CN101608016B - Polycarbonate copolymer, method for producing same, resin composition, and molded article - Google Patents
Polycarbonate copolymer, method for producing same, resin composition, and molded article Download PDFInfo
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- CN101608016B CN101608016B CN2009101394565A CN200910139456A CN101608016B CN 101608016 B CN101608016 B CN 101608016B CN 2009101394565 A CN2009101394565 A CN 2009101394565A CN 200910139456 A CN200910139456 A CN 200910139456A CN 101608016 B CN101608016 B CN 101608016B
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- phenol
- copolycarbonate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000004417 polycarbonate Substances 0.000 title abstract description 58
- 229920000515 polycarbonate Polymers 0.000 title abstract description 58
- 239000011342 resin composition Substances 0.000 title abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- 239000007864 aqueous solution Substances 0.000 claims description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 33
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 31
- 230000004048 modification Effects 0.000 claims description 29
- 238000012986 modification Methods 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 125000001118 alkylidene group Chemical group 0.000 claims description 24
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 239000010452 phosphate Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 14
- 239000003463 adsorbent Substances 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000012695 Interfacial polymerization Methods 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 3
- 239000004431 polycarbonate resin Substances 0.000 claims description 3
- 150000002009 diols Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 125000002993 cycloalkylene group Chemical group 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 92
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 64
- -1 polytetramethylene Polymers 0.000 description 33
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 32
- 239000000243 solution Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 16
- 238000000605 extraction Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 150000003606 tin compounds Chemical class 0.000 description 11
- 230000001804 emulsifying effect Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 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 9
- 238000000926 separation method Methods 0.000 description 9
- 239000002594 sorbent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 229940085991 phosphate ion Drugs 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- NFIDBGJMFKNGGQ-UHFFFAOYSA-N 2-(2-methylpropyl)phenol Chemical group CC(C)CC1=CC=CC=C1O NFIDBGJMFKNGGQ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 0 *[N+](C1=CCCCC1)[O-] Chemical compound *[N+](C1=CCCCC1)[O-] 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical group CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 3
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical group CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 3
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- VFNUNYPYULIJSN-UHFFFAOYSA-N 2,5-diisopropylphenol Chemical compound CC(C)C1=CC=C(C(C)C)C(O)=C1 VFNUNYPYULIJSN-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- KFOLLPUZRCFERL-UHFFFAOYSA-N [O-2].[Mg+2].O=[Si]=O Chemical class [O-2].[Mg+2].O=[Si]=O KFOLLPUZRCFERL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004380 ashing Methods 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
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 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
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 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 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 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
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- ADLBJVQFNZETFN-UHFFFAOYSA-N 1-(4-hydroxyphenyl)-10h-anthracen-9-one Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1C(=O)C1=CC=CC=C1C2 ADLBJVQFNZETFN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- KDBZVULQVCUNNA-UHFFFAOYSA-N 2,5-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(C(C)(C)C)C(O)=C1 KDBZVULQVCUNNA-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- YYOQJBLGFMMRLJ-UHFFFAOYSA-N 3,5-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC(O)=CC(C(C)C)=C1 YYOQJBLGFMMRLJ-UHFFFAOYSA-N 0.000 description 1
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical class CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 1
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical compound C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-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
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- GSIWIEKVNXWKLE-UHFFFAOYSA-N O=CC1CC2OC2CC1 Chemical compound O=CC1CC2OC2CC1 GSIWIEKVNXWKLE-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZCWWGVYFXOYCND-UHFFFAOYSA-N aluminum magnesium dioxosilane oxygen(2-) Chemical compound [Si](=O)=O.[O-2].[Mg+2].[O-2].[Al+3] ZCWWGVYFXOYCND-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002650 habitual effect Effects 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
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
Abstract
The present invention provides a polycarbonate copolymer and a resin composition, which can be used for a molded article of a transparent optical member, particularly an optical member such as a lens, a light guide, and an optical disk, and a method for producing the same. A polycarbonate copolymer having repeating units represented by the following general formulae and (II), and a molded article molded from the polycarbonate compositionThe content of tin (as element) is less than 0.5ppm, [ formula 1 ]]
[R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms. X is a single bond, an alkylene group (-C) having 1 to 8 carbon atomsnH2n-, C2-C8 alkylene nH2nA C) cycloalkylene group having 5 to 15 carbon atoms (-C)nH2n-2-) and a C5-15 cycloalkylene group (C)nH2n-2＝)、-S-、-SO-、-SO2-, -O-, -CO-, or any one of the groups represented by the following formula (III-1) or the following formula (III-2). R3And R4Each independently represents an alkyl group having 1 to 3 carbon atoms. Y represents a linear or branched alkylene group (-C) having 2 to 15 carbon atomsnH2n-). a to d are each independently an integer of 0 to 4, and n is an integer of 2 to 200]. [ chemical formula 2)]
Description
Technical field
Tone, Copolycarbonate and the manufacture method thereof of excellent in te pins of durability, the resin combination that contain multipolymer and the molding of the present invention during about hot forming, this molding can be used for transparent optical element, particularly the optics fields such as lens, light guide, CD.
Background technology
Polycarbonate (following sometimes referred to as PC) multipolymer is mainly take dihydroxyphenyl propane as the raw material manufacturing, and the improvement of the various characteristics of PC multipolymer never is interrupted.By the PC of the manufacturings such as dihydroxyphenyl propane, owing to its transparency, thermotolerance, mechanical characteristics (particularly shock-resistance) excellence, therefore be widely used in various uses.But, have following shortcoming: when the molding of this PC being used for the optics such as lens, light guiding plate, CD, because flowability is lower, therefore can not get gratifying molding.In order further to improve mobile, the various polycarbonate of having improved have also been proposed.
For example, as the mobile method of improvement, the method that proposes to change by copolymerization, molecule chain end being carried out modification PC multipolymer structure is arranged.For example, have and propose the PC multipolymer (for example, with reference to patent documentation 1) that molecule chain end is used long chain alkyl modified.
But, by the terminal-modified PC multipolymer that the method obtains, only limit to the molecule chain end part owing to be used for promoting mobile position, so the import volume of chain alkyl is limited, the not talkative mobile size that promotes is sufficient.
In addition, patent documentation 2 has proposed the Copolycarbonate that copolymerization polytetramethylene glycol-two (4-HBA ester) obtains.Because this multipolymer has significantly been improved flowability when being shaped, and excellent heat stability, therefore can be used as shaping raw material is applied to multiple molding condition, and the result can obtain good optical forming piece.
But, there is following problem: make continuously the copolymerization poly-1 that above-mentioned patent documentation 2 is put down in writing, 4-butyleneglycol-two (4-HBA ester) and the Copolycarbonate that obtains when using this multipolymer under surpassing 320 ℃ hot forming condition, xanthochromia occurs.
The reason of general various Copolycarbonate xanthochromias much is to remain in the Copolycarbonate because derive from the impurity of comonomer.But, because every kind of employed comonomer of multipolymer and its behaviour in service are different, therefore also different along with every kind of comonomer as impurity and the using method of reason, be difficult to solve the problem (patent documentation 3～6) of various Copolycarbonate xanthochromias.
This kind xanthochromia also has the higher reason of forming temperature, but is subjected to the impact of catalyzer contained in the multipolymer also larger.Manufacturing is during as the phenol modification glycol of Copolycarbonate raw material, particularly used in the situation of tin class catalyzer, in traditional feed purification operation (for example, with reference to patent documentation 7) and the refining step of polycarbonate is (for example, with reference to patent documentation 8) in do not remove fully, used the successive polymerizations such as interfacial polymerization and melt phase polycondensation to make in the Copolycarbonate of this phenol modification glycol, the tin compound that derives from tin class catalyzer about meeting residual several ppm～tens of ppm.
