JPS63159431A - Production of aromatic poly(thio)ether ketone - Google Patents
Production of aromatic poly(thio)ether ketoneInfo
- Publication number
- JPS63159431A JPS63159431A JP30607786A JP30607786A JPS63159431A JP S63159431 A JPS63159431 A JP S63159431A JP 30607786 A JP30607786 A JP 30607786A JP 30607786 A JP30607786 A JP 30607786A JP S63159431 A JPS63159431 A JP S63159431A
- Authority
- JP
- Japan
- Prior art keywords
- thio
- formula
- atom
- aromatic
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 poly(thio) Polymers 0.000 title claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- FDGZUBKNYGBWHI-UHFFFAOYSA-N trioctadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC FDGZUBKNYGBWHI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000010893 Bischofia javanica Nutrition 0.000 description 3
- 240000005220 Bischofia javanica Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920001643 poly(ether ketone) Polymers 0.000 description 3
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- FIPTYOFKSOWKTF-UHFFFAOYSA-N 1,2-diphenoxybenzene Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1OC1=CC=CC=C1 FIPTYOFKSOWKTF-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XZZWOTQMUOIIFX-UHFFFAOYSA-N 1-(2-diphenoxyphosphanyloxypropoxy)propan-2-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC(C)COCC(C)OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 XZZWOTQMUOIIFX-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UDONPJKEOAWFGI-UHFFFAOYSA-N 1-methyl-3-phenoxybenzene Chemical compound CC1=CC=CC(OC=2C=CC=CC=2)=C1 UDONPJKEOAWFGI-UHFFFAOYSA-N 0.000 description 1
- ISKPZIBTZDIOFY-UHFFFAOYSA-N 15,15-bis(1-hydroxy-1-phenyltetradecyl)-14,16-diphenylnonacosane-14,16-diol [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)OP(=O)(O)OP(=O)(O)O.C1(=CC=CC=C1)C(C(C(O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(O)CCCCCCCCCCCCC ISKPZIBTZDIOFY-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VYCXSCFSYHDUKP-UHFFFAOYSA-N CO[SiH2]C1=CC=CC=C1 Chemical compound CO[SiH2]C1=CC=CC=C1 VYCXSCFSYHDUKP-UHFFFAOYSA-N 0.000 description 1
- ODMOOOWWRCBHOR-UHFFFAOYSA-N Cl(=O)O.Cl(=O)O.C(C1=CC(C(=O)O)=CC=C1)(=O)O Chemical compound Cl(=O)O.Cl(=O)O.C(C1=CC(C(=O)O)=CC=C1)(=O)O ODMOOOWWRCBHOR-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- DWJBKDDHYVUEOL-UHFFFAOYSA-N P(=O)(OC(C(CCCC)C1=CC=CC=C1)(CC)C1=CC=CC=C1)(O)O Chemical compound P(=O)(OC(C(CCCC)C1=CC=CC=C1)(CC)C1=CC=CC=C1)(O)O DWJBKDDHYVUEOL-UHFFFAOYSA-N 0.000 description 1
- LZNWGSIDNAGRAJ-UHFFFAOYSA-N P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 LZNWGSIDNAGRAJ-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- QWVFZGVJZUJZGG-UHFFFAOYSA-N diethyl(phenyl)silicon Chemical compound CC[Si](CC)C1=CC=CC=C1 QWVFZGVJZUJZGG-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- OEWWJPWOUKYMKK-UHFFFAOYSA-N dihydroxy-octadecoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=S OEWWJPWOUKYMKK-UHFFFAOYSA-N 0.000 description 1
- NOCMYCSJUZYBNE-UHFFFAOYSA-N dioctadecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCCCCCCC NOCMYCSJUZYBNE-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- OYFJQPXVCSSHAI-QFPUQLAESA-N enalapril maleate Chemical group OC(=O)\C=C/C(O)=O.C([C@@H](C(=O)OCC)N[C@@H](C)C(=O)N1[C@@H](CCC1)C(O)=O)CC1=CC=CC=C1 OYFJQPXVCSSHAI-QFPUQLAESA-N 0.000 description 1
- RDJVTBNNOBFYLE-UHFFFAOYSA-N ethyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](CC)C1=CC=CC=C1 RDJVTBNNOBFYLE-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- LXBBVNPKDAKIRZ-UHFFFAOYSA-N octan-3-yl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC(CC)CCCCC)OC1=CC=CC=C1 LXBBVNPKDAKIRZ-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007868 post-polymerization treatment Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- GRAKJTASWCEOQI-UHFFFAOYSA-N tridodecylphosphane Chemical compound CCCCCCCCCCCCP(CCCCCCCCCCCC)CCCCCCCCCCCC GRAKJTASWCEOQI-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- QTKHQYWRGFZFHG-UHFFFAOYSA-N trioctylsilicon Chemical compound CCCCCCCC[Si](CCCCCCCC)CCCCCCCC QTKHQYWRGFZFHG-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- AKROLTGTPNCGRL-UHFFFAOYSA-K tripotassium;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[K+].[K+].[K+] AKROLTGTPNCGRL-UHFFFAOYSA-K 0.000 description 1
- MMYRBBZVCDXGHG-UHFFFAOYSA-N tripropylsilicon Chemical compound CCC[Si](CCC)CCC MMYRBBZVCDXGHG-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は結晶性熱可塑性芳香族ポリ（チオ）エーテルケ
トンの重合後の処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for post-polymerization treatment of crystalline thermoplastic aromatic poly(thio)etherketones.
一般式〔鳳〕
・・・・・・・ 〔鳳〕
（〔鳳〕式中、Ｒ’ ％ Ｒ”は水素原子、ノ１０ゲン
原子。General formula [Otori] ...... [Otori] (In the [Otori] formula, R' % R'' is a hydrogen atom, a hydrogen atom.
