JP2023018201A - Method for producing polycarbonate resin - Google Patents
Method for producing polycarbonate resin Download PDFInfo
- Publication number
- JP2023018201A JP2023018201A JP2021122117A JP2021122117A JP2023018201A JP 2023018201 A JP2023018201 A JP 2023018201A JP 2021122117 A JP2021122117 A JP 2021122117A JP 2021122117 A JP2021122117 A JP 2021122117A JP 2023018201 A JP2023018201 A JP 2023018201A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- aromatic dihydroxy
- bis
- dihydroxy compound
- compound represented
- 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.)
- Pending
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 54
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 241001550224 Apha Species 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- -1 4-hydroxy-3-methylphenyl Chemical group 0.000 claims description 8
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 claims description 5
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 5
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001721 carbon Chemical class 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 108010021819 N,N'-bis(hydroxycarbonylmethyl)-N,N'-bis(alpha-hydroxycarbonyl-2-hydroxytolyl)diaminoethane Proteins 0.000 description 15
- OKTLIOWWGVGPKG-PMACEKPBSA-N (2s)-2-[2-[[(s)-carboxy-(2-hydroxyphenyl)methyl]-(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-2-(2-hydroxyphenyl)acetic acid Chemical compound C1([C@@H](C(O)=O)N(CC(O)=O)CCN(CC(=O)O)[C@H](C(O)=O)C=2C(=CC=CC=2)O)=CC=CC=C1O OKTLIOWWGVGPKG-PMACEKPBSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 150000004650 carbonic acid diesters Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- RGIBXDHONMXTLI-UHFFFAOYSA-N chavicol Chemical compound OC1=CC=C(CC=C)C=C1 RGIBXDHONMXTLI-UHFFFAOYSA-N 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 2
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-UHFFFAOYSA-N 0.000 description 1
- IDTODQQHHXCCBI-UHFFFAOYSA-N (4-methylphenyl) phenyl carbonate Chemical compound C1=CC(C)=CC=C1OC(=O)OC1=CC=CC=C1 IDTODQQHHXCCBI-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- IEMXKEMFCFILAA-UHFFFAOYSA-N 2-docosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O IEMXKEMFCFILAA-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- AEMSUYNOLDIJHY-UHFFFAOYSA-N 2-ethyl-4-(3-ethyl-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(CC)=CC(OC=2C=C(CC)C(O)=CC=2)=C1 AEMSUYNOLDIJHY-UHFFFAOYSA-N 0.000 description 1
- MQSVWTXCKSCUBT-UHFFFAOYSA-N 2-ethyl-4-[9-(3-ethyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(CC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CC)C(O)=CC=2)=C1 MQSVWTXCKSCUBT-UHFFFAOYSA-N 0.000 description 1
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical compound CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- RMVLMEDROQJTSS-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(OC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 RMVLMEDROQJTSS-UHFFFAOYSA-N 0.000 description 1
- ZDRSNHRWLQQICP-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 ZDRSNHRWLQQICP-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- ZGZVGZCIFZBNCN-UHFFFAOYSA-N 4,4'-(2-Methylpropylidene)bisphenol Chemical compound C=1C=C(O)C=CC=1C(C(C)C)C1=CC=C(O)C=C1 ZGZVGZCIFZBNCN-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- KQSIVRHDEPHUII-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenoxy)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(OC=2C=C(C)C(O)=C(C)C=2)=C1 KQSIVRHDEPHUII-UHFFFAOYSA-N 0.000 description 1
- ZGRIVKAIJRLAIC-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenoxy)-2-methylphenol Chemical compound C1=C(O)C(C)=CC(OC=2C=C(C)C(O)=CC=2)=C1 ZGRIVKAIJRLAIC-UHFFFAOYSA-N 0.000 description 1
- XTEGBRKTHOUETR-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfonyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=CC=2)=C1 XTEGBRKTHOUETR-UHFFFAOYSA-N 0.000 description 1
- NRUUIOGMQXFBGB-UHFFFAOYSA-N 4-(4-hydroxy-3-phenylphenoxy)-2-phenylphenol Chemical compound C1=C(C=2C=CC=CC=2)C(O)=CC=C1OC(C=1)=CC=C(O)C=1C1=CC=CC=C1 NRUUIOGMQXFBGB-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- MIFGCULLADMRTF-UHFFFAOYSA-N 4-[(4-hydroxy-3-methylphenyl)methyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(CC=2C=C(C)C(O)=CC=2)=C1 MIFGCULLADMRTF-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- SVOBELCYOCEECO-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)cyclohexyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=CC=2)=C1 SVOBELCYOCEECO-UHFFFAOYSA-N 0.000 description 1
- XDGXPHFWSPGAIB-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)ethyl]-2-methylphenol Chemical compound C=1C=C(O)C(C)=CC=1C(C)C1=CC=C(O)C(C)=C1 XDGXPHFWSPGAIB-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 1
- OEKMLJNFAWYNOS-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cycloundecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCC1 OEKMLJNFAWYNOS-UHFFFAOYSA-N 0.000 description 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 1
- XXHIPRDUAVCXHW-UHFFFAOYSA-N 4-[2-ethyl-1-(4-hydroxyphenyl)hexyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C(CC)CCCC)C1=CC=C(O)C=C1 XXHIPRDUAVCXHW-UHFFFAOYSA-N 0.000 description 1
- ZJNKCNFBTBFNMO-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-5,7-dimethyl-1-adamantyl]phenol Chemical compound C1C(C)(C2)CC(C3)(C)CC1(C=1C=CC(O)=CC=1)CC23C1=CC=C(O)C=C1 ZJNKCNFBTBFNMO-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 1
- DEOYYDLTMHIDKY-UHFFFAOYSA-N CCC(C)C1=C(C=CC(=C1)OC2=CC(=C(C=C2)O)C(C)CC)O Chemical compound CCC(C)C1=C(C=CC(=C1)OC2=CC(=C(C=C2)O)C(C)CC)O DEOYYDLTMHIDKY-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- WIMOAMTXINAKTO-UHFFFAOYSA-N OC1=C(C=C(C=C1)OC1=CC(=C(C=C1)O)C(C)(C)C1=CC=CC=C1)C(C)(C)C1=CC=CC=C1 Chemical compound OC1=C(C=C(C=C1)OC1=CC(=C(C=C1)O)C(C)(C)C1=CC=CC=C1)C(C)(C)C1=CC=CC=C1 WIMOAMTXINAKTO-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- IZJIAOFBVVYSMA-UHFFFAOYSA-N bis(4-methylphenyl) carbonate Chemical compound C1=CC(C)=CC=C1OC(=O)OC1=CC=C(C)C=C1 IZJIAOFBVVYSMA-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、ポリカーボネート樹脂の製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a method for producing a polycarbonate resin.
ポリカーボネート樹脂は、透明性や機械的強度に優れており、様々な用途に使用されている。一般的には、ビスフェノールＡを原料モノマーとして用いたポリカーボネート樹脂が流通しているが、インキや複写機部材等の特殊な用途においては、ビス（４－ヒドロキシフェニル）エーテル（以下、「ＤＨＤＥ」と略称）を原料モノマーとして用いたポリカーボネート樹脂が知られている（例えば、特許文献１及び２）。 Polycarbonate resins are excellent in transparency and mechanical strength and are used in various applications. Polycarbonate resins using bisphenol A as a raw material monomer are generally distributed. (abbreviation)) as a raw material monomer is known (for example, Patent Documents 1 and 2).
ポリカーボネート樹脂は高い透明性を有することが特徴であり、特にインキ用途においては、着色に対して非常に厳しい品質安定性が求められていた。しかしながら、ＤＨＤＥは、ビスフェノールＡほど工業的に高品質のものが大量生産されておらず、同等の純度でもロットが異なったり（液体クロマトグラフィーなどの一般的な分析により定量される濃度だけではＤＨＤＥの品質を見極めることが難しい）、製造メーカー（製造装置）が異なると、製造されたポリカーボネート樹脂の品質が、想定外に変動してしまう場合があった。 Polycarbonate resins are characterized by having high transparency, and particularly in ink applications, very strict quality stability has been required for coloration. However, DHDE is not industrially mass-produced with a quality as high as that of bisphenol A, and even if the purity is the same, lots may differ It is difficult to determine the quality), and if the manufacturer (manufacturing equipment) is different, the quality of the manufactured polycarbonate resin may fluctuate unexpectedly.