Patent documentation 1: JP 2003-96180 communique
Patent documentation 2: JP 2005-247947 communique
Patent documentation 3: JP 2004-315747 communique
Patent documentation 4: JP 2005-336332 communique
Patent documentation 5: JP 2006-28391 communique
Patent documentation 6: JP 2007-70392 communique
Patent documentation 7: JP 2005-232287 communique
Patent documentation 8: Unexamined Patent 1-96212 communique
Summary of the invention
The present invention In view of the foregoing, purpose provides: when making the Copolycarbonate that uses phenol modification glycol, use can improve the high purity phenol modification glycol of resulting PC multipolymer thermostability at high temperature, obtains the manufacture method of Copolycarbonate, resin combination, molding and multipolymer.
People of the present invention are for solving above-mentioned problem, by finding after the research with keen determination, are derived from the foreign matter content of the synthesis material of the Copolycarbonate shown in the following general formula (I) by control, can address the above problem.The present invention is based on corresponding discovery and finish.
That is, the invention provides:
(I) a kind of Copolycarbonate is characterized in that,
It possess following general formula (I) and (II) shown in repeating unit, tin content (as element) below 0.5ppm,
[changing 1]
[R
1And R
2The alkyl that represents independently of one another carbonatoms 1～6.X is the alkylidene group (C of singly-bound, carbonatoms 1～8
nH
2n-) (alkylene), the alkylidene group (C of carbonatoms 2～8
nH
2n=) (alkylidene), the ring alkylidene group (C of carbonatoms 5～15
nH
2n-2-) (cycloalkylene), the ring alkylidene group (C of carbonatoms 5～15
nH
2n-2=) (cycloalkylene) ,-S-,-SO-,-SO
2-,-O-,-any one of the group shown in CO-or following formula (III-1) or the following formula (III-2).
[changing 2]
R
3And R
4The alkyl that represents independently of one another carbonatoms 1～3.Y represents the straight chain of carbon atom quantity 2～15 or contains the alkylidene group (C of side chain
nH
2n-).A～d independently integer of 0～4 of respectively doing for oneself, n is 2～200 integer].
(2) manufacture method of above-mentioned (1) described Copolycarbonate is characterized in that, as comonomer, use be phenol modification glycol synthetic in the presence of tin class catalyzer, that processed by phosphate aqueous solution or solid adsorbent.
(3) manufacture method of above-mentioned (2) described Copolycarbonate, wherein, the content (as element) of the tin in the above-mentioned phenol modification glycol is below 10ppm.
(4) a kind of poly carbonate resin composition wherein, contains above-mentioned (1) the described Copolycarbonate of 100 mass parts and the oxidation inhibitor of 0.01～0.5 mass parts.
(5) such as above-mentioned (4) described poly carbonate resin composition, wherein, the yellowness index of molding (YI) is below 1.5.
(6) a kind of molding that is shaped and forms by above-mentioned (4) or (5) described resin combination.
By the present invention, the tin content in the Copolycarbonate is controlled at below the 0.5ppm, can reduce the xanthochromia that produces in being shaped under the high temperature, and reduce the variable color under the endurance test, the result can obtain good molding.
Embodiment
In polycarbonate of the present invention (PC) multipolymer, be copolymerization phenol modification glycol and the polycarbonate that obtains, can be by being called as the habitual manufacture method manufacturing of interfacial polymerization.That is the method manufacturing that, can react by the carbonic ether presoma that makes dihydric phenol, phenol modification glycol and carbonyl chloride etc.
Concrete, for example, in the inert solvents such as methylene dichloride, exist in the situation of known acid acceptor and molecular weight regulator, add as required again catalyzer or branching agent, make the carbonic ether presoma reactions such as dihydric phenol, phenol modification glycol and carbonyl chloride.The PC multipolymer possess following general formula (I) and (II) shown in repeating unit.
[changing 3]
Above-mentioned general formula (I) and (II) in, [R
1And R
2The alkyl that represents independently of one another carbonatoms 1～6.X is the alkylidene group (C of singly-bound, carbonatoms 1～8
nH
2n-), the alkylidene group (C of carbonatoms 2～8
nH
2n=), the ring alkylidene group (C of carbonatoms 5～15
nH
2n-2-), the ring alkylidene group (C of carbonatoms 5～15
nH
2n-2=) ,-S-,-SO-,-SO
2-,-O-,-any one of the group shown in CO-or following formula (III-1) or the following formula (III-2).
[changing 4]
R
3And R
4The alkyl that represents independently of one another carbonatoms 1～3.Y represents the straight chain of carbon atom quantity 2～15 or contains the alkylidene group (C of side chain
nH
2n-).A～d independently integer of 0～4 of respectively doing for oneself, n is 2～200 integer, preferred 6～70 integer.
R
1～R
4Alkyl can be any of straight chain shape, chain.As R
1And R
2The object lesson of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl etc.
As R
3And R
4The object lesson of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl.
In addition, R
1And R
2It also can be the cyclic hydrocarbon group as cyclopentyl or cyclohexyl independently separately.
Alkylidene group (C as the carbonatoms 1～8 of X
nH
2n-), for example can enumerate methylene radical, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene etc.
Alkylidene group (C as the carbonatoms 2～8 of X
nH
2n=), for example can enumerate ethylidene, isopropylidene etc.
Ring alkylidene group (C as the carbonatoms 5～15 of X
nH
2n-2-), for example can enumerate ring pentylidene, cyclohexylene etc.Ring alkylidene group (C as the carbonatoms 5～15 of X
nH
2n-2=), can enumerate ring pentylidene, cyclohexylene etc.As dihydric phenol, can enumerate the compound of following general formula (Ia) expression.
[changing 5]
R in the general formula (Ia)
1And R
2, a and b, X be the same.
As the represented dihydric phenol of above-mentioned general formula (Ia), many kinds are arranged, particularly suitable is that 2,2-two (4-hydroxy phenyl) propane (is commonly called as: dihydroxyphenyl propane).As the bis-phenol beyond the dihydroxyphenyl propane, for example can enumerate, two (hydroxyaryl) paraffinic, two (hydroxyaryl) cycloalkane, the dihydroxyl aryl ethers, dihydroxyl diaryl sulfide class, dihydroxyl diaryl sulphoxide class, dihydroxyl diaryl sulfone class, dihydroxyl hexichol base class, the dihydroxyl Diarylfluorene, dihydroxyl diaryl adamantane, in addition, two (4-hydroxy phenyl) ditan, 4,4 '-[1,3-phenylene two (1-methyl ethylidene)] bis-phenol, 10,10-two (4-hydroxy phenyl)-9-anthrone, 1,5-two (4-hydroxy phenyl sulfo-)-2,3-dioxo amylene and α, alpha, omega-dihydroxy phenyl polydimethylsiloxane compound etc.These dihydric phenols can use separately separately, also can be used in combination.
As molecular weight regulator, so long as generally be used for the PC resin polymerization, then variously all can use.Concrete, as monohydric phenol, for example, phenol, adjacent normal-butyl phenol, between normal-butyl phenol, align butylphenol, adjacent isobutyl-phenol, between isobutyl-phenol, to isobutyl-phenol, o-tert-butylphenol, between tert.-butyl phenol, p-tert-butylphenol, adjacent n-pentyl phenol, between n-pentyl phenol, align amyl phenol, adjacent n-hexyl phenol, between n-hexyl phenol, align hexylphenol, to tert-octyl phenol, o cyclohexyl phenol, between cyclohexylphenol, p-cyclohexylphenol, orthoxenol, between phenyl phenol, p-phenyl phenol, adjacent n-nonyl phenol, between nonylphenol, align nonylphenol, o-isopropyl phenol, NSC 2209, australol, adjacent naphthyl phenol, between naphthyl phenol, to naphthyl phenol; 2,5-DI-tert-butylphenol compounds; 2,4-DTBP; 3,5-DI-tert-butylphenol compounds; 2,5-diisopropyl phenol; 3,5-diisopropyl phenol; P-cresol, bromophenol, tribromophenol, average carbon atom number 12～35 at the ortho position, a position or contraposition have the straight chain shape or contain the monoalkyl phenol of the alkyl of a chain; 9-(4-hydroxy phenyl)-9-(4-p-methoxy-phenyl) fluorenes; 9-(4-hydroxy-3-methyl phenyl)-9-(4-methoxyl group-3-aminomethyl phenyl) fluorenes; 4-(1-adamantyl) phenol etc.In these monohydric phenols, preferably use p-tert-butylphenol, australol, p-phenyl phenol etc.