炭化水素基、又はアルコキシ基を示し、Ｘは直接結合、
酸素又は硫黄原子を示し、ｉ＃−１０〜−の整数を示し
、ｍはＯ〜３の整数を示し、ｎはＯ又はｌである）の構
造を持つ芳香族ポリ（チオ）エーテルケトン、特に構造
式［ＩＶ）ＨＥ ＨＨ
及び〔Ｖ）
ＨＨＨＨＨＥ
の構造を持つ芳香族ポリエーテルケトンは高融点（〔■
〕、Ｔｍ＝Ｊ Ａ ｓ ”Ｃ； 〔Ｖ）、Ｔｍ＝、２．
７ ＄’Ｃ）且ｏ高カラｘ転ｓ点（（ＩＶ） 、 Ｔｔ
＝ｔ ｓ 蓼℃；（Ｖ〕。Indicates a hydrocarbon group or an alkoxy group, X is a direct bond,
an aromatic poly(thio)etherketone having the structure (representing an oxygen or sulfur atom, i# representing an integer from 10 to -, m representing an integer from O to 3, and n representing O or l), especially Aromatic polyetherketones having the structures of the structural formulas [IV) HE HH and [V] HHHHHE have high melting points ([■
], Tm=J A s ”C; [V), Tm=, 2.
7 $'C) and o high color x transition s point ((IV), Tt
=t s 蓼℃; (V).
ｒｖ＝ｚｅｌＱ）を有し、耐熱性、機械的性質。rv=zelQ), heat resistance, and mechanical properties.
電気的性質及び寸法安定性に優れ、且つ吸水率が低く、
物理的に非常１ｃ優れたポリマーでおる事が知られてい
る。又、濃硫＃１以外の溶剤には不溶であシ、耐薬品性
も非常に優れたポリマーである。Excellent electrical properties and dimensional stability, and low water absorption.
It is known that it is a polymer with very good physical properties. Furthermore, it is a polymer that is insoluble in solvents other than concentrated sulfur #1 and has excellent chemical resistance.
一方その反面、これらのポリマーの製造方法トシては％
り、ｑ′−ジフルオロベンゾフェノンとり、り′−ジヒ
ドロキシベンゾフェノン又はジヒドロキノンのアルカリ
金属塩をジフェニルス／ｌ／ ホン中で反応させる方法
が知られているが１反応温度を３０θ℃鳩上にする必要
かめる事やダ、亭〆一ジフルオロペンゾフエノンが高価
な事等、その製造方法には欠点が多い。On the other hand, the manufacturing method of these polymers is
A method is known in which q'-difluorobenzophenone is reacted with an alkali metal salt of ri'-dihydroxybenzophenone or dihydroquinone in diphenyl alcohol, but it is necessary to raise the reaction temperature to 30θ℃. There are many drawbacks to the manufacturing method, such as the high cost of difluoropenzophenone.
本発明者等は上記の点を鑑み、鋭意検討全行ない、下式
ＬＶＩ）にみられるポリエーテルケトン・ を芳香族エ
ーテル筐たはチオエーテルと芳香族カルボン酸ジノ１ラ
イドとの反応によ＃）温和な条件下で合成出来ること
（式中ＸはＯまたはＢを示す。）
（特開昭３ ？−／！９ざコロ号公報、特開昭６０−１
２０７２０号公報参照）
また、芳香族ポリエーテルケトン〔ｌＯ及び〔！〕さら
に芳香族ポリチオエーテルケトン〔鴇〕ＨＨＨＨ
全芳香族（チオ）エーテルとホスゲンとの反応によシ、
ルイスｒＩｋ存在下、非プロトン性有機溶媒中で室温付
近の温和な条件下で、しかも、著しく安価に製造する方
法を見出した。In view of the above points, the inventors of the present invention have carried out extensive studies and have determined that the polyetherketone shown in the following formula LVI) can be prepared by reacting an aromatic ether casing or a thioether with an aromatic carboxylic acid dinolide. Can be synthesized under mild conditions (X in the formula represents O or B)
(See Publication No. 20720) Also, aromatic polyetherketones [lO and [! ] Further, by reaction of aromatic polythioetherketone [HHHHH] wholly aromatic (thio)ether with phosgene,
We have found a method for producing the compound under mild conditions near room temperature in the presence of Lewis rIk in an aprotic organic solvent and at a significantly low cost.
（特開昭ＡＯ−７コ９コ３号公報、特開昭６０−１０／
／／９号公報、及び特開昭１．０−１０ダ／コロ号公報
参照）
しかし、このような方法で製造した芳香族ポリ（チオ）
エーテルケトンを触媒を失活させ、さら忙除去するため
に洗滌を行なった後、乾燥したポリマーを溶融加熱する
とゲル化してしまうような熱的に不安定な欠点を有して
いた。(Unexamined Japanese Patent Publication No. AO-7-9-3, Unexamined Japanese Patent Publication No. 60-10/
//9, and JP-A-1.0-10 Da/Colo) However, the aromatic poly(thio) produced by such a method
After washing the ether ketone to deactivate the catalyst and further remove it, the dried polymer is thermally unstable and gels when heated to melt it.
本発明者等は上記の点を改良すべく、さらに鋭意検討を
重ねた結果、重合および触媒を不活性化した後の後処理
工程において還元処理を行ない、さらにその後の工程に
おいてリン化合物を添加することによシ熱安定性が者し
く向上することを見出し、本発明に到った。In order to improve the above-mentioned points, the present inventors conducted further intensive studies and found that a reduction treatment is performed in the post-treatment step after polymerization and inactivation of the catalyst, and a phosphorus compound is further added in the subsequent step. In particular, it has been found that thermal stability is significantly improved, leading to the present invention.
すなわち、還元処理のみを行なった場合、または還元処
理を行なわずにリン化合物を添加した場合と比較して著
しい熱安定性向上効果がある。That is, there is a remarkable thermal stability improvement effect compared to the case where only the reduction treatment is performed or the case where the phosphorus compound is added without performing the reduction treatment.
