JP2008001603A - Method for preparing 6,6'-(alkylenedioxy)di-2-naphthoic acid - Google Patents
Method for preparing 6,6'-(alkylenedioxy)di-2-naphthoic acid Download PDFInfo
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- JP2008001603A JP2008001603A JP2006169814A JP2006169814A JP2008001603A JP 2008001603 A JP2008001603 A JP 2008001603A JP 2006169814 A JP2006169814 A JP 2006169814A JP 2006169814 A JP2006169814 A JP 2006169814A JP 2008001603 A JP2008001603 A JP 2008001603A
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- Prior art keywords
- naphthoic acid
- alkylenedioxy
- acid
- salt
- reaction
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000005530 alkylenedioxy group Chemical group 0.000 claims description 26
- IUJMPBDJRAXYCK-UHFFFAOYSA-N 6-[2-(6-carboxynaphthalen-2-yl)oxyethoxy]naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCOC3=CC4=CC=C(C=C4C=C3)C(=O)O)=CC=C21 IUJMPBDJRAXYCK-UHFFFAOYSA-N 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- -1 di-2-naphthoic acid monopotassium salt Chemical compound 0.000 claims description 11
- VFWZSVJNBCALDP-UHFFFAOYSA-L C1=C(C=CC2=CC=CC=C12)C(=O)[O-].C1=C(C=CC2=CC=CC=C12)C(=O)[O-].[K+].[K+] Chemical compound C1=C(C=CC2=CC=CC=C12)C(=O)[O-].C1=C(C=CC2=CC=CC=C12)C(=O)[O-].[K+].[K+] VFWZSVJNBCALDP-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002253 acid Substances 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 8
- 239000011591 potassium Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000009833 condensation Methods 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003916 acid precipitation Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- UWTIFRVJFRCNEM-UHFFFAOYSA-M potassium 6-[2-(6-carboxynaphthalen-2-yl)oxyethoxy]naphthalene-2-carboxylate Chemical compound [K+].C(OC=1C=C2C=CC(=CC2=CC1)C(=O)[O-])COC=1C=C2C=CC(=CC2=CC1)C(=O)O UWTIFRVJFRCNEM-UHFFFAOYSA-M 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 2
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 2
- CXHPKSYTQFAXIN-UHFFFAOYSA-N 1,4-difluorobutane Chemical compound FCCCCF CXHPKSYTQFAXIN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- OOLOYCGJRJFTPM-UHFFFAOYSA-N 1,3-difluoropropane Chemical compound FCCCF OOLOYCGJRJFTPM-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 description 1
- ZBQFYVZOWLAJKN-UHFFFAOYSA-N 1,5-difluoropentane Chemical compound FCCCCCF ZBQFYVZOWLAJKN-UHFFFAOYSA-N 0.000 description 1
- IAEOYUUPFYJXHN-UHFFFAOYSA-N 1,5-diiodopentane Chemical compound ICCCCCI IAEOYUUPFYJXHN-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- GVEHCXOZCZQOOM-UHFFFAOYSA-N 1,6-difluorohexane Chemical compound FCCCCCCF GVEHCXOZCZQOOM-UHFFFAOYSA-N 0.000 description 1
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- TWIHDBCAGBYTBH-UHFFFAOYSA-N O(C1=C(C=CC2=CC=CC=C12)C(=O)O)C1=C(C=CC2=CC=CC=C12)C(=O)O Chemical compound O(C1=C(C=CC2=CC=CC=C12)C(=O)O)C1=C(C=CC2=CC=CC=C12)C(=O)O TWIHDBCAGBYTBH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- IPGHHLMDDPLMEU-UHFFFAOYSA-L [K+].[K+].[O-]C(=O)c1ccc2cc(OCCOc3ccc4cc(ccc4c3)C([O-])=O)ccc2c1 Chemical compound [K+].[K+].[O-]C(=O)c1ccc2cc(OCCOc3ccc4cc(ccc4c3)C([O-])=O)ccc2c1 IPGHHLMDDPLMEU-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000002739 cryptand Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- OBNIFGYZZBTPPR-UHFFFAOYSA-M potassium;6-hydroxynaphthalene-2-carboxylate Chemical compound [K+].C1=C(C([O-])=O)C=CC2=CC(O)=CC=C21 OBNIFGYZZBTPPR-UHFFFAOYSA-M 0.000 description 1
- FJWLWIRHZOHPIY-UHFFFAOYSA-N potassium;hydroiodide Chemical compound [K].I FJWLWIRHZOHPIY-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は縮合重合体の原料である６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸の製造方法および精製方法に関する。 The present invention relates to a method for producing and purifying 6,6 '-(alkylenedioxy) di-2-naphthoic acid, which is a raw material for condensation polymers.
