WO2023277624A1 - 폴리페닐렌 옥사이드의 제조방법 - Google Patents
폴리페닐렌 옥사이드의 제조방법 Download PDFInfo
- Publication number
- WO2023277624A1 WO2023277624A1 PCT/KR2022/009454 KR2022009454W WO2023277624A1 WO 2023277624 A1 WO2023277624 A1 WO 2023277624A1 KR 2022009454 W KR2022009454 W KR 2022009454W WO 2023277624 A1 WO2023277624 A1 WO 2023277624A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amine
- pyridine
- cresol
- ortho
- polyphenylene oxide
- Prior art date
Links
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 168
- 229920006380 polyphenylene oxide Polymers 0.000 title claims abstract description 168
- 238000000034 method Methods 0.000 title claims abstract description 27
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 204
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 38
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 128
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 87
- 239000003054 catalyst Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 46
- 238000004519 manufacturing process Methods 0.000 claims description 37
- 239000000654 additive Substances 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 15
- 238000004508 fractional distillation Methods 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 150000003335 secondary amines Chemical class 0.000 claims description 13
- 230000005587 bubbling Effects 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 6
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 6
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 claims description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003927 aminopyridines Chemical class 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 4
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 claims description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 3
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 3
- 230000002152 alkylating effect Effects 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960004979 fampridine Drugs 0.000 claims description 3
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 claims description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 3
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 claims description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 2
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 claims description 2
- XYGFISRAXLLACA-UHFFFAOYSA-N 6-propan-2-ylpyridin-3-amine Chemical compound CC(C)C1=CC=C(N)C=N1 XYGFISRAXLLACA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 2
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 claims description 2
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 claims description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 claims description 2
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 claims description 2
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 2
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 claims description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 claims 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims 1
- 230000029936 alkylation Effects 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 7
- 238000002955 isolation Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000376 reactant Substances 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- -1 polyphenylene Polymers 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- OSJAVLJEMGYHGN-UHFFFAOYSA-N [Zr].[W] Chemical compound [Zr].[W] OSJAVLJEMGYHGN-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFTJOJZFWHQVDD-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C.CC1=CC=CN=C1C UFTJOJZFWHQVDD-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IPIOTZDJIIDRBQ-UHFFFAOYSA-N 4-methylpyridine;pyridine Chemical compound C1=CC=NC=C1.CC1=CC=NC=C1 IPIOTZDJIIDRBQ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- DWWOZCUXMGDXEX-UHFFFAOYSA-N [Fe+2].[O-2].[V+5] Chemical compound [Fe+2].[O-2].[V+5] DWWOZCUXMGDXEX-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 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
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011899 heat drying method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920013637 polyphenylene oxide polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
Definitions
- the present invention relates to a method for preparing polyphenylene oxide.
- Polyphenylene oxide is a type of engineering plastic that exhibits chemical resistance and high heat resistance and has excellent mechanical and electrical properties.
- Commercially available PPOs have a number average molecular weight of 20,000 to 60,000 g/mol, and are synthesized through oxidative coupling using phenolic monomers.
- the commercially available PPO is composed of an oligomer having a number average molecular weight of 1,300 to 2,700 g/mol and a polymer having a number average molecular weight of 17,000 to 29,000 g/mol.
- 2,6-xylenol among phenolic monomers used in the manufacture of PPO is obtained through alkylation of phenol.
- ortho -Cresol (o-cresol) and 2,4,6-trimethylphenol by-products are produced together. Accordingly, a separation and purification process is required for the dispersions, but since these by-products have a boiling point difference of about 10° C. from 2,6-xylenol, separation and purification are difficult and costly.
- a 140-stage column is used to separate ortho-cresol, a major by-product, or an azeotropic distillation method with decane is used, which increases the production cost of 2,6-xylenol and PPO using the same. has become a major factor leading to
- a separate separation and purification process for ortho-cresol produced after the alkylation reaction of phenol is unnecessary, thereby reducing energy costs and producing polyphenylene oxide with excellent yield under mild oxidative coupling reaction conditions. It is intended to provide a method for producing polyphenylene oxide that can be produced.
- a first step of preparing a mixture including 2,6-xylenol and ortho-cresol by alkylating phenol with methanol A second step of subjecting the mixture to an oxidative coupling reaction in the presence of a copper-based catalyst and an amine-based additive; and a third step of separating ortho-cresol from the reaction product obtained as a result of the second step and obtaining polyphenylene oxide composed of repeating units represented by the following formula (1), wherein the mixture comprises 2 of polyphenylene oxide containing ortho-cresol in a molar ratio of 0.2 to 0.8 with respect to 1 mole of ,6-xylenol, and the amine-based additive includes a secondary amine, a pyridine-based compound, or a mixture thereof
- a manufacturing method is provided:
- n is an integer greater than or equal to 1
- first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.
- the mixture contains ortho-cresol in a molar ratio of 0.2 to 0.8 with respect to 1 mole of 2,6-xylenol,
- the amine-based additive includes a secondary amine, a pyridine-based compound, or a mixture thereof:
- n is an integer greater than or equal to 1.
- the inventors of the present invention when producing polyphenylene oxide by an oxidative coupling reaction of 2,6-xylenol, 2,6-xylenol produced through an alkylation reaction with phenol was converted into an organ produced by a side reaction. It is used as it is mixed with so-cresol, but the content ratio of ortho-cresol to 2,6-xylenol is controlled by adjusting the alkylation reaction conditions, and together with an oxidation coupling reaction catalyst, It was confirmed that polyphenylene oxide having excellent processability could be produced with excellent yield by using an amine-based additive capable of acting as a ligand for the catalyst.
- ortho-cresol usually has a small boiling point difference from 2,6-xylenol, so it is not easy to separate and purify it, and there are problems in that the cost of separation and purification is high.
- the separation and purification process of ortho-cresol for 2,6-xylenol can be omitted, and after the production of polyphenylene oxide through the oxidative coupling reaction, in the reaction system By separating and removing the remaining ortho-cresol using the difference in boiling point, energy costs can be greatly reduced.
- the above steps that is, the first to third steps may proceed as a series of reactions.
- the first step is to prepare a mixture containing 2,6-xylenol and ortho-cresol through an alkylation reaction with phenol.
- the mixture includes ortho-cresol in a molar ratio of 0.2 to 0.8 with respect to 1 mole of 2,6-xylenol.
