JP5319327B2 - Method for producing carbonyl chloride - Google Patents
Method for producing carbonyl chloride Download PDFInfo
- Publication number
- JP5319327B2 JP5319327B2 JP2009043842A JP2009043842A JP5319327B2 JP 5319327 B2 JP5319327 B2 JP 5319327B2 JP 2009043842 A JP2009043842 A JP 2009043842A JP 2009043842 A JP2009043842 A JP 2009043842A JP 5319327 B2 JP5319327 B2 JP 5319327B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonyl chloride
- ppm
- content
- activated carbon
- polycarbonate resin
- 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.)
- Expired - Fee Related
Links
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 158
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000011575 calcium Substances 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000011591 potassium Substances 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 15
- NHYCGSASNAIGLD-UHFFFAOYSA-N chlorine monoxide Inorganic materials Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 229920005668 polycarbonate resin Polymers 0.000 abstract description 79
- 239000004431 polycarbonate resin Substances 0.000 abstract description 79
- 238000000465 moulding Methods 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 230000007797 corrosion Effects 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007774 longterm Effects 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000000034 method Methods 0.000 description 56
- 229910052801 chlorine Inorganic materials 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 29
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 28
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 28
- 229910052794 bromium Inorganic materials 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 235000013162 Cocos nucifera Nutrition 0.000 description 14
- 244000060011 Cocos nucifera Species 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 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
- 150000003464 sulfur compounds Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 (4-hydroxy) Phenyl Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 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
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- OREKREJVUNVFJP-UHFFFAOYSA-N 2-triacontylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O OREKREJVUNVFJP-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 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 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
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-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
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-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
- UJCYBTZHUJWCMB-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-4-propan-2-ylcyclohexyl]phenol Chemical compound C1CC(C(C)C)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UJCYBTZHUJWCMB-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
- 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 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- HCVANKFEUQUUGJ-UHFFFAOYSA-N C(=O)(Cl)Cl.[C] Chemical compound C(=O)(Cl)Cl.[C] HCVANKFEUQUUGJ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OQQZHTKTPNVFPO-UHFFFAOYSA-N ClCl.[C] Chemical compound ClCl.[C] OQQZHTKTPNVFPO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100040160 Rabankyrin-5 Human genes 0.000 description 1
- 101710086049 Rabankyrin-5 Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 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
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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Images
Abstract
Description
本発明は、塩化カルボニル生成反応触媒に特定のアルカリ（土類）金属含量の少ない活性炭を用い、さらに活性炭触媒の比表面積を適正に調整することにより、長期間にわたり、四塩化炭素含有量の低減された高純度の塩化カルボニルを製造する方法を提供する。さらに、この塩化カルボニルを原料にして、全塩素含有量、全臭素含有量及び四塩化炭素含有量の少ない、熱安定性、色相に優れたポリカーボネート樹脂の製造方法に関するものである。 The present invention reduces the carbon tetrachloride content over a long period of time by using activated carbon with a low specific alkali (earth) metal content as the carbonyl chloride production reaction catalyst and adjusting the specific surface area of the activated carbon catalyst appropriately. A method for producing a high purity carbonyl chloride is provided. Further, the present invention relates to a method for producing a polycarbonate resin having excellent thermal stability and hue, using this carbonyl chloride as a raw material and having a low total chlorine content, a total bromine content and a carbon tetrachloride content.
従来から、ポリカーボネート樹脂は光学的特性、機械的特性、電気的特性等各種特性に優れているため、食品分野、マルチメディア記録媒体等の光学分野、シリコンウエハー及びマルチメディア記録媒体等の収納容器分野、電気及び自動車分野等各種分野に幅広く使用されている。 Conventionally, polycarbonate resin is excellent in various characteristics such as optical characteristics, mechanical characteristics, electrical characteristics, etc., so the fields of food, optical fields such as multimedia recording media, and storage container fields such as silicon wafers and multimedia recording media. Widely used in various fields such as electric and automobile fields.
このポリカーボネート樹脂は一般的に塩化カルボニルを原料として製造されるが、この塩化カルボニル中に含まれる副生成物、不純物がポリカーボネート樹脂の品質に影響することはよく知られている。 This polycarbonate resin is generally produced from carbonyl chloride as a raw material, and it is well known that by-products and impurities contained in the carbonyl chloride affect the quality of the polycarbonate resin.
例えば、特許文献１には、硫黄化合物を低減した一酸化炭素を用いて塩化カルボニルを製造し、この塩化カルボニルを用いて色相の良いポリカーボネート樹脂を製造する方法が開示されている。
For example,
また、塩化カルボニルを製造する際に発生する副生成物として、四塩化炭素がある。四塩化炭素は通常の塩化カルボニル製造時には１５０〜３００ｐｐｍ程度発生し、生成塩化カルボニルに混入することが知られている。四塩化炭素はポリカーボネート樹脂の色相の悪化や、金型腐食性が悪化することが知られており、ポリカーボネート樹脂への混入量は極力少なくする必要がある。 Carbon tetrachloride is another by-product generated when carbonyl chloride is produced. It is known that carbon tetrachloride is generated in an amount of about 150 to 300 ppm during normal carbonyl chloride production and is mixed into the produced carbonyl chloride. Carbon tetrachloride is known to deteriorate the hue of the polycarbonate resin and to deteriorate the mold corrosivity, and it is necessary to reduce the amount of incorporation into the polycarbonate resin as much as possible.
これらの問題点を解決する方法についていくつか提案されている。例えば、特許文献２には、塩化カルボニルを蒸留することにより四塩化炭素含有量を少なくした塩化カルボニルを用いて金型腐食の少ないポリカーボネート樹脂の製造方法が開示されている。
Several methods have been proposed for solving these problems. For example,
特許文献３には、塩化カルボニル化反応を多段の反応槽に分けて極力反応熱を除去し、さらに得られた液化塩化カルボニルを蒸留する方法により、硫黄化合物と四塩化炭素の両方を低減した塩化カルボニルを用い、より品質の向上したポリカーボネート樹脂を得る方法が開示されている。 Patent Document 3 discloses a method in which the carbonyl chloride reaction is divided into a multistage reaction vessel to remove the heat of reaction as much as possible, and the resulting liquefied carbonyl chloride is distilled to further reduce both sulfur compounds and carbon tetrachloride. A method for obtaining a polycarbonate resin having improved quality by using carbonyl is disclosed.
特許文献４では、塩化カルボニル化反応を多段の反応槽に分けて極力反応熱を除去し、さらに得られた液化塩化カルボニルを蒸留する方法により、四塩化炭素含有量及び揮発性塩素含有量の少ない塩化カルボニルを用い、より品質の向上したポリカーボネート樹脂を得る方法が開示されている。
ただし、これらの方法を実施するには工程が大規模となり煩雑で、ガスの圧力損失が大きくなること等の問題もあり、コスト面においても好ましくない。
In Patent Document 4, the carbon chlorochloride content and the volatile chlorine content are low by dividing the carbonyl chloride reaction into a multistage reaction tank to remove reaction heat as much as possible and further distilling the obtained liquefied carbonyl chloride. A method for obtaining a polycarbonate resin with improved quality using carbonyl chloride is disclosed.
However, in order to carry out these methods, the process is large and complicated, and there are problems such as an increase in gas pressure loss, which is not preferable in terms of cost.
特許文献５では、液化塩化カルボニルを活性炭塔に通液する処理を行うことにより、塩化カルボニル中の塩素を活性炭に吸着させて、塩素濃度が１０００ｐｐｂ以下の塩化カルボニルを用いて、溶融成形後のポリカーボネート成形品から常温において揮発してくる塩素（揮発性塩素）が少ないポリカーボネート樹脂を得る方法が開示されている。 In Patent Document 5, by performing a treatment of passing liquefied carbonyl chloride through an activated carbon tower, the chlorine in the carbonyl chloride is adsorbed on the activated carbon, and the carbonyl chloride having a chlorine concentration of 1000 ppb or less is used to form a polycarbonate after melt molding. A method for obtaining a polycarbonate resin from a molded product with less chlorine (volatile chlorine) that volatilizes at room temperature is disclosed.
一方、四塩化炭素含有量等の不純物を低減した塩化カルボニルの製造方法について、いくつか提案されている。例えば、特許文献６には、比表面積１２００〜１３００ｍ２／ｇ等の特定の物性を有する活性炭を使用した四塩化炭素含有量および塩素分子含有量の少ない塩化カルボニルの製造方法が記載されている。この特許文献６では四塩化炭素量の低減が十分でなく、さらに特許文献７において、特許文献６に記載された方法で得られた塩化カルボニルを蒸留処理し四塩化炭素量の低減を図っている。
On the other hand, several methods for producing carbonyl chloride with reduced impurities such as carbon tetrachloride content have been proposed. For example,
また、特許文献８には、活性金属含有量の少ない活性炭を使用した、四塩化炭素含有量の低減された塩化カルボニルの製造方法が開示されている。活性炭の表面積については１００ｍ２／ｇより大きいものを使用することが示され、具体的には３５０〜５００ｍ２／ｇの活性炭が使用されている。 Patent Document 8 discloses a method for producing carbonyl chloride having a reduced carbon tetrachloride content using activated carbon having a low active metal content. The surface area of the activated carbon have been shown to use a larger than 100 m 2 / g, specifically has been used activated carbon 350~500m 2 / g.