このような変動をもたらす原因は解明されておらず、ＤＨＤＥを原料とするポリカーボネート樹脂の品質安定性、特に着色を抑制できる新たな製造方法の開発が求められていた。 The cause of such variations has not been elucidated, and the development of a new production method capable of stabilizing the quality of polycarbonate resins made from DHDE, particularly suppressing coloration, has been desired.
本発明者等は、上記従来における課題を解決すべく鋭意検討した結果、以下の本発明によって上記課題を解決することができることを見出した。即ち、本発明は以下の通りである。
＜１＞ 下記一般式（１）で表される芳香族ジヒドロキシ化合物に由来する構成単位を含むポリカーボネート樹脂を製造する方法であって、
前記一般式（１）で表される芳香族ジヒドロキシ化合物の濃度が３０質量％であるメタノール溶液と、前記メタノール溶液に対し９質量倍の純水とを混合してなるスラリー溶液の導電率が、５．０μＳ／ｃｍ以下である原料物質を用いて、前記一般式（１）で表される芳香族ジヒドロキシ化合物を重合する工程を含む、前記ポリカーボネート樹脂の製造方法である。
Ｒ１及びＲ２は、各々独立に、水素原子、ハロゲン原子、置換されていてもよく、分岐していてもよい炭素数１以上２０以下のアルキル基、又は、置換されていてもよい炭素数６以上３０以下のアリール基を表し、
ｍ及びｎは、各々独立に、０～４の整数を表す。）
＜２＞ 前記一般式（１）で表される芳香族ジヒドロキシ化合物が、下記一般式（１－１）で表される、上記＜１＞に記載の製造方法である。
Ｒ１、Ｒ２、ｍ及びｎは、一般式（１）とそれぞれ同じである。）
＜３＞ 前記一般式（１）で表される芳香族ジヒドロキシ化合物が、ビス（４―ヒドロキシフェニル）エーテルである、上記＜１＞又は＜２＞に記載の製造方法である。
＜４＞ 前記ポリカーボネート樹脂４ｇが２５ｍｌのメチレンクロライドに溶解してなる溶液のハーゼン単位色数（ＡＰＨＡ）が、３０以下である、上記＜１＞～＜３＞のいずれかに記載の製造方法である。
＜５＞ 前記重合工程において、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、及び２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパンからなる群より選択される少なくとも一つを原料モノマーとして更に用いる、上記＜１＞～＜４＞のいずれかに記載の製造方法である。
As a result of intensive studies aimed at solving the above-described conventional problems, the inventors of the present invention have found that the above-described problems can be solved by the present invention described below. That is, the present invention is as follows.
<1> A method for producing a polycarbonate resin containing structural units derived from an aromatic dihydroxy compound represented by the following general formula (1),
The electrical conductivity of a slurry solution obtained by mixing a methanol solution in which the concentration of the aromatic dihydroxy compound represented by the general formula (1) is 30% by mass and pure water of 9 times the mass of the methanol solution is The method for producing the polycarbonate resin, comprising the step of polymerizing the aromatic dihydroxy compound represented by the general formula (1) using a raw material having a density of 5.0 μS/cm or less.
R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an optionally substituted or branched alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number represents an aryl group of 6 or more and 30 or less,
m and n each independently represent an integer of 0 to 4; )
<2> The production method according to <1> above, wherein the aromatic dihydroxy compound represented by the general formula (1) is represented by the following general formula (1-1).
R 1 , R 2 , m and n are the same as in general formula (1). )
<3> The production method according to <1> or <2> above, wherein the aromatic dihydroxy compound represented by the general formula (1) is bis(4-hydroxyphenyl)ether.
<4> The production method according to any one of <1> to <3> above, wherein a solution obtained by dissolving 4 g of the polycarbonate resin in 25 ml of methylene chloride has a Hazen unit color number (APHA) of 30 or less. be.
<5> In the polymerization step, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, and 2,2-bis(4-hydroxy-3 The production method according to any one of <1> to <4> above, wherein at least one selected from the group consisting of -methylphenyl)propane is further used as a raw material monomer.
本発明のポリカーボネート樹脂の製造方法により、安定して色相の良いＤＨＤＥ型ポリカーボネート樹脂を確実に製造することができる。 A DHDE-type polycarbonate resin having a good hue can be reliably produced stably by the method for producing a polycarbonate resin of the present invention.
以下、本発明を詳細に説明する。尚、本発明は、以下の実施の形態に限定されるものではなく、発明の効果を有する範囲において任意に変更して実施することができる。 The present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be arbitrarily modified within the scope of the invention's effects.
一般式（１）で表される芳香族ジヒドロキシ化合物は、公知の方法で合成できる他、複数の会社から市販品を入手することもできるが、液体クロマトグラフィーなどの一般的な分析により定量される純度が同等であっても、該芳香族ジヒドロキシ化合物を用いて重合して得られたポリカーボネート樹脂は、ＡＰＨＡなどに於いてしばしば変動が見られた。
本願発明者らの検討によれば、一般式（１）で表される芳香族ジヒドロキシ化合物中には、ハロゲン化物イオン、アルカリ金属イオン、遷移金属塩イオン、有機化合物イオン等複数の不純物が検出されるものの、ＡＰＨＡに直接影響ある原因物質が特定できなかった。
The aromatic dihydroxy compound represented by the general formula (1) can be synthesized by a known method, or commercially available from multiple companies, but is quantified by general analysis such as liquid chromatography. Even if the purity is the same, the polycarbonate resins obtained by polymerization using the aromatic dihydroxy compounds often show variations in APHA and the like.
According to studies by the inventors of the present application, multiple impurities such as halide ions, alkali metal ions, transition metal salt ions, and organic compound ions have been detected in the aromatic dihydroxy compound represented by the general formula (1). However, a causative agent that directly affects APHA could not be identified.
しかしながら本願発明者らの試行錯誤の結果、一般式（１）で表される芳香族ジヒドロキシ化合物の濃度が３０質量％であるメタノール溶液と、前記メタノール溶液に対し９質量倍の純水とを混合してなるスラリー溶液の導電率が、５．０μＳ／ｃｍ以下である原料モノマーを用いる、即ち、一般式（１）で表される芳香族時ヒドロキシ化合物を３０質量％溶解したメタノール溶液に、９質量倍の純水を加えて一般式（１）で表される芳香族ジヒドロキシ化合物を析出させたスラリー溶液の導電率が、５．０μＳ／ｃｍ以下、好ましくは、４．６μＳ／ｃｍ以下、より好ましくは３．８μＳ／ｃｍ以下の原料モノマーを用いることにより、良好な色相を有するポリカーボネート樹脂を安定的に製造できることを見出した。
ここで、該スラリー溶液の導電率が５．０μＳ／ｃｍであり、一般式（１）で表される芳香族ジヒドロキシ化合物を用いないブランクの導電率が１．０μＳ／ｃｍである場合、ブランクとの差であるΔ４．０μＳ／ｃｍが、水溶性不純物による導電率上昇分と推定される。
該導電率の下限は特にないが、芳香族ジヒドロキ化合物を含まない場合（ブランク）と同等である。例えば、誘電率の下限は１．０μＳ／ｃｍである。
However, as a result of trial and error by the inventors of the present application, a methanol solution in which the concentration of the aromatic dihydroxy compound represented by the general formula (1) is 30% by mass and pure water of 9 times the mass of the methanol solution are mixed. The conductivity of the slurry solution formed by using a raw material monomer having a conductivity of 5.0 μS / cm or less, that is, in a methanol solution in which 30% by mass of the aromatic dihydroxy compound represented by the general formula (1) is dissolved, 9 The conductivity of the slurry solution obtained by adding pure water twice the mass to precipitate the aromatic dihydroxy compound represented by the general formula (1) is 5.0 μS / cm or less, preferably 4.6 μS / cm or less, or more. It has been found that a polycarbonate resin having a good hue can be stably produced by using a raw material monomer with a viscosity of preferably 3.8 μS/cm or less.