すなわち、本発明の要旨は一般式〔鳳〕・・・・・・・
［１３
（〔曹〕式中、Ｒ１〜Ｒ”は水素原子、ハロゲン原子。In other words, the gist of the present invention is the general formula [Otori]...
[13 ([Ca] In the formula, R1 to R'' are a hydrogen atom or a halogen atom.
炭化水素基、又はアルコキシ基を示し、又は直接結合、
酸素、又は硫黄原子を示し、１ＦｉＯ〜−の整数を示し
、ｍは０− Ｊの整数を示し、ｎはＯ又はｌである）
の芳香族ポリ（チオ）エーテルケトンを製造するに際し
、重合および触媒を不活性化した後の後処理工程におい
て還元処理を行ない、さらにその後の工程忙おいてリン
化合物を添加することによる熱安定性の著しい改良に存
する。Indicates a hydrocarbon group or alkoxy group, or a direct bond,
(represents an oxygen or sulfur atom, represents an integer of 1FiO~-, m represents an integer of 0-J, and n represents O or l), polymerization and The purpose of this method is to significantly improve thermal stability by carrying out a reduction treatment in a post-treatment step after inactivating the catalyst, and then adding a phosphorus compound in a subsequent step.
本発明の詳細な説明するに、この様な芳香族ポリ（チオ
）エーテルケトンのスラリー重合は、一般式［１３
％式％
（〔１〕式中、Ｒ１〜Ｒ”は水素原子、ハロゲン原子、
炭化水素基、又はアルコキシ基を示し、Ｘは直接結合、
酸素原子又は硫黄原子を示し、ｌは０〜−の整数である
）
で表わされる芳香族（チオ）エーテルと、一般式〔１ｆ
）
Ｒ” Ｒ” Ｒ１’ Ｒ”
（〔口〕式中、 Ｒ”−Ｒ”・は水素原子、ハロゲン原
子、炭化水素基、又はアルコキシ基を示し、Ｘは直接結
合、酸素原子又は硫黄原子を示し、Ｙはハロゲン原子を
示し、ｍはＯ〜３の整数である）で表わされる芳香族ジ
カルボン酸シバライドまたはホスゲンとを、ルイス酸の
存在下、非プロトン性有機溶媒中で反応させ、触媒を不
活性化した後の処理工程において還元処理を行ない、さ
らにその後の工程においてリン化合物を添加することに
よシ達成される。To explain in detail the present invention, such slurry polymerization of aromatic poly(thio)etherketone is carried out using the general formula [13% formula% ([1] formula, where R1 to R'' are hydrogen atoms, halogen atoms,
Indicates a hydrocarbon group or an alkoxy group, X is a direct bond,
(represents an oxygen atom or a sulfur atom, l is an integer from 0 to -) and the aromatic (thio)ether represented by the general formula [1f
) R"R"R1'R" ([In the formula, R"-R" represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and X represents a direct bond, an oxygen atom, or a sulfur atom. , Y represents a halogen atom, and m is an integer of O to 3) is reacted with an aromatic dicarboxylic acid civalide or phosgene in an aprotic organic solvent in the presence of a Lewis acid to form a catalyst. This is achieved by performing a reduction treatment in a treatment step after inactivation, and then adding a phosphorus compound in a subsequent step.
本発明における還元処理によシ、反応時または反応と後
処理によシ生成する下記（Ａｌまたは／および（Ｂｌの
化合物がそれぞれ下記（Ｃ１または／および（Ｄｉの化
合物に還元されるものと考えられる。It is assumed that the following (Al or/and (Bl) compounds produced during the reaction or during the reaction and post-treatment are reduced to the following (C1 or/and (Di) compounds by the reduction treatment in the present invention, respectively. It will be done.
デーフェニルキサントターフェニルキサンテン基ヒトロ
ール基 ｉｏ＋（Ｂ）トリ
スアリルメタン基
トリスアリルカルビノール残基 （Ｄｌ還
元処理としては第三級アルコールｆ！：還元する場合に
使用出来る還元剤系ならばいずれも使用可能であるが、
ギ酸とアルカリ性化合物混合系およびシラン化合物の場
合カルボン酸中で還元するとさらに効果が大きい。diphenylxanthoterphenylxanthene group hytrol group io+(B) trisallylmethane group trisallylcarbinol residue (tertiary alcohol f! for Dl reduction treatment: Any reducing agent system that can be used for reduction can be used) It is possible, but
In the case of a mixed system of formic acid and an alkaline compound and a silane compound, reduction in carboxylic acid has an even greater effect.
上述したギ酸中でのアルカリ処理はギ酸をポリマー中に
含まれるエーテル結合単位１モルに対して１モル係以上
、好ましくはｉｏモル−以上使用し、特に溶媒として使
用するような大過剰のギ酸の存在下で反応させることが
好ましい。In the alkali treatment in formic acid described above, formic acid is used in a proportion of 1 mole or more, preferably io mole or more, per mole of ether bond units contained in the polymer. It is preferable to carry out the reaction in the presence of
この場合ギ酸の他に他の溶媒を共存させておいても勿論
かまわな−０
また使用するアルカリ性化合物としてはアルカリ金属、
アルカリ土類金属、それらの水酸化物、酸化物お・よび
炭酸塩、ホウ酸塩のような弱酸塩等一般に水溶液中でア
ルカリ性を示す化合物の場合はいずれも使用出来る。具
体的な例とム等の金属、炭酸カリウム、炭酸ナトリウム
。In this case, it is of course possible to coexist other solvents in addition to formic acid.
Any compound that generally shows alkalinity in an aqueous solution can be used, such as alkaline earth metals, their hydroxides, oxides, carbonates, and weak acid salts such as borates. Specific examples include metals such as aluminum, potassium carbonate, and sodium carbonate.