従来から種々の芳香族ジカルボン酸が知られており、ポリエステル、ポリアミドのなどの如き縮合重合体の原料として広く利用されている。例えばテレフタル酸はポリエチレンテレフタレート、ポリテトラエチレンテレフタレート、ポリパラフェニレンテレフタルアミド等の原料として工業的に使用されている。その他イソフタル酸もポリマー用原料として広く利用されている。またナフタレンジカルボン酸を原料としたポリエステルであるポリエチレンナフタレートはポリエチレンテレフタレートに比べ機械的、熱的に更に高性能である事は知られている。 Conventionally, various aromatic dicarboxylic acids are known and widely used as raw materials for condensation polymers such as polyesters and polyamides. For example, terephthalic acid is industrially used as a raw material for polyethylene terephthalate, polytetraethylene terephthalate, polyparaphenylene terephthalamide and the like. Other isophthalic acids are also widely used as raw materials for polymers. Polyethylene naphthalate, which is a polyester made from naphthalenedicarboxylic acid, is known to have higher mechanical and thermal performance than polyethylene terephthalate.
特許文献１には６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を原料とするポリエステルが優れた物性、例えば機械的、熱的物性などを有する事が記載されており、６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸の精製方法に関する記述がある。 Patent Document 1 describes that a polyester using 6,6 ′-(ethylenedioxy) di-2-naphthoic acid as a raw material has excellent physical properties such as mechanical and thermal properties. There is a description regarding a method for purifying 6 '-(ethylenedioxy) di-2-naphthoic acid.
また特許文献２には６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸の製造法について記載されている。製造法は６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸のアルカリ金属塩を合成後、鉱酸や酸性ガスの添加により酸析を行うが、この処方で酸析を行なうとアルカリ金属成分が多量に残存する。このようなアルカリ金属がモノマー中に残存するとポリマーの色相の悪影響を与えるばかりか、熱的特性、機械特性に悪い影響を与える。さらに酸析後の６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸中には、２−ヒドロキシ−６−ナフトエ酸由来の不純物を含有している等の問題があった。 Patent Document 2 describes a process for producing 6,6 '-(ethylenedioxy) di-2-naphthoic acid. The production method involves synthesizing an alkali metal salt of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid, and then acidifying by adding a mineral acid or acid gas. A large amount of metal component remains. If such an alkali metal remains in the monomer, it not only adversely affects the hue of the polymer but also adversely affects the thermal and mechanical properties. Further, 6,6 '-(ethylenedioxy) di-2-naphthoic acid after acid precipitation has a problem that it contains impurities derived from 2-hydroxy-6-naphthoic acid.
本発明の目的は縮合重合体の原料である６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸の製造方法および精製方法を提供することにある。 An object of the present invention is to provide a method for producing and purifying 6,6 '-(alkylenedioxy) di-2-naphthoic acid, which is a raw material of a condensation polymer.
本発明は粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩を得て、ａ）水に懸濁し８０〜３００℃の高温度条件にて反応させる、あるいはｂ）酸析し、祖６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸得て、水に懸濁し８０〜３００℃の高温度条件にて反応させる事を特徴とする６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸の製造方法である。本発明はアルカリ金属含有量の少ない６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を提供することを目的とする。 The present invention provides crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt, a) suspended in water and reacted at a high temperature of 80 to 300 ° C., or b) acid precipitation. 6,6 ′-(alkylenedioxy) di-2-naphthoic acid is obtained, suspended in water and reacted under high temperature conditions of 80 to 300 ° C. This is a method for producing (rangeoxy) di-2-naphthoic acid. An object of the present invention is to provide 6,6 '-(alkylenedioxy) di-2-naphthoic acid having a low alkali metal content.
本発明によりアルカリ金属、着色物質、反応中間体等が効率的に除去でされた６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得ることができる。本発明で得られた６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸より、色相や熱的特性、機械特性に優れた重縮合体を得ることができる。 According to the present invention, 6,6 '-(alkylenedioxy) di-2-naphthoic acid from which an alkali metal, a colored substance, a reaction intermediate and the like are efficiently removed can be obtained. From 6,6 '-(alkylenedioxy) di-2-naphthoic acid obtained in the present invention, a polycondensate excellent in hue, thermal characteristics and mechanical characteristics can be obtained.
本発明は
１）カリウムイオンを含む水溶液の存在下、２−ヒドロキシ−６−ナフトエ酸とジハロゲン化物とを反応させて粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩を製造し、次いで
２）１）で得られた粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩に以下に示すａ）またはｂ）の処理反応を行う工程
ａ）水に懸濁し８０〜３００℃の高温度条件にて反応させる工程
ｂ）酸析し、粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得て、水に懸濁し８０〜３００℃の高温度条件にて反応させる工程、
３）２）で得られた反応混合物を固液分離し固相部から６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得る工程からなる６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸の製造方法である。これより縮合重合体を得ようとする目的で、とりわけ６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸が６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸であることが好ましい。
In the present invention, 1) crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt is obtained by reacting 2-hydroxy-6-naphthoic acid with a dihalide in the presence of an aqueous solution containing potassium ions. Step 2) in which 2) the crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt obtained in 1) is subjected to the following treatment reaction a) or b) Step b) Suspending and reacting at a high temperature of 80 to 300 ° C. Acid precipitation is performed to obtain crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid, which is suspended in water and 80 to 300 ° C. A step of reacting at a high temperature condition of
3) Solid-liquid separation of the reaction mixture obtained in 2) to obtain 6,6 ′-(alkylenedioxy) di-2-naphthoic acid from the solid phase part 6,6 ′-(alkylenedioxy) This is a method for producing di-2-naphthoic acid. For the purpose of obtaining a condensation polymer from this, in particular, 6,6 ′-(alkylenedioxy) di-2-naphthoic acid is 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. Is preferred.