Here, when the conductivity of the slurry solution is 5.0 μS / cm and the conductivity of the blank not using the aromatic dihydroxy compound represented by the general formula (1) is 1.0 μS / cm, the blank and Δ4.0 μS/cm, which is the difference between , is presumed to be the increase in conductivity due to water-soluble impurities.
Although there is no particular lower limit for the conductivity, it is equivalent to the case where the aromatic dihydroxy compound is not contained (blank). For example, the lower limit of the dielectric constant is 1.0 μS/cm.
さらに、上述の誘電率が、５．０μＳ／ｃｍを超える一般式（１）で表される芳香族ジヒドロキシ化合物に関しては、後述の導電率試験後のスラリー液から分離（濾過）した一般式（１）で表される芳香族ジヒドロキシ化合物を乾燥したものについて再度同様に導電率試験を行い５．０μＳ／ｃｍ以下になったものを用いれば、良好な色相のポリカーボネート樹脂が得られる。 Furthermore, with respect to the aromatic dihydroxy compound represented by the general formula (1) having a dielectric constant exceeding 5.0 μS / cm, the general formula (1 ) is dried and subjected to the conductivity test in the same manner, and a polycarbonate resin with a good hue can be obtained by using the one with a conductivity of 5.0 μS/cm or less.
（ａ）原料モノマー
ポリカーボネート樹脂の製造には、ポリカーボネート樹脂のポリマー鎖の構成単位を形成するための原料モノマーが用いられる。本発明で使用される原料モノマーは、一般式（１）で表される芳香族ジヒドロキシ化合物の濃度が３０質量％であるメタノール溶液と、前記メタノール溶液に対し９質量倍の純水とを混合してなるスラリー溶液の導電率が、５．０μＳ／ｃｍ以下である芳香族ジヒドロキシ化合物を含む。
Ｒ１及びＲ２は、
好ましくは、水素原子、置換されていてもよく、分岐していてもよい炭素数１以上１０以下のアルキル基、又は、置換されていてもよい炭素数６以上１６以下のアリール基であり、
より好ましくは、水素原子、置換されていてもよく、分岐していてもよい炭素数１以上６以下のアルキル基、又は、置換されていてもよい炭素数６以上１２以下のアリール基であり、
特に好ましくは、水素原子、置換されていてもよく、分岐していてもよい炭素数１以上３以下のアルキル基、又は、置換されていてもよい炭素数６以上８以下のアリール基である。
Ｒ１及びＲ２の好ましい具体例として、水素原子、メチル基、イソプロピル基、フェニル基、ヒドロキシフェニル基が挙げられ、なかでも水素原子が好ましい。
なお、アルキル基またはアリール基に置換されていてもよい置換基としては、ハロゲン原子、水酸基等が挙げられる。
(a) Raw material monomer A raw material monomer for forming a structural unit of the polymer chain of the polycarbonate resin is used for the production of the polycarbonate resin. The raw material monomer used in the present invention is obtained by mixing a methanol solution in which the aromatic dihydroxy compound represented by the general formula (1) has a concentration of 30% by mass and pure water in an amount 9 times the mass of the methanol solution. The slurry solution containing the aromatic dihydroxy compound has a conductivity of 5.0 μS/cm or less.
R 1 and R 2 are
preferably a hydrogen atom, an optionally substituted or branched alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 16 carbon atoms,
more preferably a hydrogen atom, an optionally substituted or branched alkyl group having 1 to 6 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms,
Particularly preferred are a hydrogen atom, an optionally substituted or branched alkyl group having 1 to 3 carbon atoms, or an optionally substituted aryl group having 6 to 8 carbon atoms.
Preferred specific examples of R 1 and R 2 include a hydrogen atom, a methyl group, an isopropyl group, a phenyl group and a hydroxyphenyl group, with a hydrogen atom being particularly preferred.
In addition, a halogen atom, a hydroxyl group, etc. are mentioned as a substituent with which the alkyl group or the aryl group may be substituted.
一般式（１）において、ｍ及びｎは、各々独立に、０～４の整数を表す。ｍ及びｎは、好ましくは、０～２の整数であり、より好ましくは各々独立に０または１であり、最も好ましくは０である。 In general formula (1), m and n each independently represent an integer of 0-4. m and n are preferably integers from 0 to 2, more preferably each independently 0 or 1, and most preferably 0.
一般式（１）で表される芳香族ジヒドロキシ化合物の好ましい形態の例として、下記一般式（１－１）で表されるものが挙げられる。
上記一般式（１）で表される芳香族ジヒドロキシ化合物の具体例としては、ビス（４－ヒドロキシフェニル）エーテル［＝ＤＨＤＥ］、ビス（４－ヒドロキシ－３－メチルフェニル）エーテル、ビス（４－ヒドロキシ－３，５－ジメチルフェニル）エーテル、ビス（４－ヒドロキシ－３－ｔ-ブチルフェニル）エーテル、ビス（４－ヒドロキシ－３－フェニルフェニル）エーテル、ビス（４－ヒドロキシ－３－アリルフェニル）エーテル、ビス（４－ヒドロキシ－３－エチルフェニル）エーテル、ビス（４－ヒドロキシ－３－sec－ブチルフェニル）エーテル、ビス（４－ヒドロキシ－３－クミルフェニル）エーテルなどが例示される。
これらの中でも、特に、下記式（１－ａ）で示される、ビス（４－ヒドロキシフェニル）エーテルが好ましい。
上記一般式（１）で表される芳香族ジヒドロキシ化合物中、上記式（１－ａ）で表される芳香族ジヒドロキシ化合物が、８０ｍｏｌ％以上であることが好ましく、９０ｍｏｌ％以上であることがより好ましく、９５ｍｏｌ％以上１００ｍｏｌ％以下であることが更に好ましい。
Specific examples of the aromatic dihydroxy compound represented by the general formula (1) include bis(4-hydroxyphenyl) ether [=DHDE], bis(4-hydroxy-3-methylphenyl) ether, bis(4- Hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3-t-butylphenyl) ether, bis(4-hydroxy-3-phenylphenyl) ether, bis(4-hydroxy-3-allylphenyl) Ether, bis(4-hydroxy-3-ethylphenyl)ether, bis(4-hydroxy-3-sec-butylphenyl)ether, bis(4-hydroxy-3-cumylphenyl)ether and the like are exemplified.
Among these, bis(4-hydroxyphenyl) ether represented by the following formula (1-a) is particularly preferred.
In the aromatic dihydroxy compound represented by the general formula (1), the aromatic dihydroxy compound represented by the formula (1-a) is preferably 80 mol% or more, more preferably 90 mol% or more. Preferably, it is more preferably 95 mol % or more and 100 mol % or less.
（ｂ）その他の原料モノマー（その他の芳香族ジヒドロキシ化合物）
その他の原料モノマー（その他の芳香族ジヒドロキシ化合物）として、一般式（１）で表される芳香族ジヒドロキシ化合物と併用して、下記一般式（２）で表される芳香族ジヒドロキシ化合物を用いることが好ましい。
As other raw material monomers (other aromatic dihydroxy compounds), an aromatic dihydroxy compound represented by the following general formula (2) can be used in combination with the aromatic dihydroxy compound represented by the general formula (1). preferable.
