 3,4,5,6-tetrabromo phthalic acid monomethyl ester, 3,4,5,6-tetrabromo phthalic acid monoethyl ester, 3,4 , 5,6-tetrabromo phthalic acid dimethyl ester, 3,4,5,6-tetrabromo phthalic acid diethyl ester.
본 발명에 따른 화학식 1의 화합물은 화학식 2의 프탈산 유도체와 화학식 3 의 함수산기 화합물을 1 단계 반응을 거쳐 제조할 수 있다. 또한, 필요에 따라 상기 1 단계 반응의 산물과 화학식 4의 함수산기 화합물을 2 단계 반응을 거쳐 제조할 수도 있다.The compound of Formula 1 according to the present invention may be prepared through a one-step reaction between a phthalic acid derivative of Formula 2 and a hydrous acid compound of Formula 3. In addition, if necessary, the product of the first step reaction and the hydrous acid compound of Formula 4 may be prepared through a two step reaction.
하기 반응식은 화학식 1의 화합물을 제조하기 위한 본 발명의 제조방법을 예시한 것이다.The following scheme illustrates the preparation method of the present invention for preparing the compound of Formula 1.
본 발명에 따른 화학식 1의 화합물을 제조하기 위해서 이용할 수 있는 화학식 2의 프탈산 유도체는 다음과 같다:Phthalic acid derivatives of formula (2) which may be used to prepare compounds of formula (1) according to the invention are as follows:
(상기 식에서 X는 할로겐 화합물이다)(Wherein X is a halogen compound)
본 발명에 따른 화학식 1의 화합물을 제조하기 위해서 이용할 수 있는 화학식 3의 함수산기 화합물은 다음과 같다:The hydrous acid compound of formula 3 which can be used to prepare the compound of formula 1 according to the invention is as follows:
(상기 식에서 R1은 수소 또는 C1-C6-알킬기이다)In which R 1 is hydrogen or a C 1 -C 6 -alkyl group
본 발명에 따른 화학식 1의 화합물을 제조하기 위해서 이용할 수 있는 화학식 4의 함수산기 화합물은 다음과 같다:The hydrous acid compound of formula 4 which can be used to prepare the compound of formula 1 according to the invention is as follows:
(상기 식에서 R2는 수소 또는 C1-C6-알킬기이다)Wherein R 2 is hydrogen or a C 1 -C 6 -alkyl group
본 발명에서 바람직한 화학식 3 및 4의 함수산기 화합물은 메탄올, 에탄올, 프로판올, 부탄올, 펜탄올, 헥산올을 포함한 저급 알킬 알코올이다.Preferred hydrous acid compounds of formulas 3 and 4 in the present invention are lower alkyl alcohols including methanol, ethanol, propanol, butanol, pentanol, hexanol.
본 발명에서 보다 바람직한 화학식 3 및 4의 함수산기 화합물은 메탄올, 에탄올, 1-프로판올, 2-프로판올, 1-부탄올, 1-헥산올이다.More preferred hydrous acid compound of formulas 3 and 4 in the present invention is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-hexanol.
본 발명에 따른 화학식 1을 갖는 신규 화합물을 제조하기 위한 방법은 다음과 같다.The method for preparing a novel compound having Formula 1 according to the present invention is as follows.
본 발명에 따른 화학식 1의 화합물은 화학식 2의 프탈산 유도체와 화학식 3의 함수산기 화합물을 혼합한 후 바람직하게는 대기내 수증기의 영향을 제거할 수 있는 불활성 기체 환류, 보다 바람직하게는 질소 기체 환류 하에서 1 단계 반응시켜 제조할 수 있다.The compound of formula 1 according to the present invention is preferably mixed with a phthalic acid derivative of formula 2 and a hydrous acid compound of formula 3, and preferably, under inert gas reflux, more preferably under nitrogen gas reflux, to eliminate the effects of water vapor in the atmosphere. It can be prepared by reacting in one step.