特許文献９には、少なくとも１０ｍ２／ｇの表面積を有する特定の活性炭を使用した、四塩化炭素含有量の低減された塩化カルボニルの製造方法が開示されている。具体的には約６００〜１７００ｍ２／ｇの活性炭が使用されている。 Patent Document 9 discloses a method for producing carbonyl chloride having a reduced carbon tetrachloride content, using a specific activated carbon having a surface area of at least 10 m 2 / g. Specifically, about 600 to 1700 m 2 / g of activated carbon is used.
特許文献１０には、塩化カルボニル生成反応において第一触媒と接触反応させた後に、ついで第一触媒よりも相対活性の高い第二触媒と接触することで副生四塩化炭素量を低減しつつ塩化カルボニルを高生成速度で製造する方法が示されている。 In Patent Document 10, after the contact reaction with the first catalyst in the carbonyl chloride formation reaction, the contact is then made with the second catalyst having higher relative activity than the first catalyst, thereby reducing the amount of by-product carbon tetrachloride while reducing the amount of carbon tetrachloride. A process for producing carbonyls at high production rates is shown.
上記特許文献の何れの提案においても塩化カルボニルの品質の向上について短期的視点で記載されているものの、高品質の塩化カルボニルを長期間連続で工業的に生産する方法を開示するには至っていない。塩化カルボニルを工業的に生産する場合には、得られる塩化カルボニルの品質や生産コストも重要であるが、同時に塩化カルボニルが非常に有毒な物質であるという特性により、安全面にも十分注意する必要がある。特に、触媒の寿命による触媒更新入れ替え時には、塩化カルボニルの漏洩による被災リスクも大きくなるため、触媒寿命をできるだけ長くして、入れ替え頻度をできるだけ少なくすることが強く望まれていた。 Although none of the proposals in the above-mentioned patent documents describes improvement in the quality of carbonyl chloride from a short-term viewpoint, it has not yet disclosed a method for industrially producing high-quality carbonyl chloride for a long period of time. When industrially producing carbonyl chloride, the quality and production cost of the resulting carbonyl chloride are important, but at the same time, due to the property that carbonyl chloride is a very toxic substance, careful attention to safety is required. There is. In particular, at the time of replacement of the catalyst due to the life of the catalyst, the risk of damage due to leakage of carbonyl chloride increases, so it has been strongly desired to make the catalyst life as long as possible and to reduce the replacement frequency as much as possible.
本発明の目的は、四塩化炭素、塩素分子および臭素分子量が少なく、さらに長期連続運転が可能な塩化カルボニルの製造方法および金属腐食性物質が少なく、色相に優れ、且つ成形熱安定性に優れたポリカーボネート樹脂の製造方法を提供することである。 The object of the present invention is to provide a carbon carbonyl chloride, chlorine molecule, and bromine molecular weights that are small, a method for producing carbonyl chloride capable of long-term continuous operation, and a metal corrosive substance that is excellent in hue and molding heat stability. It is providing the manufacturing method of polycarbonate resin.
本発明者は、上記目的を達成するために鋭意検討した結果、塩化カルボニル生成反応時に使用する活性炭触媒について、アルカリ金属及びアルカリ土類金属の含有量を低減し、特定の比表面積を有することにより、四塩化炭素、塩素分子および臭素分子量の低減された良好な塩化カルボニルを長期間連続的に生成可能となることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has reduced the content of alkali metals and alkaline earth metals and has a specific specific surface area for the activated carbon catalyst used during the carbonyl chloride formation reaction. The present inventors have found that good carbonyl chloride having reduced carbon tetrachloride, chlorine molecular weight, and bromine molecular weight can be continuously produced over a long period of time, and completed the present invention.
すなわち、本発明によれば、
１．塩素と一酸化炭素とを、活性炭触媒に接触させて塩化カルボニルを製造する反応において、活性炭触媒中のナトリウム、カリウムおよびカルシウムの含有量が合計で２０００ｐｐｍ以下であり、活性炭触媒の比表面積が２００〜７００ｍ２／ｇであることを特徴とする塩化カルボニルの製造方法、
２．活性炭触媒中のナトリウム、カリウムおよびカルシウムの含有量が合計で１０００ｐｐｍ以下である前項１記載の塩化カルボニルの製造方法、
３．活性炭触媒中のナトリウム含有量が１０００ｐｐｍ以下である前項１記載の塩化カルボニルの製造方法、
４．活性炭触媒中のカリウム含有量が８００ｐｐｍ以下である前項１記載の塩化カルボニルの製造方法、
５．活性炭触媒中のカルシウム含有量が２００ｐｐｍ以下である前項１記載の塩化カルボニルの製造方法、
６．塩化カルボニル化反応時の圧力が０．０５〜０．５０ＭＰａ（ゲージ圧）である前項１記載の塩化カルボニルの製造方法、
７．触媒量に対する塩化カルボニル累積生産量が２．０×１０６ ｋｇ／ｍ３および１．６×１０７ ｋｇ／ｍ３ のいずれの時点でも塩化カルボニル中の四塩化炭素含有量が３０ｐｐｍ未満であることを特徴とする前項１記載の塩化カルボニルの製造方法、
８．触媒量に対する塩化カルボニル累積生産量が２．０×１０６ ｋｇ／ｍ３および１．６×１０７ ｋｇ／ｍ３ のいずれの時点でも塩化カルボニル中の四塩化炭素含有量が２０ｐｐｍ未満であることを特徴とする前項１記載の塩化カルボニルの製造方法、
９．活性炭触媒の平均粒径が０．５〜５．０ｍｍの範囲である前項１記載の塩化カルボニルの製造方法、
１０．活性炭触媒の比表面積が２５０〜６５０ｍ２ ／ｇである前項１記載の塩化カルボニルの製造方法、
が提供される。
That is, according to the present invention,
1. In the reaction for producing carbonyl chloride by bringing chlorine and carbon monoxide into contact with the activated carbon catalyst, the total content of sodium, potassium and calcium in the activated carbon catalyst is 2000 ppm or less, and the specific surface area of the activated carbon catalyst is 200 to 200. A method for producing carbonyl chloride, characterized by being 700 m 2 / g,
2. The method for producing carbonyl chloride according to 1 above, wherein the total content of sodium, potassium and calcium in the activated carbon catalyst is 1000 ppm or less,
3. The method for producing carbonyl chloride according to 1 above, wherein the sodium content in the activated carbon catalyst is 1000 ppm or less,
4). The method for producing carbonyl chloride according to 1 above, wherein the potassium content in the activated carbon catalyst is 800 ppm or less,
5. The method for producing carbonyl chloride according to 1 above, wherein the calcium content in the activated carbon catalyst is 200 ppm or less,
6). The method for producing carbonyl chloride according to 1 above, wherein the pressure during the carbonyl chloride reaction is 0.05 to 0.50 MPa (gauge pressure),
7). The carbon tetrachloride content in the carbonyl chloride is less than 30 ppm at any point of 2.0 × 10 6 kg / m 3 and 1.6 × 10 7 kg / m 3 with respect to the catalyst amount. The method for producing carbonyl chloride according to
8). The carbon tetrachloride content in the carbonyl chloride is less than 20 ppm at any time point where the cumulative production of carbonyl chloride with respect to the catalyst amount is 2.0 × 10 6 kg / m 3 and 1.6 × 10 7 kg / m 3. The method for producing carbonyl chloride according to
9. The method for producing carbonyl chloride according to 1 above, wherein the activated carbon catalyst has an average particle size in the range of 0.5 to 5.0 mm,
10. The method for producing carbonyl chloride according to 1 above, wherein the activated carbon catalyst has a specific surface area of 250 to 650 m 2 / g,
Is provided.
なお、本明細書において、塩素分子とは二つの塩素原子が結合した分子であり、塩化カルボニル中では通常気体で存在する。ポリカーボネート樹脂中の全塩素含有量とは塩素分子、臭化塩素分子、塩化カルボニル分子等の塩素原子を含む分子について、これら成分のうち塩素原子に相当する成分の総量を示す。また、本明細書において、臭素分子とは二つの臭素原子が結合した分子であり、塩化カルボニル中では通常気体で存在する。ポリカーボネート樹脂中の全臭素含有量とは臭素分子、臭化塩素分子、臭化カルボニル分子等の臭素原子を含む分子について、これら成分のうち臭素原子に相当する成分の総量を示す。 In the present specification, a chlorine molecule is a molecule in which two chlorine atoms are bonded, and is usually present in gas in carbonyl chloride. The total chlorine content in the polycarbonate resin refers to the total amount of components corresponding to chlorine atoms among these components, including molecules containing chlorine atoms, such as chlorine molecules, chlorine bromide molecules, and carbonyl chloride molecules. Moreover, in this specification, a bromine molecule is a molecule in which two bromine atoms are bonded, and is usually present in a gas in carbonyl chloride. The total bromine content in the polycarbonate resin indicates the total amount of components corresponding to bromine atoms among these components, including bromine molecules, chlorine bromide molecules, and carbonyl bromide molecules.
本発明では、副反応が充分に抑制され、高純度の優れた塩化カルボニルが得られ、且つこの塩化カルボニルを用いて得られたポリカーボネート樹脂は非常に色相に優れ、更に、成形時の熱安定性にも優れ、金属腐食性も良好なことから、光学用途、自動車用途、シリコンウエハー、電気・電子機器収納容器及び眼鏡レンズ等広範囲の用途に有用であり、その奏する産業上の効果は格別である。 In the present invention, side reactions are sufficiently suppressed, an excellent carbonyl chloride with high purity is obtained, and the polycarbonate resin obtained using this carbonyl chloride is very excellent in hue, and further has a thermal stability during molding. It is also excellent in metal corrosion and is useful for a wide range of applications such as optical applications, automotive applications, silicon wafers, electrical / electronic equipment containers, and eyeglass lenses, and the industrial effects that it exhibits are exceptional. .