一般式（２）で表される芳香族ジヒドロキシ化合物の具体的としては、４，４’－ビフェニルジオール、ビス（４－ヒドロキシフェニル）メタン、ビス（２－ヒドロキシフェニル）メタン、２，４’－ジヒドロキシジフェニルメタン、ビス（４－ヒドロキシフェニル）スルホン、２，４’－ジヒドロキシジフェニルスルホン、ビス（２－ヒドロキシフェニル）スルホン、ビス（４－ヒドロキシ-３-メチルフェニル）スルホン、ビス（４－ヒドロキシフェニル）スルホキシド、ビス（４－ヒドロキシフェニル）スルファイド、ビス（４－ヒドロキシフェニル）ケトン、１，１-ビス（４－ヒドロキシフェニル）エタン、１，１-ビス（４－ヒドロキシフェニル）－１－フェニルエタン、ビス（４－ヒドロキシフェニル）ジフェニルメタン、２，２-ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、１，１－ビス（４－ヒドロキシ－３－メチルフェニル）エタン、ビス（４－ヒドロキシ－３－メチルフェニル）メタン、２，２－ビス（４－ヒドロキシ－３－ｔ－ブチルフェニル）プロパン、２，２－ビス（４－ヒドロキシフェニル）ブタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、１，１－ビス（４－ヒドロキシ－３－メチルフェニル）シクロヘキサン、１，１－ビス（４－ヒドロキシフェニル）シクロウンデカン、１，１－ビス（４－ヒドロキシフェニル）シクロドデカン、２，２－ビス（４－ヒドロキシ－３－アリルフェニル）プロパン、３，３，５－トリメチル－１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、９，９－ビス（４－ヒドロキシ－３－エチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン、９，９－ビス（４－ヒドロキシフェニル）フルオレン、α，ω－ビス［３－（ｏ－ヒドロキシフェニル）プロピル］ポリジメチルジフェニルランダム共重合シロキサン、α，ω－ビス［３－（ｏ－ヒドロキシフェニル）プロピル］ポリジメチルシロキサン、４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスフェノール、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスフェノール、アダマンタン、２，２－ビス（４－ヒドロキシフェニル）ブタン、１，１－ビス（４－ヒドロキシフェニル）－２－エチルヘキサン、１，１－ビス（４－ヒドロキシフェニル）－２－メチルプロパン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、１，１－ビス（４－ヒドロキシフェニル）デカン、１，３－ビス（４－ヒドロキシフェニル）－５，７－ジメチルアダマンタン、２，２－ビス（４－ヒドロキシフェニル）ヘキサフルオロプロパンなどが例示される。これらは、２種類以上併用することも可能である。また、これらの中でも、特に１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、及び２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパンが好ましい。 Specific examples of aromatic dihydroxy compounds represented by general formula (2) include 4,4′-biphenyldiol, bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, 2,4′- Dihydroxydiphenylmethane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, Bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3 -methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane , 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis (4-hydroxyphenyl)cyclododecane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9 -bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,ω-bis[ 3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4′-[1,4-phenylenebis (1-methylethylidene)]bisphenol, 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol, adamantane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis (4-Hydroxyphenyl)-2-ethylhexane, 1,1-bis(4 -hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl )-5,7-dimethyladamantane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and the like. Two or more of these can be used in combination. Also among these, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, and 2,2-bis(4-hydroxy-3- Methylphenyl)propane is preferred.
本発明のポリカーボネート樹脂は、ホモポリマーであってもコポリマーであってもよい。例えば、一般式（１）で表される芳香族ジヒドロキシ化合物の使用量は、全芳香族ジヒドロキシ化合物中、１０～１００ｍｏｌ％であることが好ましく、より好ましくは２０～８０ｍｏｌ％、さらに好ましくは３０～７０ｍｏｌ％である。 The polycarbonate resins of the present invention may be homopolymers or copolymers. For example, the amount of the aromatic dihydroxy compound represented by the general formula (1) used is preferably 10 to 100 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 100 mol% of the total aromatic dihydroxy compound. 70 mol %.
一般式（２）で表される芳香族ジヒドロキシ化合物の使用量は、全芳香族ジヒドロキシ化合物中、０～９０ｍｏｌ％であることが好ましく、より好ましくは２０～８０ｍｏｌ％、さらに好ましくは３０～７０ｍｏｌ％である。 The amount of the aromatic dihydroxy compound represented by the general formula (2) used is preferably 0 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 30 to 70 mol% of the total aromatic dihydroxy compound. is.
（ｃ）その他の原料モノマー（芳香族ジヒドロキシ化合物以外）
ポリカーボネート樹脂を界面重縮合法により製造する場合、前述の芳香族ジヒドロキシ化合物以外の原料モノマーとして、炭酸エステル形成化合物、末端停止剤も用いられる。
(c) Other raw material monomers (other than aromatic dihydroxy compounds)
When a polycarbonate resin is produced by an interfacial polycondensation method, a carbonic acid ester-forming compound and a terminal terminator are also used as raw material monomers other than the above-mentioned aromatic dihydroxy compound.
炭酸エステル形成化合物は、芳香族ジヒドロキシ化合物に由来の構成単位を結合させるために用いられ、ポリカーボネート樹脂のポリマー鎖にカルボニル基（－Ｃ（＝Ｏ）－）を形成する。炭酸エステル形成化合物としては、例えばホスゲン、トリホスゲンが用いられ、好ましくはホスゲンが用いられる。 The carbonate-forming compound is used to bind structural units derived from the aromatic dihydroxy compound and forms a carbonyl group (--C(=O)--) on the polymer chain of the polycarbonate resin. As the carbonate-forming compound, for example, phosgene and triphosgene are used, and phosgene is preferably used.
末端停止剤は、原料モノマーの重合反応を停止させるために用いられ、ポリカーボネート樹脂のポリマー鎖の末端基を形成する。末端停止剤としては、１価フェノールが好適に用いられる。
末端停止剤としては、フェノール、ｐ－クレゾール、o－クレゾール、２，４－キシレノール、p－t－ブチルフェノール、o－アリルフェノール、ｐ－アリルフェノール、ｐ－ヒドロキシスチレン、ｐ－ヒドロキシ－α－メチルスチレン、ｐ－プロピルフェノール、ｐ－クミルフェノール、ｐ－フェニルフェノール、ｏ－フェニルフェノール、ｐ－トリフルオロメチルフェノール、ｐ－ノニルフェノール、ｐ－ドデシルフェノール、オイゲノール、アミルフェノール、ヘキシルフェノール、ヘプチルフェノール、オクチルフェノール、ノニルフェノール、デシルフェノール、ドデシルフェノール、ミリスチルフェノール、パルミチルフェノール、ステアリルフェノール、ベヘニルフェノール等のアルキルフェノール及びパラヒドロキシ安息香酸のメチルエステル、エチルエステル、プロピルエステル、ブチルエステル、アミルエステル、ヘキシルエステル、ヘプチルエステル等のパラヒドロキシ安息香酸アルキルエステルが挙げられる。また、上記１価フェノールのいずれかを２種類以上併用して使用することも可能である。
A terminal terminator is used to terminate the polymerization reaction of raw material monomers and forms the terminal groups of the polymer chains of the polycarbonate resin. Monohydric phenol is preferably used as the terminal terminator.
Terminal terminating agents include phenol, p-cresol, o-cresol, 2,4-xylenol, p-t-butylphenol, o-allylphenol, p-allylphenol, p-hydroxystyrene, p-hydroxy-α-methyl styrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, p-nonylphenol, p-dodecylphenol, eugenol, amylphenol, hexylphenol, heptylphenol, Alkylphenols such as octylphenol, nonylphenol, decylphenol, dodecylphenol, myristylphenol, palmitylphenol, stearylphenol and behenylphenol, and methyl, ethyl, propyl, butyl, amyl, hexyl and heptyl esters of parahydroxybenzoic acid. Examples include parahydroxybenzoic acid alkyl esters such as esters. It is also possible to use two or more of the above monohydric phenols in combination.
末端停止剤の使用量は、ポリカーボネート樹脂の目的とされる分子量等に応じて適宜定められるが、芳香族ジヒドロキシ化合物と末端停止剤との使用量のモル比の好ましい範囲は、１００：１～１０：１であり、さらに好ましくは５０：１～１５：１であり、より好ましくは４０：１～２０：１、例えば２５：１である。 The amount of the terminal terminator to be used is appropriately determined according to the target molecular weight of the polycarbonate resin, etc., and the preferable range of the molar ratio of the amount of the aromatic dihydroxy compound and the terminal terminator to be used is 100:1 to 10. :1, more preferably 50:1 to 15:1, more preferably 40:1 to 20:1, for example 25:1.