６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸は下記式（Ｉ）
（Ｒ１は炭素数２〜６ののアルキレン基である）
で表される。
6,6 ′-(alkylenedioxy) di-2-naphthoic acid has the following formula (I)
(R 1 is an alkylene group having 2 to 6 carbon atoms)
It is represented by
＜工程１）＞
工程１）は、カリウムイオンを含む水溶液の存在下、２−ヒドロキシ−６−ナフトエ酸とジハロゲン化物とを反応させて粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩を得る工程である。
<Process 1)>
Step 1) comprises reacting 2-hydroxy-6-naphthoic acid with a dihalide in the presence of an aqueous solution containing potassium ions to obtain crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt. It is a process to obtain.
６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩は下記式（II）
（Mはカリウム金属、Ｒ１は炭素数２〜６のアルキレン基であり、Ｒ２はカリウム金属または水素原子である）
で表される。カリウム金属塩としてはモノカリウム金属塩が好ましいが、酸析等の処理を行う目的では水溶液に溶解可能なジカリウム金属塩も好ましい。
6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt has the following formula (II)
(M is potassium metal, R 1 is an alkylene group having 2 to 6 carbon atoms, and R 2 is potassium metal or a hydrogen atom)
It is represented by As the potassium metal salt, a monopotassium metal salt is preferable, but a dipotassium metal salt that can be dissolved in an aqueous solution is also preferable for the purpose of treatment such as acid precipitation.
工程１）ではカリウム金属を水に溶解した水溶液が用いられる。水溶液のカリウム金属濃度は５〜２０重量％が好ましい。
また工程１）におけるジハロゲン化物としては１，２−ジクロロエタン、１，２−ジブロモエタン、１，２−ジヨードエタン、１，２−ジフロオロエタン、１，３−ジクロロプロパン、１，３―ジブロモプロパン、１，３−ジヨードプロパン、１，３−ジフロオロプロパン、１，４−ジクロロブタン、１，４−ジブロモブタン、１，４−ジヨードブタン、１，４−ジフルオロブタン、１，５−ジクロロペンタン、１，５−ジブロモペンタン、１，５−ジヨードペンタン、１，５−ジフルオロペンタン、１，６−ジクロロへキサン、１，６−ジブロモへキサン、１，６−ジヨードヘキサン、１，６−ジフルオロヘキサン等が挙げられる。このうち炭素数が偶数である１，２−ジクロロエタン、１，２−ジブロモエタン、１，２−ジヨードエタン、１，２−ジフロオロエタン、１，４−ジクロロブタン、１，４−ジブロモブタン、１，４−ジヨードブタン、１，４−ジフルオロブタンが好ましく、さらに好ましくは１，２−ジハロエタン、なかでも経済的な点から１，２−ジクロロエタン、１，２−ジブロモエタンが好ましい。特に好ましくは１，２−ジクロロエタンである。
In step 1), an aqueous solution in which potassium metal is dissolved in water is used. The potassium metal concentration of the aqueous solution is preferably 5 to 20% by weight.
The dihalides in step 1) include 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,2-difluoroethane, 1,3-dichloropropane, 1,3-dibromopropane, 1, 3-diiodopropane, 1,3-difluoropropane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,4-diiodobutane, 1,4-difluorobutane, 1,5-dichloropentane, 1 , 5-dibromopentane, 1,5-diiodopentane, 1,5-difluoropentane, 1,6-dichlorohexane, 1,6-dibromohexane, 1,6-diiodohexane, 1,6-difluoro Hexane etc. are mentioned. Of these, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,2-difluoroethane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,4 having an even number of carbon atoms -Diiodobutane and 1,4-difluorobutane are preferable, 1,2-dihaloethane is more preferable, and 1,2-dichloroethane and 1,2-dibromoethane are particularly preferable from the economical viewpoint. Particularly preferred is 1,2-dichloroethane.
またジハロゲン化物の使用割合は前記２−ヒドロキシ−６−ナフトエ酸のカリウム塩１モルに対し、０．４ないし、１．５モル程である。理論量は０．５モルであるが副反応によって消費されるので理論量よりも多くしてもよい。２−ヒドロキシ−６−ナフトエ酸のカリウム塩とジハロゲン化物との反応は溶媒中で行なうのが好ましい。かかる溶媒としては水が特に好ましいが、その他、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類、テトラヒドロフラン、ジオキサン等のエーテル類、メタノール、エタノール、プロパノール等のアルコール類、アセトン、メチルイソブチルケトン等のケトン類、エチレングリコール、プロピレングリコール等のグリコール類、アセトニトリル等のニトリル類が使用できる。 The proportion of dihalide used is about 0.4 to 1.5 moles per mole of the 2-hydroxy-6-naphthoic acid potassium salt. The theoretical amount is 0.5 mol, but may be larger than the theoretical amount because it is consumed by side reactions. The reaction between the potassium salt of 2-hydroxy-6-naphthoic acid and the dihalide is preferably carried out in a solvent. As such a solvent, water is particularly preferable. In addition, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and propanol, acetone, Ketones such as methyl isobutyl ketone, glycols such as ethylene glycol and propylene glycol, and nitriles such as acetonitrile can be used.