以下、本発明についてさらに詳細に説明する。
（塩化カルボニルについて）
塩化カルボニルの製造方法としては、通常多孔質固体触媒を用いて一酸化炭素（以下、ＣＯと略称することがある）と塩素（以下、Ｃｌ２と略称することがある）とを反応させる。
Hereinafter, the present invention will be described in more detail.
(About carbonyl chloride)
As a method for producing carbonyl chloride, carbon monoxide (hereinafter sometimes abbreviated as CO) and chlorine (hereinafter sometimes abbreviated as Cl 2 ) are usually reacted with a porous solid catalyst.
本発明においては、この塩化カルボニルの製造方法において、特定のアルカリ金属及びアルカリ土類金属の含有量を低減し、且つ比表面積を調整し、さらに望ましくは平均粒径を調整した特殊な活性炭触媒を使用することにより、長期間に渡って反応時の副反応や酸化反応を抑制でき、高品質な塩化カルボニルを得ることができる方法を開示する。 In the present invention, in the method for producing carbonyl chloride, a special activated carbon catalyst in which the content of specific alkali metal and alkaline earth metal is reduced, the specific surface area is adjusted, and the average particle size is more preferably adjusted. Disclosed is a method by which by using it, side reactions and oxidation reactions during the reaction can be suppressed over a long period of time, and high-quality carbonyl chloride can be obtained.
活性炭触媒はその種類の多さ、価格や廃棄コストが比較的安価であること、さらに取り扱いや廃棄方法も簡便である等のメリットから広く用いられているが、活性炭炭素と塩素分子の副反応により四塩化炭素を生じやすいという大きな問題がある。また、活性炭炭素と反応ガス中に微量存在する酸素や水素との副反応も想定され、長期運転時には活性炭炭素が経時的に徐々に消失することも良く知られている。 Activated carbon catalysts are widely used because of their many types, relatively low cost and disposal costs, and easy handling and disposal methods. There is a big problem that carbon tetrachloride is easily generated. In addition, side reactions between activated carbon and oxygen and hydrogen present in a trace amount in the reaction gas are assumed, and it is well known that activated carbon gradually disappears with time during long-term operation.
つまり、活性炭触媒を用いて塩素と一酸化炭素を反応させて塩化カルボニルを生成させる反応では、以前よりこれら二つの問題、（ｉ）四塩化炭素が多量に副生する、（ｉｉ）活性炭触媒が徐々に消失するため長期間の連続運転が出来ない、ということが大きな問題点として知られ、改善が強く望まれていた。 In other words, in the reaction of reacting chlorine and carbon monoxide by using an activated carbon catalyst to produce carbonyl chloride, these two problems have been observed, (i) a large amount of carbon tetrachloride is by-produced, (ii) It is known that a long-term continuous operation cannot be performed because it gradually disappears, and there has been a strong demand for improvement.
特に、四塩化炭素の副生低減策は前述の通りいくつかの方法が開示されているものの、四塩化炭素を低減し、さらに触媒寿命を大幅に伸長し、長期連続運転する為の方法は未だ開示されておらず、これまで大きな課題であった。この問題は、活性炭触媒の寿命が短いと触媒を頻繁に更新する必要が生じ非効率的になるだけでなく、触媒更新時には触媒中に吸着、残留している塩化カルボニルが周辺環境に漏洩する可能性もあり非常に危険な作業となる為、生産効率及び安全の両面から高性能触媒の長期連続運転技術の開発が強く望まれていた。 In particular, although some methods for reducing carbon tetrachloride by-products have been disclosed as described above, there are still no methods for reducing carbon tetrachloride, extending the catalyst life significantly, and operating for a long period of time. It has not been disclosed, and has been a big problem so far. This problem is not only inefficient when the activated carbon catalyst has a short life, and it becomes inefficient, but when the catalyst is renewed, carbonyl chloride adsorbed and remaining in the catalyst may leak to the surrounding environment. Therefore, the development of long-term continuous operation technology for high-performance catalysts has been strongly desired from the viewpoints of both production efficiency and safety.
四塩化炭素を低減する方法として、一般的にはＣＯとＣｌ２ガスの通気量を少なくし、反応槽内での発熱量を少なくする方法が考えられるが、この方法では生産性に劣り、充分な塩化カルボニルを確保することが困難となる。さらに他の方法として、生成した塩化カルボニルから四塩化炭素を蒸留分離する方法がよく知られているが、蒸留分離する方法では四塩化炭素の分離は可能でも塩素分子及び臭素分子を低減する効果は殆どなく、これだけでは高品質の塩化カルボニルを得る事はできない。また、蒸留により回収した四塩化炭素の処理にも専用の設備が必要となるため工業的には好ましい方法とは云えない。 As a method of reducing carbon tetrachloride, generally, a method of reducing the amount of aeration of CO and Cl 2 gas and reducing the amount of heat generated in the reaction vessel is considered, but this method is inferior in productivity and sufficient. It is difficult to secure a sufficient carbonyl chloride. As another method, a method of distilling and separating carbon tetrachloride from the produced carbonyl chloride is well known, but the method of distilling and separating carbon can separate carbon tetrachloride, but the effect of reducing chlorine and bromine molecules is There is almost no high quality carbonyl chloride alone. In addition, since a special facility is also required for the treatment of carbon tetrachloride recovered by distillation, it is not an industrially preferable method.
これらの背景のもと、今回、四塩化炭素の副生をなるべく抑制し、且つ塩素分子および臭素分子量の低減された純度の高い塩化カルボニルを工業的に長期間にわたり連続して得るための条件を鋭意検討した結果、使用する活性炭触媒中の特定のアルカリ金属及びアルカリ土類金属の含有量を一定以下に低減し、且つ活性炭の比表面積を調整し、さらに望ましくは活性炭の平均粒径を調整することにより、これらの問題を大幅に改善できることを見出し、本発明に至った。 Based on these backgrounds, the conditions for suppressing carbon tetrachloride by-product as much as possible and obtaining high purity carbonyl chloride with reduced molecular weight of chlorine and bromine for a long period of time on an industrial scale have been established. As a result of intensive studies, the content of specific alkali metals and alkaline earth metals in the activated carbon catalyst used is reduced below a certain level, the specific surface area of the activated carbon is adjusted, and more preferably the average particle size of the activated carbon is adjusted. As a result, it was found that these problems can be greatly improved, and the present invention has been achieved.
すなわち、本発明で使用される活性炭触媒は、活性炭中に含有するナトリウム、カリウムおよびカルシウムの含有量が合計で２０００ｐｐｍ以下であり、より好ましくは１５００ｐｐｍ以下であり、さらに好ましくは１０００ｐｐｍ以下である。上記特定のアルカリ金属及びアルカリ土類金属の含有量がこれよりも多いと、塩化カルボニル生成反応時の副反応が増加し、塩化カルボニルガス中の四塩化炭素が増加する上に、さらに活性炭の消失速度も著しく速くなるため、高純度の塩化カルボニルを長期間連続して得る事が出来なくなる。 That is, the activated carbon catalyst used in the present invention has a total content of sodium, potassium and calcium contained in the activated carbon of 2000 ppm or less, more preferably 1500 ppm or less, and even more preferably 1000 ppm or less. If the content of the above-mentioned specific alkali metal and alkaline earth metal is larger than this, side reactions during the carbonyl chloride formation reaction increase, carbon tetrachloride in the carbonyl chloride gas increases, and the disappearance of activated carbon further occurs. Since the speed is remarkably increased, high-purity carbonyl chloride cannot be obtained continuously for a long period of time.
また、活性炭触媒中に含有するナトリウムの含有量は１０００ｐｐｍ以下が好ましく、８００ｐｐｍ以下がより好ましく、６００ｐｐｍ以下がさらに好ましく、５００ｐｐｍ以下が特に好ましい。活性炭触媒中に含有するカリウムの含有量は８００ｐｐｍ以下が好ましく、７００ｐｐｍ以下がより好ましく、５００ｐｐｍ以下がさらに好ましく、３００ｐｐｍ以下が特に好ましい。活性炭触媒中に含有するカルシウムの含有量は２００ｐｐｍ以下が好ましく、１００ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましく、３０ｐｐｍ以下が特に好ましい。上記範囲を満足すると塩化カルボニル生成反応時の副反応が減少し、塩化カルボニルガス中の四塩化炭素が低減する上に、さらに活性炭の消失速度も遅くなるため、高純度の塩化カルボニルを長期間連続して得る事ができる。 In addition, the content of sodium contained in the activated carbon catalyst is preferably 1000 ppm or less, more preferably 800 ppm or less, further preferably 600 ppm or less, and particularly preferably 500 ppm or less. The content of potassium contained in the activated carbon catalyst is preferably 800 ppm or less, more preferably 700 ppm or less, further preferably 500 ppm or less, and particularly preferably 300 ppm or less. The content of calcium contained in the activated carbon catalyst is preferably 200 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, and particularly preferably 30 ppm or less. If the above range is satisfied, side reactions during the carbonyl chloride formation reaction are reduced, carbon tetrachloride in the carbonyl chloride gas is reduced, and the rate of disappearance of the activated carbon is also slowed down. You can get it.