また、ポリカーボネート樹脂をエステル交換法により製造することも可能である。エステル交換法においては、芳香族ジヒドロキシ化合物以外の成分として、炭酸ジエステル、エステル交換触媒等も用いられる。 Moreover, it is also possible to manufacture a polycarbonate resin by the transesterification method. In the transesterification method, carbonic acid diesters, transesterification catalysts, etc. are also used as components other than the aromatic dihydroxy compound.
炭酸ジエステルとしては、ジフェニルカーボネート、ジトリールカーボネート、ビス（クロロフェニル）カーボネート、ｍ－クレジルカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジシクロヘキシルカーボネート等が挙げられる。これらの中でも特にジフェニルカーボネートが反応性と純度の観点から好ましい。炭酸ジエステルは、芳香族ジヒドロキシ化合物に対し０．７０～１．２０モルの比率で用いられ、特に好ましくは、１．００～１．２０モルの比率で用いられる。このモル比率を調整することにより、ポリカーボネート樹脂の分子量が好ましい範囲に制御される。 Carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Among these, diphenyl carbonate is particularly preferred from the viewpoint of reactivity and purity. Carbonic acid diester is used in a ratio of 0.70 to 1.20 mol, particularly preferably in a ratio of 1.00 to 1.20 mol, relative to the aromatic dihydroxy compound. By adjusting this molar ratio, the molecular weight of the polycarbonate resin is controlled within a preferred range.
エステル交換触媒としては、アルカリ金属化合物、アルカリ土類金属化合物、および含窒素化合物等が挙げられる。
アルカリ金属化合物としては、例えばアルカリ金属の有機酸塩、無機塩、酸化物、水酸化物、水素化物又はアルコキシド等が挙げられる。触媒効果、価格、流通量、樹脂の色相への影響などの観点から、炭酸ナトリウム、及び炭酸水素ナトリウムが好ましい。
アルカリ土類金属化合物としては、例えばアルカリ土類金属化合物の有機酸塩、無機塩、酸化物、水酸化物、水素化物又はアルコキシド等が挙げられる。
含窒素化合物としては、例えば４級アンモニウムヒドロキシドおよびそれらの塩、アミン類等が挙げられる。
Examples of transesterification catalysts include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like.
Examples of alkali metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals. Sodium carbonate and sodium bicarbonate are preferred from the viewpoint of catalytic effect, price, distribution volume, influence on color of resin, and the like.
Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metal compounds.
Nitrogen-containing compounds include, for example, quaternary ammonium hydroxides and their salts, and amines.
エステル交換触媒としては、亜鉛、スズ、ジルコニウム、鉛の塩が好ましく用いられ、これらは単独もしくは組み合わせて用いることができる。また、上述したアルカリ金属化合物やアルカリ土類金属化合物と組み合わせて用いてもよい。
エステル交換触媒として、具体的には、炭酸ナトリウム、炭酸水素ナトリウム、炭酸セシウム、酢酸亜鉛、安息香酸亜鉛、２－エチルヘキサン酸亜鉛、塩化スズ（ＩＩ）、塩化スズ（ＩＶ）、酢酸スズ（ＩＩ）、酢酸スズ（ＩＶ）、ジブチルスズジラウレート、ジブチルスズオキサイド、ジブチルスズジメトキシド、ジルコニウムアセチルアセトナート、オキシ酢酸ジルコニウム、ジルコニウムテトラブトキシド、酢酸鉛（ＩＩ）、酢酸鉛（ＩＶ）、酢酸ジルコニウム、チタンテトラブトキサイド等が用いられる。なかでも、チタンテトラブトキサイド、炭酸ナトリウム、炭酸水素ナトリウム、及び炭酸セシウムが好ましく、炭酸水素ナトリウム及び炭酸セシウムがより好ましい。
Salts of zinc, tin, zirconium and lead are preferably used as transesterification catalysts, and these can be used alone or in combination. It may also be used in combination with the alkali metal compound or alkaline earth metal compound described above.
Specific examples of transesterification catalysts include sodium carbonate, sodium hydrogen carbonate, cesium carbonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin acetate (II ), tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV), zirconium acetate, titanium tetrabutoxide etc. are used. Among them, titanium tetrabutoxide, sodium carbonate, sodium hydrogencarbonate, and cesium carbonate are preferred, and sodium hydrogencarbonate and cesium carbonate are more preferred.
エステル交換触媒の合計使用量は、全ジヒドロキシ化合物の合計１モルに対して、１×１０－９～１×１０－３モルの比率で、好ましくは１×１０－７～１×１０－４モルの比率で用いられる。 The total amount of transesterification catalyst used is a ratio of 1×10 −9 to 1×10 −3 mol, preferably 1×10 −7 to 1×10 −4 mol, per 1 mol of all dihydroxy compounds. used in a ratio of
（ｄ）ポリカーボネート樹脂の製造方法
本発明のポリカーボネート樹脂の製造方法は、上述の一般式（１）で表される芳香族ジヒドロキシ化合物を重合させる重合工程を含んでおり、製造されるポリカーボネート樹脂は、一般式（１）で表される芳香族ジヒドロキシ化合物に由来する構成単位を含む。
本発明の重合工程においては、前記一般式（１）で表される芳香族ジヒドロキシ化合物の濃度が３０質量％であるメタノール溶液と、前記メタノール溶液に対し９質量倍の純水とを混合してなるスラリー溶液の導電率が、５．０μＳ／ｃｍ以下である原料物質を用いる。
(d) Method for producing polycarbonate resin The method for producing a polycarbonate resin of the present invention includes a polymerization step of polymerizing the aromatic dihydroxy compound represented by the above general formula (1), and the produced polycarbonate resin is It contains a structural unit derived from the aromatic dihydroxy compound represented by general formula (1).
In the polymerization step of the present invention, a methanol solution having a concentration of 30% by mass of the aromatic dihydroxy compound represented by the general formula (1) and pure water of 9 times the mass of the methanol solution are mixed. A raw material having a slurry solution conductivity of 5.0 μS/cm or less is used.
本発明のポリカーボネート樹脂は、一般式（１）で表される芳香族ジヒドロキシ化合物と炭酸エステル形成化合物を含む原料モノマーを反応させることによって、製造することができるものであり、ビスフェノールＡから誘導されるポリカーボネート樹脂を製造する際に用いられている公知の方法、例えば芳香族ジヒドロキシ化合物とホスゲンとの直接反応（ホスゲン法）、あるいは芳香族ジヒドロキシ化合物とビスアリールカーボネートとのエステル交換反応（エステル交換法）などの方法を採用することができる。 The polycarbonate resin of the present invention can be produced by reacting an aromatic dihydroxy compound represented by the general formula (1) with a raw material monomer containing a carbonate-forming compound, and is derived from bisphenol A. Known methods used for producing polycarbonate resins, such as direct reaction of aromatic dihydroxy compounds and phosgene (phosgene method), or transesterification reactions of aromatic dihydroxy compounds and bisaryl carbonates (transesterification method) etc. can be adopted.
ホスゲン法においては、通常、酸結合剤および溶媒の存在下において、前記一般式（１）で表される芳香族ジヒドロキシ化合物、或いは前記一般式（１）で表される芳香族ジヒドロキシ化合物及び前記一般式（２）で表される芳香族ジヒドロキシ化合物を、ホスゲンと反応させる。酸結合剤としては、例えばピリジンや、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物などが用いられ、また溶媒としては、例えば塩化メチレン、クロロホルムなどが用いられる。さらに、縮重合反応を促進するために、トリエチルアミンのような第三級アミンまたはベンジルトリエチルアンモニウムクロライド等の第四級アンモニウム塩などの触媒を、また重合度調節には、フェノール、ｐ－ｔ－ブチルフェノール、ｐ－クミルフェノール、ｐ－ヒドロキシ安息香酸ｎ－ブチルなどのアルキルエステル置換フェノール、長鎖アルキル置換フェノール等一官能基化合物を分子量調節剤として加えることが好ましい。また、所望に応じ亜硫酸ナトリウム、ハイドロサルファイトなどの酸化防止剤や、フロログルシン、イサチンビスフェノールなど分岐化剤を小量添加してもよい。反応は通常０～１５０℃、好ましくは５～４０℃の範囲とするのが適当である。反応時間は反応温度によって左右されるが、通常０．５分～１０時間、好ましくは１分～２時間である。また、反応中は、反応系のｐＨを１０以上に保持することが望ましい。 In the phosgene method, usually in the presence of an acid binder and a solvent, the aromatic dihydroxy compound represented by the general formula (1), or the aromatic dihydroxy compound represented by the general formula (1) and the general An aromatic dihydroxy compound represented by formula (2) is reacted with phosgene. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride and chloroform. Furthermore, catalysts such as tertiary amines such as triethylamine or quaternary ammonium salts such as benzyltriethylammonium chloride are added to promote the polycondensation reaction, and phenol and pt-butylphenol are used to control the degree of polymerization. , p-cumylphenol, alkyl ester-substituted phenols such as n-butyl p-hydroxybenzoate, and monofunctional compounds such as long-chain alkyl-substituted phenols are preferably added as molecular weight modifiers. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction temperature is generally 0 to 150°C, preferably 5 to 40°C. Although the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. Moreover, it is desirable to keep the pH of the reaction system at 10 or higher during the reaction.