As the catalyzer of interfacial polymerization, can preferably use alternate moving catalyst, for example, tertiary amine or its salt, quaternary ammonium salt, quaternary alkylphosphonium salt etc.As tertiary amine, for example can enumerate, triethylamine, Tributylamine, N, N-dimethylcyclohexylamine, pyridine, xylidine etc. in addition, as tertiary ammonium salt, for example can be enumerated, the hydrochloride of these tertiary amines, bromate etc.As quaternary ammonium salt, for example can enumerate, chlorination benzyl trimethyl ammonium, chlorination triethyl benzyl ammonium, chlorination tributyl benzyl ammonium, chlorination trioctylphosphine first ammonium, TBAC tetrabutylammonium chloride, bromination tetrabutylammonium etc. are as quaternary alkylphosphonium salt, for example can enumerate chlorination 4-butyl-phosphonium, Xiuization 4-butyl-phosphonium etc.These catalyzer can use separately separately, also can be used in combination.In the above-mentioned catalyzer, preferred tertiary amine, particularly triethylamine.
As inert organic solvents, have multiple.For example can enumerate methylene dichloride; Trichloromethane; Tetracol phenixin; 1,1-ethylene dichloride; 1,2-ethylene dichloride; 1，1，1-trichloroethane; Vinyl trichloride; Unsym.-tetraehloroethane; Sym.-tetrachloroethane; Pentaline; The chlorinated hydrocarbon of chlorobenzene etc., toluene, methyl phenyl ketone etc.These organic solvents can use separately separately, also can be used in combination.Wherein, specially suitable is methylene dichloride.
As branching agent, for example can use 1,1,1-three (4-hydroxy phenyl) ethane; 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-methylethyl] phenyl] ethylidene] bis-phenol; α, α ', α "-three (4-hydroxy phenyls)-1,3, the 5-triisopropylbenzene; 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α ', α '-two (4 "-hydroxy phenyl) ethyl] benzene; Phloroglucinol, trimellitic acid, isatin two (ortho-cresol) etc. have the compound of 3 above functional groups.
Employed phenol modification glycol is represented by following general formula (IIa) among the present invention.
[changing 6]
In the general formula (IIa), in the formula, R
3And R
4The alkyl that represents independently of one another carbonatoms 1～3, Y represent the straight chain of carbonatoms 2～15 or contain the alkylidene group (C of side chain
nH
2n-).C and d independently 0～4 the integer of respectively doing for oneself, n is 2～450 integer.
As R
3And R
4Represented alkyl can be enumerated, methyl, ethyl, n-propyl and sec.-propyl.A plurality of R are arranged
3The time, a plurality of R
3Can be identical or different, a plurality of R are arranged
4The time, a plurality of R
4Can be identical or different.As the straight chain of the represented carbonatoms 2～15 of Y or contain the alkylidene group (C of side chain
nH
2n-), can enumerate the alkylidene group (C such as ethylene, trimethylene, tetramethylene, Isosorbide-5-Nitrae-isobutylidene, pentamethylene and 1,5-isopentylidene
nH
2n-), the alkylidene group (C such as ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene
nH
2n=) residue.N is preferred 2～200, and more preferably 6～70.
The represented phenol modification glycol of above-mentioned general formula (IIa) is to carry out esterification or transesterification reaction and the compound of deriving by the represented Para Hydroxy Benzoic Acid of following general formula (IV) or logical formula V or its alkyl ester and polyether glycol described later.
[changing 7]
[changing 8]
In above-mentioned logical formula V and the general formula (IV), R
3The alkyl of expression carbonatoms 1～3.C is 0～4 integer.The alkyl of carbonatoms 1～3 is the same.
In the logical formula V, R
4The alkyl of expression carbonatoms 1～3.R
5The alkyl of expression carbonatoms 1～10.D is 0～4 integer.As the alkyl of carbonatoms 1～10,, also can enumerate normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, decyl etc. except the alkyl of above-mentioned carbonatoms 1～3.
As the represented Para Hydroxy Benzoic Acid of above-mentioned general formula (IV), can enumerate, to material of the replacement of alkyl that carbonatoms 1～3 is arranged on Para Hydroxy Benzoic Acid, m-hydroxybenzoic acid, adjacent Para Hydroxy Benzoic Acid (Whitfield's ointment) and their phenyl ring etc.
The alkyl ester of the Para Hydroxy Benzoic Acid that above-mentioned logical formula V is represented, its typical example be, for example, and to the Para Hydroxy Benzoic Acid methyl esters, to the Para Hydroxy Benzoic Acid ethyl ester and to Para Hydroxy Benzoic Acid n-propyl etc.
Polyether glycol is by HO-(Y-O)
nThe group of explanation is identical in-H[Y and the general formula (II)] expression, consisted of by the straight chain shape of the carbonatoms 2～15 that repeats or the alkyl oxide that contains a chain.Polyoxyethylene glycol, polypropylene glycol, poly-BDO etc. specifically can have been enumerated.From starting with easily and the hydrophobicity viewpoint, particularly preferably gather BDO.
The repeat number n of the ether moiety of polyether glycol is 2～200, preferred 6～70.N is more than 2, and the efficient during copolymerization phenol modification glycol is good, and n has the less advantage of PC multipolymer thermotolerance decline below 70.
The esterification of Para Hydroxy Benzoic Acid or its alkyl ester and polyether glycol or transesterification reaction are carried out in the situation that tin class catalyzer exists.
The usage quantity of tin class catalyzer is, for Para Hydroxy Benzoic Acid class or Para Hydroxy Benzoic Acid alkyl esters, usually about 0.01～10 quality %, about preferred 0.05～5 quality %, more preferably about 0.1～3 quality %.By more than 0.01 quality %, can obtain sufficient reactive behavior, by below 10 quality %, can suppress side reaction, and, can reduce the usage quantity of phosphate aqueous solution described later or solid adsorbent, further reduce the tin content in the resulting phenol modification glycol.
The refining phenol modification glycol that obtains for these methods to reduce tin content, is necessary.Concrete, can clean the process for purification of the thick liquid of reaction that contains phenol modification glycol by using phosphate aqueous solution or solid adsorbent, reduce the tin content in the phenol modification glycol, by having used the above-mentioned interfacial polymerization of this phenol modification glycol, can obtain the of the present invention Copolycarbonate of tin content (as element) below 0.5ppm.
When processing with phosphate aqueous solution, phosphoric acid and non-Combination organic solvent, such organic solvent diluting esterification or the resulting crude reaction resultant of transesterification reaction of for example methylene dichloride, pass through liquid-liquid extraction, the impurity such as tin compound that are derived from tin class catalyzer are extracted into the phosphoric acid layer, reduce content in the target compound with this.Preferred 0.5～40 quality % of the concentration of phosphate aqueous solution, more preferably 1.0～10 quality %, most preferably 2～5 quality %.By making phosphoric acid concentration more than 0.5 quality %, can guarantee the efficient of the impurity such as extraction of tin compound.By making phosphoric acid concentration below 10 quality %, can prevent the phosphorous draining of high density, protection of the environment, and can prevent unnecessarily excessive use phosphate aqueous solution, prevent that economy from descending.