一方、触媒の比表面積に関しては、Ｎ２吸着法で測定した比表面積が２００〜７００ｍ２／ｇの範囲であり、２５０〜６５０ｍ２／ｇの範囲が好ましく、３００〜６００ｍ２／ｇの範囲が特に好ましい、比表面積が２００ｍ２／ｇよりも小さいと触媒の反応活性が劣り、未反応の塩素が残留し生成ガスに混入する等の問題が生じる。一方、比表面積が７００ｍ２／ｇを超えると触媒の反応活性が過剰となり、副反応も促進されて、生成する塩化カルボニル中に多量の四塩化炭素が混入し、製品品質に影響する。 On the other hand, with respect to the specific surface area of the catalyst, ranges specific surface area measured by N 2 adsorption method is 200-700 2 / g, preferably in the range of 250~650m 2 / g, in the range of 300 to 600 m 2 / g When the specific surface area is particularly smaller than 200 m 2 / g, the reaction activity of the catalyst is inferior, and problems such as unreacted chlorine remaining and mixing into the product gas arise. On the other hand, if the specific surface area exceeds 700 m 2 / g, the reaction activity of the catalyst becomes excessive, side reactions are also promoted, and a large amount of carbon tetrachloride is mixed into the produced carbonyl chloride, affecting the product quality.
また、触媒の粒径に関しては、平均粒径０．５〜５．０ｍｍの範囲が好ましく、１．０〜４．０ｍｍの範囲がより好ましく、１．５〜３．０ｍｍの範囲が特に好ましい。平均粒径が０．５ｍｍよりも小さいとハンドリング性の悪化や圧力損失の増大等の物理的悪影響だけでなく、反応性が高すぎるために反応温度が非常に高温となり、四塩化炭素副生量が増えたり、触媒寿命が短くなったりという化学的な悪影響が考えられる。一方、平均粒径が５．０ｍｍよりも大きくなると、反応性が不十分となり、得られる塩化カルボニル中に塩素分子や臭素分子が残留しやすくなる。
なお、反応層を複数使用する場合は、第一反応層で使用する触媒を上記特性を有する触媒とすることが好ましい。
Moreover, regarding the particle size of the catalyst, the average particle size is preferably in the range of 0.5 to 5.0 mm, more preferably in the range of 1.0 to 4.0 mm, and particularly preferably in the range of 1.5 to 3.0 mm. If the average particle size is less than 0.5 mm, not only the physical adverse effects such as deterioration of handling properties and increase of pressure loss, but also the reaction temperature becomes very high due to the too high reactivity, carbon tetrachloride by-product amount. The chemical adverse effect of increasing the catalyst life or shortening the catalyst life can be considered. On the other hand, when the average particle diameter is larger than 5.0 mm, the reactivity becomes insufficient, and chlorine molecules and bromine molecules tend to remain in the obtained carbonyl chloride.
When a plurality of reaction layers are used, the catalyst used in the first reaction layer is preferably a catalyst having the above characteristics.
また、活性炭触媒には椰子殻由来のものや石炭由来のもの等いろいろな種類があるが、これら原料や製法の種類には特に区別や制限は無く、上記の金属含有量及び好ましくは平均粒径や比表面積を満たす触媒であれば本発明の触媒として使用できる。実際に、本発明者は椰子殻由来と石炭由来の活性炭触媒についてそれぞれ評価を実施したが、特に異なる傾向は見られず、むしろ金属含有量や粒径等の物性による影響の方が顕著なことが分かった。 In addition, there are various types of activated carbon catalysts such as those derived from coconut shells and those derived from coal, but there is no particular distinction or limitation on the types of these raw materials and manufacturing methods, and the above metal content and preferably the average particle size Any catalyst satisfying the specific surface area can be used as the catalyst of the present invention. Actually, the present inventor conducted evaluations on activated carbon catalysts derived from coconut shells and coal, but there was no particular tendency, but rather the effect of physical properties such as metal content and particle size was more pronounced. I understood.
また、本発明において塩化カルボニルを得る反応槽としては、多管式等の熱交換機型が望ましいが、これ以外の構造であってもよく、さらに反応段数は一段式でも二段以上の多段式のどちらでも可能であるが、より高純度の塩化カルボニルを効率よく得るためには多段式の反応槽にて活性炭触媒の反応活性を段階的に上げて、塩化カルボニルへの転嫁率を徐々に向上させるとともに、反応発熱も徐々に除冷する方法が好ましい。 In the present invention, the reaction vessel for obtaining carbonyl chloride is preferably a heat exchanger type such as a multi-tubular type, but may have a structure other than this, and the number of reaction stages may be one or two or more. Either method is possible, but in order to obtain carbonyl chloride of higher purity efficiently, the reaction activity of the activated carbon catalyst is increased stepwise in a multistage reaction vessel, and the pass-through rate to carbonyl chloride is gradually improved. In addition, a method in which the reaction exotherm is gradually cooled is preferable.
反応槽に導入するＣＯとＣｌ２とのモル比は、ＣＯ／Ｃｌ２で表して１．０１５〜１．０７０の範囲が好ましく、１．０２０〜１．０５０の範囲がより好ましい。モル比が高過ぎると収率が低下することがある。 The molar ratio of CO and Cl 2 introduced into the reaction vessel is preferably in the range of 1.015 to 1.070, more preferably in the range of 1.020 to 1.050, expressed as CO / Cl 2 . If the molar ratio is too high, the yield may decrease.
本発明において、塩化カルボニル化反応時の圧力は、０．０５〜０．５０ＭＰａ（ゲージ圧を示す。以下同様）の範囲が好ましく、０．０６〜０．４０ＭＰａの範囲がより好ましく、０．０７〜０．３０ＭＰａの範囲がさらに好ましい。反応圧力が０．５０ＭＰａより大きくなると、反応速度が大きくなるため反応温度も高くなり、その結果、塩化カルボニル中の四塩化炭素含有量が多くなる場合がある。一方、反応圧力が０．０５ＭＰａ未満になると、反応速度が小さくなりすぎるため、その結果塩化カルボニル中に塩素分子及び臭素分子が多量に残存する場合がある。
上述した反応方法により得られた塩化カルボニルは、ブラインを通液したコンデンサーにより冷却し液化塩化カルボニル貯槽を設けて貯槽することができる。
In the present invention, the pressure during the carbonyl chloride reaction is preferably in the range of 0.05 to 0.50 MPa (indicating gauge pressure; the same applies hereinafter), more preferably in the range of 0.06 to 0.40 MPa, and 0.07. A range of ˜0.30 MPa is more preferable. When the reaction pressure is greater than 0.50 MPa, the reaction rate increases and the reaction temperature also increases, and as a result, the carbon tetrachloride content in the carbonyl chloride may increase. On the other hand, when the reaction pressure is less than 0.05 MPa, the reaction rate becomes too low, and as a result, a large amount of chlorine molecules and bromine molecules may remain in the carbonyl chloride.
The carbonyl chloride obtained by the above-described reaction method can be stored by cooling with a condenser through which brine is passed and providing a liquefied carbonyl chloride storage tank.
本発明の塩化カルボニルの製造方法で得られる塩化カルボニルは、その四塩化炭素含有量は３０ｐｐｍ以下が好ましく、２０ｐｐｍ以下がより好ましく、１５ｐｐｍ以下がさらに好ましく、１０ｐｐｍ以下が特に好ましい。また、塩素分子含有量は３０ｐｐｍ以下が好ましく、２５ｐｐｍ以下がより好ましく、２０ｐｐｍ以下が特に好ましい。臭素分子含有量は２０ｐｐｍ以下が好ましく、１５ｐｐｍ以下がより好ましく、１０ｐｐｍ以下が特に好ましい。塩化カルボニル中の四塩化炭素含有量が３０ｐｐｍ、塩素分子含有量が３０ｐｐｍまたは臭素分子含有量が２０ｐｐｍを越えた場合は塩化カルボニルの品質が悪化し、また、四塩化炭素含有量３ｐｐｍ以下、全塩素含有量２ｐｐｍ以下及び全臭素含有量１ｐｐｍ以下であるポリカーボネート樹脂が得られず、かかるポリカーボネート樹脂は色相および金属腐食性に劣り広範囲の用途に適用できない。 The carbonyl chloride obtained by the method for producing carbonyl chloride of the present invention has a carbon tetrachloride content of preferably 30 ppm or less, more preferably 20 ppm or less, further preferably 15 ppm or less, and particularly preferably 10 ppm or less. The chlorine molecule content is preferably 30 ppm or less, more preferably 25 ppm or less, and particularly preferably 20 ppm or less. The bromine molecule content is preferably 20 ppm or less, more preferably 15 ppm or less, and particularly preferably 10 ppm or less. If the carbon tetrachloride content in the carbonyl chloride is 30 ppm, the chlorine molecule content is 30 ppm or the bromine molecule content exceeds 20 ppm, the quality of the carbonyl chloride deteriorates, and the carbon tetrachloride content is 3 ppm or less and the total chlorine A polycarbonate resin having a content of 2 ppm or less and a total bromine content of 1 ppm or less cannot be obtained, and such a polycarbonate resin is inferior in hue and metal corrosion and cannot be applied to a wide range of uses.