상기 1 단계 반응에서 화학식 2의 프탈산 유도체 대 화학식 3의 함수산기 화합물의 몰(mole)비는 바람직하게는 1:5 내지 1:500이다.The mole ratio of the phthalic acid derivative of Formula 2 to the hydrous acid compound of Formula 3 in the one-step reaction is preferably 1: 5 to 1: 500.
반응 온도는 10 내지 150℃가 적합하고, 20 내지 100℃가 바람직하며, 65 내지 80℃가 더욱 바람직하다. 반응 시간은 1 내지 12시간이 적합하고, 3 내지 8시 간이 바람직하며, 5 내지 7시간이 더욱 바람직하다.10-150 degreeC is suitable, 20-100 degreeC is preferable and 65-80 degreeC is more preferable. The reaction time is preferably 1 to 12 hours, preferably 3 to 8 hours, further preferably 5 to 7 hours.
상기 1 단계 반응을 촉진시키기 위하여 필요에 따라 메탄술폰산(methanesufonic acid), p-톨루엔술폰산(p-toluenesulfonic acid) 또는 디부틸틴옥사이드(dibutyltin oxide)와 같은 촉매를 사용할 수 있다.A catalyst such as methanesufonic acid, p-toluenesulfonic acid or dibutyltin oxide may be used as necessary to promote the one-step reaction.
상기 1 단계 반응을 무촉매 하에서 진행시키면 R1 또는 R2가 수소인 화학식 1의 화합물을 수득할 수 있다.By proceeding the one-step reaction under a catalyst, it is possible to obtain a compound of formula 1 wherein R 1 or R 2 is hydrogen.
또한, 본 발명에 따른 화학식 1의 화합물은 상기 1 단계 반응 산물을 예를 들면, 티오닐 클로라이드와 같은 화합물과 반응시키고 여기에 화학식 4의 함수산기 화합물을 혼합하고 환류 하에서 2 단계 반응시켜 제조할 수 있다.In addition, the compound of formula 1 according to the present invention can be prepared by reacting the one-step reaction product with a compound such as, for example, thionyl chloride, and mixing the hydrous acid compound of formula 4 with the reaction in two steps under reflux. have.
상기 2 단계 반응에서 1 단계 반응 산물 대 화학식 4의 함수산기 화합물의 몰(mole)비는 바람직하게는 1:1 내지 1:6이며, 더욱 바람직하게는 1:2 내지 1:1이다.The mole ratio of the one-step reaction product to the hydrous acid compound of Formula 4 in the two-step reaction is preferably 1: 1 to 1: 6, more preferably 1: 2 to 1: 1.
반응 온도는 -20 내지 100℃가 적합하다. 반응 시간은 1 내지 20 시간이 적합하다.The reaction temperature is preferably -20 to 100 ° C. The reaction time is preferably 1 to 20 hours.
상기 2 단계 반응을 통하여 R1 및 R2가 C1-C6-알킬기인 화학식 1의 화합물을 수득할 수 있다. 이 때, R1과 R2는 서로 같거나 상이할 수 있다.Through the two step reaction, a compound of Chemical Formula 1, in which R 1 and R 2 may be a C 1 -C 6 -alkyl group, may be obtained. At this time, R 1 and R 2 may be the same or different from each other.
상기 2 단계 반응을 촉진시키기 위하여 필요에 따라 상술한 메탄술폰산(methanesufonic acid), p-톨루엔술폰산(p-toluenesulfonic acid) 또는 디부틸틴옥 사이드(dibutyltin oxide)와 같은 촉매를 사용할 수 있다.In order to promote the two-step reaction, a catalyst such as methanesufonic acid, p-toluenesulfonic acid, or dibutyltin oxide may be used as necessary.