The capacity of the phosphate aqueous solution that uses is preferably below the 26 capacity % of full capacity.By below 26 quality %, because organic layer is that disperse phase, phosphate aqueous solution are external phase during liquid-liquid extraction, can prevent from being derived from the decline of extraction efficiency of the tin compound of tin class catalyzer.Tin content (as element) in the phenol modification glycol is below 10ppm, below the preferred 5ppm.
During solid adsorbent is processed, by with organic solvent diluting esterification or the resulting crude reaction resultants of transesterification reaction such as methylene dichloride, make solid adsorbent disperse wherein, absorption is derived from the such impurity of tin compound of tin class catalyzer, can reduce content in the target compound with this.
As solid adsorbent, can use the compound adsorbent that is consisted of by atlapulgite, acidic white earth, ion exchange resin, resin, activated carbon, silicon-dioxide magnesium oxide aluminum oxide etc.Commercially available prod as sorbent material, for example can enumerate, (marshy land chemical industrial company makes ミ ズ カ ラ イ Off F-2G, silicon-dioxide magnesium oxide class sorbent material), (above-mentioned company makes ミ ズ カ ラ イ Off P-1, silicon-dioxide magnesium oxide class sorbent material), (above-mentioned company makes ガ レ オ Application ア one ス V2, atlapulgite class sorbent material), (above-mentioned company makes ミ ズ カ ソ one Block C-1, silica-based sorbent material), (Japanese atlapulgite company makes SA-1, atlapulgite class sorbent material), (Japanese atlapulgite company makes R15, atlapulgite class sorbent material), (consonance chemical industrial company makes キ ヨ one ワ one De KW700SL, silica alumina class sorbent material), (Japanese エ Application バ イ ロ ケ ミ カ Le ズ company makes egression A, activated carbon class sorbent material), CR11 (Japan's refining waters corporation manufacturing, resin).Because ミ ズ カ ラ イ Off F-2G (manufacturing of marshy land chemical industrial company), ミ ズ カ ラ イ Off P-1 (identical) are excellent to the absorption property of tin compound, therefore particularly preferably.
When processing operation by solid adsorbent, also can in tower, fill solid adsorbent, make the crude reaction resultant by this packing layer, adsorb the such impurity of tin compound that is derived from tin class catalyzer with this.
Also can suitably make at the reaction back segment is interior decompression, heats up in a steamer superfluous raw material (for example, Para Hydroxy Benzoic Acid or its alkyl ester).
In addition, in order effectively to remove impurity Para Hydroxy Benzoic Acid class, the pre-treatment as above-mentioned phosphate aqueous solution is processed or the solid adsorbent processing operates also can extract by weak base aqueous solution.
The pH of weak base aqueous solution is 8～11, preferably uses 8～10.PH is less than 8, and the extraction of Para Hydroxy Benzoic Acid class is not enough, and pH surpasses 11, and comonomer can be hydrolyzed.
As above-mentioned weak alkaline aqueous solution, can use basic metal (sodium, potassium etc.) or the oxyhydroxide of alkaline-earth metal (magnesium, calcium etc.) or the aqueous solution of carbonate, supercarbonate etc.
The extraction of the processing operation of phosphate aqueous solution, the processing operation of solid adsorbent and weak base aqueous solution can be carried out at normal temperatures, also can heat to about 30～40 ℃ and carry out.The extraction treatment of the processing operation of phosphate aqueous solution, the processing operation of solid adsorbent and weak base aqueous solution can repeatedly be carried out separately.
In the manufacturing process of PC multipolymer, for phenol modification glycol, in order to prevent that it from going bad, and preferably uses dichloromethane solution as far as possible.In the time that dichloromethane solution can't being used, can use the alkali aqueous solution of NaOH etc.
In the PC multipolymer, increase the copolymerization amount of phenol modification glycol, although can improve liquidity, thermotolerance can descend.Therefore, the copolymerization amount of phenol modification glycol is preferably selected according to desired flowability and stable on heating balance.The copolymerization amount of phenol modification glycol surpasses 40 quality %, shown in JP 62-79222 communique, can become the elastomerics shape, possibly can't be suitable for the purposes same with general PC resin.For keeping the thermotolerance more than 100 ℃, the amount of contained phenol modification diol residue in the PC multipolymer is 1～30 quality % in the present invention, preferred 1～20 quality %, more preferably 1～15 quality %.
PC multipolymer of the present invention, reduced viscosity are that 30～71[is equivalent to Mv (viscosity-average molecular weight)=10,000～28,100], preferred 37～62[is equivalent to Mv=13, and 100～24,100].Like this too in the PC copolymer compositions described later.Reduced viscosity is 30 when above, and mechanical properties is good, and reduced viscosity can well be brought into play the copolymerization effect of comonomer 70 when following.In addition, manifest high workability, comonomer that must be a large amount of, and reduced viscosity for the use of comonomer, can significantly not reduce thermotolerance below 71.In addition, reduced viscosity is measured according to ISO1628-4 (1999).
PC multipolymer of the present invention, the yield point value in the time of 280 ℃ (Q value) preferred 30 * 10
-2ML/ is more than second, and more preferably 40 * 10
-2ML/ is more than second.Yield point value (Q value) is the melt viscosity of measuring according to JIS K7210, use overhead system flow rate detection device, and yield point value (Q value) is 30 * 10
-2When mL/ second was above, it is too high that the melt viscosity of PC multipolymer can not become.PC copolymer compositions described later also is same.
PC copolymer compositions of the present invention is the composition that contains the oxidation inhibitor of 0.01～0.5 mass parts for the PC multipolymer of 100 mass parts.
As oxidation inhibitor, can enumerate aryl phosphine class, phosphorous acid esters, phosphoric acid ester, hindered phenolic etc.
In addition, PC copolymer compositions of the present invention also can be the composition that has mixed other the PC resins of tin content (as element) below 0.5ppm.
In addition, when these PC copolymer compositions are used for light guiding plate or optical lens etc., in order to improve light penetration, the preferred molecular weight that adds is about 1000～100,000 acrylic resin, more preferably except adding this acrylic resin, also added alicyclic epoxy compound or contain the PC based resin composition of the polysiloxane compound that is selected from alkoxyl group, vinyl and phenyl more than a kind.
As other PC resins that PC multipolymer of the present invention adds, can use the resin of tin content (as element) below 0.5ppm of market sale.The addition of other PC resin, based on the angle of not damaging effect of the present invention, preferably the PC multipolymer for 100 mass parts is below 300 mass parts, more preferably 10～200 mass parts.
Acrylic resin, at least a of monomeric unit that refers to be selected from vinylformic acid, acrylate, vinyl cyanide and derivative thereof is the polymkeric substance of repeating unit, be independent polymkeric substance or with the multipolymer of vinylbenzene, divinyl etc.Polyacrylic acid, polymethylmethacrylate (PMMA), polyacrylonitrile, ethyl propenoate-vinylformic acid-2-chloroethene ester copolymer, n-butyl acrylate-acrylonitrile copolymer, acrylonitritrile-styrene resin, acrylonitrile butadiene copolymer, acrylonitrile-butadiene-styrene copolymer etc. specifically can have been enumerated.Wherein, be particularly suitable for using polymethylmethacrylate (PMMA).
The molecular weight of propylene resin about 1000～100,000, preferred 20,000～60,000.Molecular weight is 1000～100,000, can not occur during shaping being separated too fastly between PC multipolymer, other PC resins and propylene resin, so molding has the sufficient transparency.As polymethylmethacrylate (PMMA), can use known material, general, preferably in the situation that superoxide, azo polymerization starter exist, methyl methacrylate monomer is carried out mass polymerization and make.