- the reaction product obtained as a result of the alkylation reaction contains 95% by weight or more of 2,6-xylenol and ortho-cresol based on the total weight of the reaction product, and 5% by weight of 2,4,6-trimethylphenol. % or less.
- the mixture of 95% by weight or more of 2,6-xylenol and ortho-cresol 60% by weight or more of 2,6-xylenol and 40% by weight or less of ortho-cresol are present. More specifically, 75 to 80% by weight of 2,6-xylenol and 20 to 25% by weight of ortho-cresol.
- ortho-cresol improves the dielectric constant of the solvent and the solubility of the catalyst during the oxidative coupling reaction for producing polyphenylene oxide, and polyphenylene
- the content of ortho-cresol in the mixture used in the preparation of ren oxide was controlled.
- the mixture contains ortho-cresol in a molar ratio of 0.2 to 0.8 with respect to 1 mol of 2,6-xylenol, so that the ortho-cresol can increase the dielectric constant of the solvent used in the oxidative coupling reaction and It can improve the solubility of the catalyst and improve the yield of the resulting PPO.
- the ortho-cresol content is less than 0.2 mol, the effect of improving the dielectric constant of the solvent and the solubility of the catalyst is insignificant, resulting in a decrease in the yield of PPO, and a decrease in physical properties, especially molecular weight distribution characteristics, of the resulting PPO. It can be.
- ortho-cresol in a molar ratio of 0.2 to 0.8 with respect to 1 mol of 2,6-xylenol
- ortho-cresol may be coordinated to the catalyst due to an excessively high content, reducing the catalytic activity, and ortho-cresol may be copolymerized in the PPO to be produced, resulting in the formation of PPO. properties may deteriorate.
- the mixture is more specifically 2,6-xylenol 0.2 mol or more, or 0.3 mol or more, or 0.35 mol or more, or 0.4 mol or more, or 0.45 mol or more, or 0.48 mol or more, and 0.8 mol or less, or 0.75 mol or less, or 0.6 mol or more, per 1 mol mol or less, or 0.55 mol or less, or 0.5 mol or less.
- the alkylation reaction in the first step is a reaction such as a reactant and its input amount, catalyst, reaction temperature, etc. to satisfy the condition of the content ratio of ortho-cresol in the final mixture. Conditions can be adjusted appropriately.
- methanol may be used in an amount of 2 to 8 moles per mole of phenol. If the ratio of methanol to phenol is too small, the amount of ortho-cresol produced greatly increases, whereas if the ratio of methanol to phenol is large, the content of 2,6-xylenol increases, but there is concern about the generation of side reactions due to unreacted methanol there is Therefore, considering the content ratio of 2,6-xylenol and ortho-cresol in the mixture containing 2,6-xylenol and ortho-cresol obtained as a result of the alkylation reaction, methanol within the above range It is desirable to appropriately adjust the input amount.
- the methanol may be used in a ratio of 2 moles or more, or 3 moles or more, and 8 moles or less, or 5 moles or less with respect to 1 mole of phenol, so that the above molar ratio conditions can be implemented.
- the alkylation reaction is an alkylation reaction such as a zirconium-tungsten-based catalyst, a magnesium oxide-based catalyst, an iron-vanadium oxide-based catalyst, a manganese oxide-based catalyst, a cobalt-ferride-type catalyst, an alumina catalyst, or a Y-zeolite-type catalyst. It can be carried out in the presence of a catalyst.
- the alkylation reaction catalyst may be used in the form of a supported catalyst supported on a carrier such as silica.
- a zirconium-tungsten-based catalyst that exhibits excellent catalytic activity during an alkylation reaction may be used, and the catalyst may be a supported catalyst supported on silica.
- water may be selectively added during the alkylation reaction, and in this case, it may be added in a ratio of 3 moles or less, more specifically, 1 to 3 moles, based on 1 mole of phenol.
- the alkylation reaction may be carried out at a temperature of 250 °C to 500 °C, more specifically, 250 °C or higher, or 300 °C or higher, and 500 °C or lower, or 450 °C or lower.
- the alkylation reaction may be performed under pressure conditions of 1 atm to 3 atm, more specifically, 1 atm or more, or 1.2 atm or more, and 3 atm or less, or 1.5 atm or less.
- the alkylation reaction may be carried out under an inert gas atmosphere such as nitrogen or argon, or under a reducing atmosphere such as hydrogen depending on the catalyst used.
- an inert gas atmosphere such as nitrogen or argon
- a reducing atmosphere such as hydrogen depending on the catalyst used.
- 2,6-xylenol and ortho-cresol are produced as side-reactants, and the resulting ortho-cresol satisfies the content ratio condition as described above.
- 2,6-xylenol or ortho-cresol is further added to increase the content ratio of ortho-cresol to 2,6-xylenol within the above content ratio range.
- the manufacturing method according to the present invention selectively adds 2,6-xylenol or ortho-cresol to the obtained mixture after the alkylation reaction to satisfy the above-described ortho-cresol content condition. can be further included.
- the mixture in the present invention includes 2,6-xylenol and ortho-cresol so as to satisfy the above content ratio range conditions, but may further include 2,4,6-trimethylphenol.
- 2,4,6-trimethylphenol it is greater than 0 wt%, or 0.0001 wt% or more, and less than 2 wt%, or 1 wt% or less, or 0.1 wt% or less, based on the total weight of the mixture, or 2,4,6-trimethylphenol may be further included in an amount of 0.01% by weight or less.
- the second step is a step of subjecting the mixture prepared in the first step to an oxidative coupling reaction.
- the oxidative coupling reaction may be performed in the presence of a copper-based catalyst and an amine-based additive.
- the copper-based catalyst examples include cuprous compounds such as cuprous oxide, cuprous halide, cuprous sulfate, or cuprous nitrate; cupric compounds such as cupric oxide, cupric halide, cupric sulfate, or cupric nitrate; or salts thereof, and any one or a mixture of two or more of them may be used.
- the copper-based catalyst may be specifically used in an amount of 0.001 to 0.1 mole based on 1 mole of 2,6-xylenol. When used within the above content range, the yield of polyphenylene oxide is improved due to sufficient catalytic activity, and color development by the catalyst can be prevented.