一方、エステル交換法においては、前記一般式（１）で表される芳香族ジヒドロキシ化合物とビスアリールカーボネートとを混合し、減圧下で高温において反応させる。ビスアリールカーボネートの例としては、ジフェニルカーボネート、ジ－ｐ－トリルカーボネート、フェニル－ｐ－トリルカーボネート、ジ－ｐ－クロロフェニルカーボネート、ジナフチルカーボネートなどが挙げられる。これらの化合物は２種類以上併用して使用することも可能である。反応は通常１５０～３５０℃、好ましくは２００～３００℃の範囲の温度において行われ、また減圧度は最終で好ましくは１mmHg以下にして、エステル交換反応により生成した、該ビスアリールカーボネートから由来するフェノール類を系外へ留去させる。反応時間は反応温度や減圧度などによって左右されるが、通常１～２４時間程度である。反応は窒素やアルゴンなどの不活性ガス雰囲気下で行うことが好ましく、また、所望に応じ、分子量調節剤、酸化防止剤や分岐化剤を添加して反応を行ってもよい。 On the other hand, in the transesterification method, the aromatic dihydroxy compound represented by the general formula (1) and the bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. Examples of bisaryl carbonates include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, and the like. Two or more of these compounds can be used in combination. The reaction is usually carried out at a temperature in the range of 150 to 350° C., preferably 200 to 300° C., and the final degree of vacuum is preferably 1 mmHg or less. Distill off the residue out of the system. The reaction time depends on the reaction temperature, degree of pressure reduction, etc., but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and if desired, the reaction may be carried out with the addition of a molecular weight modifier, antioxidant or branching agent.
本発明のポリカーボネート樹脂においては、ＪＩＳ Ｋ７３６７－１に沿って後述する方法で測定される極限粘度の値が、０．２～２．０ｄｌ／ｇであることが好ましく、より好ましくは、０．３～１．５ｄｌ／ｇであり、さらに好ましくは、０．４～１．０ｄｌ／ｇである。 In the polycarbonate resin of the present invention, the value of the intrinsic viscosity measured by the method described later in accordance with JIS K7367-1 is preferably 0.2 to 2.0 dl/g, more preferably 0.3. ~1.5 dl/g, more preferably 0.4 to 1.0 dl/g.
本発明のポリカーボネート樹脂は、ポリカーボネート樹脂４ｇが２５ｍｌのメチレンクロライドに溶解してなる溶液のハーゼン単位色数（ＡＰＨＡ）が、３０以下であることが好ましく、５～２７であることがより好ましく、１０～２５であることが特に好ましい。ＡＰＨＡの測定方法は、後述する実施例に記載の通り、ＪＩＳ Ｋ００７１－１に沿って行うことができる。 In the polycarbonate resin of the present invention, the Hazen unit color number (APHA) of a solution obtained by dissolving 4 g of the polycarbonate resin in 25 ml of methylene chloride is preferably 30 or less, more preferably 5 to 27, and 10 ~25 is particularly preferred. APHA can be measured according to JIS K0071-1, as described in Examples below.
以下に本発明の実施例を比較例と共に示し、発明の内容を詳細に示すが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Examples of the present invention are shown below together with comparative examples to describe the content of the invention in detail, but the present invention is not limited to these examples.
＜ＡＰＨＡ＞
４ｇのポリカ－ボネート樹脂に２５ｍｌのメチレンクロライドを加え溶解し、溶液のハーゼン単位色数（ＡＰＨＡ）をＪＩＳ Ｋ００７１－１の目視による測定で求めた。
<APHA>
25 ml of methylene chloride was added to 4 g of polycarbonate resin and dissolved, and the Hazen unit color number (APHA) of the solution was determined by visual measurement according to JIS K0071-1.
＜ＤＨＤＥ導電率＞
３ｇのＤＨＤＥを７ｇの市販特級メタノールに溶解し、マグネットスターラーで撹拌しながら９０ｇの純水を加え、ＤＨＤＥを析出させたスラリー液の導電率を導電率計（ハンナインスツルメンツジャパン株式会社製ＨＩ８7３３Ｎ）で測定した。ＤＨＤＥを用いないブランクの導電率は１．０μＳ／ｃｍであった。
<DHDE conductivity>
Dissolve 3 g of DHDE in 7 g of commercially available special grade methanol, add 90 g of pure water while stirring with a magnetic stirrer, and precipitate DHDE. It was measured. The conductivity of the blank without DHDE was 1.0 μS/cm.
＜極限粘度＞
得られたポリカーボネート樹脂の極限粘度［η］デシリットル／グラムは以下のように求めた。ＪＩＳ Ｋ７３６７－１に沿って、０．５グラム／デシリットルのポリカーボネート樹脂の塩化メチレン溶液について、ウベローデ毛管粘度計によって２５℃の温度で落液時間を測定し、ハギンズ定数０．４５を用いて、極限粘度を求めた。
<Intrinsic Viscosity>
The intrinsic viscosity [η] deciliter/gram of the obtained polycarbonate resin was determined as follows. According to JIS K7367-1, for a methylene chloride solution of polycarbonate resin of 0.5 g/deciliter, the liquid drop time is measured at a temperature of 25 ° C. with an Ubbelohde capillary viscometer, and using a Huggins constant of 0.45, the limit Viscosity was determined.
＜ＤＨＤＥ純度＞
溶離液（メタノール/超純水＝７５％/２５％）、ＯＤＳカラム（直径６ｍｍ×１５０ｍｍ）、検出器ＵＶ２８０ｎｍ、ＤＨＤＥ試料濃度１００ｐｐｍ（溶離液と同じ組成で注入量２０μＬ）、カラム温度３０℃、流速１ｍｌ/分の条件で、約３．５分のピークをメインピークとし、液体クロマトグラフィー（日本ウォーターズ株式会社製AllianceHPLC）を用いた定量値より純度を算出した。
<DHDE Purity>
Eluent (methanol/ultrapure water = 75%/25%), ODS column (diameter 6 mm x 150 mm), detector UV 280 nm, DHDE sample concentration 100 ppm (injection volume 20 μL with the same composition as the eluent), column temperature 30°C, The peak at about 3.5 minutes was defined as the main peak under the conditions of a flow rate of 1 ml/minute, and the purity was calculated from the quantitative value using liquid chromatography (Alliance HPLC manufactured by Nippon Waters Co., Ltd.).
＜実施例と比較例に用いたＤＨＤＥの種類＞
市販されている各種ＤＨＤＥを入手し、ＤＨＤＥ純度および導電率の測定を行った。結果を表１に示す。
Various commercially available DHDEs were obtained, and DHDE purity and conductivity were measured. Table 1 shows the results.