The addition of propylene resin is, for the PC multipolymer of the present invention of 100 mass parts or in PC multipolymer of the present invention, mixed the PC copolymer compositions of other PC resins, usually about 0.01～1 mass parts, preferred 0.05～0.5 mass parts, more preferably 0.1～0.3 mass parts.The addition of propylene resin can improve the transparency of molding more than 0.01 mass parts, below 1 mass parts, can keep the transparency on the basis of the physical property that can't harm other expectations.
As the alicyclic epoxy compound, refer to have the ester ring type epoxy group(ing), be on the vinyl bonds in the aliphatics ring addition 1 Sauerstoffatom and the ring-shaped fat compounds of group of the epoxy group(ing) that obtains, concrete, following formula (1)～(10) shown in the applicable Unexamined Patent 11-158364 communique are represented.
[changing 9]
[changing 10]
[changing 11]
In general formula (2) and (3), R is hydrogen atom or methyl.
[changing 12]
[changing 13]
In the general formula (5), respectively do for oneself 0～10 integer of a and b, a+b is 1～10 integer.
[changing 14]
In the general formula (6), respectively do for oneself 0～10 integer of a, b, c and d, a+b+c+d is 1～10 integer.
[changing 15]
In the general formula (7), respectively do for oneself 0～10 integer of a, b and c, a+b+c is 1～10 integer.
[changing 16]
In the general formula (8), n is 1～10 integer.
[changing 17]
In the general formula (9), R is the alkyl of hydrogen atom or above-mentioned carbonatoms 1～6.
[changing 18]
In the general formula (10), n is 1～10 integer, and R is the residue of the such compound with active hydrogen base of TriMethylolPropane(TMP).
The addition of above-mentioned each alicyclic epoxy compound is, to be generally about 0.01～1 mass parts preferred 0.02～0.2 mass parts for the PC copolymer compositions of 100 mass parts.By making this addition more than 0.01 mass parts, can obtain additive effect, by below 1 mass parts, can not produce and be separated, have the transparency.
Polysiloxane compound is to have introduced the reactive silicon compounds that is selected from functional group at least a in alkoxyl group (for example, methoxyl group, oxyethyl group), vinyl and the phenyl in the silicon compounds, can enumerate organopolysiloxane etc.This polysiloxane compound is the compound that plays a role as stablizer in the PC resin combination, adds polysiloxane compound, and bad order, the bubble of the xanthochromia that the thermal degradation when in the time of can preventing from being shaped causes, silver (silver bar) etc. are sneaked into.The addition of polysiloxane compound is for the Copolycarbonate of 100 mass parts, usually about 0.01～3 mass parts, preferably suitably to select in 0.05～2 mass parts.More than 0.01 mass parts, can manifest additive effect, 3 mass parts are following, can not produce smudgy etc. in the molding.
In the resin combination of the present invention, except above-mentioned each composition, also can as required, in the scope of not damaging effect of the present invention, add various additives.For example, the UV light absorber such as benzotriazole category, benzophenone can have been enumerated; The photostabilizers such as steric hindrance amine; The internal lubricants such as aliphatic carboxylic acid esters,'s class, paraffin class, silicone oil, polyvinyl wax; Fire retardant commonly used, flame retardant, releasing agent, static inhibitor, tinting material etc.
Embodiment
With comparative example the present invention is further specified by the following examples, but the present invention is not limited to these examples.In addition, the impurity level in each example is measured by the following method.
[Production Example 1-is poly--BDO-two (4-HBA ester) synthetic]
Stirrer is arranged, import nitrogen in the reaction vessel of thermometer, reflux cooler, raw material supplying mouth, gas introduction tube possessing, supply with poly--1 of 100 mass parts, 4-butyleneglycol [PTMG, Mn (number-average molecular weight)=2000], 15.8 mass parts to the Para Hydroxy Benzoic Acid methyl esters and as the dibutyl tin oxide of 0.05 mass parts of tin class catalyzer, be heated to 220 ℃, heat up in a steamer the methyl alcohol that generates on one side, Yi Bian carry out transesterification reaction.After reaction finishes, to reducing pressure in the reaction system, heat up in a steamer superfluously to the Para Hydroxy Benzoic Acid methyl esters, obtain the crude reaction resultant.
The crude reaction resultant is dissolved in methylene dichloride, makes the solution of concentration 20 quality %.In this dichloromethane solution of 80 capacity parts, add 0.1 % by mole the sodium bicarbonate aqueous solution of 20 capacity parts, 20 ℃ mix 30 minutes in having the steel basin of baffle plate, and the impurity that the water extractive reaction generates is to Para Hydroxy Benzoic Acid, then by standing separation, take the methylene dichloride phase.
The methylene dichloride of 75 capacity parts mutually in, add the 3.5 quality % phosphate aqueous solutions of 25 capacity parts, 20 ℃ mix 180 minutes in having the steel basin of baffle plate, and the water extraction is derived from the tin compound of tin class catalyzer, then by standing separation, take the methylene dichloride phase.
Again the methylene dichloride of 75 capacity parts mutually in, add the 3.5 quality % phosphate aqueous solutions of 25 capacity parts, 20 ℃ mix 180 minutes in having the steel basin of baffle plate, and the water extraction is derived from the tin compound of tin class catalyzer, then by standing separation, take the methylene dichloride phase.
In order to remove the micro-phosphoric acid of methylene dichloride in mutually, the methylene dichloride of 75 capacity parts mutually in, the pure water that adds 25 capacity parts, 20 ℃ mix 60 minutes in having the steel basin of baffle plate, then the water phosphoric acid extraction by standing separation, takes the methylene dichloride phase.
With methylene dichloride phase concentrating under reduced pressure, obtain the i.e. poly--BDO-two (4-HBA ester) [being designated hereinafter simply as PTMG-BHB] of phenol modification glycol.
By following HPLC (high performance liquid chromatography) quantitatively, tin quantitatively and phosphate ion quantitatively, confirm among the PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.2 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is (as element, together lower) be not enough 2ppm, phosphorus (as element, lower same) is 3ppm.
[Production Example 2-is poly--BDO-two (4-HBA ester) synthetic]
Use poly--BDO (Mn=1000) to replace the PTMG of Mn=2000, be 31.6 mass parts to the Para Hydroxy Benzoic Acid methyl esters, in addition, carry out in the same manner with Production Example 1, obtain PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively, tin quantitatively and phosphate ion quantitatively, confirm among the PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.2 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is not enough 2ppm, and phosphorus is not enough 2ppm.
[Production Example 3]
Use 1.0 quality % phosphate aqueous solutions to replace 3.5 quality % phosphate aqueous solutions, in addition, carry out in the same manner with Production Example 1, obtain PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively, tin quantitatively and phosphate ion quantitatively, confirm among the PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.2 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is 10ppm, and phosphorus is not enough 2ppm.
[Production Example 4]
Make 5.0 quality % phosphate aqueous solutions and replace 3.5 quality % phosphate aqueous solutions, in addition, carry out in the same manner with Production Example 1, obtain PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively, tin quantitatively and phosphate ion quantitatively, confirm Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.2 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is 5ppm, phosphorus is 4ppm.
[Production Example 5]
Until it is identical with embodiment 1 to heat up in a steamer the superfluous operation to the Para Hydroxy Benzoic Acid methyl esters, obtain the crude reaction resultant.
The crude reaction resultant is dissolved in the methylene dichloride, make the solution of concentration 20 quality %, the ミ ズ カ ラ イ Off F-2G (manufacturing of marshy land chemical industrial company) that wherein adds 5 quality %, 20 ℃ mix 3 hours, behind the absorption tin compound, use the membrane filter filtration under diminished pressure of aperture 0.2 μ m, filter F-2G.