이렇게 제조된 본 발명의 화합물은 브롬 등 할로겐 원소를 함유하기 때문에 난연성을 나타내므로 난연화를 부여하고자 하는 다양한 수지에 적용할 수 있다. 그러한 수지는 예를 들면, 폴리아세탈, 폴리에스테르, 폴리아미드, 폴리카보네이트, 폴리부틸렌 테레프탈레이트 등의 엔지니어링 플라스틱 수지, 폴리프로필렌, 폴리스티렌 등의 범용 수지, 폴리우레탄, 에폭시 수지, 페놀 수지, 폴리메틸메트아크릴레이트(PMMA) 등을 포함하지만, 이에 제한되는 것은 아니다. Since the compound of the present invention thus prepared is flame retardant because it contains a halogen element such as bromine, it can be applied to various resins to impart flame retardancy. Such resins include, for example, engineering plastic resins such as polyacetal, polyester, polyamide, polycarbonate, polybutylene terephthalate, general purpose resins such as polypropylene and polystyrene, polyurethane, epoxy resins, phenol resins, polymethyl Methacrylate (PMMA) and the like, but is not limited thereto.
또한, 본 발명에 따른 화합물은 수지에 혼합되어도 수지의 색상을 변화시키지 않는 물성을 갖고 있다. 따라서 임의의 수지에 투명성과 난연성을 동시에 부여하고자 하는 경우에 본 발명의 화합물이 유용하게 이용될 수 있다. 그러한 수지의 예로는 폴리메틸메트아크릴레이트, 폴리에스테르, 불포화 폴리에스테르, 폴리카보네이트, 폴리스티렌, 에폭시 수지, 폴리우레탄 등이 있다. In addition, the compound according to the present invention has physical properties that do not change the color of the resin even when mixed with the resin. Therefore, the compound of the present invention can be usefully used to provide transparency and flame retardancy to any resin at the same time. Examples of such resins include polymethylmethacrylate, polyesters, unsaturated polyesters, polycarbonates, polystyrenes, epoxy resins, polyurethanes, and the like.
본 발명에 따른 화합물을 난연제로서 수지에 포함시킬 경우에는 수지 조성물 전체 중량당 1 내지 60중량%, 바람직하게는 5 내지 50중량%, 보다 바람직하게는 10 내지 30중량%의 양으로 첨가할 수 있다.When the compound according to the present invention is included in the resin as a flame retardant, it may be added in an amount of 1 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight of the resin composition. .
이하, 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the examples are only for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, those skilled in the art. Will be self-evident.
<실시예 1><Example 1>
3,4,5,6-테트라브로모 프탈산 모노메틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monomethyl ester
3,4,5,6-테트라브로모프탈산 무수물(Grate Lakes사 PHT-4) 46.3g(0.1mol), 메탄올(대정화금(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 65℃에서 1시간 동안 환류시켰다. 실온으로 냉각시킨 후 회전 증발기(rotary evaporator)에서 메탄올을 제거한 후 에틸 아세테이트(대정화금(주)) 300㎖에 상기 반응액을 용해하였다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트(대정화금(주))를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 생성물 45.1g을 얻었으며 분석결과 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride (PHT-4 from Grate Lakes) and 100 g of methanol (Great Gold Co., Ltd.) were added to a 500 ml flask, followed by nitrogen atmosphere. It was refluxed at 1 ° C. for 1 hour. After cooling to room temperature, methanol was removed from a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate (Great Gold Co., Ltd.). After washing three times with 150 ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate (Great Gold Co., Ltd.). Ethyl acetate was removed from the rotary evaporator and dried in vacuo to give 45.1 g of the product.