なお、上述した塩化カルボニルの品質は、充分長期間にわたって維持されなければ工業的に使用するに値しない。すなわち、工業的に使用する為には、触媒を使用開始してから比較的新しい時期（例えば、触媒量１ｍ３に対して塩化カルボニル生産量が２．０×１０６ｋｇ／ｍ３）においても、長期間使用した後（例えば、触媒量１ｍ３に対して塩化カルボニル生産量が１．６×１０７ｋｇ／ｍ３）においても、どちらの時期でも安定して上述したような良好な品質の塩化カルボニルを得る必要がある。 The quality of the carbonyl chloride described above is not worth using industrially unless it is maintained for a sufficiently long period of time. That is, for industrial use, even at a relatively new time after the start of use of the catalyst (for example, carbonyl chloride production is 2.0 × 10 6 kg / m 3 with respect to 1 m 3 of catalyst). Even after long-term use (for example, the amount of carbonyl chloride produced is 1.6 × 10 7 kg / m 3 with respect to 1 m 3 of catalyst) It is necessary to obtain carbonyl chloride.
また、塩化カルボニルの製造に用いる塩素は、臭素及び臭化塩素等の臭素成分含有量が１５０ｐｐｍ以下、好ましくは１２５ｐｐｍ以下、特に１００ｐｐｍ以下が好ましい。臭素成分含有量が１５０ｐｐｍを越えると塩化カルボニル中の臭素分子含有量が１０ｐｐｍより多くなりやすく、この塩化カルボニルを用いて得られたポリカーボネート樹脂は全臭素含有量が０．５ｐｐｍを越えやすくなり、ポリカーボネート樹脂の品質に問題が生じやすくなる。臭素成分の比較的少ない塩素は、電解ソーダ法、タウンズ法等各種の方法で製造されたものを使用することができるが、なかでも電解ソーダ法を用いて製造する方法が最も経済的且つ一般的である。 Further, chlorine used for the production of carbonyl chloride has a bromine component content such as bromine and chlorine bromide of 150 ppm or less, preferably 125 ppm or less, particularly preferably 100 ppm or less. If the bromine component content exceeds 150 ppm, the bromine molecule content in the carbonyl chloride tends to exceed 10 ppm, and the polycarbonate resin obtained using this carbonyl chloride tends to exceed the total bromine content of 0.5 ppm. Problems with resin quality are likely to occur. Chlorine having a relatively small bromine component can be produced by various methods such as the electrolytic soda method and the Towns method. Among them, the method using the electrolytic soda method is the most economical and general. It is.
また、塩化カルボニルの製造に用いる一酸化炭素は、硫黄化合物の含有量が好ましくは１０ｐｐｍ以下、より好ましくは５ｐｐｍ以下、さらに好ましくは０．５ｐｐｍ以下である。一酸化炭素中の硫黄化合物が１０ｐｐｍを越えると塩化カルボニル中の硫黄化合物含有量が５ｐｐｍを越え、この塩化カルボニルを用いて得られたポリカーボネート樹脂は硫黄化合物含有量が１００ｐｐｂを越えやすくなり、ポリカーボネート樹脂の品質に問題が生じやすくなる。硫黄化合物が１０ｐｐｍ以下の一酸化炭素は、コークスと酸素と反応させて得られた一酸化炭素を金属添加触媒例えば銅（Ｃｕ）、クロム（Ｃｒ）、バナジュウム（Ｖ）、モリブデン（Ｍｏ）等の金属酸化物及びまたは金属塩を添着した活性炭または活性アルミナ等に接触せしめ、次いで、か性ソーダ水溶液に接触せしめる方法やか性ソーダ水溶液に接触せしめた後に活性アルミナに接触せしめる方法等によって得られる。 Carbon monoxide used for the production of carbonyl chloride preferably has a sulfur compound content of 10 ppm or less, more preferably 5 ppm or less, and even more preferably 0.5 ppm or less. If the sulfur compound in the carbon monoxide exceeds 10 ppm, the sulfur compound content in the carbonyl chloride exceeds 5 ppm, and the polycarbonate resin obtained using this carbonyl chloride tends to exceed 100 ppb in the sulfur compound content. Problems with quality are likely to occur. Carbon monoxide whose sulfur compound is 10 ppm or less is obtained by reacting carbon monoxide obtained by reacting coke with oxygen, such as a metal addition catalyst such as copper (Cu), chromium (Cr), vanadium (V), molybdenum (Mo), etc. It can be obtained by contacting with activated carbon or activated alumina impregnated with a metal oxide and / or metal salt, then contacting with an aqueous caustic soda solution, contacting with an aqueous caustic soda solution, and then contacting with activated alumina.
（ポリカーボネート樹脂について）
本発明で対象とするポリカーボネート樹脂は通常二価フェノールとカーボネート前駆体とを溶液法で反応させて得られるものである。ここで使用される二価フェノールの代表的な例としては、ハイドロキノン、レゾルシノール、４，４’−ビフェノール、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）プロパン（通称“ビスフェノールＡ”）、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）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）−１−フェニルエタン、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−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、４，４’−（ｐ−フェニレンジイソプロピリデン）ジフェノール、４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサン、ビス（４−ヒドロキシフェニル）オキシド、ビス（４−ヒドロキシフェニル）スルフィド、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）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）エステル、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン、ビス（３，５−ジブロモ−４−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）スルフィド、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン等が挙げられる。これらは単独あるいは２種以上使用することができる。これらの中でも、ビス（４−ヒドロキシフェニル）アルカン、特にビスフェノールＡ（以下“ＢＰＡ”と略称することがある）が汎用されている。
(About polycarbonate resin)
The polycarbonate resin targeted by the present invention is usually obtained by reacting a dihydric phenol and a carbonate precursor by a solution method. Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as “bisphenol A”), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) ) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy) Phenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl) Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. These can be used alone or in combination of two or more. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.
一方、カーボネート前駆体としては、カルボニルハライド、カーボネートエステル又はハロホルメート等が使用され、具体的には塩化カルボニル、ジフェニルカーボネート又は２価フェノールのジハロホルメート等が挙げられるが、この中で本発明で対象とするのは塩化カルボニルである。 On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate, or the like is used, and specifically, carbonyl chloride, diphenyl carbonate, dihaloformate of dihydric phenol, and the like are mentioned. Is carbonyl chloride.
このような２価フェノールとカーボネート前駆体とから界面重合法によってポリカーボネートを製造するに当っては、必要に応じて触媒、末端停止剤、２価フェノールが酸化するのを防止するための酸化防止剤等を使用してもよい。また、ポリカーボネートは３官能以上の多官能性芳香族化合物を共重合した分岐ポリカーボネートであってもよい。ここで使用される３官能以上の多官能性芳香族化合物としては、１，１，１−トリス（４−ヒドロキシフェニル）エタン、１，１，１−トリス（３，５−ジメチル−４−ヒドロキシフェニル）エタン等が挙げられる。分岐ポリカーボネートを生ずる多官能性化合物を含む場合、その量は、ポリカーボネート全量中、０．００１〜１モル％、好ましくは０．００５〜０．９モル％、特に好ましくは０．０１〜０．８モル％である。 In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like. When a polyfunctional compound that produces a branched polycarbonate is included, the amount thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol, based on the total amount of the polycarbonate. Mol%.
ポリカーボネートの重合反応において、界面重縮合法による反応は、通常、２価フェノールと塩化カルボニルとの反応であり、酸結合剤及び有機溶媒の存在下に反応させる。酸結合剤としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物又はピリジン等のアミン化合物が用いられる。有機溶媒としては、例えば、塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。また、反応促進のために、例えば、トリエチルアミン、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルホスホニウムブロマイド等の３級アミン、４級アンモニウム化合物、４級ホスホニウム化合物等の触媒を用いることもできる。その際、反応温度は通常０〜４０℃、反応時間は１０分〜５時間程度、反応中のｐＨは９以上に保つのが好ましい。 In the polymerization reaction of polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and carbonyl chloride, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.
また、かかる重合反応においては、通常、末端停止剤が使用される。かかる末端停止剤として単官能フェノール類を使用することができる。単官能フェノール類としては、例えば、フェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−クミルフェノール等の単官能フェノール類を用いるのが好ましい。さらに、単官能フェノール類としては、デシルフェノール、ドデシルフェノール、テトラデシルフェノール、ヘキサデシルフェノール、オクタデシルフェノール、エイコシルフェノール、ドコシルフェノール及びトリアコンチルフェノール等の炭素数１０以上の長鎖アルキル基で核置換された単官能フェノールを挙げることができ、該フェノールは流動性の向上及び耐加水分解性の向上に効果がある。かかる末端停止剤は単独で使用しても２種以上併用してもよい。 In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As the monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, as monofunctional phenols, long chain alkyl groups having 10 or more carbon atoms such as decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. A monofunctional phenol substituted with a nucleus can be mentioned, and the phenol is effective in improving fluidity and hydrolysis resistance. Such end terminators may be used alone or in combination of two or more.
ポリカーボネート樹脂の粘度平均分子量は限定されない。しかしながら、粘度平均分子量は、１．０×１０４未満であると衝撃強度等の機械物性が低下し、５．０×１０４を超えると成形加工特性が低下するようになるので、１．０×１０４〜５．０×１０４の範囲が好ましく、１．２×１０４〜３．０×１０４の範囲がより好ましく、１．５×１０４〜２．８×１０４の範囲がさらに好ましい。この場合、成形性等が維持される範囲内で、粘度平均分子量が上記範囲外であるポリカーボネートを混合することも可能である。例えば、粘度平均分子量が５．０×１０４を超える高分子量のポリカーボネート成分を配合することも可能である。 The viscosity average molecular weight of the polycarbonate resin is not limited. However, if the viscosity average molecular weight is less than 1.0 × 10 4 , mechanical properties such as impact strength are lowered, and if it exceeds 5.0 × 10 4 , the molding process properties are lowered. The range of × 10 4 to 5.0 × 10 4 is preferable, the range of 1.2 × 10 4 to 3.0 × 10 4 is more preferable, and the range of 1.5 × 10 4 to 2.8 × 10 4 is preferable. Further preferred. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 5.0 × 10 4 can be blended.