- the copper-based catalyst is more specifically 0.001 mol or more, or 0.003 mol or more, or 0.005 mol or more, or 0.0075 mol or more, or 0.008 mol or more based on 1 mol of 2,6-xylenol, or 0.01 mole or more, and may be used in an amount of 0.1 mole or less, or 0.05 mole or less, or 0.03 mole or less.
- the amine-based additive serves as a ligand for the copper-based catalyst.
- the amine-based additive specifically includes a secondary amine, a pyridine-based compound, or a mixture thereof.
- the secondary amine specifically has two C 1-20 aliphatic alkyl groups in the molecule. More specifically, it has two C 1-20 straight-chain or branched alkyl groups. Due to such a structure, coordination with a copper-based catalyst is easy, and as a result, catalytic reactivity can be increased. Accordingly, compared to the case of using a primary amine, a tertiary amine, a diamine containing two amino groups in a molecule, or a secondary amine containing a cycloalkyl group or an aromatic ring structure, the yield of polyphenylene oxide can be greatly increased. there is.
- the secondary amine examples include dimethyl amine, diethyl amine, di-n-propyl amine, di-i-propyl amine, di-n-butyl amine (or dibutyl amine), di-i-butyl amine, di -t-butyl amine, dipentylamine, dihexylamine, dioctyl amine, didecyl amine, methylethyl amine, methylpropyl amine, or methylbutyl amine; any one or a mixture of two or more of these may be used.
- the pyridine-based compound is specifically 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4-dimethylaminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2, aminopyridine compounds such as 6-diamino pyridine, 2-amino-6-methyl pyridine, 3-amino-6-isopropyl pyridine, or 4-pyrrolidino pyridine; monoalkyl pyridine-based compounds such as 2-methyl pyridine, 3-methyl pyridine, and 4-methyl pyridine; Or 2,3-dimethyl pyridine (or 2,3-lutidine (2,3-lutidine)), 2,4-dimethyl pyridine, 2,5-dimethyl pyridine, 2,6-dimethyl pyridine, 3,4-dimethyl dialkyl pyridine-based compounds such as pyridine or 3,5-dimethyl pyridine; and the like, and any one or a mixture of two or more of them may
- the amine-based additive may be appropriately selected and used according to the type of the copper-based catalyst described above.
- a copper-based catalyst and an amine-based additive are used in an optimal combination, the yield of polyphenylene oxide can be further increased and the physical properties of the produced polyphenylene oxide can be further improved.
- a cuprous compound specifically cuprous oxide, cuprous halide, cuprous sulfate, cuprous nitrate or a salt thereof is used as the copper-based catalyst, and a pyridine-based compound is used as the amine-based additive
- the cuprous compound may be more specifically a cuprous halide compound such as cuprous chloride or cuprous bromide, and more specifically may be cuprous chloride.
- the pyridine-based compound may be an aminopyridine-based compound such as 2-amino pyridine, 3-amino pyridine, or 4-amino pyridine.
- the aminomyridine-based compound may exhibit a more excellent effect of improving the yield of polyphenylene oxide and the effect of improving the processability of polyphenylene oxide due to the structural characteristics of easy coordination with the catalyst.
- cupric compound specifically cupric oxide, cupric halide, cupric sulfate, cupric nitrate or a salt thereof
- a secondary amine is used as the amine-based additive
- the yield of phenylene oxide can be increased, and the processability of the polyphenylene oxide produced can be improved.
- the cupric compound may be more specifically a cupric halide compound such as cupric chloride or cupric bromide, and more specifically may be cupric chloride.
- the secondary amine may have two C 1-8 or C 2-6 chain-type alkyl groups, and more specifically, di-n-butylamine, diethylamine, di-n-hexylamine , or di-n-propylamine.
- the secondary amine is not only easy to coordinate with the catalyst, but also the coordinated complex can exhibit high reactivity, further improving the yield of polyphenylene oxide, and also increasing the molecular weight of the polyphenylene oxide produced and The effect of improving thermal characteristics can be realized.
- the amine-based additive may be used in an amount of 0.1 to 1 mole based on 1 mole of the 2,6-xylenol.
- the amount of the amine-based additive is 0.1 mol or more, or 0.2 mol or more, or 0.3 mol or more, or 0.34 mol or more, or 0.4 mol or more, based on 1 mol of 2,6-xylenol, and 1 mol or less, or 0.8 moles or less, or 0.7 moles or less, or 0.68 moles or less, or 0.5 moles or less may be used.
- the oxidative coupling reaction may be performed under oxygen or air conditions.
- the manufacturing process can be performed under mild reaction conditions compared to the conventional oxidative coupling reaction performed under conditions of oxygen input.
- the oxidation coupling reaction may be performed by introducing air at a rate of 80 to 350 cc/min by air bubbling.
- the oxygen content in the air is specifically 30% or less, more specifically 21% or less, and may be 10% or more.
- Oxygen in the air acts to accelerate the oxidative coupling reaction, but when the oxidative coupling reaction is performed under conditions of oxygen input as in the prior art, there are problems such as a decrease in yield and an explosion.
- process safety and yield can be improved by performing the oxidative coupling reaction in an air condition with a low oxygen content as described above.
- the air may be introduced at a rate of 80 to 350 cc/min as described above. If the addition rate is too slow, it is difficult to uniformly mix the air in the reaction system, and as a result, the yield of polyphenylene oxide may decrease and chain extension may be limited, resulting in deterioration in physical properties. In addition, if the addition rate is too fast, the oxygen concentration in the solvent increases, resulting in copolymerization of ortho-cresol or a coupling reaction of 2,6-xylenol, resulting in generation of by-products. In the present invention, the effect of improving the yield and physical properties of polyphenylene oxide can be further improved by introducing air in the above speed range.
- the air may be introduced by air bubbling at a rate of 80 cc/min or more, or 90 cc/min or more, or 100 cc/min or more, and 350 cc/min or less, or 330 cc/min or less, or 300 cc/min or less. there is.
- the air may be introduced by air bubbling under conditions satisfying the above-described introduction rate so that the air may be uniformly mixed in the reaction system.
- the oxidative coupling reaction described above may be performed in an aromatic solvent such as benzene, toluene, or xylene. These aromatic solvents exhibit high solubility in the catalyst and polyphenylene oxide, and thus may be more advantageous in the production of polyphenylene oxide.
- the third step is a step of separating ortho-cresol from the reaction product obtained as a result of the second step and obtaining polyphenylene oxide.