<실시예 2><Example 2>
3,4,5,6-테트라브로모 프탈산 디메틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid dimethyl ester
3,4,5,6- 테트라브로모프탈산 무수물 46.3g(0.1mol), 메탄올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 65℃에서 6시간 동안 환류시켰다. 냉각조(ice bath)를 이용하여 반응온도를 -5~5℃로 유지하면서 KOH(대정화금(주)) 6.7g(0.12mol)을 투입하고 30분간 교반하였다. 디메틸 설페이트(삼전순약) 18.9g(0.15mol)을 적가한 후 3시간 동안 교반하고 2시간 동안 환류시켰다. 메탄올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g, 암모니아수(삼전순약)(28%) 5㎖ 및 에틸 아세테이트 300㎖를 투입하고 1시간 교반하었다. 분액 깔때기에서 유기층을 분리하고 증류수로 2회 세척한 후 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 45.5g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of methanol were added to a 500 ml flask, and the mixture was refluxed at 65 ° C. for 6 hours under a nitrogen atmosphere. 6.7 g (0.12 mol) of KOH (Large Sterling Co., Ltd.) was added thereto while maintaining the reaction temperature at -5 to 5 ° C. using an ice bath, followed by stirring for 30 minutes. 18.9 g (0.15 mol) of dimethyl sulfate (Samjeon Pure Chemical Co., Ltd.) was added dropwise, followed by stirring for 3 hours and refluxing for 2 hours. Methanol and low boiling point were distilled off in a rotary evaporator, and then 100 g of distilled water, 5 ml of ammonia water (Samjeon Pure Chemical Co., Ltd.) (28%) and 300 ml of ethyl acetate were added and stirred for 1 hour. The organic layer was separated from the separatory funnel, washed twice with distilled water, and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 45.5 g of product. The results were in accordance with the following formula.
<실시예 3><Example 3>
3,4,5,6-테트라브로모 프탈산 모노에틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monoethyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 에탄올(대정화금(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 78℃에서 6시간 동안 환류시켰다. 실온으로 냉각시킨 후 회전 증발기에서 에탄올을 제거한 후 에틸 아세테이트 300㎖에 상기 반응액을 용해시켰다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 생성물 44.2g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of ethanol (Great Gold Co., Ltd.) were added to a 500 ml flask, and the mixture was refluxed at 78 ° C. for 6 hours under a nitrogen atmosphere. After cooling to room temperature, ethanol was removed from a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate. After washing three times with 150ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and then dried in vacuo to yield 44.2 g of product.
<실시예 4><Example 4>
3,4,5,6-테트라브로모 프탈산 디에틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid diethyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 에탄올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 78℃에서 5시간 동안 환류시켰다. 냉각조를 이용하여 반응온도를 -5~5℃로 유지하면서 KOH 6.7g(0.12mol)을 투입하고 30분간 교반하였다. 디에틸설페이트(삼전순약) 23.1g(0.15mol)을 적가한 후 3시간 동안 교반하고 2시간 동안 환류시켰다. 에탄올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g, 암모니아수(28%) 5㎖ 및 에틸 아세테이트 300㎖를 투입하고 1시간 교반하었다. 분액 깔때기에서 유기층을 분리하고 증류수로 2회 세척한 후 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 47.1g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of ethanol were added to a 500 ml flask, and the mixture was refluxed at 78 ° C. for 5 hours under a nitrogen atmosphere. KOH 6.7g (0.12mol) was added and stirred for 30 minutes, maintaining the reaction temperature at -5 ~ 5 ℃ using a cooling bath. 23.1 g (0.15 mol) of diethyl sulfate (Samjeon Pure Chemical Co., Ltd.) was added dropwise, followed by stirring for 3 hours and refluxing for 2 hours. After distilling off the ethanol and the low boiling point material in a rotary evaporator, 100 g of distilled water, 5 ml of ammonia water (28%), and 300 ml of ethyl acetate were added and stirred for 1 hour. The organic layer was separated from the separatory funnel, washed twice with distilled water, and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 47.1 g of product. The results were in accordance with the following formula.
<실시예 5>Example 5
3,4,5,6-테트라브로모 프탈산 모노프로필 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monopropyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-프로판올(대정화금(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 97℃에서 6시간 환류시켰다. 실온으로 냉각시킨 후 회전 증발기에서 1-프로판올을 제거한 후 에틸 아세테이트 300㎖에 상기 반응액을 용해시켰다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 생성물 45.3g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-propanol (Great Gold Co., Ltd.) were added to a 500 ml flask, and the mixture was refluxed at 97 ° C. for 6 hours under a nitrogen atmosphere. . After cooling to room temperature, 1-propanol was removed in a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate. After washing three times with 150ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and then dried in vacuo to afford 45.3 g of product.