In the resulting dichloromethane solution of 80 capacity parts, the 0.1 % by mole of sodium bicarbonate aqueous solution that adds 20 capacity parts, 20 ℃ mix 30 minutes in having the steel basin of baffle plate, the impurity that generates in the water extractive reaction is namely to Para Hydroxy Benzoic Acid, then by standing separation, take the methylene dichloride phase.
In order to remove the Trace Sodium of methylene dichloride in mutually, at the pure water that the methylene dichloride of 75 capacity parts adds 25 capacity parts in mutually, 20 ℃ mix 60 minutes in having the steel basin of baffle plate, and then water extraction sodium by standing separation, take the methylene dichloride phase.
Methylene dichloride is under reduced pressure concentrated mutually, and obtaining phenol modification glycol is PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively and tin quantitatively, among the affirmation PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.2 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is 5ppm.
[Production Example 6]
Except not using phosphate aqueous solution extraction to be derived from the tin compound of tin class catalyzer, carry out in the same manner with Production Example 1, obtain PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively and tin quantitatively, confirm among the PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.3 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is 190ppm.
[Production Example 7]
Make 0.5 quality % phosphate aqueous solution and replace 3.5 quality % phosphate aqueous solutions, in addition, carry out in the same manner with Production Example 1, obtain PTMG-BHB.By following HPLC (high performance liquid chromatography) quantitatively and tin quantitatively, confirm among the PTMG-BHB to Para Hydroxy Benzoic Acid less than 10 quality ppm, be 0.3 quality % to the Para Hydroxy Benzoic Acid methyl esters, tin is 70ppm, phosphorus is not enough 2ppm.
＜HPLC (high performance liquid chromatography) is quantitative 〉
By the HPLC (high performance liquid chromatography) of following condition, carry out quantitatively according to typical curve, this typical curve is by making to Para Hydroxy Benzoic Acid and to the standard substance of Para Hydroxy Benzoic Acid methyl esters.
(chromatogram) post: GL サ イ エ Application ス company makes ODS-3
(chromatogram) column temperature: 40 ℃
Solvent: the mixed solution of 0.5 quality % phosphate aqueous solution and acetonitrile (volume ratio 1: 2)
Flow velocity: 1.0ml/ minute
Tin in the＜comonomer quantitatively
(1) pre-treatment of test portion
The PTMG-BHB of weighing 1.0g in platinum (Pt) crucible adds vitriol oil 0.8ml, make its heating solid after, processed ashing 10 hours for 550 ℃.
Add sal enixum 0.5g, after the roasting kiln heating, heat behind the hydrochloric acid 3ml of adding 6mol/l, the dissolving ash content is decomposed in acid.
(2) measure
After above-mentioned sour decomposing solution let cool, be 25ml with the solution constant volume, 5 times of redilution, (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one company makes, and is SPS5100) quantitative at ICP-OES (high-frequency induction coupled plasma Emission Spectrophotometer) device with this solution.Emission Spectrophotometer is according to JIS K0116.
Tin in the＜polycarbonate quantitatively
(1) pre-treatment of test portion
The polycarbonate of weighing 3.0g in platinum dish adds vitriol oil 3.0ml, make its heating solid after, processed ashing 10 hours for 550 ℃.
Add the tetraboric acid acid anhydride lithium of 0.1g and the mixture that lithium fluoride adds with mass ratio at 9: 1, process after 30 minutes for 930 ℃, the tartaric aqueous nitric acid (mixed dissolution 5g tartrate, 40ml nitric acid, the 500ml water that add 15ml, add again entry, whole constant volume is 1000ml), heated and stirred, modulation alkali dissolution solution.
(2) measure
After above-mentioned alkaline solution let cool, constant volume was 25ml, 2.5 times of redilution, and (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one company makes, and is SPS5100) quantitative at ICP-OES with this solution.Emission Spectrophotometer is according to JIS K0116.
＜phosphorus quantitatively
Take the PTMG-BHB of 10g with the teflon (registered trademark) of capacity 200ml ス キ one Block ロ processed one ト weighing.
The refining methylene dichloride of adding 100ml (
*1), vibration dissolving PTMG-BHB.Add the 10ml pure water, vibrate 30 minutes with bobbing machine with 240 beats/mins speed, the phosphate ion in the test portion is extracted in water.
Then standing separation organic layer and water layer take water layer, and (Dionex corp. makes, DX-120) quantitative phosphate ion amount with the chromatography of ions map device.Reference liquid uses the phosphoric acid reference liquid.
Chromatography of ions figure is according to JIS K0127.
*Refining methylene dichloride: methylene dichloride and pure water are vibrated at teflon (registered trademark) ス キ one Block ロ processed one ト, clean methylene dichloride with pure water.Carry out this operation until the pure water of chromatography of ions map device after to extraction analyzed and do not detected phosphate ion again.Resulting methylene dichloride uses as refining methylene dichloride.
[embodiment P-1]
(1) polycarbonate (PC) oligopolymer synthesis procedure
In the aqueous sodium hydroxide solution of concentration 5.6 quality %, adding is the V-Brite B of 2000 quality ppm for the dihydroxyphenyl propane (BPA) of after a while dissolving, dissolve BPA in this solution, making BPA concentration is 13.5 quality %, the aqueous sodium hydroxide solution of modulation BPA.In the tube-type reactor of internal diameter 6mm, pipe range 30m, pass into continuously respectively aqueous sodium hydroxide solution and the methylene dichloride of above-mentioned BPA with the flow of 40l/ hour and 15l/ hour, pass into continuously carbonyl chloride with 4.0kg/ hour flow simultaneously.Tube-type reactor has the chuck part, passes into water coolant in the chuck, keeps the temperature of reaction solution below 40 ℃.
The reaction solution of sending from tube-type reactor is imported to possess continuously the tank reactor that retreats the wing, internal volume 40l, has baffle plate, again with 2.8l/ hour flow supply with BPA aqueous sodium hydroxide solution, with 0.07l/ hour flow supply with 25 quality % aqueous sodium hydroxide solution, with 17l/ hour flow for feedwater, supply with the triethylamine aqueous solution of 1 quality % with 0.64l/ hour flow, 29～32 ℃ of reactions.From tank reactor extraction liquid, standing separation is removed water continuously, takes the methylene dichloride phase.The oligomer concentrations of the polycarbonate oligomer solution that so obtains is 329g/l, and chloroformic acid ester group concentration is 0.74mol/l.
(2) polymerization process of PC multipolymer
Supply with to T.K PIPELINE emulsifying homogeneous machine (HOMO MIXER) 2SL type (manufacturing of プ ラ イ ミ Network ス company) with 20l/ hour flow: 40 quality % dichloromethane solutions, 3 quality % triethylamine aqueous solutions of 400ml/ hour flow and the 6.4 quality % aqueous sodium hydroxide solutions of 2.3kg/ hour flow of the PTMG-BHB that the synthesis example 1 of the methylene dichloride of the PC oligopolymer that above-mentioned synthesis procedure obtains, 12l/ hour flow, 868kg/ hour obtains, under the rotating speed of 3000rpm, prepare polymerization, obtain preparing polymer fluid.
Then, supply with to T.K PIPELINE emulsifying homogeneous machine 2SL type (manufacturing of プ ラ イ ミ Network ス company): this preparation polymer fluid of 960g/ hour flow and the 20 quality % dichloromethane solutions of PTBP (p-tert-butylphenol); 14.1kg/ BPA being dissolved in 6.4 quality % aqueous sodium hydroxide solutions of hour flow and to make its concentration be the aqueous solution that 8.8 quality % obtain.Under the rotating speed of 3000rpm, carry out emulsification, obtain emulsion.Then, this emulsion is imported the second reactor, this second reactor is to possess chuck is arranged, to have 2 orifice plates with 3 diameter 0.8mm holes to insert the orifice mixers of 19.05mm (3/4 inch) pipe arrangement, resupply to the 3rd reactor, the 3rd reactor is the tower steel basin of three sections on the oar formula wing of the jacketed 50l of tool, carries out polymerization.Stream has 15 ℃ water coolant in the chuck, and the temperature out of polymer fluid is made as 30 ℃.