炭酸マグネシウム、炭酸ストロンチウム、酸化カルシウ
ム、酸化マグネシウム、水酸化カリウム、水酸化ナトリ
ウム、水酸化カルシウム、水酸化マグネシウム、水酸化
バリウム、ホウ酸カルシウム、ホウ酸ナトリウム、酢酸
ナトリウム、酢酸カリウム、酢酸マグネシウム、酢酸ス
トロンチウム等が挙げられるがこれらＩＣ限定されるも
のではない。またこれらのアルカリ性化合物の使用量は
ポリマー中のエーテル結合のモル数に対して１モル係以
上、好ましくは１０モル係以上使用される。Magnesium carbonate, strontium carbonate, calcium oxide, magnesium oxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium borate, sodium borate, sodium acetate, potassium acetate, magnesium acetate, acetic acid Examples include strontium, but are not limited to these ICs. The amount of these alkaline compounds to be used is 1 molar or more, preferably 10 molar or more, based on the number of moles of ether bonds in the polymer.
反応温度は室温以上、好ましくは参〇℃以上。The reaction temperature is at least room temperature, preferably at least 0°C.
さらに好ましくはＡ Ｏ’Ｃ以上で行なわれ、加圧金
下で反応が行なってもよい。反応時間は反応条件によシ
異なるが５分以上で行なわれる。More preferably, the reaction is carried out at a temperature of A O'C or higher, and the reaction may be carried out under pressure. Although the reaction time varies depending on the reaction conditions, it is carried out for 5 minutes or more.
また、シラン化合物によシ還元する際は下記一般式〔鴇
〕
（式中、ａｌ 、ａｍ 、 Ａｓ基は置換基を有しても
よいアルキル基、アリール基、シクロアルキル基および
アラルキル基または水素原子であシ、但しＡ’、Ａ−お
よびＡａのすべてが水素原子である場合を除く）
で表わされるシラン化合物で還元処理することによ〕連
成される。In addition, when carrying out silane reduction with a silane compound, the following general formula [To] (in the formula, al, am, and As groups are alkyl groups, aryl groups, cycloalkyl groups, and aralkyl groups that may have substituents, or hydrogen atoms (except when all of A', A- and Aa are hydrogen atoms).
上述した一般式〔橿〕での後処理は溶媒として酸の存在
下、％にカルボン酸の存在下で行なわれ、カルボン酸を
ポリマー忙対して大過剰、あるいはカルボン酸と他の溶
媒との混合物中で行なわれる。The post-treatment according to the above general formula [Kashi] is carried out in the presence of an acid as a solvent and a carboxylic acid as a solvent. It takes place inside.
使用するシラ／化合物の具体例としては、トリエチルシ
ラン、トリｎ−プロピルシラン、トリｎ−オクチルシラ
ン、ジエチルシラン、トリフェニルシラン、ジフェニル
シラン、フェニルシラン、ジエチルフェニルシラン、ジ
フェニルエチルシラン、トリーｐ−メトキシフェニルシ
ランなどがめげられるがこれらに限定されず。Specific examples of the sila/compounds used include triethylsilane, tri-n-propylsilane, tri-n-octylsilane, diethylsilane, triphenylsilane, diphenylsilane, phenylsilane, diethylphenylsilane, diphenylethylsilane, tri-p- Examples include, but are not limited to, methoxyphenylsilane.
一般式〔鴇〕で示されるシラン化合物はいずれも使用可
能である。またシラン化合物としてトリエチルシランが
鯉も好ましい。シラン化合物の使用量はポリマー中のエ
ーテル結合のモル数に対して１モル係以上、好ましくは
１０モモル係上使用される。また共用する酸としてはカ
ルボン酸類が好ましく、その具体例としては酢酸、トリ
フロロ酢酸、ジクロルｌＦモノクロル酢酸、フロピオン
酸、酪酸等いずれのカルボン酸も使用可能であるがそれ
らの中でジクロル酢酸、トリフルオロ酢酸が特に好まし
い。カルボン酸は二種以上混合して使用してもよいし、
他の溶媒と組合せて使用してもよい。Any silane compound represented by the general formula [To] can be used. Further, as the silane compound, triethylsilane is also preferred. The amount of the silane compound to be used is 1 mole or more, preferably 10 mole or more, based on the number of moles of ether bonds in the polymer. As the common acid, carboxylic acids are preferable, and specific examples include acetic acid, trifluoroacetic acid, dichlorolF monochloroacetic acid, flopionic acid, butyric acid, and any other carboxylic acid can be used. Acetic acid is particularly preferred. Two or more carboxylic acids may be used in combination, or
It may be used in combination with other solvents.
反応社室温（２０−２１℃）で行った。反応温度は特に
限定はされないが、加熱下で行ってもよい。又、加圧下
で反応を行なってもよい。The reaction was carried out at room temperature (20-21°C). Although the reaction temperature is not particularly limited, the reaction may be carried out under heating. Alternatively, the reaction may be carried out under pressure.
反応時間は反応条件によシ異なるが一般に５分以上で行
なわれる。Although the reaction time varies depending on the reaction conditions, it is generally carried out for 5 minutes or more.
次に、リン化合物の添加は還元処理後の処理工程におい
て、または還元処理、乾燥後にリン化合物を添加するこ
とＫよシ達成される。Next, the addition of the phosphorus compound is accomplished in a treatment step after the reduction treatment, or by adding the phosphorus compound after the reduction treatment and drying.
上述したリン化合物の添加はリン化合物の菫をポリマー
のエーテル結合ユニットに対して０．０１モルチ〜コＯ
モル％、好まシ＜ｕｏ、１モル係〜／ｊモル係、さらに
好ましくは１モル俤〜１０モル係であシ、リン化合物は
洗滌時または洗滌後の濾過時、あるいはＰ滓に添加する
か、乾燥時に添加してもよいし、また乾燥後ドライブレ
ンドするか、ウェットブレンドとしてもよい。The above-mentioned addition of the phosphorus compound adds 0.01 mole of the phosphorus compound to the ether bond unit of the polymer.