<실시예 6><Example 6>
3,4,5,6-테트라브로모 프탈산 디프로필 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid dipropyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-프로판올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 97℃에서 6시간 동안 환류시켰다. 냉각조를 이용하여 반응온도를 -5~5℃로 유지하면서 티오닐 클로라이드(대정화금(주)) 17.8g(0.15mol)을 적가한 후 3시간 동안 교반하고 2시간 동안 환류시켰다. 1-프로 판올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g을 투입하고 에틸 아세테이트로 추출하였다. 유기층을 포화 소듐 비카르보네이트(대정화금(주)) 수용액 100㎖로 세척하고 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 47.3g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-propanol were added to a 500 ml flask, and the mixture was refluxed at 97 ° C. for 6 hours under a nitrogen atmosphere. 17.8 g (0.15 mol) of thionyl chloride (Corporation Co., Ltd.) was added dropwise while maintaining the reaction temperature at -5 to 5 ° C. using a cooling bath, followed by stirring for 3 hours and refluxing for 2 hours. After distilling off 1-propanol and a low boiling point material in a rotary evaporator, 100 g of distilled water was added thereto, and extracted with ethyl acetate. The organic layer was washed with 100 ml of saturated sodium bicarbonate (Cater Co., Ltd.) aqueous solution and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 47.3 g of product. The results were in accordance with the following formula.
<실시예 7><Example 7>
3,4,5,6-테트라브로모 프탈산 모노이소프로필 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monoisopropyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 2-프로판올(대정화금(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 82℃에서 6시간 동안 환류시켰다. 실온으로 냉각시킨 후 회전 증발기에서 2-프로판올을 제거한 후 에틸 아세테이트 300㎖에 상기 반응액을 용해하였다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 48.1g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 2-propanol (Great Gold Co., Ltd.) were added to a 500 ml flask, and the mixture was refluxed at 82 ° C. for 6 hours under a nitrogen atmosphere. I was. After cooling to room temperature, 2-propanol was removed in a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate. After washing three times with 150ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate. Ethyl acetate was removed from the rotary evaporator and dried in vacuo to give 48.1 g. The results were in accordance with the following chemical formula.
<실시예 8><Example 8>
3,4,5,6-테트라브로모 프탈산 디이소프로필 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid diisopropyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 2-프로판올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 82℃에서 6시간 동안 환류시켰다. 냉각조를 이용하여 반응온도를 -5~5℃로 유지하면서 티오닐 클로라이드 17.8g을 적가한 후 3시간 동안 교반하고 2시간 동안 환류시켰다. 2-프로판올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g을 투입하고 에틸 아세테이트로 추출하였다. 유기층을 포화 소듐 비카르보네이트 수용액 100㎖로 세척하고 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 49.4g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 2-propanol were added to a 500 ml flask, and the mixture was refluxed at 82 ° C. for 6 hours under a nitrogen atmosphere. 17.8 g of thionyl chloride was added dropwise while maintaining the reaction temperature at -5 to 5 ° C. using a cooling bath, followed by stirring for 3 hours and refluxing for 2 hours. 2-propanol and low boiling point were distilled off in a rotary evaporator, and then 100 g of distilled water was added and extracted with ethyl acetate. The organic layer was washed with 100 mL of saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 49.4 g of product. The results were in accordance with the following formula.
<실시예 9>Example 9
3,4,5,6-테트라브로모 프탈산 모노부틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monobutyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-부탄올(Tokyo Kasei Kogyo(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 117℃에서 6시간 동안 환류시켰다. 실온으로 냉각시킨 후 회전 증발기에서 1-부탄올을 제거한 후 에틸 아세테이트 300㎖에 상기 반응액을 용해하였다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 생성물 48.5g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-butanol (Tokyo Kasei Kogyo) were added to a 500 ml flask, and the mixture was refluxed at 117 ° C. for 6 hours under a nitrogen atmosphere. I was. After cooling to room temperature, 1-butanol was removed in a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate. After washing three times with 150ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate. Ethyl acetate was removed from the rotary evaporator and dried in vacuo to give 48.5 g of the product.