本発明でいう粘度平均分子量は、まず、次式にて算出される比粘度（ηＳＰ）を２０℃で塩化メチレン１００ｍｌに芳香族ポリカーボネート０．７ｇを溶解した溶液からオストワルド粘度計を用いて求め、
比粘度（ηＳＰ）＝（ｔ−ｔ０）／ｔ０
［ｔ０は塩化メチレンの落下秒数、ｔは試料溶液の落下秒数］
求められた比粘度（ηＳＰ）から次の数式により粘度平均分子量Ｍを算出する。
ηＳＰ／ｃ＝［η］＋０．４５×［η］２ｃ（但し［η］は極限粘度）
［η］＝１．２３×１０−４Ｍ０．８３
ｃ＝０．７
The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η SP ) calculated by the following formula. ,
Specific viscosity (η SP ) = (t−t 0 ) / t 0
[T 0 is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η SP ) by the following formula.
η SP /c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 −4 M 0.83
c = 0.7
なお、本発明の樹脂組成物における粘度平均分子量を測定する場合は、次の要領で行う。すなわち、該樹脂組成物をその２０〜３０倍重量の塩化メチレンに溶解し、可溶分をセライト濾過により採取した後、溶液を除去して十分に乾燥し、塩化メチレン可溶分の固体を得る。かかる固体０．７ｇを塩化メチレン１００ｍｌに溶解した溶液から２０℃における比粘度（ηＳＰ）を、オストワルド粘度計を用いて求め、上式によりその粘度平均分子量Ｍを算出する。 In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.
本発明で得られるポリカーボネート樹脂は、上述したように四塩化炭素、塩素および臭素の低減された塩化カルボニルを用いることにより、ポリカーボネート樹脂中の四塩化炭素含有量が３ｐｐｍ以下、全塩素含有量が２ｐｐｍ以下、且つ全臭素含有量が１ｐｐｍ以下であることが望ましい。該ポリカーボネート樹脂は色相および金属腐食性に優れる。四塩化炭素含有量、全塩素含有量および全臭素含有量のいずれかが上記範囲を外れると色相または金属腐食性に劣るポリカーボネート樹脂となる。 As described above, the polycarbonate resin obtained in the present invention has a carbon tetrachloride content of 3 ppm or less and a total chlorine content of 2 ppm in the polycarbonate resin by using carbonyl chloride with reduced carbon tetrachloride, chlorine and bromine. The total bromine content is preferably 1 ppm or less. The polycarbonate resin is excellent in hue and metal corrosivity. If any of the carbon tetrachloride content, the total chlorine content, and the total bromine content is out of the above range, a polycarbonate resin having poor hue or metal corrosivity is obtained.
ポリカーボネート樹脂中の四塩化炭素含有量は２ｐｐｍ以下が好ましく、１．５ｐｐｍ以下がより好ましい。全塩素含有量は１．５ｐｐｍ以下が好ましく、１ｐｐｍ以下がより好ましい。全臭素含有量は０．７ｐｐｍ以下が好ましく、０．５ｐｐｍ以下がより好ましい。 The carbon tetrachloride content in the polycarbonate resin is preferably 2 ppm or less, and more preferably 1.5 ppm or less. The total chlorine content is preferably 1.5 ppm or less, and more preferably 1 ppm or less. The total bromine content is preferably 0.7 ppm or less, and more preferably 0.5 ppm or less.
本発明のポリカーボネート樹脂には、通常ポリカーボネート樹脂に配合される各種の添加剤、例えばリン系安定剤、ヒンダードフェノール系安定剤、紫外線吸収剤、難燃剤、ブルーイング剤、光拡散剤、帯電防止剤、熱線吸収能を有する化合物、無機充填材、流動改質剤、抗菌剤、光触媒系防汚剤、赤外線吸収剤、フォトクロミック剤、染料または顔料等を含むことができる。また、他の樹脂やエラストマーを本発明の目的が損なわれない範囲で少割合使用することもできる。 In the polycarbonate resin of the present invention, various additives usually blended in the polycarbonate resin, such as phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, flame retardants, bluing agents, light diffusing agents, antistatic agents. Agents, compounds having heat-absorbing ability, inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, infrared absorbers, photochromic agents, dyes or pigments. In addition, other resins and elastomers can be used in a small proportion within a range in which the object of the present invention is not impaired.
本発明のポリカーボネート樹脂は、溶融押出法により製造されたペレットを成形して各種製品を製造することができる。かかる成形においては、通常は射出成形により効率的に成形品を得るが、これには一般的な成形方法だけでなく、適宜目的に応じて、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形（超臨界流体の注入によるものを含む）、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などの射出成形法を用いて成形品を得ることができる。これら各種成形法の利点は既に広く知られるところである。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。 The polycarbonate resin of the present invention can produce various products by molding pellets produced by a melt extrusion method. In such molding, usually, a molded product is efficiently obtained by injection molding. This is not only a general molding method but also injection compression molding, injection press molding, gas assist injection molding, Injection molding such as foam molding (including by supercritical fluid injection), insert molding, in-mold coating molding, heat insulation mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding The molded product can be obtained using the method. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.
また、本発明のポリカーボネート樹脂は、押出成形により各種異形押出成形品、シート、フィルムなどの形で使用することもできる。またシート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法なども使用可能である。 The polycarbonate resin of the present invention can also be used in the form of various shaped extrusions, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used.
本発明のポリカーボネート樹脂は、色相、成形時の熱安定性、金属腐食性等に優れ、光学用途、自動車用途、シリコンウエハー、電気・電子機器収納容器及び眼鏡レンズ等広範囲の用途に好ましく適用できる。また、かかる用途以外にも、建設機械の窓ガラス、ビル、家屋、および温室などの窓ガラス、ガレージおよびアーケードなどの屋根、照灯用レンズ、信号機レンズ、光学機器のレンズ、ミラー、眼鏡レンズ、ゴーグル、消音壁、バイクの風防、銘板、太陽電池カバーまたは太陽電池基材、ディスプレー装置用カバー、タッチパネル、並びに遊技機（パチンコ機など）用部品（回路カバー、シャーシ、パチンコ玉搬送ガイドなど）などの幅広い用途に使用可能である。 The polycarbonate resin of the present invention is excellent in hue, heat stability during molding, metal corrosiveness and the like, and can be preferably applied to a wide range of applications such as optical applications, automotive applications, silicon wafers, electrical / electronic device containers and spectacle lenses. In addition to such applications, window glass for construction machinery, window glass for buildings, houses, and greenhouses, roofs for garages and arcades, lighting lenses, traffic light lenses, optical equipment lenses, mirrors, spectacle lenses, Goggles, sound deadening walls, motorcycle windshields, nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and parts for game machines (such as pachinko machines) (circuit covers, chassis, pachinko ball transport guides, etc.), etc. It can be used for a wide range of applications.
さらに、本発明のポリカーボネート樹脂からなる成形品には、各種の表面処理を行うことが可能である。ここでいう表面処理とは、蒸着（物理蒸着、化学蒸着など）、メッキ（電気メッキ、無電解メッキ、溶融メッキなど）、塗装、コーティング、印刷などの樹脂成形品の表層上に新たな層を形成させるものであり、通常のポリカーボネート樹脂に用いられる方法が適用できる。表面処理としては、具体的には、ハードコート、撥水・撥油コート、紫外線吸収コート、赤外線吸収コート、並びにメタライジング（蒸着など）などの各種の表面処理が例示される。 Furthermore, various surface treatments can be performed on the molded article made of the polycarbonate resin of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).
以下、実施例に従って、本発明を具体的に説明するが本発明は要旨を越えない限り、これらの実施例によって限定されるものではない。尚、実施例中「部」とあるのは「重量部」、「ｐｐｍ」とあるのは「ｗｔ（重量）ｐｐｍ」を示し、また各種の評価および評価用成形は次の方法で行った。 Hereinafter, the present invention will be described in detail according to examples, but the present invention is not limited to these examples unless it exceeds the gist. In the examples, “parts” indicates “parts by weight”, “ppm” indicates “wt (weight) ppm”, and various evaluations and moldings for evaluation were performed by the following methods.
（１）活性炭中に含有するナトリウム、カリウムおよびカルシウムの含有量：活性炭試料（１ｇ）を加熱灰化させた後、灰化残分を硝酸、フッ化水素酸に加熱溶解、乾固後、希王水に溶解して定容とした。この溶液について、ＩＣＰ 発光分光分析法（エスアイアイ・ナノテクノロジー製ＳＰＳ３０００）で定性・半定量分析を行なった。 (1) Content of sodium, potassium and calcium contained in activated carbon: Activated charcoal sample (1 g) is incinerated, and then the incinerated residue is dissolved in nitric acid and hydrofluoric acid by heating, dried and diluted. Dissolve in aqua regia to make a constant volume. This solution was subjected to qualitative and semi-quantitative analysis by ICP emission spectroscopic analysis (SPS3000 manufactured by SII Nanotechnology).