Mol%, preferably 1 mol to /j mol, more preferably 1 mol to 10 mol. The phosphorus compound is added during washing, filtration after washing, or to the P slag. , may be added during drying, or may be dry blended after drying or may be wet blended.
便用するリン化合物としては３価のリン化合物、５価の
リン化合物いずれも使用可能である。As the phosphorus compound for toilet use, both trivalent phosphorus compounds and pentavalent phosphorus compounds can be used.
具体的な例として、３価のリン化合物としてはトリフェ
ニルホスファイト、トリス（ノニルフェニル）ホスファ
イト、トリエチルホスファイ）、ｌＪス（コーエチルペ
キンル）ホスファイト、トリデシルホスファイト、トリ
ステアリルホスファイト、ジフェニルモノ（−一エチル
ヘキシル）ホスファイト、ジフェニルモノトリデシルホ
スファイト、ジラウリルハイドロジエンホスファイト、
ジフェニルハイドロジエンホスファイト、テトラフェニ
ルジプロピレンクリコールジホスファイト、テトラフェ
ニルテトラ（トリデシル）ペンタエリスリトールテトラ
ホスファイト、テトラ（トリデシル）ａ、ｅ’−インプ
ロピリデンジフェニルホスファイト、トリラウリルトリ
チオホスファイト、ビス（ノニルフェニル）ペンタエリ
スリトールジホスファイト、トリｊ（コ、亭−ジタージ
ャリーブナルフェニル）ホスファイト、トリステアリル
チオホスファイト、トリス（トリエチルホスファイト、
トリデシルホスファイト、ジステアリルペンタエリスリ
トールジホスファイト、ステアリルジハイドロジエンホ
スファイトのような亜すン酸エステル類、トリフェニル
ホスフィン、トリス（ノニルフェニル）ホスフィン、ト
リラウリルホスフィン、トリステアリルホスフィン、ト
リラウリフェニルフオスフエート、トリスノニルフェニ
ルホスフェート、トリエチルホスフェート。As specific examples, trivalent phosphorus compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, triethyl phosphite), lJs(coethylpequinyl) phosphite, tridecyl phosphite, and tristearylphosphite. phyto, diphenyl mono(-monoethylhexyl) phosphite, diphenyl monotridecyl phosphite, dilaurylhydrodiene phosphite,
diphenylhydrodiene phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)a,e'-inpropylidene diphenylphosphite, trilauryltrithiophosphite, Bis(nonylphenyl)pentaerythritol diphosphite, trij(co,tei-ditarjarybenalphenyl)phosphite, tristearylthiophosphite, tris(triethylphosphite,
Phosphites such as tridecyl phosphite, distearyl pentaerythritol diphosphite, stearyl dihydrodiene phosphite, triphenylphosphine, tris(nonylphenyl)phosphine, trilaurylphosphine, tristearylphosphine, trilauri Phenyl phosphate, trisnonylphenyl phosphate, triethyl phosphate.
トリス（−一エチルへキシル）ホスフェートトリドデシ
ルホスフェート、トリステアリルホスフェート、ジフェ
ニル（−一エチルへキシル〕ホスフェート、スチアリル
チオホスフエート、テトラフェニルテトラ（トリデシル
）ペンタエリスリトールテトラホスフェートのようなホ
スフェ−）類、 ）リフェニルホスフインオキシド、
トリステアリルチオホスフィンオキシト等のホスフィン
オキシト類が挙げられるがこれらに特に限定されるもの
ではない。これらの中で０１以上のアルキル基を南する
ホスファイト、ホスフェートが轡に好ましい。Phosphates such as tris(-monoethylhexyl)phosphate tridodecyl phosphate, tristearyl phosphate, diphenyl(-monoethylhexyl) phosphate, stearylthiophosphate, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphate) , ) Riphenylphosphine oxide,
Examples include, but are not limited to, phosphine oxides such as tristearylthiophosphine oxide. Among these, phosphites and phosphates containing 01 or more alkyl groups are particularly preferred.
具体的な代表例としてテトラ（トリデシル）ｌＩ註′イ
ングロビリデンジフェニルホスファイト、トリステアリ
ルホスファイト、トリス（トリデシル）ホスファイト、
トリデシルホスファイト、ジステアリルペンタエリスリ
チルジホスファイト、トリステアリルホスフェート、ジ
ステアリルハイドロジエンホスファイト等が牟げられる
。Specific representative examples include tetra(tridecyl)lI Note: inglopylidene diphenyl phosphite, tristearyl phosphite, tris(tridecyl) phosphite,
Examples include tridecyl phosphite, distearyl pentaerythrityl diphosphite, tristearyl phosphate, distearyl hydrogen phosphite, and the like.
尚こｎらのリン化合物による熱安定性は触媒として使用
したルイス酸または／および後処理によるその変成物と
リン化合物のコンプレックス化によシ達成されると予想
している。The thermal stability of these phosphorus compounds is expected to be achieved by complexing the phosphorus compound with the Lewis acid used as a catalyst and/or its modified product through post-treatment.
尚溶融加熱後の熱安定性の評価は易性製作所製高化式フ
ローテスターＣＦ Ｔ −４０ＯＡを用いて、ＷＯＯ℃
に於て所定時間放置後押し出されたストランドの押し出
し性、押し出し物の外鉄および硫酸に対してポリマーを
／ ？／ｄ１ｊ濃度において溶解させた場合の溶解性お
よび７１ｎｈの測定等よシ判断した。The thermal stability after melting and heating was evaluated using a Koka type flow tester CF T-40OA manufactured by Yoshi Seisakusho at WOO℃.