<실시예 10><Example 10>
3,4,5,6-테트라브로모 프탈산 디부틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid dibutyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-부탄올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 117℃에서 6시간 동안 환류시켰다. 냉각조를 이용하여 반응온도를 -5~5℃로 유지하면서 티오닐 클로라이드 17.8g(0.15mol)을 적가한 후 3시간 동안 교반하고 2시간 동안 환류시켰다. 1-부탄올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g을 투입하고 에틸 아세테이트로 추출하였다. 유기층을 포화 소듐 비카르보네이트 수용액 100㎖로 세척하고 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 49.5g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-butanol were added to a 500 ml flask, and the mixture was refluxed at 117 ° C. for 6 hours under a nitrogen atmosphere. 17.8 g (0.15 mol) of thionyl chloride was added dropwise while maintaining the reaction temperature at -5 to 5 ° C. using a cooling bath, followed by stirring for 3 hours and refluxing for 2 hours. After distilling off 1-butanol and a low boiling point material in a rotary evaporator, 100 g of distilled water was added and extracted with ethyl acetate. The organic layer was washed with 100 mL of saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 49.5 g of product. The results were in accordance with the following formula.
<실시예 11><Example 11>
3,4,5,6-테트라브로모 프탈산 모노헥실 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid monohexyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-헥산올(Tokyo Kasei Kogyo(주)) 100g을 500㎖ 플라스크에 투입한 후 질소 분위기 100~110℃에서 6시간 동안 교반시켰다. 실온으로 냉각시킨 후 회전 증발기에서 1-헥산올을 제거한 후 에틸 아세테이트 300㎖에 상기 반응액을 용해하였다. 증류수 150㎖로 3회 세척한 후 유기층을 무수 소듐 설페이트를 이용하여 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거한 후 진공 건조하여 생성물 52.1g을 얻었으며 분석결과 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-hexanol (Tokyo Kasei Kogyo Co., Ltd.) were added to a 500 ml flask, followed by nitrogen at 100 to 110 ° C. for 6 hours. Was stirred. After cooling to room temperature, 1-hexanol was removed in a rotary evaporator, and the reaction solution was dissolved in 300 ml of ethyl acetate. After washing three times with 150ml of distilled water, the organic layer was dehydrated using anhydrous sodium sulfate. Ethyl acetate was removed from the rotary evaporator and then dried in vacuo to give 52.1 g of the product.
<실시예 12><Example 12>
3,4,5,6-테트라브로모 프탈산 디헥실 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid dihexyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 1-헥산올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기 100~110℃에서 6시간 동안 교반시켰다. 냉각조를 이용하여 반응온도를 0~5℃로 유지하면서 티오닐 클로라이드 17.8g(0.15mol)을 적가한 후 3시간 동안, 80~90℃에서 2시간 동안 교반하였다. 1-헥산올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g을 투입하고 에틸 아세테이트로 추출하였다. 유기층을 포화 소듐 비카르보네이트 수용액 100㎖로 세척하고 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 55.2g을 얻었으며 분석결과 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 1-hexanol were added to a 500 ml flask, followed by stirring at 100 to 110 ° C. for 6 hours in a nitrogen atmosphere. 17.8 g (0.15 mol) of thionyl chloride was added dropwise while maintaining the reaction temperature at 0 ° C to 5 ° C using a cooling bath, followed by stirring for 3 hours at 80 ° C to 90 ° C. After distilling off 1-hexanol and a low boiling point material on a rotary evaporator, 100 g of distilled water was added and extracted with ethyl acetate. The organic layer was washed with 100 mL of saturated sodium bicarbonate aqueous solution and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 55.2 g of product.