（２）塩素中の臭素含有量：塩素ガス１Ｌを高純度の２０％ＮａＯＨ水溶液４０ｍＬで分解し、分解液を１０倍希釈後、陽イオン除去フィルター処理したサンプル液を陰イオンクロマトグラフ（日本ダイオネクス製ＤＸ−３００）に注入し、臭素イオン定量分析を行った。 (2) Bromine content in chlorine: 1 L of chlorine gas was decomposed with 40 mL of high-purity 20% NaOH aqueous solution, the decomposition solution was diluted 10 times, and the sample solution treated with the cation removal filter was subjected to anion chromatography (Nippon Dionex) DX-300) and bromine ion quantitative analysis.
（３）塩化カルボニル中の四塩化炭素量：塩化カルボニル１μｌを電子捕獲型検出器付きガスクロマトグラフ装置（日立製作所製２６３型）に注入し測定した。 (3) Carbon tetrachloride amount in carbonyl chloride: 1 μl of carbonyl chloride was injected into a gas chromatograph with an electron capture detector (type 263, manufactured by Hitachi, Ltd.) and measured.
（４）塩化カルボニル中の塩素分子含有量及び臭素分子含有量：塩化カルボニルガスをマルチウェーブ型プロセスフォトメーター（ＤＫＫ電気化学計器株式会社製３４０１型）に注入し、塩素分子、臭素分子の各定量分析を行った。 (4) Chlorine molecule content and bromine molecule content in carbonyl chloride: Carbonyl chloride gas is injected into a multi-wave type process photometer (model 3401 manufactured by DKK Electrochemical Instrument Co., Ltd.), and each quantification of chlorine molecule and bromine molecule is determined. Analysis was carried out.
（５）ポリカーボネート樹脂中の四塩化炭素量：１２０ｍｌのステンレス製容器にペレット５ｇを入れて密栓し、２５０℃で２時間加熱した後、ヘッドスペースガス１ｍｌを電子捕獲型検出器付きガスクロマトグラフ装置（日立製作所製２６３型）に注入し測定した。 (5) Carbon tetrachloride content in polycarbonate resin: 5 g of pellets were put in a 120 ml stainless steel container, sealed, heated at 250 ° C. for 2 hours, and then 1 ml of headspace gas was gas chromatograph with electron capture detector ( It was injected into Hitachi Model 263) and measured.
（６）ポリカーボネート樹脂中の全塩素含有量及び全臭素含有量：ポリマーパウダーを１９０℃にて加温圧縮成形したプレートについて、蛍光Ｘ線（理学電気工業製ＲＩＸ２０００）にてＣｌ原子強度およびＢｒ原子強度を測定した。 (6) Total chlorine content and total bromine content in polycarbonate resin: Cl atomic strength and Br atom by fluorescent X-ray (RIX2000 manufactured by Rigaku Denki Kogyo Co., Ltd.) on a plate obtained by warm compression molding of polymer powder at 190 ° C. The strength was measured.
（７）ポリカーボネート樹脂成形品の色相：シリンダー温度３１０℃にて射出成形（住友重機械工業(株)製ＳＧ２６０Ｍ−ＨＰ）した厚さ２．０ｍｍの成形板を日本電色（株）製色差計Ｚ−１００１ＤＰ型を用いて透過光を測定したＸ，ＹおよびＺ値からＡＳＴＭ−Ｅ１９２５に基づき、下記式を用いて算出した。ＹＩ値が大きいほど成形板の黄色味が強いことを示す。
ＹＩ＝［１００（１．２８Ｘ−１．０６Ｚ）］／Ｙ
(7) Color of polycarbonate resin molded product: Nippon Denshoku Co., Ltd. color difference meter made of 2.0mm thick molded plate injection molded (SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 310 ° C Based on ASTM-E1925, it computed using the following formula from the X, Y, and Z value which measured the transmitted light using the Z-1001DP type | mold. It shows that the yellowness of a shaping | molding board is so strong that YI value is large.
YI = [100 (1.28X−1.06Z)] / Y
（８）ポリカーボネート樹脂の成形熱安定性：上記評価（７）と同様の形状であって、１０分間成形機シリンダー内に滞留させた樹脂より成形された成形板のＹＩ値を、上記評価（７）と同様に測定した。滞留後の試験片のＹＩ値から滞留前の試験片のＹＩ値を差し引き、かかる差をΔＹＩとして示した。 (8) Molding heat stability of polycarbonate resin: The YI value of a molded plate having the same shape as in the above evaluation (7) and molded from the resin retained in the molding machine cylinder for 10 minutes is evaluated as above (7 ) And measured in the same manner. The YI value of the test piece before staying was subtracted from the YI value of the test piece after staying, and this difference was shown as ΔYI.
（９）ポリカーボネート樹脂成形時の金型腐食性の評価：図１に示す素通し型のヘッドランプレンズを射出成形機（住友重機械工業(株)製ＳＧ２６０Ｍ−ＨＰ）を用いてシリンダー温度３１０℃、金型温度８０℃にて連続で２００枚成形し、その後、金型表面部を相対湿度１００％、温度１２０℃にて２４時間湿熱処理した後、表面の腐食状況を観察した。腐食状況評価は１〜５までの５段階とし、数字の大きいほうが腐食度合いがより大きいものとする。つまり、腐食ランク１はほとんど腐食が発生せず、腐食ランク２は僅かに腐食が発生しており、腐食ランク３はより腐食が進行し、腐食ランク４はさらに腐食度合いが悪化し、腐食ランク５は激しく腐食した状態である。このランク分けのうち、腐食ランク１及び２は塩化カルボニルの品質が良好で腐食度合いも良好と判断した。腐食ランク３は若干腐食が進行した状態である。腐食ランク４及び５は激しく腐食が進行する異常状態と判断した。腐食ランク４及び５のポリカーボネート樹脂を用いて成形加工した場合には、成形機スクリューや金型表面に腐食が発生し易く、品質不良を生じ易い。
(9) Evaluation of mold corrosivity during molding of polycarbonate resin: A cylinder head temperature of 310 ° C. was used by using an injection molding machine (SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd.) with a through-type headlamp lens shown in FIG. 200 sheets were continuously molded at a mold temperature of 80 ° C., and then the surface of the mold was subjected to wet heat treatment at a relative humidity of 100% and a temperature of 120 ° C. for 24 hours, and the surface corrosion state was observed. Corrosion condition evaluation is made into 5 steps from 1 to 5, and the larger the number, the greater the degree of corrosion. That is, the
［実施例１］
反応熱を除去する機能を有した多管式反応槽のシェル側に４０℃の冷却水を通水し、チューブ側に比表面積５５０ｍ２／ｇ、平均粒径２．５ｍｍの椰子殻活性炭を充填した第一反応槽の後に、比表面積９００ｍ２／ｇの、平均粒径３．５ｍｍの椰子殻活性炭を充填した第二反応槽を通気反応させ、次いで−２５℃のブラインを通液したコンデンサーと液化塩化カルボニル貯槽を設け、これらの装置を直列に接続した反応槽から、ＣＯ／Ｃｌ２のモル比１．０３０になるようにＣＯガス１０．３０Ｎｍ３／ＨｒとＣｌ２ガス１０．００Ｎｍ３／Ｈｒを圧力０．１５ＭＰａ（ゲージ圧）で通気して塩化カルボニルを得た。なお、第一反応層と第二反応層の活性炭充填体積比率は８／２とし、第一反応槽の反応温度は５４０℃、第二反応槽の反応温度は４５℃であった。また、第一反応槽に用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は１００ｐｐｍ、Ｋ含有量は１００ｐｐｍ、Ｃａ含有量は２０ｐｐｍであり、Ｃｌ２ガス中の臭素含有量は１２０ｐｐｍであった。
[Example 1]
Cooling water of 40 ° C is passed through the shell side of a multi-tubular reactor having a function to remove reaction heat, and coconut shell activated carbon having a specific surface area of 550 m 2 / g and an average particle diameter of 2.5 mm is filled into the tube side. A condenser having a specific surface area of 900 m 2 / g and filled with coconut shell activated carbon having an average particle size of 3.5 mm, and then passing a brine of −25 ° C. liquefied carbonyl chloride storage tank provided, from the reactor which connect these devices in series, CO / CO gas 10.30Nm such that Cl 2 molar ratio 1.030 3 / Hr and Cl 2 gas 10.00Nm 3 / Hr was aerated at a pressure of 0.15 MPa (gauge pressure) to obtain carbonyl chloride. In addition, the activated carbon filling volume ratio of the 1st reaction layer and the 2nd reaction layer was 8/2, the reaction temperature of the 1st reaction tank was 540 degreeC, and the reaction temperature of the 2nd reaction tank was 45 degreeC. Moreover, when the metal content of the activated carbon used in the first reaction tank was analyzed, the Na content was 100 ppm, the K content was 100 ppm, the Ca content was 20 ppm, and the bromine content in the Cl 2 gas was 120 ppm. there were.