- the order of performing the process of separating ortho-cresol and obtaining polyphenylene oxide is not particularly limited. Specifically, a process for separating ortho-cresol may be performed after obtaining polyphenylene oxide, or a process for obtaining polyphenylene oxide may be performed after separating ortho-cresol. Alternatively, polyphenylene oxide may be obtained through a separation process of ortho cresol.
- ortho-cresol when performing the separation process of ortho-cresol after the process of obtaining polyphenylene oxide, alcohol is introduced into the reaction product obtained as a result of the oxidative coupling reaction to precipitate polyphenylene oxide, and filtration and After drying, ortho-cresol may be separated by fractional distillation of the filtrate obtained as a result of the filtration at a temperature range of 180 to 220°C or 190 to 200°C.
- the alcohol introduced for the precipitation of the polyphenylene oxide specifically, lower alcohol having 1 to 3 carbon atoms, such as methanol, ethanol, isopropyl alcohol, and the like, may be used.
- polyphenylene oxide can be precipitated with a better yield when methanol is added, and it is also more advantageous in terms of removal through fractional distillation thereafter.
- the amount of alcohol added is not particularly limited, and is added so that a sufficient precipitation reaction with polyphenylene oxide can occur.
- an acid such as hydrochloric acid may be selectively further added in order to promote the precipitation reaction of polyphenylene oxide and thereby improve the yield.
- the acid may be added in an amount of 0.01 to 0.5 parts by weight, more specifically, 0.1 to 0.3 parts by weight, based on 100 parts by weight of alcohol.
- polyphenylene oxide When polyphenylene oxide is precipitated by the addition of the above alcohol, it can be obtained by filtering and separating, and drying the separated polyphenylene oxide.
- the filtration and drying process may be performed according to a conventional method.
- the filtration may be performed using a filter, and the drying may be performed by a heat drying method using an oven or the like.
- the drying is preferably performed under a vacuum or inert gas atmosphere.
- the precipitation, filtration and drying processes to obtain the polyphenylene oxide may be repeated twice or more.
- the filtrate obtained as a result of the filtration process is subjected to a fractional distillation process at a temperature range of 180 to 220 ° C. or 190 to 210 ° C. -Cresol can be separated.
- the fractional distillation process for separating the ortho-cresol may be performed according to a conventional method, except that it is performed under the above temperature conditions.
- the reaction obtained as a result of the second step may be obtained by fractional distillation at a temperature range of 180 to 220 ° C. or 190 to 210 ° C. to separate ortho-cresol, and then to precipitate polyphenylene oxide by adding alcohol to the resulting reactant, and filtering and drying the product. there is.
- ortho cresol in the mixture introduced during the oxidative coupling reaction exists in the reaction system. Since the boiling point (or decomposition temperature) of polyphenylene oxide differs greatly from that of ortho-cresol, ortho-cresol can be separated and removed through fractional distillation in the present invention. Specifically, since the boiling point of ortho-cresol is 191 ° C and the degradation temperature of polyphenylene oxide is 400 ° C or higher, fractional distillation in the temperature range of 180 to 220 ° C or 190 to 200 ° C is performed. Ortho-cresols can be isolated.
- the fractional distillation process for separating the ortho-cresol may be performed according to a conventional method, except that it is performed under the above temperature conditions.
- isomers such as 2,4,6-trimethylphenol may further exist in addition to ortho cresol. Since these isomers also have a large boiling point difference from polyphenylene oxide, these isomers can be simultaneously separated by the above-described fractional distillation process, and as a result, polyphenylene oxide can be obtained with higher purity.
- the process of precipitation, filtration and separation of polyphenylene oxide may be performed in the same manner as described above.
- alcohol may be introduced to precipitate the polyphenylene oxide.
- the ortho-cresol separated through the fractional distillation may be reused as an intermediate in the synthesis of 2,6-xylenol in an alkylation reaction for producing 2,6-xylenol.
- the manufacturing method according to the present invention may further include a step of introducing the separated ortho-cresol during the alkylation reaction after separating the ortho-cresol.
- PPO can be produced in excellent yield under mild oxidative coupling reaction conditions. Specifically, PPO can be produced with a high yield of 70% by weight or more, or 80% by weight or more, or 90% by weight or more, or 95% by weight or more, or 99% by weight or more by the above-described preparation method.
- the yield can be calculated according to Equation 1 below from the amount of 2,6-xylenol introduced during the production of PPO and the amount of PPO finally produced.
- the PPO prepared according to the above production method is a linear homopolymer composed of repeating units represented by the following formula (1):
- n is an integer greater than or equal to 1, and more specifically, may be 10 to 100.
- ortho-cresol-derived structures included as by-products in 2,6-xylenol are included as repeating units of the polymer, but the production method according to the present invention uses ortho as a reactant. Despite the high content of so-cresol, high selectivity for 2,6-xylenol is exhibited, and the above homopolymer can be prepared.
- PPO prepared according to the above preparation method does not show an ortho-cresol peak in the range of 6.8 to 7.4 ppm in 1 H NMR analysis:
- the PPO prepared by the above-described manufacturing method is an oligomeric PPO having a number average molecular weight of 1,600 to 3,500 g/mol, and a molecular weight distribution (PDI, Mw/Mn) of 1.7 to 3 and a glass temperature of 140 to 180 ° C. As it has a transition temperature (Tg), it can exhibit excellent workability.
- the PPO has a number average molecular weight of 1,600 g/mol or more and a Mn of 3,500 g/mol or less, or 3,000 g/mol or less, compared to oligomeric PPO prepared by a conventional manufacturing method. Accordingly, excellent processability can be exhibited when manufacturing a compound using the same.
- the number average molecular weight of the PPO is 1,600 g / mol or more, 1,750 g / mol or more, or 1,900 g / mol or more, or 2,000 g / mol or more, or 2,100 g / mol or more, or 2,200 g / mol or more 2,300 g/mol or more, or 2,400 g/mol or more, and 3,500 g/mol or less, or 3,300 g/mol or less, or 3,200 g/mol or less, or 3,000 g/mol or less, or 2,800 g/mol or less, or 2,700 less than g/mol.
- the PPO has a molecular weight distribution (PDI, Mw/Mn) of 1.7 to 3, compared to oligomeric PPO prepared by a conventional manufacturing method, and has a wide molecular weight distribution, and as a result, excellent processability can be exhibited. More specifically, the molecular weight distribution of the PPO is 1.7 or more, or 1.8 or more, or 1.9 or more, or 2.0 or more, or 2.1 or more, or 2.2 or more, or 2.3 or more, or 2.45 or more, or 3 or less, or 2.8 or less, or 2.7 or less. , or less than 2.5.