The extrudability of the extruded strand after being left for a predetermined period of time, the polymer against the outer iron and sulfuric acid of the extrudate? The determination was made by measuring the solubility and 71nh when dissolved at a concentration of /d1j.
また本発明に用いられる前記一般式〔１〕で表わされる
芳香族（チオ）エーテルとしては、ジフェニルエーテル
％／、４ｃｍジフェノキシベンゼン、ビフェニル、ビス
（４Ｉ−フェノキシフェニル）エーテル、り、ダ′−ビ
ス（ターフエノキシフェニル）ジフェニルエーテル、Ｊ
、、？’−シメｆルフェニルエーテル、八へ−ビス（３
−メチルフェノキシ）ベンゼン、 ３．Ｊ’−ジメトキ
シフェニルエーテル、／、弘−ビス（３−メトキシフェ
ノキシラベンゼン、ｌ謙−ビス（コークロロフェノキシ
）ベンゼン、ジフェニルサルファイド。Further, the aromatic (thio)ether represented by the general formula [1] used in the present invention includes diphenyl ether%/, 4cm diphenoxybenzene, biphenyl, bis(4I-phenoxyphenyl)ether, di, da'-bis (terphenoxyphenyl)diphenyl ether, J
,,? '-F phenyl ether, eight he-bis (3
-methylphenoxy)benzene, 3. J'-dimethoxyphenyl ether, /, Hiro-bis(3-methoxyphenoxylabenzene, l-Ken-bis(cochlorophenoxy)benzene, diphenyl sulfide.
ダーツエノキシジフェニルサルファイド、／、４ｔ−ビ
ス−（フェニルメルカプト）ベンゼン、ターフェニル、
亭−フェノキシビフェニル、弘、９′−ジフェノキシビ
フェニルなどが挙げられるが一般式〔１〕で表わされる
ものはいずれも使用可能であり、必ずしもこれらに限定
されるものではない。又、これらの芳香族（チオ）エー
テルは単独もしくは混合して使用してもよい。dartenoxydiphenyl sulfide, /, 4t-bis-(phenylmercapto)benzene, terphenyl,
Examples include tei-phenoxybiphenyl, Hiroshi, and 9'-diphenoxybiphenyl, but any of those represented by the general formula [1] can be used, and the present invention is not necessarily limited to these. Further, these aromatic (thio)ethers may be used alone or in combination.
又、本発明に用いられる前記一般式〔ｕ〕で表わされる
芳香族ジカルボン酸シバライドとしては、テレフタル酸
ジクロライド、イソフタル酸ジクロライト、ジフェニル
エーテルーダ、ダ′−ジカルボン酸ジクロライド、／、
＋＋−ビス（タークロロホルミル・フェニル）ベンゼン
、λ、ｊ−ジメチルテレフタル酸ジクロライド、ジフェ
ニルサルファイド−弘、り′−ジカルボン酸ジクロライ
ド。Further, the aromatic dicarboxylic acid civalide represented by the general formula [u] used in the present invention includes terephthalic acid dichloride, isophthalic acid dichlorite, diphenyl etheruda, da'-dicarboxylic acid dichloride, /,
++-bis(terchloroformyl phenyl)benzene, λ,j-dimethylterephthalic acid dichloride, diphenyl sulfide-hiro, ri'-dicarboxylic acid dichloride.
り、り′−ジフェン酸ジクロライド、１．６−す７タレ
ンジカルボン酸ジクロライドなどが挙げられるが一般式
（Ｉｆ）で示されるものはいずれも使用可能であり、必
すしもこれらに限定されるものではない。又、これらの
芳香族ジカルボン酸シバライドは単独もしくは混合して
便用してもよい。又、これらの芳香族ジカルボン酸ジノ
１ライドはホスゲンとも混合して開用してもよい。Examples include ri, ri'-diphenic acid dichloride, 1,6-s7thalenedicarboxylic acid dichloride, etc., but any of those represented by the general formula (If) can be used, but it is not necessarily limited to these. isn't it. Further, these aromatic dicarboxylic acid cybarides may be used alone or in combination. Further, these aromatic dicarboxylic acid dino 1rides may also be mixed with phosgene for use.
本発明で用いられる非プロトン性有機溶媒としては、塩
化メチレン、塩化エチレン、ｌ、−−ジクロルエタン、
／、／、コ、−一テトラクロルエタン、クロロホルム
、四塩化炭素、ニトロベンゼン、ニトロメタン、二硫化
炭素、エチルエーテル、ジブチルエーテル、ペンタン、
ヘキサン。Examples of the aprotic organic solvent used in the present invention include methylene chloride, ethylene chloride, l,--dichloroethane,
/, /, co, -1-tetrachloroethane, chloroform, carbon tetrachloride, nitrobenzene, nitromethane, carbon disulfide, ethyl ether, dibutyl ether, pentane,
hexane.
ヘプｊン、オルトジクロルベンゼンなどが用いられるが
必ずしもこれらに限定されるものではない。溶媒の使用
量は、用いられるジフェニルエーテルの／〜ＳＯＯ倍ｆ
（重量比ン、好ましくは５−ｉｏｏ倍量（重量比）であ
る。Hepone, orthodichlorobenzene, etc. are used, but are not necessarily limited to these. The amount of solvent used is /~SOO times f of the diphenyl ether used.
(weight ratio), preferably 5-ioo times (weight ratio).
本発明に用いられるルイス酸としては、無水三塩化アル
ミニウム、無水玉臭化アルミニウム、無水三塩化カリウ
ム、三沸化硼素ｌエチルエーテルコンプレックス、塩化
第二スズ、塩化第一スズ、塩化第二鉄、四塩化チタン、
三塩化硼素。The Lewis acids used in the present invention include anhydrous aluminum trichloride, anhydrous aluminum bromide, anhydrous potassium trichloride, boron trifluoride l ethyl ether complex, stannic chloride, stannous chloride, ferric chloride, titanium tetrachloride,
Boron trichloride.