工程１）の反応温度は、好ましくは１００〜２５０℃、特に好ましくは１２０〜２００℃であり、反応は常圧〜加圧下で実施できる。本発明では、ヨウ素カリウム等の触媒、銅などの安定剤を添加剤として用いてよく、また２−ヒドロキシ−６−ナフトエ酸またはそのカリウム塩を反応系に存在させてもよい。必要により相間移動反応系で行ってもよく、この場合には、水−芳香族炭化水素系、水−ハロゲン化炭化水素系等を溶媒として用い、クラウンエーテル類、クリプタンド類、４級アンモニウム塩等を相間移動触媒として用いる方法が挙げられる。 The reaction temperature in step 1) is preferably 100 to 250 ° C., particularly preferably 120 to 200 ° C., and the reaction can be carried out under normal pressure to increased pressure. In the present invention, a catalyst such as potassium iodine and a stabilizer such as copper may be used as additives, and 2-hydroxy-6-naphthoic acid or its potassium salt may be present in the reaction system. If necessary, a phase transfer reaction system may be used. In this case, a water-aromatic hydrocarbon system, a water-halogenated hydrocarbon system or the like is used as a solvent, and crown ethers, cryptands, quaternary ammonium salts, etc. Can be used as a phase transfer catalyst.
上記芳香族炭化水素としてはベンゼン、キシレン、トルエンなどが挙げられる。またハロゲン化炭化水素としてはジクロロメタン、ジクロロエタン、クロロホルムなどが例示される。 Examples of the aromatic hydrocarbon include benzene, xylene, toluene and the like. Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform and the like.
かかる方法により粗６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム塩が生成する。本発明においては粗６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム塩を経て粗６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸を得る事を特徴としている。一方６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ナトリウム塩の場合には６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸モノナトリウム塩、６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジナトリウム塩が考えられるが、どちらの反応物も水への溶解度が低く、本発明における＜工程２＞、＜工程３＞に適しない。 By this method, crude 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium salt is produced. The present invention is characterized in that crude 6,6- (alkylenedioxy) -di-2-naphthoic acid is obtained via crude 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium salt. On the other hand, in the case of 6,6- (alkylenedioxy) -di-2-naphthoic acid sodium salt, 6,6- (alkylenedioxy) -di-2-naphthoic acid monosodium salt, Oxy) -di-2-naphthoic acid disodium salt can be considered, but both reactants have low solubility in water and are not suitable for <Step 2> and <Step 3> in the present invention.
反応溶媒として水を用いた場合には、該生成物が６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸モノカリウム塩が極めて溶解度が低く反応系からろ過によって単離できる。また６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウム塩は上記の６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸モノカリウム塩にカリウムイオンを加える事で容易に得る事ができる。６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウム塩の場合には一時溶解するが冷却する事によって析出するので単離する事ができる。 When water is used as the reaction solvent, the product, 6,6- (alkylenedioxy) -di-2-naphthoic acid monopotassium salt, has very low solubility and can be isolated from the reaction system by filtration. In addition, 6,6- (alkylenedioxy) -di-2-naphthoic acid dipotassium salt can be easily obtained by adding potassium ion to the above-mentioned 6,6- (alkylenedioxy) -di-2-naphthoic acid monopotassium salt. I can get it. In the case of 6,6- (alkylenedioxy) -di-2-naphthoic acid dipotassium salt, it can be isolated because it dissolves temporarily but precipitates upon cooling.
また反応物の異物除去および着色成分の除去を行う場合には６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸のジカリウム塩にして一旦溶解し、ろ過および活性炭処理などを施す事が好ましい。６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウムは６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸モノカリウムにさらにアルカリ成分を添加する事で容易に得る事が出来、溶解性も高い事から特に好ましい。このようにジカリウム塩とする際の温度は室温でも構わないが一般には加熱下で行うことが好ましい。加熱下で行うと、ジカリウム塩溶解度が向上し釜効率が良くなる。この加熱処理は通常０．５〜５時間で行い不溶物がある時は濾別して除く。上記のようにして得られる水溶液中の６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸のジカリウム金属塩の濃度は、通常０．２〜３０重量％である。この処理は酸析前に行う事が好ましい。 In addition, when removing foreign substances from the reaction product and removing colored components, it is necessary to dissolve the dipotassium salt of 6,6- (alkylenedioxy) -di-2-naphthoic acid once, and subject to filtration and activated carbon treatment. preferable. Dipotassium 6,6- (alkylenedioxy) -di-2-naphthoate can be easily obtained by adding an alkali component to monopotassium 6,6- (alkylenedioxy) -di-2-naphthoate. It is particularly preferable because of its high solubility. Thus, although the temperature at the time of setting it as a dipotassium salt may be room temperature, generally it is preferable to carry out under heating. When carried out under heating, the dipotassium salt solubility is improved and the pot efficiency is improved. This heat treatment is usually carried out for 0.5 to 5 hours, and when there is insoluble matter, it is filtered off. The concentration of the dipotassium metal salt of 6,6- (alkylenedioxy) -di-2-naphthoic acid in the aqueous solution obtained as described above is usually 0.2 to 30% by weight. This treatment is preferably performed before acid precipitation.