In the dilution trap that possesses the 50l that oar type agitating wing is arranged, give with 11l/ hour flow continuous supplying: the polymer fluid that overflows from above-mentioned tower reactor and the methylene dichloride that is used for dilution.Then, the resulting emulsion of dilution trap is imported K.C.C centrifugal extractor (trade(brand)name, Kawasaki Heavy Industries company makes, internal volume 4l, turner diameter 430mm), carry out Centrifugical extraction with rotating speed 3000rpm, separate water layer and organic layer.
(3) the clean operation of alkali cleaning
Supply with to T.K PIPELINE emulsifying homogeneous machine 2SL type (manufacturing of プ ラ イ ミ Network ス company) with 7.8l/ hour flow: the organic layer that is obtained by above-mentioned centrifugal extractor and the aqueous sodium hydroxide solution of 0.03mol/l mix under the rotating speed of 3000rpm.From the outlet of emulsifying homogeneous machine mixed solution is imported centrifugal extractor, carry out Centrifugical extraction with rotating speed 3000rpm, separate water layer and organic layer.Then, the resulting emulsion of dilution trap is imported K.C.C centrifugal extractor (trade(brand)name, the manufacturing of Kawasaki Heavy Industries company, internal volume 4l, turner diameter 430mm), carry out Centrifugical extraction with rotating speed 3000rpm, separate water layer and organic layer, organic layer then is supplied to the clean operation of pickling.
(4) the clean operation of pickling
Supply with to T.K PIPELINE emulsifying homogeneous machine 2SL type (manufacturing of プ ラ イ ミ Network ス company) with 7.8l/ hour flow: the organic layer that obtains from the centrifugal extractor of the clean operation of alkali cleaning and the aqueous hydrochloric acid of 0.2mol/l mix under the rotating speed of 3000rpm.From the outlet of emulsifying homogeneous machine mixed solution is imported the standing separation groove, separate water layer and organic layer, organic layer then is supplied to the first washing step.
(5) first washing steps
Supplied with to T.K PIPELINE emulsifying homogeneous machine 2SL type (manufacturing of プ ラ イ ミ Network ス company) with 7.8l/ hour: organic layer and pure water from above-mentioned centrifugal extractor obtains mix under the rotating speed of 3000rpm.From the outlet of emulsifying homogeneous machine mixed solution is imported centrifugal extractor, carry out Centrifugical extraction with 3000rpm, separate water layer and organic layer, organic layer then is supplied to the second washing step.
(6) second washing steps
Supplied with to T.K PIPELINE emulsifying homogeneous machine 2SL type (manufacturing of プ ラ イ ミ Network ス company) with 7.8l/ hour: organic layer and pure water from centrifugal extractor obtains mix under the rotating speed of 3000rpm.From the outlet of emulsifying homogeneous machine mixed solution is imported centrifugal extractor, carry out Centrifugical extraction with rotating speed 3000rpm, separate water layer and organic layer, obtain the dichloromethane solution (organic layer) of refining polycarbonate.
(7) concentrated, drying process
The dichloromethane solution of refining polycarbonate is concentrated, pulverize, to the thin slice that obtains 105 ℃ of dryings under reduced pressure.The proterties of the Copolycarbonate that obtains is as follows.The amount of the PTMG-BHB residue of being tried to achieve by NMR is 4.0 quality %.The reduced viscosity of measuring according to ISO 1628-4 (1999) is 37.0 (Mv=13100).
[embodiment P-2]
434kg/ hour flow of 40 quality % dichloromethane solutions of the PTMG-BHB that obtains with Production Example 2,868kg/ hour flow of 40 quality % dichloromethane solutions of the PTMG-BHB that replacement Production Example 1 obtains, identical with embodiment P-1 in addition, obtain Copolycarbonate.
[embodiment P-3～P-5 and comparative example P-1, P-2]
The PTMG-BHB that the PTMG-BHB that obtains with Production Example 3～7 replaces Production Example 1 to obtain, identical with embodiment P-1 in addition, obtain Copolycarbonate.The physical property of the Copolycarbonate that embodiment P-1～P-5 and comparative example P-1, P-2 obtain is as shown in table 1.
[table 1]
Table 1
| Residue weight (quality %) | Reduced viscosity | Tin content (ppm) | |
| Embodiment P-1 | 4.0 | 37.0 | ＜0.1 |
| Embodiment P-2 | 4.0 | 37.1 | ＜0.1 |
| Embodiment P-3 | 4.0 | 36.9 | 0.4 |
| Embodiment P-4 | 4.0 | 37.0 | 0.2 |
| Embodiment P-5 | 4.0 | 37.0 | 0.2 |
| Comparative example P-1 | 4.0 | 36.9 | 7.0 |
| Comparative example P-2 | 4.0 | 37.0 | 2.5 |
[application examples 1]
Mix the Copolycarbonate that the embodiment P-1 of 100 mass parts obtains, the ア デ カ ス タ プ PEP-36 (trade(brand)name as oxidation inhibitor of 0.05 mass parts, ADEKA company makes), by possessing the 40mm φ forcing machine of ventilation hole (outlet), with 260 ℃ of granulations of resin temperature, obtain particle.The particle that use obtains is according to the flat board of following molding condition injection molding forming 35mm * 25mm * 2mm.
＜molding condition 〉
Forming mill: Toshiba Machine Co. Ltd makes, EC40N (trade(brand)name)
Shaping barrel zone temperature: 340 ℃
Residence time in the cylinder: 10 minutes
Take 5 the 13rd to penetrate (shot) molding afterwards, measure separately yellowness index (YI), try to achieve its mean value.The result is as shown in table 2.The measuring method of YI is as follows.
<YI>
Make the thick molding of 2.0mm by injection molding forming, the spectral photometric colour measuring meter ∑ 90 made from Japanese electric look industrial is to measure the penetrant method mensuration of area 30 φ, C2 light source.
[application examples 2～5]
Mix the Copolycarbonate that the embodiment P-2～P-5 of 75 mass parts obtains, the タ Off ロ Application FN1500 (trade(brand)name of 25 mass parts, the Bis-A polycarbonate that the emerging product of bright dipping company makes, VN=39.5), the ア デ カ ス タ Block PEP-36 (trade(brand)name as oxidation inhibitor of 0.05 mass parts, ADEKA company makes), by possessing the 40mm φ extruding machine of ventilation hole (outlet), with 260 ℃ of granulations of resin temperature, obtain particle.Other are identical with application examples 1, measure YI.
[using comparative example 1～2]
The Copolycarbonate that the Copolycarbonate replacement embodiment P-1 that obtains except usage comparison example P-1～P-2 obtains, other are identical with application examples 1, obtain particle, measure YI.
[application examples 6]
Mix the Copolycarbonate that the embodiment P-1 of 75 mass parts obtains, the タ Off ロ Application FN1500 (trade(brand)name of 25 mass parts, the Bis-A polycarbonate that bright dipping petroleum chemistry company makes, VN=39.5), 0.05 the ア デ カ ス タ Block PEP-36 (trade(brand)name as oxidation inhibitor of mass parts, ADEKA company makes), 0.1 the ダ イ ャ Na one Le BR83 (trade(brand)name of mass parts, the レ of Mitsubishi one ヨ Application company makes, acrylic resin, molecular weight 40000), 0.1 the KR511 (trade(brand)name of mass parts, シ リ コ one Application company of SHIN-ETSU HANTOTAI makes, organo-siloxane with methoxyl group and vinyl), 0.05 the セ ロ キ サ イ De 2021P (trade(brand)name of mass parts, the alicyclic epoxy resin of above-mentioned formula (1) expression that ダ イ セ Le chemical industrial company makes), by possessing the 40mm φ extruding machine of ventilation hole (outlet), with 260 ℃ of granulations of resin temperature, obtain particle.