実施例１
Ｄ－１を３１．５ｇ（０．１５６ｍｏｌ）と１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン（以下、「ＢＰＺ」と略称：本州化学工業株式会社製）４２．０ｇ（０．１５７ｍｏｌ）とハイドロサルファイト０．３ｇを５ｗ／ｗ％の水酸化ナトリウム水溶液８００ｍｌに溶解した。
これにメチレンクロライド４５０ｍｌを加えて撹拌しつつ、１５～２０℃に保ちながら、ついでホスゲン４３ｇを４０分で吹き込んだ。
ホスゲン吹き込み終了後、分子量調節剤としてｐ－ヒドロキシ安息香酸ｎ－ブチル（以下、「ＰＯＢＢ」と略称：株式会社エーピーアイコーポレーション製）１．５５ｇと９ｗ／ｗ％の水酸化ナトリウム水溶液１００ｍｌを加え激しく撹拌して、反応液を乳化させ、乳化後、０．６ｍｌのトリエチルアミンを加え、１９～２５℃にて約４０分撹拌し、重合させた。
重合終了後、反応液を水相と有機相に分離し、有機相をリン酸で中和し、先液（水相）の導電率が１０μＳ／ｃｍ以下になるまで水洗を繰り返した。得られた重合体溶液を、６０℃に保った温水に滴下し、溶媒を蒸発除去して白色粉末状沈殿物を得た。得られた沈殿物を濾過し、１２０℃、１８時間乾燥して、重合体粉末を得た。
この重合体の塩化メチレンを溶媒とする濃度０．５ｇ／ｄｌの溶液の２０℃における極限粘度は０．６３ｄｌ／ｇであった。得られた重合体を赤外線吸収スペクトルにより分析した結果、１７７０ｃｍ－１付近の位置にカルボニル基による吸収、１２４０ｃｍ－１付近の位置にエーテル結合による吸収が認められ、カーボネート結合を有するポリカーボネート樹脂（以下「ＰＣ－１」と略称）であることが確認された。
得られたＰＣ－１を用いて、ＡＰＨＡ測定を実施した。
Example 1
31.5 g (0.156 mol) of D-1 and 42.0 g (0.157 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as “BPZ”: manufactured by Honshu Chemical Industry Co., Ltd.) 0.3 g of hydrosulfite was dissolved in 800 ml of 5 w/w % sodium hydroxide aqueous solution.
To this, 450 ml of methylene chloride was added, and while the mixture was kept at 15 to 20° C. while stirring, 43 g of phosgene was blown thereinto over 40 minutes.
After the completion of the phosgene blowing, 1.55 g of n-butyl p-hydroxybenzoate (hereinafter abbreviated as "POBB"; manufactured by API Corporation) as a molecular weight modifier and 100 ml of a 9 w/w% sodium hydroxide aqueous solution were vigorously added. The reaction solution was emulsified by stirring, and after emulsification, 0.6 ml of triethylamine was added and stirred at 19 to 25° C. for about 40 minutes to polymerize.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the electrical conductivity of the previous solution (aqueous phase) became 10 μS/cm or less. The resulting polymer solution was added dropwise to hot water maintained at 60° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The resulting precipitate was filtered and dried at 120° C. for 18 hours to obtain polymer powder.
The intrinsic viscosity of a solution of this polymer in methylene chloride at a concentration of 0.5 g/dl at 20° C. was 0.63 dl/g. As a result of analyzing the obtained polymer by infrared absorption spectrum, an absorption due to a carbonyl group at a position near 1770 cm -1 and an absorption due to an ether bond at a position near 1240 cm -1 were observed. A polycarbonate resin having a carbonate bond (hereinafter " abbreviated as "PC-1").
Using the obtained PC-1, APHA measurement was carried out.
実施例２
Ｄ－１の代わりにＤ－２（ＤＨＤＥ導電率２．７μＳ／ｃｍ）に変更した以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．６４ｄｌ／ｇ、以下「ＰＣ－２」と略称）を得た。得られたＰＣ－２を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Example 2
Polymerization was carried out in the same manner as in Example 1 except that D-1 was changed to D-2 (DHDE conductivity 2.7 μS / cm), polycarbonate resin (intrinsic viscosity: 0.64 dl / g, hereinafter “PC- 2”) was obtained. Using the obtained PC-2, APHA measurement was carried out in the same manner as in Example 1.
実施例３
Ｄ－１の代わりに、Ｄ－３（ＤＨＤＥ導電率１．５μＳ／ｃｍ）に変更した以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．６４ｄｌ／ｇ、以下「ＰＣ－３」と略称）を得た。得られたＰＣ－３を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Example 3
Polymerization was carried out in the same manner as in Example 1 except that D-3 (DHDE conductivity 1.5 μS / cm) was used instead of D-1, and a polycarbonate resin (intrinsic viscosity: 0.64 dl / g, hereinafter “PC -3”) was obtained. APHA measurement was carried out in the same manner as in Example 1 using the obtained PC-3.
実施例４
Ｄ－１の代わりにＤ－４（ＤＨＤＥ導電率４．６μＳ／ｃｍ）に変更し、ＰＯＢＢを０．６９３ｇに変更した以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：１．００ｄｌ／ｇ、以下「ＰＣ－４」と略称）を得た。得られたＰＣ－４を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Example 4
Polymerization was carried out in the same manner as in Example 1 except that D-1 was changed to D-4 (DHDE conductivity 4.6 μS / cm) and POBB was changed to 0.693 g, polycarbonate resin (intrinsic viscosity: 1 .00 dl/g, hereinafter abbreviated as "PC-4"). Using the obtained PC-4, APHA measurement was carried out in the same manner as in Example 1.
実施例５
Ｄ－１を１８．２ｇ（０．０９０ｍｏｌ）、ＢＰＺを３６．４ｇ（０．１３６ｍｏｌ）に変更し、さらに２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン（以下、「ＭＩＢＫ」と略称、本州化学工業株式会社製）６．２ｇ（０．０２３ｍｏｌ）とハイドロサルファイト０．３ｇを３．９ｗ／ｗ％の水酸化ナトリウム水溶液８４０ｍｌに溶解した。
これにメチレンクロライド５４０ｍｌを加えて撹拌しつつ、１５～２０℃に保ちながら、ついでホスゲン３５ｇを約３０分で吹き込んだ。
ホスゲン吹き込み終了後、分子量調節剤としてｐ－ｔ－ブチルフェノール（以下、「ＰＴＢＰ」と略称：ＤＩＣ株式会社製）０．４２ｇと９ｗ／ｗ％の水酸化ナトリウム水溶液１４０ｍｌを加え激しく撹拌して、反応液を乳化させ、乳化後、０．６ｍｌのトリエチルアミンを加え、１９～２５℃にて約４０分撹拌し、重合させた。
以下、実施例１と同様に精製、固形化、乾燥を行い、ポリカーボネート樹脂（極限粘度：０．９８ｄｌ／ｇ、以下「ＰＣ－５」と略称）を得た。得られたＰＣ－５を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Example 5
D-1 was changed to 18.2 g (0.090 mol), BPZ was changed to 36.4 g (0.136 mol), and 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter, “MIBK” abbreviated as Honshu Chemical Industry Co., Ltd.) and 0.3 g of hydrosulfite were dissolved in 840 ml of a 3.9 w/w % sodium hydroxide aqueous solution.
To this, 540 ml of methylene chloride was added, and while the mixture was being stirred and maintained at 15 to 20° C., 35 g of phosgene was blown thereinto over about 30 minutes.
After the completion of the phosgene blowing, 0.42 g of pt-butylphenol (hereinafter abbreviated as "PTBP": manufactured by DIC Corporation) as a molecular weight modifier and 140 ml of a 9 w/w% sodium hydroxide aqueous solution were added and vigorously stirred to react. The liquid was emulsified, and after emulsification, 0.6 ml of triethylamine was added, and the mixture was stirred at 19 to 25° C. for about 40 minutes to polymerize.
Thereafter, purification, solidification and drying were carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity: 0.98 dl/g, hereinafter abbreviated as "PC-5"). Using the obtained PC-5, APHA measurement was carried out in the same manner as in Example 1.