活性炭処理法は流通式又は回分式で行う。例えば流通式の場合には粒状の活性炭をカラムに充填しアップフロ−又はダウンフロ−で６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウム塩水溶液を流通させる。処理温度は室温〜６０℃で行うが通常は室温で充分である。回分式の場合には水溶液中の６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウム塩に対して１〜１０重量％程度の粉末活性炭を加え１〜５時間撹拌下処理する。活性炭処理は強塩基で処理するよりも中性付近のほうが処理効果が大きい。活性炭種には特に制限は無くどんな種類のものでも使用できる。この後、６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸ジカリウム塩を含む水溶液に炭酸ガスを吹き込んで６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸モノカリウム塩を析出させて分離し、本発明記載の方法により６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸を得る事ができる。 The activated carbon treatment method is carried out by a distribution method or a batch method. For example, in the case of a circulation type, granular activated carbon is packed in a column and an aqueous solution of 6,6- (alkylenedioxy) -di-2-naphthoic acid dipotassium salt is circulated by up-flow or down-flow. The treatment temperature is from room temperature to 60 ° C., but room temperature is usually sufficient. In the case of a batch system, about 1 to 10% by weight of powdered activated carbon is added to 6,6- (alkylenedioxy) -di-2-naphthoic acid dipotassium salt in an aqueous solution, and the mixture is treated with stirring for 1 to 5 hours. The activated carbon treatment is more effective in the vicinity of neutrality than the treatment with a strong base. There are no particular restrictions on the type of activated carbon, and any type can be used. Thereafter, carbon dioxide is blown into an aqueous solution containing 6,6- (alkylenedioxy) -di-2-naphthoic acid dipotassium salt to obtain 6,6- (alkylenedioxy) -di-2-naphthoic acid monopotassium salt. It can be precipitated and separated, and 6,6- (alkylenedioxy) -di-2-naphthoic acid can be obtained by the method of the present invention.
＜工程２）＞
工程２）では１）で得られた粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム金属塩をａ）水に懸濁し８０〜３００℃の高温度条件にて反応させる、あるいはｂ）酸析し、粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得て、水に懸濁し８０〜３００℃の高温度条件にて反応させる。
<Process 2)>
In step 2), the crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium metal salt obtained in 1) is suspended in a) water and reacted at a high temperature of 80 to 300 ° C., Alternatively, b) acid precipitation is performed to obtain crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid, which is suspended in water and reacted at a high temperature of 80 to 300 ° C.
ａ）の工程における粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム金属塩はモノカリウム塩であることが好ましい。該６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩、あるいは粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を水に懸濁する時の水の使用量は５〜１００重量倍が好ましい。５重量倍より少ないと反応が進行しないし、１００重量倍以上加えると事は経済的に好ましくない。よって好ましくは１０〜７０重量倍、さらに好ましくは２０〜５０重量倍の範囲である。また反応温度は高温であればあるほど良いが、おおよそ１００℃〜３００℃程度の反応温度で反応を行う事が好ましい。好ましくは１００℃〜２００℃の範囲である。必要により加圧下で反応を行っても良い。 The crude 6,6 '-(alkylenedioxy) di-2-naphthoic acid potassium metal salt in step a) is preferably a monopotassium salt. Amount of water used when the 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt or crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid is suspended in water Is preferably 5 to 100 times by weight. If it is less than 5 times by weight, the reaction does not proceed, and if it is added 100 times by weight or more, it is economically undesirable. Therefore, the range is preferably 10 to 70 times by weight, more preferably 20 to 50 times by weight. The higher the reaction temperature, the better, but it is preferable to carry out the reaction at a reaction temperature of about 100 ° C to 300 ° C. Preferably it is the range of 100 to 200 degreeC. If necessary, the reaction may be carried out under pressure.