- the PPO has a glass transition temperature of 140 to 180°C.
- the glass transition temperature is high, the processing temperature is increased and workability is deteriorated, and when the glass transition temperature is low, thermal stability is deteriorated.
- the PPO according to the present invention has a glass transition temperature within the above range, it can exhibit excellent processability without deterioration in thermal stability.
- the glass transition temperature of the PPO is 140 ° C or higher, or 145 ° C or higher, or 148 ° C or higher, or 150 ° C or higher, or 152 ° C or higher, or 155 ° C or higher, or 156 ° C or higher, and 180 ° C or lower, or 175°C or less, or 170°C or less, or 169°C or less, or 165°C or less, or 162°C or less, or 160°C or less, or 159°C or less.
- the number average molecular weight and molecular weight distribution (PDI, Mw/Mn) of the PPO can be measured using gel permeation chromatography, and the glass transition temperature can be measured using a differential scanning calorimeter. Specific measurement methods and conditions will be described in detail in the following experimental examples.
- high molecular weight PPO or high molecular weight PPO
- water It is also possible to prepare high molecular weight PPO with an average molecular weight of 4,000 g/mol or more. Accordingly, in the production method according to the present invention, after the separation of the ortho-cresol, the obtained polyphenylene oxide, specifically oligomeric PPO, is subjected to a secondary oxidation coupling reaction in the presence of a copper-based catalyst and an amine-based additive Further steps may be included.
- the copper-based catalyst, amine-based additives, and oxidative coupling reaction conditions that can be used in the preparation of the high molecular weight PPO are as described above.
- the copper-based catalyst may be used in an amount of 0.001 to 0.1 mol based on 1 mol of oligomeric PPO, and more specifically, 0.001 mol or more, or 0.003 mol or more, or 0.005 mol or more, 0.1 mol based on 1 mol of oligomeric PPO. or less, or 0.05 mole or less, or 0.01 mole or less.
- the amine-based additive may be used in a ratio of 0.1 to 1 mole based on 1 mole of the oligomeric PPO, and more specifically, 0.1 mole or more, or 0.3 mole or more, or 0.5 mole or more based on 1 mole of the oligomeric PPO, 1 mole or less, or 0.8 mole or less, or 0.7 mole or less, or 0.68 mole or less may be used.
- the high molecular weight PPO produced by the above-mentioned manufacturing process specifically, has a number average molecular weight of 4,000 g/mol or more, or 5,000 g/mol or more, or 8,000 g/mol or more, or 10,000 g/mol or more, or 12,000 g /mol or more and less than or equal to 20,000 g/mol, or less than or equal to 18,000 g/mol, or less than or equal to 16,500 g/mol, or less than or equal to 16,200 g/mol, or less than or equal to 15,000 g/mol.
- the high molecular weight PPO has a molecular weight distribution (PDI, Mw/Mn) of 2 to 3, more specifically, 2 or more, or 2.1 or more, or 2.2 or more, and 3 or less, or 2.8 or less, or 2.6 or less, or 2.5 or less, it can exhibit excellent processability by having a wider molecular weight distribution than before.
- PDI, Mw/Mn molecular weight distribution
- the number average molecular weight and molecular weight distribution of the polymer type PPO can be measured through gel permeation chromatography analysis, and the specific measurement method and conditions will be described in detail in the following experimental examples.
- a separate separation and purification process for ortho-cresol produced after the alkylation reaction for phenol is unnecessary, so energy costs can be reduced, and PPO can be obtained with excellent yield under mild oxidation coupling reaction conditions.
- the prepared PPO may exhibit excellent processability.
- Example 1 is a 1H NMR analysis graph of polyphenylene oxide prepared in Example 1-1.
- catalyst CuCl 2 was added in an amount of 0.0075 mole based on 1 mole of 2,6-xylenol, stirred at 25° C. for 5 minutes, and then 2.8 mmol of din-butylamine (2,6-xylenol) was added. Corresponding to 0.34 mole ratio based on 1 mole of nol) was added, and the polymerization reaction was performed by air bubbling. At this time, air bubbling was performed at a rate of 100 cc/min using a flow controller.
- the resulting reactant was slowly added to a flask containing 100 ml of HCl/MeOH solution (HCl content: 0.1% by weight) to precipitate the synthesized polymer, that is, polyphenylene oxide.
- the precipitated polymer was isolated by filtering and dried in a vacuum oven. A process of dissolving the dried polymer in dichloromethane and then precipitating it with methanol was repeated twice to obtain polyphenylene oxide.
- the solution remaining after separation of the polyphenylene oxide contains methanol, toluene and ortho-cresol. Accordingly, while heating the solution at 190 to 220°C, methanol, toluene, and ortho-cresol were sequentially fractionated and separated at temperatures around 65°C, 110°C, and 190°C. In addition, the ortho-cresol separated through the fractional distillation was subsequently recycled as an intermediate during the alkylation reaction of 2,6-xylenol.
- Polyphenylene oxide was prepared in the same manner as in Example 1-1, except that the input amount of reactants and polymerization conditions were changed to the conditions shown in Table 1 below.
- catalyst CuCl was added in a molar ratio of 0.01 based on 1 mole of 2,6-xylenol, stirred at 25 ° C for 5 minutes, and then 2.8 mmol of 3-aminopyridine (2,6-xylenol) Corresponding to 0.34 mole ratio based on 1 mole) was added, and the polymerization reaction was performed by air bubbling. At this time, air bubbling was performed at a rate of 100 cc/min using a flow controller.
- the resulting reactant was slowly added to a flask containing 100 ml of HCl/MeOH solution (HCl content: 0.1% by weight) to precipitate the synthesized polymer, that is, polyphenylene oxide.
- the precipitated polymer was isolated by filtering and dried in a vacuum oven. A process of dissolving the dried polymer in dichloromethane and then precipitating it with methanol was repeated twice to obtain polyphenylene oxide.
- the solution remaining after separation of the polyphenylene oxide contains methanol, toluene and ortho-cresol. Accordingly, while heating the solution at 190 to 220 ° C, methanol, toluene and ortho-cresol were sequentially fractionated and separated at temperatures around 65 ° C, 110 ° C and 190 ° C. In addition, ortho -Cresol was then recycled as an intermediate during the alkylation reaction of 2,6-xylenol.