五塩化アンチモン、三塩化リン、五塩化リン。Antimony pentachloride, phosphorus trichloride, phosphorus pentachloride.
五塩化テルル、五塩化にオプ、六塩化タングステンなど
が挙げられるが、必ずしもこれら忙限定されるものでは
ないが、周期律表第１族ノ１０ゲン化物、特に塩化アル
ミニウムが好ましい。Examples include tellurium pentachloride, tungsten pentachloride, tungsten hexachloride, etc., but are not necessarily limited to these, but preferred are decogenides of group 1 of the periodic table, particularly aluminum chloride.
これらのルイス酸の使用量は芳香族（チオ〕エーテルに
対して、モル比で０．０／〜１００．好ましくは０．
／ ％ ／ ０．０でろる。The amount of these Lewis acids to be used is 0.0/-100, preferably 0.0/-100, in molar ratio to the aromatic (thio)ether.
/ % / 0.0.
尚重合温度は特に制限はないが一１０′ｃ以上（通常１
００′Ｃ以下）という温和な条件下で行なわれる。また
、加圧下で反応を行なってもよい。The polymerization temperature is not particularly limited, but is 10'C or higher (usually 1
It is carried out under mild conditions (below 00'C). Alternatively, the reaction may be carried out under pressure.
以下、本発明を実施例によシさらに詳細に説明する。 Hereinafter, the present invention will be explained in more detail using examples.
実施例１〜よ
３０００ｍｌの反応器にジフェニルエーテル７八ダ９．
９ （０，ダコモル）、テレフタル酸クロリドＡ １．
コ／９（０，，１９モル）、およびイソフタル酸クロリ
ド／り、０！ｒｌｉ（０，０７３モル）を入れ、さらに
予めモレキュラーシープ３Ａで乾ＩＪ Ｌだジクロルエ
タン／ ５００ ｍｌを卯えた後。Example 1 - Add 7, 8, and 9 grams of diphenyl ether to a 3,000 ml reactor.
9 (0, dacomole), terephthalic acid chloride A 1.
co/9 (0,,19 mol), and isophthalic acid chloride/li, 0! After adding rli (0,073 mol) and adding 500 ml of dichloroethane/dichloroethane, which had been dried in advance with Molecular Sheep 3A.
反応器を氷冷°する。次に塩化アルミニウム／亭Ａ、４
７ｇ（へ１モル）を加え撹拌下、水冷下で７時間さらに
呈龜で９時間反応後、メタノール／！ｒ００ｍｌを加え
、触媒を失活させ１過を行なう。次に／！００１１１の
メタノールを加え。Cool the reactor on ice. Next, aluminum chloride/Tei A, 4
7 g (1 mol) was added and reacted for 7 hours under stirring and water cooling, and then for 9 hours under stirring, followed by methanol/! Add 00ml of r00ml to deactivate the catalyst and conduct one filtration. next/! Add 00111 methanol.
３０分間還流して洗滌し、その後５％−塩酸水溶液ｉｓ
ｏｏｍｔでＪＯ分間ｔθ℃攪拌下で一回洗滌を繰シ返す
。さらに脱塩水で３０分間１０℃、攪拌下で２回洗滌を
行ない、７２０℃でｌ昼夜乾燥する。得られたポリマー
の収率はほぼ１００チであり、９ざ６−４硫酸中で／
＆／ｄｌｌの濃度で３０℃で測定したηｉｎｈは表／に
示す通りである。Wash by refluxing for 30 minutes, then 5% aqueous hydrochloric acid is
Washing was repeated once under stirring at oomt for JO minutes at tθ°C. Further, it was washed twice with demineralized water for 30 minutes at 10°C under stirring, and then dried at 720°C for 1 day and night. The yield of the obtained polymer was approximately 100%, and the yield of the obtained polymer was approximately 100%.
The ηinh measured at 30° C. at the concentration of &/dll is shown in Table/.
次にこのポリマー３ｆ！と９０９６ギ酸６０−１炭酸す
） ＩＪウム八へコｇとの混合物を還流下で１時間加熱
する。冷却後、ポリマーを１過し中性になるまで水洗を
くシかえず。その後／、１０−であった◎
このようにして還元処理を行なった。Next is this polymer 3f! A mixture of 9096 formic acid 60-1 carbonic acid and 9096 formic acid 60-1 carbonic acid is heated under reflux for 1 hour. After cooling, rinse the polymer with water until it becomes neutral, without changing it. After that, the result was 10-◎ The reduction treatment was performed in this manner.
次Ｋｌｔ”用する表−／に記載のリン化合物の所定量を
ｎ−ヘキサン、四塩化炭素などの活剤に希釈しておき、
ポリマー−９とブレンド後ろ０℃で一昼夜乾燥して溶剤
を除去した。そのポリマーについて高化式フローテスタ
ー（易性製作断裂、０ＦＴ−３００Ａ）を用いてりｏｏ
℃で１０〜１５分間俗融加熱を行なった。ストランドの
押出しは容易であった。さらに押出されたサンプルを？
ｆ％硫酸に／ ！／／６１の濃度で溶解したところ完全
に溶解し、ηｉｎｈの測定をしたが、加熱浴融前後のη
ｉｎｈの変化は小さい。A predetermined amount of the phosphorus compound listed in the following table for use in "Klt" is diluted with an activator such as n-hexane or carbon tetrachloride,
After blending with Polymer-9, the mixture was dried at 0°C overnight to remove the solvent. Test the polymer using a Koka type flow tester (easy fabrication and tearing, 0FT-300A).
Gradual melt heating was performed at <0>C for 10-15 minutes. Extrusion of the strands was easy. More extruded samples?
f% to sulfuric acid/! When dissolved at a concentration of //61, it was completely dissolved and ηinh was measured.
The change in inh is small.