ｂ）の工程における酸析では、６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム塩を酸と反応せしめる。このとき６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム塩はモノカリウム塩であっても、ジカリウム塩であっても良い。なかでもモノカリウム塩であることが好ましい。該反応の溶媒としては水が特に好ましいが、その他エチレングリコール、プロピレングリコール、の如きグリコール類なども好ましく用いられる。酸としてはカリウムと反応溶媒に可溶な塩を形成することができ、かかる酸としては硫酸、塩酸、燐酸などの無機酸の他に酢酸、蓚酸、アジピン酸などの脂肪族カルボン酸類、安息香酸、テレフタル酸、イソフタル酸、２−ヒドロキシ−６−ナフトエ酸等の芳香族カルボン酸等が使用できる。水溶液中の６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム塩の濃度は、通常０．２〜３０重量％である。このようにし６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸カリウム金属塩を溶媒中に分散または溶解させておき、撹拌下に酸を加え酸析して６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸の結晶を得る。酸の希釈濃度は任意であり本発明の効果にはほとんど問題ないが、通常は、例えば、硫酸であれば１〜５０重量％程度のものを使用する。酸の添加は反応液のｐＨが２付近になるまで加える。添加速度は添加量にもよるが、通常は０．０１〜１０時間で、酸添加後も攪拌を３〜３０分間そのまま続ける。酸析の温度は室温から溶媒の沸点程度で行うが、加圧下沸点以上の高温で行うこともできる。生成した６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸の結晶は、濾別後、十分水洗し乾燥する。得られる６，６−（アルキレンジオキシ）−ジ−２−ナフトエ酸の結晶粒径は、通常、１〜５００μｍとなる。 In acid precipitation in the step b), 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium salt is reacted with an acid. At this time, the 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium salt may be a monopotassium salt or a dipotassium salt. Of these, a monopotassium salt is preferable. As the solvent for the reaction, water is particularly preferred, but glycols such as ethylene glycol and propylene glycol are also preferably used. As an acid, potassium and a salt soluble in a reaction solvent can be formed. As such an acid, in addition to inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, aliphatic carboxylic acids such as acetic acid, succinic acid and adipic acid, and benzoic acid Aromatic carboxylic acids such as terephthalic acid, isophthalic acid and 2-hydroxy-6-naphthoic acid can be used. The concentration of 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium salt in the aqueous solution is usually 0.2 to 30% by weight. In this way, 6,6- (alkylenedioxy) -di-2-naphthoic acid potassium metal salt was dispersed or dissolved in a solvent, acid was added with stirring and acidified to give 6,6- (alkylenedioxy). Crystals of (oxy) -di-2-naphthoic acid are obtained. The dilution concentration of the acid is arbitrary, and there is almost no problem with the effect of the present invention. Usually, for example, about 1 to 50% by weight of sulfuric acid is used. The acid is added until the pH of the reaction solution reaches about 2. Although the addition rate depends on the addition amount, it is usually 0.01 to 10 hours, and stirring is continued for 3 to 30 minutes after the acid addition. The acid precipitation temperature is from room temperature to the boiling point of the solvent, but can also be carried out at a high temperature above the boiling point under pressure. The produced 6,6- (alkylenedioxy) -di-2-naphthoic acid crystals are separated by filtration, sufficiently washed with water and dried. The crystal grain size of the obtained 6,6- (alkylenedioxy) -di-2-naphthoic acid is usually 1 to 500 μm.
＜工程３）＞
工程３）は、２）で得られた反応混合物を固液分離し固相部から６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得る工程である。
６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を分離した母液は６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸ジカリウム塩を含有しているので、そのまま或いは濃縮して再び６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩を析出させる工程へ循環することが好ましい。すなわち、３）の工程において固液分離し得られた液相部に炭酸ガスを作用させることにより、６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩を単離し、その後２）の工程に供することが好ましい。
<Process 3)>
Step 3) is a step of solid-liquid separation of the reaction mixture obtained in 2) to obtain 6,6 ′-(alkylenedioxy) di-2-naphthoic acid from the solid phase part.
Since the mother liquor from which 6,6 ′-(alkylenedioxy) di-2-naphthoic acid has been separated contains 6,6 ′-(alkylenedioxy) di-2-naphthoic acid dipotassium salt, it can be concentrated as it is. It is preferable to circulate again to the step of depositing 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt. That is, 6,6 ′-(alkylenedioxy) di-2-naphthoic acid monopotassium salt is isolated by allowing carbon dioxide to act on the liquid phase part obtained by solid-liquid separation in step 3), and then It is preferable to use for the process of 2).
炭酸ガスを通じる場合には一般に炭酸ガスの圧力が高い程、反応温度が低いほどモノカリウム塩の析出する比率が高い。好ましい反応温度は０℃〜１００℃の範囲である。炭酸ガスの圧力は、反応温度及びアルカリ塩の循環によって異なる。適時好ましい範囲で反応を行う事が好ましい。 When carbon dioxide gas is passed, generally, the higher the pressure of carbon dioxide gas and the lower the reaction temperature, the higher the proportion of monopotassium salt precipitated. The preferred reaction temperature is in the range of 0 ° C to 100 ° C. The pressure of carbon dioxide varies depending on the reaction temperature and the circulation of the alkali salt. It is preferable to carry out the reaction within a preferable range in a timely manner.
＜得られる６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸＞
本発明方法よりカリウム金属の含有量が１〜５００ｐｐｍの６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得ることができる。好ましくはカリウム金属の含有量が１〜２００ｐｐｍであると縮合重合体の原料として好ましく、より好ましくは１〜１００ｐｐｍの範囲である。
所定のカリウム金属含有量になるように２）と３）の工程を繰り返し行うことでカリウム金属含有量を低減する事ができる。
本発明で得られた６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸より色相や熱的特性、機械特性に優れた重縮合体を得ることができる。
<6,6 ′-(alkylenedioxy) di-2-naphthoic acid obtained>
6,6 ′-(alkylenedioxy) di-2-naphthoic acid having a potassium metal content of 1 to 500 ppm can be obtained from the method of the present invention. The content of potassium metal is preferably 1 to 200 ppm as a raw material for the condensation polymer, and more preferably in the range of 1 to 100 ppm.
The potassium metal content can be reduced by repeating the steps 2) and 3) so as to obtain a predetermined potassium metal content.
A polycondensate excellent in hue, thermal properties and mechanical properties can be obtained from 6,6 ′-(alkylenedioxy) di-2-naphthoic acid obtained in the present invention.