<실시예 13>Example 13
3,4,5,6-테트라브로모 프탈산 1-이소프로필 에스테르 2-메틸 에스테르의 합성Synthesis of 3,4,5,6-tetrabromo phthalic acid 1-isopropyl ester 2-methyl ester
3,4,5,6-테트라브로모프탈산 무수물 46.3g(0.1mol), 2-프로판올 100g을 500㎖ 플라스크에 투입한 후 질소 분위기하 82℃에서 6시간 동안 환류시켰다. 냉각조(ice bath)를 이용하여 반응온도를 -5~5℃로 유지하면서 KOH 6.7g(0.12mol)을 투입하고 30분간 교반하였다. 디메틸 설페이트 18.9g(0.15mol)을 적가한 후 6시간 동안 교반하였다. 2-프로판올 및 저비점 물질을 회전 증발기에서 증류 제거한 후 증류수 100g, 암모니아수(28%) 5㎖ 및 에틸 아세테이트 300㎖를 투입하고 1시간 교반하였다. 분액 깔때기에서 유기층을 분리하고 증류수로 2회 세척한 후 무수 소듐 설페이트로 탈수하였다. 회전 증발기에서 에틸 아세테이트를 제거하고 진공 건조하여 생성물 45.5g을 얻었으며 분석결과는 다음 화학식과 일치하였다.46.3 g (0.1 mol) of 3,4,5,6-tetrabromophthalic anhydride and 100 g of 2-propanol were added to a 500 ml flask, and the mixture was refluxed at 82 ° C. for 6 hours under a nitrogen atmosphere. 6.7 g (0.12 mol) of KOH was added thereto and stirred for 30 minutes while maintaining the reaction temperature at -5 to 5 ° C by using an ice bath. 18.9 g (0.15 mol) of dimethyl sulfate was added dropwise and stirred for 6 hours. After 2-propanol and low boiling point were distilled off in a rotary evaporator, 100 g of distilled water, 5 ml of ammonia water (28%), and 300 ml of ethyl acetate were added and stirred for 1 hour. The organic layer was separated from the separatory funnel, washed twice with distilled water, and dehydrated with anhydrous sodium sulfate. Ethyl acetate was removed on a rotary evaporator and dried in vacuo to afford 45.5 g of product. The results were in accordance with the following formula.
<실시예 14><Example 14>
3,4,5,6-테트라브로모 프탈산 모노메틸 에스테르의 투과율 분석Permeability Analysis of 3,4,5,6-Tetrabromo Phthalic Acid Monomethyl Ester
실시예 1에서 제조한 3,4,5,6-테트라브로모프탈산 모노메틸 에스테르 20 중 량%와 메틸메트아크릴레이트(Tokyo Kasei Kogyo(주)) 79.9 중량%를 실온에서 녹인 후 벤조일 퍼옥사이드 0.1 중량%를 투입하여 용해시켰다. 이러한 혼합물을 유리 재질의 시트 몰드에 투입한 후 항온조를 이용하여 70℃에서 24시간 경화시켜서 투명한 PMMA 시트를 얻었다. 이렇게 수득한 PMMA 시트의 시감 투과율을 측정한 결과 88.4%였다.20% by weight of 3,4,5,6-tetrabromophthalic acid monomethyl ester prepared in Example 1 and 79.9% by weight of methyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) were dissolved at room temperature, and then benzoyl peroxide 0.1. Dissolved by adding weight%. The mixture was poured into a sheet mold made of glass, and then cured at 70 ° C. for 24 hours using a thermostat to obtain a transparent PMMA sheet. The luminous transmittance of the PMMA sheet thus obtained was measured, and found to be 88.4%.