- Polyphenylene oxide was prepared in the same manner as in Examples 1-11, except that the amounts of reactants and polymerization conditions were changed to the conditions shown in Table 2 below.
- Example 1-1 except that the alkylation reaction step was not performed and 2,6-xylene (1 g, 8.2 mmol) was used instead of the mixture containing 2,6-xylenol and ortho-cresol. In the same manner as in, polyphenylene oxide was prepared.
- Polyphenylene oxide was prepared in the same manner as in Example 1-1, except that the input amount of reactants and polymerization conditions were changed to the conditions shown in Table 1 below.
- Polyphenylene oxide was prepared in the same manner as in Example 1-1, except that the input amount of reactants and polymerization conditions were changed to the conditions shown in Table 1 below.
- Polyphenylene oxide was prepared in the same manner as in Examples 1-11, except that the amounts of reactants and polymerization conditions were changed to the conditions shown in Table 2 below.
- Examples 1-11 except that the alkylation reaction step was not performed and 2,6-xylene (1 g, 8.2 mmol) was used instead of the mixture containing 2,6-xylenol and ortho-cresol. In the same manner as in, polyphenylene oxide was prepared.
- Polyphenylene oxide was prepared in the same manner as in Examples 1-11, except that the amounts of reactants and polymerization conditions were changed to the conditions shown in Table 2 below.
- Example 1-1 PPO prepared in Example 1-1 was dissolved in CDCl 3 , and then 1 H NMR analysis was performed using Varian's 500 MHz NMR. The results are shown in Figure 1.
- the PPO prepared by the production method of the present invention is a homopolymer composed only of repeating units derived from 2,6-xylenol.
- the yield was calculated according to Equation 1 below from the amount of 2,6-xylenol introduced during the preparation of PPO according to Examples and Comparative Examples and the amount of PPO finally prepared.
- the glass transition temperature was measured using a differential scanning calorimeter (DSC) under the following conditions:
- a Waters PL-GPC220 instrument was used as the GPC device, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 40 °C, chloroform was used as a solvent, and the flow rate was 1.0 mL/min. Polymer samples according to Examples and Comparative Examples were pretreated by melting in chloroform containing 0.0125% BHT at 160 ° C. for 10 hours using a GPC analyzer (PL-GP220), and prepared at a concentration of 1 mg / 1mL, It was supplied in an amount of 100 ⁇ l.
- Weight average molecular weight (Mw) and number average molecular weight (Mn) were derived using a calibration curve formed using polystyrene standard specimens, and molecular weight distribution (PDI, Mw/Mn) was obtained by dividing the weight average molecular weight by the number average molecular weight was calculated.
- the weight average molecular weight (Mw) of the polystyrene standard specimen was 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol 9 types of mol, 10000000 g/mol were used.
- the combination of the copper-based catalyst and the amine-based additive in the present invention significantly increased the yield of PPO compared to the prior art, and the produced PPO had optimal ranges of Tg, Mn and PDI, indicating excellent processability. confirmed.
- polymerization of oligomeric PPO was possible even under mild conditions of air injection by the production method of the present invention.
- ortho-cresol serves to improve the dielectric constant of the solvent and the solubility of the catalyst during the oxidative coupling reaction, but Comparative Examples 1-1 and 1-7 use ortho-cresol This is because the solubility of the catalyst is lowered by not doing so.
- Comparative Example 1-4 using triethylamine and Comparative Example 1-6 using n-butylamine as an amine additive were compared with Examples 1-2, 1-8, and 1-14, and PPO It was confirmed that the yield was greatly reduced, the Tg of the PPO produced was low, and the Mn and PDI decreased.
- the oligomeric polyphenylene oxide (PPO) prepared in Example 1-1 was placed in a glass jar containing a magnetic bar, and 10 ml of toluene was added thereto to dissolve while stirring.
- the resulting reactant was slowly added to a flask containing 100 ml of HCl/MeOH solution (HCl content: 0.1 wt%) to precipitate the synthesized polymer.
- the precipitated polymer was isolated by filtering and dried in a vacuum oven. A process of dissolving the dried polymer in dichloromethane and then precipitating it with methanol was repeated twice to obtain high molecular weight polyphenylene oxide.
- Polyphenylene oxide was prepared in the same manner as in Example 2-1, except that the amounts of reactants and polymerization conditions were changed to the conditions shown in Table 5 below.
- the oligomeric PPO prepared in Examples 1-11 was placed in a glass jar containing a magnetic bar, and 10 ml of toluene was added thereto to dissolve while stirring.
- the resulting reactant was slowly added to a flask containing 100 ml of HCl/MeOH solution (HCl content: 0.1 wt%) to precipitate the synthesized polymer.
- the precipitated polymer was isolated by filtering and dried in a vacuum oven. A process of dissolving the dried polymer in dichloromethane and then precipitating it with methanol was repeated twice to obtain high molecular weight polyphenylene oxide.
- Polyphenylene oxide was prepared in the same manner as in Examples 2-4, except that the amount of reactants and polymerization conditions were changed to the conditions shown in Table 5 below.
- the high molecular weight polyphenylene oxide prepared in Examples 2-1 to 2-5 was subjected to GPC analysis in the same manner as in Experimental Example 2 to determine number average molecular weight (Mn) and molecular weight distribution (PDI, Mw/Mn). ) was measured. The results are shown in Table 5 below.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
Claims (15)
- 페놀을 메탄올로 알킬화 반응시켜, 2,6-자일레놀 및 오르쏘-크레졸을 포함하는 혼합물을 제조하는 제1 단계;상기 혼합물을 구리계 촉매 및 아민계 첨가제의 존재 하에, 산화 커플링 반응시키는 제2 단계; 및상기 제2단계의 결과로 수득한 반응 생성물로부터 오르쏘-크레졸을 분리하고, 하기 화학식 1로 표시되는 반복단위로 이루어진 폴리페닐렌 옥사이드를 수득하는 제3 단계;를 포함하며,상기 혼합물은 2,6-자일레놀 1몰에 대하여 오르쏘-크레졸을 0.2 내지 0.8의 몰비로 포함하고,상기 아민계 첨가제는 2차 아민, 피리딘계 화합물, 또는 이들의 혼합물을 포함하는,폴리페닐렌 옥사이드의 제조방법:[화학식 1]상기 화학식 1에서 n은 1 이상의 정수이다.