次に、かかる塩化カルボニルを用いてポリカーボネート樹脂を製造した。温度計、撹拌機及び還流冷却器付き反応器にイオン交換水２１９．４部、４８％水酸化ナトリウム水溶液４０．２部を仕込み、これに２，２−ビス（４−ヒドロキシフェニル）プロパン５７．５部（０．２５２モル）およびハイドロサルファイト０．１２部を溶解した後、塩化メチレン１８１部を加え、撹拌下１５〜２５℃で上記塩化カルボニル２８．３部を４０分要して吹込んだ。塩化カルボニル吹き込み終了後、４８％水酸化ナトリウム水溶液７．２部およびｐ−ｔｅｒｔ−ブチルフェノール２．４２部を加え、撹拌を始め、乳化後トリエチルアミン０．０６部を加え、さらに２８〜３３℃で１時間撹拌して反応を終了した。 Next, a polycarbonate resin was produced using the carbonyl chloride. A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 219.4 parts of ion-exchanged water and 40.2 parts of 48% sodium hydroxide aqueous solution, and 2,2-bis (4-hydroxyphenyl) propane 57. After 5 parts (0.252 mol) and 0.12 part of hydrosulfite are dissolved, 181 parts of methylene chloride are added, and 28.3 parts of the above carbonyl chloride are added for 40 minutes at 15 to 25 ° C. with stirring. It is. After completion of the carbonyl chloride blowing, 7.2 parts of 48% aqueous sodium hydroxide solution and 2.42 parts of p-tert-butylphenol were added, stirring was started, 0.06 part of triethylamine was added after emulsification, and 1 at 28 to 33 ° C. The reaction was terminated by stirring for a period of time.
反応終了後、生成物を塩化メチレンで希釈して水洗した後塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで、この塩化メチレン溶液を軸受け部に異物取出口を有する隔離室を設けたニーダーの温水中に滴下して塩化メチレンを蒸発して、粘度平均分子量１５，１００のポリカーボネート樹脂パウダーを得た。このパウダーを１４５℃、６時間乾燥し、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトを０．００４重量％、ステアリン酸モノグリセリドを０．０６重量％加えた。次に、かかるパウダーをベント式二軸押出機［神戸製鋼（株）製ＫＴＸ−４６］によりシリンダー温度２４０℃で脱気しながら溶融混練し、ポリカーボネート樹脂ペレットを得た。得られた塩化カルボニル及びポリカーボネート樹脂の評価結果を表１に示した。
さらに、各塩化カルボニル生成反応触媒の寿命を確認するため、通気開始間もない塩化カルボニル累積生産量；触媒量１ｍ３に対して２．０ｘ１０６ｋｇ／ｍ３時点の品質とともに、長期運転後の塩化カルボニル累積生産量；１．６ｘ１０７ｋｇ／ｍ３時点の品質も確認し表２に示した。
After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, this methylene chloride solution is collected on the bearing. The methylene chloride was evaporated by dropping into warm water of a kneader provided with an isolation chamber having an outlet to obtain a polycarbonate resin powder having a viscosity average molecular weight of 15,100. This powder was dried at 145 ° C. for 6 hours, and 0.004% by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.06% by weight of stearic acid monoglyceride were added. Next, this powder was melt-kneaded while venting at a cylinder temperature of 240 ° C. with a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel) to obtain polycarbonate resin pellets. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1.
Furthermore, each for confirming the carbonyl chloride product life of the catalyst, the ventilation starts shortly carbonyl chloride accumulated production volume; together with the quality of 2.0x10 6 kg / m 3 when the catalyst amount 1 m 3, after long-term operation Accumulated carbonyl chloride production; the quality at 1.6 × 10 7 kg / m 3 was also confirmed and shown in Table 2.
［実施例２］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は４００ｐｐｍ、Ｋ含有量は３００ｐｐｍ、Ｃａ含有量は４０ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Example 2]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 400 ppm, the K content was 300 ppm, and the Ca content was 40 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例３］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は４００ｐｐｍ、Ｋ含有量は４００ｐｐｍ、Ｃａ含有量は２５ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Example 3]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 400 ppm, the K content was 400 ppm, and the Ca content was 25 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例４］
上記実施例３において、反応圧力を０．４０ＭＰａ（ゲージ圧）に変更した以外は、上記実施例３と全く同条件にて塩化カルボニル化反応を行い、液化塩化カルボニルを得た。また、実施例３と同様の方法でポリカーボネート樹脂ペレットを得た。得られた塩化カルボニル及びポリカーボネート樹脂の評価結果を表１に示した。さらに、同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を、表２に示した。
[Example 4]
In Example 3, except that the reaction pressure was changed to 0.40 MPa (gauge pressure), the carbonyl chloride reaction was performed under exactly the same conditions as in Example 3 to obtain liquefied carbonyl chloride. Further, polycarbonate resin pellets were obtained in the same manner as in Example 3. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Furthermore, similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例５］
上記実施例３において、第一反応で用いる活性炭の平均粒径を４．０ｍｍに変更した以外は、上記実施例３と全く同条件にて塩化カルボニル化反応を行い、液化塩化カルボニルを得た。また、実施例３と同様の方法でポリカーボネート樹脂ペレットを得た。得られた塩化カルボニル及びポリカーボネート樹脂の評価結果を表１に示した。さらに、同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を、表２に示した。
[Example 5]
In Example 3 above, except that the average particle size of the activated carbon used in the first reaction was changed to 4.0 mm, a carbonyl chloride reaction was carried out under exactly the same conditions as in Example 3 above to obtain liquefied carbonyl chloride. Further, polycarbonate resin pellets were obtained in the same manner as in Example 3. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Furthermore, similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例６］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は６００ｐｐｍ、Ｋ含有量は３００ｐｐｍ、Ｃａ含有量は２５ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Example 6]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 600 ppm, the K content was 300 ppm, and the Ca content was 25 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例７］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は１０００ｐｐｍ、Ｋ含有量は６００ｐｐｍ、Ｃａ含有量は４５ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Example 7]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 1000 ppm, the K content was 600 ppm, and the Ca content was 45 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［実施例８］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は８００ｐｐｍ、Ｋ含有量は７００ｐｐｍ、Ｃａ含有量は１５０ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Example 8]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 800 ppm, the K content was 700 ppm, and the Ca content was 150 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［比較例１］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は１２００ｐｐｍ、Ｋ含有量は８００ｐｐｍ、Ｃａ含有量は５０ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Comparative Example 1]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 1200 ppm, the K content was 800 ppm, and the Ca content was 50 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［比較例２］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は１０００ｐｐｍ、Ｋ含有量は１０００ｐｐｍ、Ｃａ含有量は１００ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Comparative Example 2]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 1000 ppm, the K content was 1000 ppm, and the Ca content was 100 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［比較例３］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本実施例で用いた活性炭の含有金属量を分析したところ、Ｎａ含有量は１３００ｐｐｍ、Ｋ含有量は７００ｐｐｍ、Ｃａ含有量は３０ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Comparative Example 3]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. When the metal content of the activated carbon used in this example was analyzed, the Na content was 1300 ppm, the K content was 700 ppm, and the Ca content was 30 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
［比較例４］
上記実施例１において、第一反応に用いる椰子殻活性炭の種類を変更した以外は、上記実施例１と同様の方法で塩化カルボニルおよびポリカーボネート樹脂ペレットを得た。本比較例は、第１反応層に比表面積７５０ｍ２／ｇ、平均粒径２．５ｍｍの椰子殻活性炭を用い、第２反応層に比表面積９００ｍ２／ｇ、平均粒径３．５ｍｍの椰子殻活性炭を充填した。さらに、含有金属量を分析したところ、Ｎａ含有量は１００ｐｐｍ、Ｋ含有量は１００ｐｐｍ、Ｃａ含有量は２０ｐｐｍであった。得られた塩化カルボニルおよびポリカーボネート樹脂の評価結果を表１に示した。同様に長期運転後の塩化カルボニルおよびポリカーボネート樹脂の評価結果を表２に示した。
[Comparative Example 4]
In the said Example 1, the carbonyl chloride and the polycarbonate resin pellet were obtained by the method similar to the said Example 1 except having changed the kind of the coconut shell activated carbon used for a 1st reaction. This comparative example uses coconut shell activated carbon having a specific surface area of 750 m 2 / g and an average particle diameter of 2.5 mm for the first reaction layer, and an insulator having a specific surface area of 900 m 2 / g and an average particle diameter of 3.5 mm for the second reaction layer. Filled with shell activated carbon. Furthermore, when the metal content was analyzed, the Na content was 100 ppm, the K content was 100 ppm, and the Ca content was 20 ppm. The evaluation results of the obtained carbonyl chloride and polycarbonate resin are shown in Table 1. Similarly, the evaluation results of carbonyl chloride and polycarbonate resin after long-term operation are shown in Table 2.
本発明の方法で得られる塩化カルボニルは、ポリカーボネート樹脂の原料として有用である。 The carbonyl chloride obtained by the method of the present invention is useful as a raw material for polycarbonate resin.
１ ヘッドランプレンズ本体
２ レンズのドーム状部分（凸側が可動側金型に対応する）
３ レンズの外周部分
４ 成形品のゲート（幅３０ｍｍ、ゲート部の厚み４ｍｍ）
５ スプルー（ゲート部の直径７ｍｍφ）
６ レンズの外周部分の直径（２２０ｍｍ）
７ レンズのドーム部分の直径（２００ｍｍ）
８ レンズのドーム部分の高さ（２０ｍｍ）
９ レンズ成形品の厚み（４ｍｍ）
1
3 Lens outer peripheral part 4 Molded product gate (width 30 mm, gate part thickness 4 mm)
5 Sprue (diameter 7mmφ of gate part)
6 Diameter of the outer periphery of the lens (220mm)
7 Lens dome diameter (200mm)
8 Height of lens dome (20mm)
9 Lens molded product thickness (4mm)
Claims (10)
１記載の塩化カルボニルの製造方法。 The method for producing carbonyl chloride according to claim 1, wherein the pressure during the carbonyl chloride reaction is 0.05 to 0.50 MPa (gauge pressure).
ルの製造方法。 The method for producing carbonyl chloride according to claim 1, wherein the average particle diameter of the activated carbon catalyst is in the range of 0.5 to 5.0 mm.
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