The particle that use obtains, identical with application examples 1, measure YI.YI is 0.9.
[table 2]
Table 2
| YI | |
| Application examples 1 | 1.0 |
| Application examples 2 | 1.0 |
| Application examples 3 | 1.1 |
| Application examples 4 | 1.0 |
| Application examples 5 | 1.0 |
| Application examples 6 | 0.9 |
| Use comparative example 1 | 2.3 |
| Use comparative example 2 | 1.7 |
The industry utilizability
The molding of the Copolycarbonate that the resulting tin content of the present invention is lower is suitable for using in transparent optical element, particularly the optics fields such as lens, light guide, CD.
Claims (4)
1. a Copolycarbonate is characterized in that,
It possess following general formula (I) and (II) shown in repeating unit, form below 0.5ppm and by the interfacial polymerization copolymerization as the content of the tin of element,
[changing 1]
In the formula, R
1And R
2The alkyl that represents independently of one another carbonatoms 1～6, X represent the alkylidene group-C of singly-bound, carbonatoms 1～8
nH
2n-, the alkylidene group C of carbonatoms 2～8
nH
2n=, the ring alkylidene group-C of carbonatoms 5～15
nH
2n-2-, the ring alkylidene group C of carbonatoms 5～15
nH
2n-2=,-S-,-SO-,-SO
2-,-O-,-any one of the group shown in CO-or following formula (III-1) or the following formula (III-2),
[changing 2]
R
3And R
4The alkyl that represents independently of one another carbonatoms 1～3, Y represent the straight chain of carbon atom quantity 2～15 or contain the alkylidene group-C of side chain
nH
2n-, a～d is 0～4 integer independently of one another, n is 2～200 integer,
The amount of contained phenol modification diol residue is 1～30 quality % in the multipolymer,
And described multipolymer is 30～71 according to the reduced viscosity that ISO 1628-4 (1999) measures.
2. the manufacture method of Copolycarbonate claimed in claim 1, it is characterized in that, as comonomer, what use is phenol modification glycol synthetic in the presence of tin class catalyzer, that processed with phosphate aqueous solution or solid adsorbent, and in the described phenol modification glycol as the content of the tin of element below 10ppm.
3. poly carbonate resin composition wherein, contains the Copolycarbonate of claim 1 of 100 mass parts and the oxidation inhibitor of 0.01～0.5 mass parts.
4. molding that is shaped and forms by resin combination claimed in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008158394 | 2008-06-17 | ||
| JP2008158394A JP5654727B2 (en) | 2008-06-17 | 2008-06-17 | POLYCARBONATE COPOLYMER, PROCESS FOR PRODUCING THE SAME, RESIN COMPOSITION AND MOLDED ARTICLE |
| JP2008-158394 | 2008-06-17 |
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| CN101608016A CN101608016A (en) | 2009-12-23 |
| CN101608016B true CN101608016B (en) | 2013-04-10 |
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| CN2009101394565A Expired - Fee Related CN101608016B (en) | 2008-06-17 | 2009-06-17 | Polycarbonate copolymer, method for producing same, resin composition, and molded article |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5654727B2 (en) |
| KR (1) | KR20090131261A (en) |
| CN (1) | CN101608016B (en) |
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| WO2013088796A1 (en) | 2011-12-13 | 2013-06-20 | 出光興産株式会社 | Aromatic polycarbonate resin composition and optical molded article |
| JP5879124B2 (en) | 2011-12-28 | 2016-03-08 | 出光興産株式会社 | Method for producing polycarbonate resin composition pellets |
| WO2015047046A1 (en) * | 2013-09-30 | 2015-04-02 | (주) 엘지화학 | Polycarbonate having high fluidity and production method therefor |
| KR101856329B1 (en) * | 2015-07-01 | 2018-05-11 | 주식회사 엘지화학 | Copolycarbonate resin and method for preparing the same |
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| US5239020A (en) * | 1985-08-21 | 1993-08-24 | Eastman Kodak Company | Polyester/polycarbonate blends |
| CN1110283A (en) * | 1994-04-14 | 1995-10-18 | 大世吕化学工业株式会社 | Process for the preparation of (co)polycarbonate |
| CN1918210A (en) * | 2004-02-19 | 2007-02-21 | 出光兴产株式会社 | Method for preparing polycarbonate copolymer |
| CN1926171A (en) * | 2004-03-03 | 2007-03-07 | 出光兴产株式会社 | Copolycarbonates, copolycarbonate compositions, and optical molded articles obtained therefrom |
| CN1976974A (en) * | 2004-07-01 | 2007-06-06 | 出光兴产株式会社 | Method for producing polycarbonate copolymer and polycarbonate copolymer |
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|---|---|---|---|---|
| DE2827325A1 (en) * | 1978-06-22 | 1980-01-10 | Bayer Ag | METHOD FOR THE PRODUCTION OF ALIPHATIC-AROMATIC POLYCARBONATES WITH DIPHENOL CARBONATE END GROUPS AND THE USE THEREOF FOR THE PRODUCTION OF THERMOPLASTICALLY PROCESSABLE, HIGHLY MOLECULAR, SEGMENTED, ALIPHATIC-AROMATIC-AROMATIC-AROMATIC-AROMATIC-AROMATIC-AROMATIC |
| US4663399A (en) * | 1985-08-22 | 1987-05-05 | General Electric Company | Polycarbonate-polyether block copolymers, polymer blends containing same and intermediates for the production thereof |
| JPS6284035A (en) * | 1985-10-08 | 1987-04-17 | Mitsui Petrochem Ind Ltd | Triphenol compound |
| JP3315477B2 (en) * | 1992-10-14 | 2002-08-19 | ダイセル化学工業株式会社 | Production method of polycarbonate |
| JPH0725830A (en) * | 1993-07-08 | 1995-01-27 | Daicel Chem Ind Ltd | Method for purifying carbonic acid diester and polycarbonate produced by using carbonic acid diester obtained by the same method for purification |
| DE69425130T2 (en) * | 1994-04-14 | 2000-11-09 | Daicel Chem | Process for the production of (co) polycarbonates |
| JPH10168175A (en) * | 1996-12-10 | 1998-06-23 | Mitsui Chem Inc | Purification of aliphatic polyester |
-
2008
- 2008-06-17 JP JP2008158394A patent/JP5654727B2/en not_active Expired - Fee Related
-
2009
- 2009-06-12 TW TW098119747A patent/TW201011056A/en unknown
- 2009-06-16 KR KR1020090053396A patent/KR20090131261A/en not_active Application Discontinuation
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| US5239020A (en) * | 1985-08-21 | 1993-08-24 | Eastman Kodak Company | Polyester/polycarbonate blends |
| CN1110283A (en) * | 1994-04-14 | 1995-10-18 | 大世吕化学工业株式会社 | Process for the preparation of (co)polycarbonate |
| CN1918210A (en) * | 2004-02-19 | 2007-02-21 | 出光兴产株式会社 | Method for preparing polycarbonate copolymer |
| CN1926171A (en) * | 2004-03-03 | 2007-03-07 | 出光兴产株式会社 | Copolycarbonates, copolycarbonate compositions, and optical molded articles obtained therefrom |
| CN1976974A (en) * | 2004-07-01 | 2007-06-06 | 出光兴产株式会社 | Method for producing polycarbonate copolymer and polycarbonate copolymer |
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| KR20090131261A (en) | 2009-12-28 |
| TW201011056A (en) | 2010-03-16 |
| JP2009298994A (en) | 2009-12-24 |
| JP5654727B2 (en) | 2015-01-14 |
| CN101608016A (en) | 2009-12-23 |
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