- 제1항에 있어서,상기 단계들은 일련의 연속된 반응으로 진행되는, 제조방법.
- 제1항에 있어서,상기 구리계 촉매는 산화 제1구리, 할로겐화 제1구리, 황산 제1구리, 질산 제1구리, 산화 제2구리, 할로겐화 제2구리, 황산 제2구리, 질산 제2구리, 및 이들의 염으로 이루어진 군에서 선택되는 1종 이상인, 제조방법.
- 제1항에 있어서,상기 구리계 촉매는 2,6-자이레놀 1몰 기준 0.001 내지 0.1몰의 비로 사용되는, 제조방법.
- 제1항에 있어서,상기 2차 아민은, 분자내 C1-20 지방족 알킬기를 두개 갖는, 제조방법.
- 제1항에 있어서,상기 2차 아민은, 디메틸 아민, 디에틸 아민, 디-n-프로필 아민, 디-i-프로필 아민, 디-n-부틸 아민, 디-i-부틸 아민, 디-t-부틸 아민, 디펜틸 아민, 디헥실아민, 디옥틸 아민, 디데실 아민, 메틸에틸 아민, 메틸프로필 아민, 또는 메틸부틸 아민인, 제조방법.
- 제1항에 있어서,상기 피리딘계 화합물은, 아미노피리딘계 화합물, 모노알킬피리딘계 화합물, 또는 디알킬피리딘계 화합물인, 제조방법.
- 제1항에 있어서,상기 피리딘계 화합물은, 2-아미노 피리딘, 3-아미노 피리딘, 4-아미노 피리딘, 4-디메틸아미노피리딘, 2,3-디아미노 피리딘, 2,5-디아미노 피리딘, 2,6-디아미노 피리딘, 2-아미노-6-메틸 피리딘, 3-아미노-6-이소프로필 피리딘, 4-피롤리디노 피리딘, 2-메틸 피리딘, 3-메틸 피리딘, 4-메틸 피리딘, 2,3-디메틸 피리딘, 2,4-디메틸 피리딘, 2,5-디메틸 피리딘, 2,6-디메틸 피리딘, 3,4-디메틸피리딘, 또는 3,5-디메틸 피리딘인, 제조방법.
- 제1항에 있어서,상기 아민계 첨가제는 2,6-자일레놀 1몰 기준 0.1 내지 1몰의 비로 사용되는, 제조방법.
- 제1항에 있어서,상기 구리계 촉매는 산화 제1구리, 할로겐화 제1구리, 황산 제1구리, 질산 제1구리, 및 이들의 염으로 이루어진 군에서 선택되는 1종 이상이고, 상기 아민계 첨가제는 피리딘계 화합물이거나; 또는상기 구리계 촉매는 산화 제2구리, 할로겐화 제2구리, 황산 제2구리, 질산 제2구리, 및 이들의 염으로 이루어진 군에서 선택되는 1종 이상이고, 상기 아민계 첨가제는 2차 아민인, 제조방법.
- 제1항에 있어서,상기 산화 커플링 반응은 에어 버블링에 의해 80 내지 350cc/min의 속도로 공기를 투입하여 수행되는, 제조방법.
- 제1항에 있어서,상기 오르쏘-크레졸은 분별 증류에 의해 분리되는, 제조방법.
- 제1항에 있어서,상기 폴리페닐렌 옥사이드는, 수평균 분자량이 1,600 내지 3,500 g/mol이고, 분자량 분포가 1.7 내지 3이며, 유리전이온도가 140 내지 180℃인 올리고머형 폴리페닐렌 옥사이드인, 제조방법.
- 제1항에 있어서,상기 제3 단계에서 수득한 폴리페닐렌 옥사이드를, 구리계 촉매 및 아민계 첨가제의 존재 하에서 2차 산화 커플링 반응시키는 단계를 더 포함하는, 제조방법.
- 제1항에 있어서,상기 제3 단계에서의 오르쏘-크레졸의 분리 후, 분리된 오르쏘-크레졸을 상기 제1 단계에서의 알킬화 반응에 투입하는 단계를 더 포함하는, 제조방법.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023550105A JP2024507517A (ja) | 2021-07-02 | 2022-06-30 | ポリフェニレンオキシドの製造方法 |
EP22833677.2A EP4273186A4 (en) | 2021-07-02 | 2022-06-30 | PROCESS FOR PREPARING POLYPHENYLENE OXIDE |
US18/276,211 US20240117116A1 (en) | 2021-07-02 | 2022-06-30 | Method for preparing polyphenylene oxide |
CN202280016108.2A CN116981712A (zh) | 2021-07-02 | 2022-06-30 | 聚苯醚的制备方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2021-0087374 | 2021-07-02 | ||
KR10-2021-0087375 | 2021-07-02 | ||
KR1020210087375A KR20230006317A (ko) | 2021-07-02 | 2021-07-02 | 폴리페닐렌 옥사이드의 제조방법 |
KR1020210087374A KR20230006316A (ko) | 2021-07-02 | 2021-07-02 | 폴리페닐렌 옥사이드의 제조방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023277624A1 true WO2023277624A1 (ko) | 2023-01-05 |
Family
ID=84691882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/009454 WO2023277624A1 (ko) | 2021-07-02 | 2022-06-30 | 폴리페닐렌 옥사이드의 제조방법 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240117116A1 (ko) |
EP (1) | EP4273186A4 (ko) |
JP (1) | JP2024507517A (ko) |
WO (1) | WO2023277624A1 (ko) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5668631A (en) * | 1979-11-06 | 1981-06-09 | Mitsui Toatsu Chem Inc | Storing method of 2,6-dimethylphenol |
JPS57177018A (en) * | 1981-04-23 | 1982-10-30 | Asahi Chem Ind Co Ltd | Improved poly(2,6-dimethyl-1,4-phenylene)ether and its preparation |
KR960004115A (ko) * | 1994-07-21 | 1996-02-23 | 한스-울리히 슈타이거, 한스-위르겐 마우테 | 자동차용 승객안전장치의 측면 에어백을 작동시키는 방법 |
KR20040019388A (ko) * | 2001-08-07 | 2004-03-05 | 아사히 가세이 케미칼즈 가부시키가이샤 | 2,6-디메틸페놀 조성물 |
KR20060066167A (ko) * | 2003-07-02 | 2006-06-15 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 이작용성 페닐렌에테르 올리고머의 제조방법 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4092294A (en) * | 1976-08-30 | 1978-05-30 | General Electric Company | Method for preparing polyphenylene ethers |
US5001214A (en) * | 1989-06-23 | 1991-03-19 | General Electric Company | Low odor polyphenylene ether produced in the absence of odor causing amine, in presence of manganese chelate complex catalyst |