以下に実施例及び比較例を挙げ、本発明をより具体的に説明する。２−ヒドロキシー６−ナフトエ酸はアルドリッチ（株）から、ジクロロエタン、水酸化カリウム、エタノールは和光純薬工業から入手した。アルカリ成分は原子吸光法（日立製作所製偏光ゼーマン原子吸光光度計Ｚ５０００）により定量分析を行った。また元素分析はヤナコ(株)製元素分析装置ＭＴ−６により定量分析を行った。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. 2-Hydroxy-6-naphthoic acid was obtained from Aldrich Co., Ltd., and dichloroethane, potassium hydroxide, and ethanol were obtained from Wako Pure Chemical Industries. The alkali component was quantitatively analyzed by an atomic absorption method (polarized Zeeman atomic absorption photometer Z5000 manufactured by Hitachi, Ltd.). Elemental analysis was carried out quantitatively with an element analyzer MT-6 manufactured by Yanaco.
［実施例１］
１０Ｌの攪拌付きオートクレーブに２−ヒドロキシー６−ナフトエ酸１０００重量部、水酸化カリウム５９７重量部、ジクロロエタン２６３重量部、水５０００重量部を仕込み窒素置換後、窒素圧０．３Ｍｐａを掛け攪拌下１２０℃〜１３０℃で反応した。反応後冷却・ろ過することにより６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩を主成分とする固体を得た。この生成物の乾燥重量３８０重量部であった。６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩２０重量部に、イオン交換水１０００重量部を１Ｌのオートクレーブに仕込み窒素置換後０．２ＭＰａを掛け攪拌下１５０℃で６時間反応した。反応後懸濁溶液を、吸引ろ過し６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を得た。この６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸のカリウム金属含有量は８００ｐｐｍであった。
[Example 1]
A 10 L autoclave with stirring was charged with 1000 parts by weight of 2-hydroxy-6-naphthoic acid, 597 parts by weight of potassium hydroxide, 263 parts by weight of dichloroethane, and 5000 parts by weight of water. Reacted at ~ 130 ° C. After the reaction, the mixture was cooled and filtered to obtain a solid mainly composed of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt. The dry weight of this product was 380 parts by weight. To 20 parts by weight of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt, 1000 parts by weight of ion-exchanged water was charged into a 1 L autoclave, and after substituting with nitrogen, 0.2 MPa was applied at 150 ° C. with stirring. Reacted for hours. After the reaction, the suspension solution was subjected to suction filtration to obtain 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. The potassium metal content of this 6,6 ′-(ethylenedioxy) di-2-naphthoic acid was 800 ppm.
［実施例２］
実施例１で得られた６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸２０重量部に、イオン交換水１０００重量部を１Ｌのオートクレーブに仕込み窒素置換後０．２ＭＰａを掛け攪拌下１５０℃で６時間反応した。反応後懸濁溶液を、吸引ろ過し６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を得た。この６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸のカリウム金属含有量は２００ｐｐｍであった。
[Example 2]
To 20 parts by weight of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid obtained in Example 1, 1000 parts by weight of ion-exchanged water was placed in a 1 L autoclave, and after nitrogen substitution, 0.2 MPa was applied while stirring. The reaction was carried out at 150 ° C. for 6 hours. After the reaction, the suspension solution was subjected to suction filtration to obtain 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. The potassium metal content of this 6,6 ′-(ethylenedioxy) di-2-naphthoic acid was 200 ppm.
［実施例３］
１０Ｌの攪拌付きオートクレーブに２−ヒドロキシー６−ナフトエ酸１０００重量部、水酸化カリウム５９７重量部、ジクロロエタン２６３重量部、水５０００重量部を仕込み、窒素置換後、窒素圧０．３Ｍｐａを掛け攪拌下１２０℃〜１３０℃で反応した。反応後、冷却・ろ過することにより６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩を主成分とする固体を得た。この生成物の乾燥重量３８０重量部であった。この固体に水６０００重量部、硫酸１３５重量部を加え温度９５℃で酸析を行った。酸析後、析出した固体をろ過し水洗し減圧乾燥した。含有カリウム量は１〜２ｗ％であった。このようにして得られた粗６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸２０重量部に、イオン交換水１０００重量部を１Ｌのオートクレーブに仕込み窒素置換後０．２ＭＰａを掛け攪拌下１５０℃で６時間反応した。反応後懸濁溶液を、吸引ろ過し固相から６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を得た。この６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸のカリウム金属含有量は１５０ｐｐｍであった。
[Example 3]
A 10 L autoclave with stirring was charged with 1000 parts by weight of 2-hydroxy-6-naphthoic acid, 597 parts by weight of potassium hydroxide, 263 parts by weight of dichloroethane, and 5000 parts by weight of water. After substituting with nitrogen, a nitrogen pressure of 0.3 Mpa was applied while stirring. The reaction was carried out at a temperature between 130C and 130C. After the reaction, cooling and filtering were performed to obtain a solid mainly composed of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt. The dry weight of this product was 380 parts by weight. 6000 parts by weight of water and 135 parts by weight of sulfuric acid were added to the solid, and acid precipitation was performed at a temperature of 95 ° C. After acid precipitation, the precipitated solid was filtered, washed with water, and dried under reduced pressure. The amount of potassium contained was 1 to 2 w%. To 20 parts by weight of the crude 6,6 ′-(ethylenedioxy) di-2-naphthoic acid thus obtained, 1000 parts by weight of ion-exchanged water was charged into a 1 L autoclave and purged with nitrogen, followed by 0.2 MPa and stirring. The reaction was carried out at 150 ° C. for 6 hours. After the reaction, the suspension solution was subjected to suction filtration to obtain 6,6 ′-(ethylenedioxy) di-2-naphthoic acid from the solid phase. The potassium metal content of this 6,6 ′-(ethylenedioxy) di-2-naphthoic acid was 150 ppm.