実施例６
Ｄ－１を２７ｇ（０．１３４ｍｏｌ）、ＢＰＺの代わりに２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン（以下、「ＢＰＣ」と略称、本州化学工業株式会社製）６３．０ｇ（０．２４６ｍｏｌ）に変更し、さらにトリエチルベンジルアンモニウムクロリド０．１０ｇとハイドロサルファイト０．３ｇを６．６ｗ／ｗ％の水酸化ナトリウム水溶液７５０ｍｌに溶解した。
これにメチレンクロライド３６０ｍｌを加えて撹拌しつつ、１５～２０℃に保ちながら、ついでホスゲン５４ｇを約４０分で吹き込んだ。
ホスゲン吹き込み終了後、分子量調節剤としてｐ－ｔ－ブチルフェノール（以下、「ＰＴＢＰ」と略称：ＤＩＣ株式会社製）０．７６ｇと９ｗ／ｗ％の水酸化ナトリウム水溶液１００ｍｌを加え激しく撹拌して、反応液を乳化させ、乳化後、０．６ｍｌのトリエチルアミンを加え、１７～２７℃にて約４０分撹拌し、重合させた。
以下、実施例１と同様に精製、固形化、乾燥を行い、ポリカーボネート樹脂（極限粘度：１．００ｄｌ／ｇ、以下「ＰＣ－６」と略称）を得た。得られたＰＣ－６を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Example 6
27 g (0.134 mol) of D-1, 63.0 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as "BPC", manufactured by Honshu Chemical Industry Co., Ltd.) instead of BPZ (0.246 mol), and 0.10 g of triethylbenzylammonium chloride and 0.3 g of hydrosulfite were dissolved in 750 ml of a 6.6 w/w % sodium hydroxide aqueous solution.
To this, 360 ml of methylene chloride was added, and while the mixture was being stirred and maintained at 15 to 20° C., 54 g of phosgene was blown thereinto over about 40 minutes.
After the completion of the phosgene blowing, 0.76 g of pt-butylphenol (hereinafter abbreviated as "PTBP": manufactured by DIC Corporation) as a molecular weight modifier and 100 ml of a 9 w/w% sodium hydroxide aqueous solution were added and vigorously stirred to react. The liquid was emulsified, and after emulsification, 0.6 ml of triethylamine was added and stirred at 17 to 27° C. for about 40 minutes to polymerize.
Thereafter, purification, solidification and drying were carried out in the same manner as in Example 1 to obtain a polycarbonate resin (intrinsic viscosity: 1.00 dl/g, hereinafter abbreviated as "PC-6"). APHA measurement was performed in the same manner as in Example 1 using the obtained PC-6.
比較例１
Ｄ－１の代わりＤ－５を用いた以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．６３ｄｌ／ｇ、以下「ＰＣ－７」と略称）を得た。得られたＰＣ－７を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 1
Polymerization was carried out in the same manner as in Example 1 except that D-5 was used instead of D-1 to obtain a polycarbonate resin (intrinsic viscosity: 0.63 dl/g, hereinafter abbreviated as "PC-7"). APHA measurement was performed in the same manner as in Example 1 using the obtained PC-7.
比較例２
Ｄ－１の代わりにＤ－６を用いた以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．６４ｄｌ／ｇ、以下「ＰＣ－８」と略称）を得た。得られたＰＣ－８を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 2
Polymerization was carried out in the same manner as in Example 1 except that D-6 was used instead of D-1 to obtain a polycarbonate resin (intrinsic viscosity: 0.64 dl/g, hereinafter abbreviated as "PC-8"). Using the obtained PC-8, APHA measurement was carried out in the same manner as in Example 1.
比較例３
Ｄ－１の代わりにＤ－７を用いた以外は実施例１と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．６３ｄｌ／ｇ、以下「ＰＣ－９」と略称）を得た。得られたＰＣ－９を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 3
Polymerization was carried out in the same manner as in Example 1 except that D-7 was used instead of D-1 to obtain a polycarbonate resin (intrinsic viscosity: 0.63 dl/g, hereinafter abbreviated as "PC-9"). APHA measurement was carried out in the same manner as in Example 1 using the obtained PC-9.
比較例４
Ｄ－４の代わりにＤ－５を用いた以外は実施例４と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．９９ｄｌ／ｇ、以下「ＰＣ－１０」と略称）を得た。得られたＰＣ－１０を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 4
Polymerization was carried out in the same manner as in Example 4 except that D-5 was used instead of D-4 to obtain a polycarbonate resin (intrinsic viscosity: 0.99 dl/g, hereinafter abbreviated as "PC-10"). APHA measurement was performed in the same manner as in Example 1 using the obtained PC-10.
比較例５
Ｄ－１の代わりにＤ－８を用いた以外は実施例５と同様に重合を行い、ポリカーボネート樹脂（極限粘度：０．９９ｄｌ／ｇ、以下「ＰＣ－１１」と略称）を得た。得られたＰＣ－１１を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 5
Polymerization was carried out in the same manner as in Example 5 except that D-8 was used instead of D-1 to obtain a polycarbonate resin (intrinsic viscosity: 0.99 dl/g, hereinafter abbreviated as "PC-11"). Using the obtained PC-11, APHA measurement was carried out in the same manner as in Example 1.
比較例６
Ｄ－１の代わりにＤ－５を用いた以外は実施例６と同様に重合を行い、ポリカーボネート樹脂（極限粘度：１．００ｄｌ／ｇ、以下「ＰＣ－１２」と略称）を得た。得られたＰＣ－１２を用いて、実施例１と同様にＡＰＨＡ測定を実施した。
Comparative example 6
Polymerization was carried out in the same manner as in Example 6 except that D-5 was used instead of D-1 to obtain a polycarbonate resin (intrinsic viscosity: 1.00 dl/g, hereinafter abbreviated as "PC-12"). Using the obtained PC-12, APHA measurement was carried out in the same manner as in Example 1.
実施例および比較例で得られたポリカーボネート樹脂の極限粘度及びＡＰＨＡの測定結果を表２に示した。 Table 2 shows the measurement results of the intrinsic viscosity and APHA of the polycarbonate resins obtained in Examples and Comparative Examples.
本発明の製造方法を用いると、得られたポリカーボネート樹脂は、色合わせが重要な印刷インキ用バインダー樹脂や光学レンズなどの用途に応用することが可能である。 Using the production method of the present invention, the polycarbonate resin obtained can be applied to applications such as binder resins for printing inks and optical lenses in which color matching is important.
Claims (5)
前記一般式（１）で表される芳香族ジヒドロキシ化合物の濃度が３０質量％であるメタノール溶液と、前記メタノール溶液に対し９質量倍の純水とを混合してなるスラリー溶液の導電率が、５．０μＳ／ｃｍ以下である原料物質を用いて、前記一般式（１）で表される芳香族ジヒドロキシ化合物を重合する工程を含む、前記ポリカーボネート樹脂の製造方法。
Ｒ１及びＲ２は、各々独立に、水素原子、ハロゲン原子、置換されていてもよく、分岐していてもよい炭素数１以上２０以下のアルキル基、又は、置換されていてもよい炭素数６以上３０以下のアリール基を表し、
ｍ及びｎは、各々独立に、０～４の整数を表す。） A method for producing a polycarbonate resin containing structural units derived from an aromatic dihydroxy compound represented by the following general formula (1),
The electrical conductivity of a slurry solution obtained by mixing a methanol solution in which the concentration of the aromatic dihydroxy compound represented by the general formula (1) is 30% by mass and pure water of 9 times the mass of the methanol solution is A method for producing the polycarbonate resin, comprising the step of polymerizing the aromatic dihydroxy compound represented by the general formula (1) using a raw material having a concentration of 5.0 μS/cm or less.
R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an optionally substituted or branched alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number represents an aryl group of 6 or more and 30 or less,
m and n each independently represent an integer of 0 to 4; )
Ｒ１、Ｒ２、ｍ及びｎは、一般式（１）とそれぞれ同じである。） The production method according to claim 1, wherein the aromatic dihydroxy compound represented by the general formula (1) is represented by the following general formula (1-1).
R 1 , R 2 , m and n are the same as in general formula (1). )
In the polymerization step, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, and 2,2-bis(4-hydroxy-3-methylphenyl ) The production method according to any one of claims 1 to 4, wherein at least one selected from the group consisting of propane is further used as a raw material monomer.
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