<실시예 15><Example 15>
3,4,5,6-테트라브로모 프탈산 디메틸 에스테르의 투과율 분석Permeability Analysis of 3,4,5,6-Tetrabromo Phthalic Acid Dimethyl Ester
실시예 2에서 제조한 3,4,5,6-테트라브로모프탈산 디메틸 에스테르 20 중량%를 사용하여 상기 실시예 14와 동일한 절차에 따라 투명한 PMMA 시트를 제조하였고 시감 투과율을 측정한 결과 90.5%였다.A transparent PMMA sheet was prepared according to the same procedure as in Example 14 using 20% by weight of 3,4,5,6-tetrabromophthalic acid dimethyl ester prepared in Example 2, and the luminous transmittance was measured to be 90.5%. .
<실시예 16><Example 16>
3,4,5,6-테트라브로모 프탈산 디에틸 에스테르의 투과율 분석Permeability Analysis of 3,4,5,6-Tetrabromo Phthalic Acid Diethyl Ester
실시예 4에서 제조한 3,4,5,6-테트라브로모프탈산 디에틸 에스테르 20 중량%를 사용하여 상기 실시예 14와 동일한 절차에 따라 투명한 PMMA 시트를 제조하였고 시감 투과율을 측정한 결과 91.9%였다.A transparent PMMA sheet was prepared according to the same procedure as in Example 14 using 20 wt% of 3,4,5,6-tetrabromophthalic acid diethyl ester prepared in Example 4, and the luminous transmittance was measured to be 91.9%. It was.
<비교예 1>Comparative Example 1
PMMA의 투과율 분석Permeability Analysis of PMMA
메틸메트아크릴레이트 99.9 중량%와 벤조일 퍼옥사이드 0.1 중량%를 혼합하여 용해시켰다. 이러한 혼합물을 유리 재질의 시트 몰드에 투입한 후 항온조를 이용하여 70℃에서 24시간 경화시켜서 PMMA 시트를 제조하였고 시감 투과율을 측정한 결과 91.6%였다.99.9% by weight of methyl methacrylate and 0.1% by weight of benzoyl peroxide were mixed and dissolved. The mixture was poured into a sheet mold made of glass, and then cured at 70 ° C. for 24 hours using a thermostat to prepare a PMMA sheet, and the luminous transmittance was 91.6%.
전술한 실시예 14 내지 16과 비교예 1에 기술된 PMMA 시트의 투과율 측정 결과로부터 본 발명에 따른 화학식 1의 화합물은 PMMA 시트의 투명성을 유지 또는 개선시키는 것을 확인할 수 있었다.From the results of the measurement of the transmittance of the PMMA sheets described in Examples 14 to 16 and Comparative Example 1, it was confirmed that the compound of Formula 1 according to the present invention maintains or improves the transparency of the PMMA sheet.
본 발명에 따른 화합물은 수지에 혼합되었을 때 상기 수지에 난연성을 부여함과 동시에 상기 수지의 투명성을 유지시킬 수 있다.The compound according to the present invention can impart flame retardancy to the resin when mixed with the resin and at the same time maintain transparency of the resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923916A (en) * | 1987-10-30 | 1990-05-08 | Pennwalt Corporation | Tetrahalophthalate esters as flame retardants for polystyrene resins |
| US5049697A (en) * | 1987-09-21 | 1991-09-17 | Atochem North America, Inc. | High yield method for preparation of dialkyl esters of polyhaloaromatic acids |
| KR20010013947A (en) * | 1997-06-18 | 2001-02-26 | 데이비드 디. 샌더스 | Novel flame retardant plasticizers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049697A (en) * | 1987-09-21 | 1991-09-17 | Atochem North America, Inc. | High yield method for preparation of dialkyl esters of polyhaloaromatic acids |
| US5208366A (en) * | 1987-09-21 | 1993-05-04 | Elf Atochem North America, Inc. | High yield method for preparation of dialkyl esters of polyhaloaromatic acids |
| US4923916A (en) * | 1987-10-30 | 1990-05-08 | Pennwalt Corporation | Tetrahalophthalate esters as flame retardants for polystyrene resins |
| KR20010013947A (en) * | 1997-06-18 | 2001-02-26 | 데이비드 디. 샌더스 | Novel flame retardant plasticizers |
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