［実施例４］
実施例３で得られた６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸２０重量部に、イオン交換水１０００重量部を１Ｌのオートクレーブに仕込み窒素置換後０．２ＭＰａを掛け攪拌下１５０℃で６時間反応した。反応後懸濁溶液を、吸引ろ過し６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を得た。この６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸のカリウム金属含有量は３０ｐｐｍであった。
[Example 4]
To 20 parts by weight of 6,6 ′-(ethylenedioxy) di-2-naphthoic acid obtained in Example 3, 1000 parts by weight of ion-exchanged water was placed in a 1 L autoclave, and after nitrogen substitution, 0.2 MPa was applied while stirring. The reaction was carried out at 150 ° C. for 6 hours. After the reaction, the suspension solution was subjected to suction filtration to obtain 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. The potassium metal content of this 6,6 ′-(ethylenedioxy) di-2-naphthoic acid was 30 ppm.
［実施例５］
実施例３の６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸ジカリウム塩を含む該反応後懸濁液の母液に炭酸ガスを常圧で吹き込むと白色沈殿を生じた。この白色沈殿は６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩であった。この白色沈殿物の元素分析結果を表１に示す。
[Example 5]
Carbon dioxide was blown into the mother liquor of the post-reaction suspension containing 6,6 ′-(ethylenedioxy) di-2-naphthoic acid dipotassium salt of Example 3 to form a white precipitate. This white precipitate was 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt. Table 1 shows the results of elemental analysis of this white precipitate.
この６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸モノカリウム塩は＜工程２＞へ回され最終的に６，６’−（エチレンジオキシ）ジ−２−ナフトエ酸を得る事ができる。 This 6,6 ′-(ethylenedioxy) di-2-naphthoic acid monopotassium salt is passed to <Step 2> to finally obtain 6,6 ′-(ethylenedioxy) di-2-naphthoic acid. Can do.
Claims (5)
２）１）で得られた粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸カリウム塩に以下に示すａ）またはｂ）の処理反応を行う工程、
ａ）水に懸濁し８０〜３００℃の高温度条件にて反応させる工程
ｂ）酸析し、粗６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得て、水に懸濁し８０〜３００℃の高温度条件にて反応させる工程、
３）２）で得られた反応混合物を固液分離し固相部から６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸を得る工程からなる、６，６’−（アルキレンジオキシ）ジ−２−ナフトエ酸の製造方法。 1) A step of reacting 2-hydroxy-6-naphthoic acid with a dihalide in the presence of an aqueous solution containing potassium ions to obtain a crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt, Next, 2) a step of subjecting the crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid potassium salt obtained in 1) to the following treatment reaction a) or b):
a) Step of suspending in water and reacting at a high temperature of 80 to 300 ° C. b) Aciding out to obtain crude 6,6 ′-(alkylenedioxy) di-2-naphthoic acid, which is suspended in water. A step of reacting under a high temperature condition of 80 to 300 ° C.,
3) Solid-liquid separation of the reaction mixture obtained in 2) to obtain 6,6 ′-(alkylenedioxy) di-2-naphthoic acid from the solid phase part, 6,6 ′-(alkylenedioxy) ) Method for producing di-2-naphthoic acid.
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| JP2009007317A (en) * | 2007-06-29 | 2009-01-15 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009120540A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009137866A (en) * | 2007-12-05 | 2009-06-25 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009155230A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for producing recycled 6-hydroxy-2-naphthoic acid |
| JP2009155231A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for recovering 6-hydroxy-2-naphthoic acid |
| JP2010070686A (en) * | 2008-09-19 | 2010-04-02 | Fine Clay Co Ltd | Method for producing acidic carboxymethyl cellulose |
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| JP2009007317A (en) * | 2007-06-29 | 2009-01-15 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009120540A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009137866A (en) * | 2007-12-05 | 2009-06-25 | Ueno Fine Chem Ind Ltd | Method for producing 6,6'-(ethylenedioxy)bis-2-naphthoic acid |
| JP2009155230A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for producing recycled 6-hydroxy-2-naphthoic acid |
| JP2009155231A (en) * | 2007-12-25 | 2009-07-16 | Ueno Fine Chem Ind Ltd | Method for recovering 6-hydroxy-2-naphthoic acid |
| JP2010070686A (en) * | 2008-09-19 | 2010-04-02 | Fine Clay Co Ltd | Method for producing acidic carboxymethyl cellulose |
| JP2012140344A (en) * | 2010-12-28 | 2012-07-26 | Teijin Ltd | Method for producing metal salt of 6,6'-(ethylenedioxy)di-2-naphthoic acid |
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