比較例／
後
井＃処理を行なわなかったサンプルを実施例１と同様に
高化式フローテスターを用いｅｏ。Comparative Example/ A sample that was not subjected to Goi# treatment was subjected to eo using a Koka type flow tester in the same manner as in Example 1.
℃でＳ分間溶融加熱を行なったところ、押出し物は押出
し性も悪く、さらに押出されたサンプル紫ｑｇ％硫酸に
／ ｆｌ／ｄｌｌの濃度で溶解したところ、はとんど済
解しなかった。即ちポリマーがゲル化してしまったと４
！ＩＪ足される。When melting and heating was performed at ℃ for S minutes, the extrudability of the extrudate was poor, and when the extruded sample was dissolved in purple qg% sulfuric acid at a concentration of / fl / dll, it was hardly dissolved. In other words, the polymer has gelled.
! IJ is added.
表 ／
〔発明の効果〕
取上のように、本発明によると熱安定性が改良された芳
香族ポリ（チオ）エーテルケトンを得ることができる。Table / [Effects of the Invention] As mentioned above, according to the present invention, an aromatic poly(thio)etherketone with improved thermal stability can be obtained.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 − ほか／名Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/names
Claims (3)
ゲン原子、炭化水素基、又はアルコキシ基を示し、Ｘは
直接結合、酸素原子又は硫黄原子を示し、ｌは０〜２の
整数である） で表わされる芳香族（チオ）エーテルと、一般式〔II〕 ▲数式、化学式、表等があります▼・・・・〔II〕 （〔II〕式中、Ｒ＾１＾３〜Ｒ＾２＾０は水素原子、ハ
ロゲン原子、炭化水素基、又はアルコキシ基を示し、Ｘ
は直接結合、酸素原子又は硫黄原子を示し、Ｙはハロゲ
ン原子を示し、ｍは０〜３の整数である） で表わされる芳香族ジカルボン酸ジハライド、又は、ホ
スゲンとを、ルイス酸の存在下、非プロトン性有機溶媒
中で反応させて、一般式〔III〕 ▲数式、化学式、表等があります▼ ・・・・・・・〔III〕 （〔III〕式中、Ｒ＾１〜Ｒ＾２＾０は水素原子、ハロ
ゲン原子、炭化水素基、又はアルコキシ基を示し、Ｘは
直接結合、酸素原子又は硫黄原子を示し、ｌは０〜２の
整数を示し、ｍは０〜３の整数を示し、ｎは０又は１で
ある） の繰り返し単位を有する芳香族ポリ（チオ）エーテルケ
トンを製造する方法に於て、重合および触媒を不活性化
した後の後処理工程において、還元処理を行ない、さら
にその後の工程においてリン化合物を添加することを特
徴とする芳香族ポリ（チオ）エーテルケトンの製造方法
。(1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] (In the [I] formula, R^1 to R^1^2 are hydrogen atoms, halogen atoms, carbonization represents a hydrogen group or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, and l is an integer of 0 to 2) and the general formula [II] ▲Math. , chemical formulas, tables, etc.▼...[II] (In the [II] formula, R^1^3 to R^2^0 represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X
represents a direct bond, an oxygen atom or a sulfur atom, Y represents a halogen atom, and m is an integer of 0 to 3) or phosgene, in the presence of a Lewis acid, By reacting in an aprotic organic solvent, the general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ・・・・・・・・・ [III] (In the [III] formula, R^1 ~ R^2 ^0 represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, l represents an integer of 0 to 2, and m represents an integer of 0 to 3. In the method for producing an aromatic poly(thio)etherketone having a repeating unit of A method for producing an aromatic poly(thio)etherketone, which further comprises adding a phosphorus compound in a subsequent step.
用いる特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, in which a Group III halide of the periodic table is used as the Lewis acid.
は無水ハロゲン化ガリウムを用いる特許請求の範囲第１
項または第２項記載の製造方法。(3) Claim 1 using anhydrous aluminum halide or anhydrous gallium halide as the Lewis acid
The manufacturing method according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30607786A JPH0721053B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing aromatic poly (thio) etherketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30607786A JPH0721053B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing aromatic poly (thio) etherketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159431A true JPS63159431A (en) | 1988-07-02 |
| JPH0721053B2 JPH0721053B2 (en) | 1995-03-08 |
Family
ID=17952760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30607786A Expired - Lifetime JPH0721053B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing aromatic poly (thio) etherketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0721053B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008069212A (en) * | 2006-09-12 | 2008-03-27 | Tokyo Institute Of Technology | Thioether fluorene skeleton-containing polymer and method for producing the same |
| WO2020130290A1 (en) * | 2018-12-17 | 2020-06-25 | 한화솔루션 주식회사 | Polyether ketone ketone mixture resin composition and preparation method therefor |
| WO2020130289A1 (en) * | 2018-12-18 | 2020-06-25 | 한화솔루션 주식회사 | Method for preparing polyether ketone ketone mixture resin composition, and polyether ketone ketone prepared thereby |
| JP2021527748A (en) * | 2018-06-21 | 2021-10-14 | ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー | Poly (etherketoneketone) (PEKK) composite material |
-
1986
- 1986-12-22 JP JP30607786A patent/JPH0721053B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008069212A (en) * | 2006-09-12 | 2008-03-27 | Tokyo Institute Of Technology | Thioether fluorene skeleton-containing polymer and method for producing the same |
| JP2021527748A (en) * | 2018-06-21 | 2021-10-14 | ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー | Poly (etherketoneketone) (PEKK) composite material |
| WO2020130290A1 (en) * | 2018-12-17 | 2020-06-25 | 한화솔루션 주식회사 | Polyether ketone ketone mixture resin composition and preparation method therefor |
| WO2020130289A1 (en) * | 2018-12-18 | 2020-06-25 | 한화솔루션 주식회사 | Method for preparing polyether ketone ketone mixture resin composition, and polyether ketone ketone prepared thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0721053B2 (en) | 1995-03-08 |
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