US6261987B1 (en) * | 2000-02-29 | 2001-07-17 | General Electric Company | Method for preparing an alkylation catalyst, and for ortho-alkylating hydroxyaromatic compounds; and related compositions |
JP2004339343A (ja) * | 2003-05-15 | 2004-12-02 | Asahi Kasei Chemicals Corp | ポリフェニレンエーテル |
-
2022
- 2022-06-30 JP JP2023550105A patent/JP2024507517A/ja active Pending
- 2022-06-30 US US18/276,211 patent/US20240117116A1/en active Pending
- 2022-06-30 EP EP22833677.2A patent/EP4273186A4/en active Pending
- 2022-06-30 WO PCT/KR2022/009454 patent/WO2023277624A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5668631A (en) * | 1979-11-06 | 1981-06-09 | Mitsui Toatsu Chem Inc | Storing method of 2,6-dimethylphenol |
JPS57177018A (en) * | 1981-04-23 | 1982-10-30 | Asahi Chem Ind Co Ltd | Improved poly(2,6-dimethyl-1,4-phenylene)ether and its preparation |
KR960004115A (ko) * | 1994-07-21 | 1996-02-23 | 한스-울리히 슈타이거, 한스-위르겐 마우테 | 자동차용 승객안전장치의 측면 에어백을 작동시키는 방법 |
KR20040019388A (ko) * | 2001-08-07 | 2004-03-05 | 아사히 가세이 케미칼즈 가부시키가이샤 | 2,6-디메틸페놀 조성물 |
KR20060066167A (ko) * | 2003-07-02 | 2006-06-15 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 이작용성 페닐렌에테르 올리고머의 제조방법 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4273186A4 * |
Also Published As
Publication number | Publication date |
---|---|
US20240117116A1 (en) | 2024-04-11 |
EP4273186A1 (en) | 2023-11-08 |
EP4273186A4 (en) | 2024-07-10 |
JP2024507517A (ja) | 2024-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2019235799A1 (ko) | 비스포스핀 리간드 화합물, 크롬 화합물, 에틸렌 올리고머화 촉매 시스템, 및 에틸렌 올리고머 제조 방법 | |
WO2017111300A1 (ko) | 신규 구조의 디아민 모노머를 적용한 폴리아믹산 용액 및 이를 포함하는 폴리이미드 필름 | |
WO2018182174A1 (ko) | 폴리올레핀-폴리스티렌계 다중블록 공중합체, 이를 제조하기 위한 유기 아연 화합물 및 폴리올레핀-폴리스티렌계 다중블록 공중합체 제조 방법 | |
WO2022265240A1 (ko) | 트리사이클로데칸 디메탄올 조성물 및 이의 제조방법 | |
WO2017146443A1 (ko) | 폴리에틸렌글리콜 디알데히드 유도체의 제조방법 | |
WO2017191914A2 (ko) | 아미노실란계 화합물의 신규 제조방법 | |
WO2021054771A1 (ko) | 말단이 불포화기로 캡핑된 인 함유 수지, 이의 제조방법 및 상기 말단이 불포화기로 캡핑된 인 함유 수지를 포함하는 수지 조성물 | |
WO2023277624A1 (ko) | 폴리페닐렌 옥사이드의 제조방법 | |
WO2014104496A1 (ko) | 모노머, 상기 모노머를 포함하는 하드마스크 조성물 및 상기 하드마스크 조성물을 사용하는 패턴형성방법 | |
WO2015072692A1 (ko) | 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체, 이를 포함하는 기체분리막 및 그 제조방법 | |
WO2023277347A1 (ko) | 트리사이클로데칸 디메탄올 조성물 및 이의 제조방법 | |
WO2021034041A1 (ko) | 유기 보레이트계 촉매, 이를 이용한 이소부텐 올리고머의 제조방법 및 이로부터 제조된 이소부텐 올리고머 | |
WO2019190289A1 (ko) | 블록 공중합체 조성물 | |
WO2019088377A1 (ko) | 두 고리 구조를 갖는 포스포라미다이트 유도체, 이의 제조방법 및 그 용도 | |
WO2020153771A1 (ko) | 디아민 화합물, 및 이를 이용한 폴리이미드 전구체 및 폴리이미드 필름 | |
WO2020060262A1 (ko) | 프탈로니트릴 올리고머를 포함하는 경화성 수지 조성물 및 이의 프리폴리머 | |
WO2015072694A1 (ko) | 가교구조를 갖는 열전환 폴리(벤즈옥사졸-이미드) 공중합체를 포함하는 배연가스 분리용 막 및 그 제조방법 | |
WO2020218835A1 (ko) | 신규 폴리이미드 타입 고분자 및 이의 제조방법 | |
WO2019088431A1 (ko) | 세척액 조성물 및 이를 이용한 중합 장치 세척 방법 | |
WO2023277333A1 (ko) | 아지도 포르메이트의 무촉매 C-H 삽입 반응을 통해 제조된 긴 사슬 가지 달린 α-올레핀 중합체 및 그의 제조방법 | |
WO2023224240A1 (ko) | 사슬 말단에 설포닐 아자이드기 또는 설포닐 플루오라이드기를 포함하는 고분자 화합물 및 이의 제조 방법 | |
WO2021162304A1 (ko) | 음이온 중합 개시제, 음이온 중합 개시제 조성물 및 이의 제조방법 | |
WO2024101782A1 (ko) | 가교 공중합체, 이를 포함하는 고분자 막, 및 상기 고분자 막을 포함하는 음이온 교환막 | |
WO2022107992A1 (ko) | 표면 개질 2차원 맥신 및 이의 제조방법 | |
WO2024096665A1 (ko) | 분지형 폴리(3-하이드록시프로피온산) 중합체 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22833677 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18276211 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2022833677 Country of ref document: EP Effective date: 20230803 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023550105 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280016108.2 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |