JP2008255229A - Production method of solvent resisting polyphenylene ether - Google Patents
Production method of solvent resisting polyphenylene ether Download PDFInfo
- Publication number
- JP2008255229A JP2008255229A JP2007099167A JP2007099167A JP2008255229A JP 2008255229 A JP2008255229 A JP 2008255229A JP 2007099167 A JP2007099167 A JP 2007099167A JP 2007099167 A JP2007099167 A JP 2007099167A JP 2008255229 A JP2008255229 A JP 2008255229A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- polymerization
- group
- precipitation
- optionally substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 115
- 239000002904 solvent Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 105
- 238000001556 precipitation Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- -1 phenol compound Chemical class 0.000 claims description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 24
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001880 copper compounds Chemical group 0.000 claims description 6
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 5
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 5
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- 150000002989 phenols Chemical class 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012673 precipitation polymerization Methods 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 3
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 3
- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- LTRVUFFOMIUCPJ-UHFFFAOYSA-N 2-ethyl-5-methylphenol Chemical compound CCC1=CC=C(C)C=C1O LTRVUFFOMIUCPJ-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 2
- AYGDIAGADYTJRY-UHFFFAOYSA-N 5-ethyl-2-methylphenol Chemical compound CCC1=CC=C(C)C(O)=C1 AYGDIAGADYTJRY-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YRGVKPIUZUOJSJ-UHFFFAOYSA-N n,n'-dibutylethane-1,2-diamine Chemical compound CCCCNCCNCCCC YRGVKPIUZUOJSJ-UHFFFAOYSA-N 0.000 description 2
- VATUKUMHBXZSCD-UHFFFAOYSA-N n,n'-dipropylethane-1,2-diamine Chemical compound CCCNCCNCCC VATUKUMHBXZSCD-UHFFFAOYSA-N 0.000 description 2
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 2
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 description 2
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000000710 polymer precipitation Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
本発明は、耐溶剤性及び耐熱性に優れたポリフェニレンエーテルの製造方法に関する。さらに詳しくは、良溶媒と貧溶媒を用いて重合体を沈殿析出させる方法であって、沈殿析出後に重合温度を上昇させる、耐溶剤性及び耐熱性に優れたポリフェニレンエーテルの製造方法に関する。 The present invention relates to a method for producing polyphenylene ether excellent in solvent resistance and heat resistance. More specifically, the present invention relates to a method for precipitating a polymer using a good solvent and a poor solvent, and increasing the polymerization temperature after precipitation, and producing a polyphenylene ether excellent in solvent resistance and heat resistance.
ポリフェニレンエーテルは加工性、生産性に優れ、溶融射出成型や溶融押出成型などの成型方法により、所望の形状の製品や部品を効率よく生産できるため、電気・電子材料分野、自動車分野、その他各種工業材料分野、食品の包装分野の製品や部品用の材料として幅広く用いられている。用途の多様化に伴い、分子量やガラス転移温度等の特性の異なる多種類のポリフェニレンエーテルが求められ、耐熱性が高く、機械的特性や耐溶剤性に優れたポリフェニレンエーテルが望まれるようになってきている。 Polyphenylene ether is excellent in processability and productivity, and can efficiently produce products and parts of the desired shape by molding methods such as melt injection molding and melt extrusion molding. Therefore, electrical and electronic materials, automobiles, and other industries. It is widely used as a material for products and parts in the material field and food packaging field. With the diversification of applications, various kinds of polyphenylene ethers having different characteristics such as molecular weight and glass transition temperature are required, and polyphenylene ethers having high heat resistance and excellent mechanical properties and solvent resistance have been desired. ing.
従来、耐熱性の高いポリフェニレンエーテルとして、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールからなるポリフェニレンエーテルが知られており、その製造方法に関しても種々検討されている。例えば、特許文献１には、フェノール化合物を曇点温度以上の反応温度で酸化カップリングし、ポリフェニレンエーテルを製造する方法が開示されている。しかしながら、この方法は、重合形態が溶液重合であるため、重合の進行に伴う粘度上昇を抑制するためにモノマー化合物の濃度を低くする必要があり、工業的に効率の良い方法とは言えない。また得られるポリフェニレンエーテルに関しても耐溶剤性に劣る傾向がある。 Conventionally, polyphenylene ether composed of 2,6-dimethylphenol and 2,3,6-trimethylphenol is known as a highly heat-resistant polyphenylene ether, and various methods for producing the same have been studied. For example, Patent Document 1 discloses a method for producing polyphenylene ether by oxidative coupling of a phenol compound at a reaction temperature equal to or higher than the cloud point temperature. However, since this polymerization method is solution polymerization, it is necessary to reduce the concentration of the monomer compound in order to suppress an increase in the viscosity accompanying the progress of the polymerization, and this is not an industrially efficient method. Also, the resulting polyphenylene ether tends to be poor in solvent resistance.
特許文献２には、触媒の存在下、ポリフェニレンエーテルに対する良溶媒と貧溶媒を用いて重合を行い、ポリフェニレンエーテルを沈殿析出させる方法が開示されており、従来のポリフェニレンエーテルよりも５℃以上ガラス転移温度の高い耐熱性に優れたポリフェニレンエーテルの製造に成功している。 Patent Document 2 discloses a method in which polymerization is performed using a good solvent and a poor solvent for polyphenylene ether in the presence of a catalyst to precipitate polyphenylene ether, and the glass transition is 5 ° C. or more than that of conventional polyphenylene ether. We have succeeded in producing polyphenylene ether with high temperature and heat resistance.
さらに、特許文献３には、触媒の存在下、ポリフェニレンエーテルに対する良溶媒と貧溶媒を用いて重合を行い、ポリマーが沈殿析出した後に貧溶媒をさらに加え、分子量の調節されたポリフェニレンエーテルを製造する方法が開示されている。 Furthermore, in Patent Document 3, polymerization is performed using a good solvent and a poor solvent for polyphenylene ether in the presence of a catalyst, and after the polymer is precipitated, a poor solvent is further added to produce polyphenylene ether with a controlled molecular weight. A method is disclosed.
しかし、いずれの方法においても、得られるポリフェニレンエーテルに充分な耐溶剤性を付与することができていない。ところで、特許文献４には、触媒の存在下、フェノール化合物を酸化カップリングした後に溶媒を濃縮し、さらにポリフェニレンエーテルに対する貧溶媒を加えることによってポリフェニレンエーテルを沈殿析出させる方法が開示されている。当該方法では、乾燥方式により一概には言えないが乾燥時に設備のフィルターが詰まるトラブルを招いたり、ポリフェニレンエーテルパウダーの空送時にパウダーとガスを分離するのが困難になる、或いは押出時のスクリュー噛込み不良を招く等の原因となる、微粉の発生を低減させることに成功している。しかしながら、この方法では、未だに約４質量％程度の微粉の発生があり、上記課題を充分に解決しているとは言えない。 However, in any method, sufficient solvent resistance cannot be imparted to the resulting polyphenylene ether. By the way, Patent Document 4 discloses a method of precipitating polyphenylene ether by concentrating a solvent after oxidative coupling of a phenol compound in the presence of a catalyst, and further adding a poor solvent for polyphenylene ether. In this method, although it cannot be generally stated depending on the drying method, problems such as clogging of the filter of the equipment at the time of drying, it becomes difficult to separate the powder and gas when the polyphenylene ether powder is air-fed, or the screw biting during the extrusion It has succeeded in reducing the generation of fine powder, which causes inconvenience. However, this method still generates about 4% by mass of fine powder, and it cannot be said that the above problem has been sufficiently solved.
一方、多種類のポリフェニレンエーテルを造り分ける場合においては、バッチ重合方式が有用であり、広い範囲においてガラス転移温度の設計が可能な効率的なポリフェニレンエーテルの製造方法が望まれている。バッチ重合の際に発生し得る反応器へのスケールは、ポリフェニレンエーテルの収率を悪化させるため原料であるフェノール化合物を必要以上に用いなければならず、さらに環境への負荷を増大させるおそれもある。
上記事情に鑑み、本発明が解決しようとする課題は、耐溶剤性及び耐熱性に優れたポリフェニレンエーテルを、微粉の発生やスケールの発生を抑制しながら、効率良く安定に製造する方法を提供することである。 In view of the above circumstances, the problem to be solved by the present invention is to provide a method for efficiently and stably producing polyphenylene ether excellent in solvent resistance and heat resistance while suppressing generation of fine powder and generation of scale. That is.
本発明者らは、上記課題に対して鋭意研究を行った結果、特定の構造を有するポリフェニレンエーテルを、触媒の存在下、ポリフェニレンエーテルに対する良溶媒と貧溶媒を用いて沈殿析出重合するに際し、沈殿析出後に重合温度を上昇させることにより、耐溶剤性及び耐熱性に優れたポリフェニレンエーテルを、微粉の発生やスケールの発生を抑制しながら効率良く安定に製造できることを見出し、本発明を完成させた。 As a result of intensive studies on the above problems, the present inventors have conducted precipitation polymerization when polyphenylene ether having a specific structure is subjected to precipitation polymerization using a good solvent and a poor solvent for polyphenylene ether in the presence of a catalyst. By increasing the polymerization temperature after precipitation, it was found that polyphenylene ether excellent in solvent resistance and heat resistance can be efficiently and stably produced while suppressing the generation of fine powder and scale, and the present invention was completed.
すなわち、本発明は以下の通りである。
（１）下記式（１）
That is, the present invention is as follows.
(1) The following formula (1)
（式中、Ｒ1及びＲ2は、それぞれ独立して、水素原子、ハロゲン原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいアルコキシ基を示す）
で表されるフェノール化合物（Ａ）及び／又は、
下記式（２）
(In the formula, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group or a substituted group. An aryl group which may be substituted, an aralkyl group which may be substituted, or an alkoxy group which may be substituted)
A phenol compound (A) and / or
Following formula (2)
（式中、Ｒ3及びＲ4は、それぞれ独立して、水素原子、ハロゲン原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいアルコキシ基を示し、Ｒ5は、ハロゲン原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいアルコキシ基を示す）
で表されるフェノール化合物（Ｂ）からなる混合フェノール化合物を、触媒の存在下、少なくとも１種以上のポリフェニレンエーテルの良溶媒及び少なくとも１種以上のポリフェニレンエーテルの貧溶媒からなる混合溶媒中で、酸素含有ガスを用いて酸化カップリングし、重合体を沈殿析出させるポリフェニレンエーテルの製造方法であって、沈殿析出後に重合温度を上昇させる、ポリフェニレンエーテルの製造方法。
（２）沈殿析出前の重合温度が４５℃未満、沈殿析出後の重合温度が４５℃以上である、上記（１）記載のポリフェニレンエーテルの製造方法。
（３）沈殿析出前と沈殿析出後の温度差が１０℃以上である、上記（１）又は（２）に記載のポリフェニレンエーテルの製造方法。
（４）前記混合フェノール化合物が、フェノール化合物（Ａ）６０質量％〜９５質量％及びフェノール化合物（Ｂ）５質量％〜４０質量％からなる混合フェノール化合物である、上記（１）〜（３）のいずれか記載のポリフェニレンエーテルの製造方法。
（５）前記フェノール化合物（Ａ）が２,６−ジメチルフェノール、前記フェノール化合物（Ｂ）が２,３,６−トリメチルフェノールである、上記（１）〜（４）のいずれか記載のポリフェニレンエーテルの製造方法。
（６）前記貧溶媒が炭素数１〜１０のアルコールを主成分とする、少なくとも１種以上の溶媒である、上記（１）〜（５）のいずれか記載のポリフェニレンエーテルの製造方法。
（７）前記炭素数１〜１０のアルコールがメタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、２−ブタノール、ｔｅｒｔ−ブタノールからなる群から選ばれる少なくとも１種である、上記（６）記載のポリフェニレンエーテルの製造方法。
（８）前記触媒の構成成分が銅化合物、ハロゲン化合物及び下記式（３）
(In the formula, R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or a substituted group. Represents an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, and R 5 represents a halogen atom, an optionally substituted alkyl group, or an optionally substituted An alkenyl group, an alkynyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, or an alkoxy group which may be substituted)
In the presence of a catalyst, a mixed phenol compound consisting of the phenol compound (B) represented by the formula (1) is mixed with a good solvent of at least one polyphenylene ether and a poor solvent of at least one polyphenylene ether. A method for producing polyphenylene ether, which comprises oxidative coupling using a contained gas to precipitate a polymer, wherein the polymerization temperature is increased after precipitation.
(2) The method for producing a polyphenylene ether according to the above (1), wherein the polymerization temperature before precipitation is less than 45 ° C and the polymerization temperature after precipitation is 45 ° C or higher.
(3) The method for producing a polyphenylene ether according to the above (1) or (2), wherein the temperature difference before and after precipitation is 10 ° C. or more.
(4) Said (1)-(3) whose said mixed phenol compound is a mixed phenol compound which consists of 60 mass%-95 mass% of phenol compounds (A) and 5 mass%-40 mass% of phenol compounds (B). The manufacturing method of polyphenylene ether in any one of these.
(5) The polyphenylene ether according to any one of (1) to (4), wherein the phenol compound (A) is 2,6-dimethylphenol and the phenol compound (B) is 2,3,6-trimethylphenol. Manufacturing method.
(6) The method for producing a polyphenylene ether according to any one of the above (1) to (5), wherein the poor solvent is at least one kind of solvent mainly composed of an alcohol having 1 to 10 carbon atoms.
(7) The above (6), wherein the alcohol having 1 to 10 carbon atoms is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and tert-butanol. ) A process for producing a polyphenylene ether as described above.
(8) The constituent components of the catalyst are a copper compound, a halogen compound and the following formula (3)
（式中、Ｒ6、Ｒ7、Ｒ8及びＲ9は、それぞれ独立して、水素原子、炭素数１〜６の直鎖状又は分岐鎖状のアルキル基を示し（但し、全てが同時に水素ではない）、Ｒ10は炭素数２〜５の直鎖状又は分岐鎖状のアルキレン基を示す）
で表されるジアミン化合物を含む、上記（１）〜（７）のいずれか記載のポリフェニレンエーテルの製造方法。
（９）沈殿析出後、少なくとも１０分以上重合を継続する、上記（１）〜（８）のいずれか記載のポリフェニレンエーテルの製造方法。
（１０）重合方式がバッチ方式である、上記（１）〜（９）のいずれか記載のポリフェニレンエーテルの製造方法。
（１１）前記混合フェノール化合物の全量を、沈殿析出を開始し重合溶液がスラリー状態を呈し始める以前に重合槽内に添加する、上記（１）〜（１０）のいずれか記載のポリフェニレンエーテルの製造方法。
(In the formula, R 6 , R 7 , R 8 and R 9 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (provided that all of them are simultaneously hydrogenated). R 10 represents a linear or branched alkylene group having 2 to 5 carbon atoms)
The manufacturing method of the polyphenylene ether in any one of said (1)-(7) containing the diamine compound represented by these.
(9) The method for producing a polyphenylene ether according to any one of (1) to (8), wherein the polymerization is continued for at least 10 minutes after precipitation.
(10) The method for producing polyphenylene ether according to any one of (1) to (9), wherein the polymerization method is a batch method.
(11) The production of the polyphenylene ether according to any one of (1) to (10), wherein the total amount of the mixed phenol compound is added to the polymerization tank before the precipitation starts and the polymerization solution starts to exhibit a slurry state. Method.
本発明によれば、耐溶剤性及び耐熱性に優れたポリフェニレンエーテルを、微粉の発生やスケールの発生を抑制しながら、効率良く安定に製造する方法を提供することができる。また、本発明により製造されたポリフェニレンエーテルは、耐溶剤性及び耐熱性に優れているため、機械部品、自動車部品、電気電子部品、特に、電子電子部品、フィルム、シート等に好適に利用することが可能である。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing polyphenylene ether excellent in solvent resistance and heat resistance efficiently and stably, suppressing generation | occurrence | production of a fine powder and generation | occurrence | production of a scale can be provided. In addition, since the polyphenylene ether produced by the present invention is excellent in solvent resistance and heat resistance, it should be suitably used for machine parts, automobile parts, electric and electronic parts, particularly electronic and electronic parts, films, sheets and the like. Is possible.
以下、本発明を、望ましい実施に形態とともに詳細に説明するが、本発明はこれらの態様に限定されるものではない。 Hereinafter, the present invention will be described in detail together with preferred embodiments, but the present invention is not limited to these embodiments.
本発明のポリフェニレンエーテルの製造方法は、上記式（１）及び／又は上記式（２）で表されるフェノール化合物からなる混合フェノール化合物を、触媒の存在下、少なくとも１種以上のポリフェニレンエーテルの良溶媒及び少なくとも１種以上のポリフェニレンエーテルの貧溶媒からなる混合溶媒中で、酸素含有ガスを用いて酸化カップリングし、重合体を沈殿析出させる方法であって、沈殿析出後に重合温度を上昇させることを特徴としている。 The method for producing polyphenylene ether of the present invention is a method in which a mixed phenol compound composed of a phenol compound represented by the above formula (1) and / or the above formula (2) is treated with at least one polyphenylene ether in the presence of a catalyst. A method of oxidative coupling using an oxygen-containing gas in a mixed solvent comprising a solvent and a poor solvent of at least one polyphenylene ether to precipitate a polymer, and raising the polymerization temperature after precipitation It is characterized by.
以下、本発明における各記号の説明を行う。
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子などが挙げられ、好ましくは、塩素原子、臭素原子である。
Hereinafter, each symbol in the present invention will be described.
Examples of the halogen atom represented by R 1 , R 2 , R 3 , R 4 and R 5 include a fluorine atom, a chlorine atom and a bromine atom, preferably a chlorine atom and a bromine atom.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアルキル基の「アルキル基」としては、炭素数が１〜６、好ましくは１〜３の、直鎖状又は分岐鎖状のアルキル基を示し、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシルなどが挙げられ、好ましくは、メチル、エチルであり、より好ましくはメチルである。 The “alkyl group” of the optionally substituted alkyl group represented by R 1 , R 2 , R 3 , R 4 and R 5 is a straight chain having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Or a branched alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, etc., preferably methyl, ethyl, Preferably it is methyl.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアルケニル基の「アルケニル基」としては、例えば、エテニル、１−プロペニル、２−プロペニル、３−ブテニル、ペンテニル、ヘキセニルなどが挙げられ、好ましくはエテニル、１−プロペニルである。 Examples of the “alkenyl group” of the optionally substituted alkenyl group represented by R 1 , R 2 , R 3 , R 4 and R 5 include ethenyl, 1-propenyl, 2-propenyl, 3-butenyl and pentenyl. Hexenyl and the like, preferably ethenyl and 1-propenyl.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアルキニル基の「アルキニル基」としては、エチニル、１−プロピニル、２−プロピニル（プロパルギル）、３−ブチニル、ペンチニル、ヘキシニルなどが挙げられ、好ましくはエチニル、１−プロピニル、２−プロピニル（プロパルギル）である。 Examples of the “alkynyl group” of the optionally substituted alkynyl group represented by R 1 , R 2 , R 3 , R 4 and R 5 include ethynyl, 1-propynyl, 2-propynyl (propargyl), 3-butynyl, Examples thereof include pentynyl and hexynyl, and ethynyl, 1-propynyl and 2-propynyl (propargyl) are preferable.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアリール基の「アリール基」としては、例えば、フェニル、ナフチルなどが挙げられ、好ましくはフェニルである。 Examples of the “aryl group” of the optionally substituted aryl group represented by R 1 , R 2 , R 3 , R 4 and R 5 include phenyl, naphthyl and the like, preferably phenyl.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアラルキル基の「アラルキル基」としては、例えば、ベンジル、フェネチル、２−メチルベンジル、４−メチルベンジル、α―メチルベンジル、２−ビニルフェネチル、４−ビニルフェネチルなどが挙げられ、好ましくはベンジルである。 Examples of the “aralkyl group” of the optionally substituted aralkyl group represented by R 1 , R 2 , R 3 , R 4 and R 5 include benzyl, phenethyl, 2-methylbenzyl, 4-methylbenzyl, α -Methylbenzyl, 2-vinylphenethyl, 4-vinylphenethyl and the like can be mentioned, and benzyl is preferable.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示される置換されていてもよいアルコキシ基の「アルコキシ基」としては、炭素数が１〜６、好ましくは１〜３の、直鎖状又は分岐鎖状のアルコキシ基を示し、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、ｓｅｃ−ブトキシ、ｔｅｒｔ−ブトキシ、ペンチルオキシ、ヘキシルオキシなどが挙げられ、好ましくはメトキシ、エトキシである。 The “alkoxy group” of the optionally substituted alkoxy group represented by R 1 , R 2 , R 3 , R 4 and R 5 is a straight chain having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Alternatively, it represents a branched alkoxy group, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, and preferably methoxy and ethoxy.
Ｒ1、Ｒ2、Ｒ3、Ｒ4及びＲ5で示されるアルキル基、アリール基、アルケニル基、アルキニル基、アラルキル基、アルコキシ基は、置換可能な位置に、１又は２以上の置換基で置換されていてもよい。そのような置換基としては、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子）、炭素数１〜６のアルキル基（例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル）、アリール基（例えば、フェニル、ナフチル）、アルケニル基（例えば、エテニル、１―プロペニル、２−プロペニル）、アルキニル基（例えば、エチニル、１−プロピニル、２―プロピニル）、アラルキル基（例えば、ベンジル、フェネチル）、アルコキシ基（例えば、メトキシ、エトキシ）等が挙げられる。 The alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group and alkoxy group represented by R 1 , R 2 , R 3 , R 4 and R 5 are each substituted with one or more substituents at substitutable positions. May be substituted. Examples of such a substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl), aryl groups (eg, phenyl, naphthyl), alkenyl groups (eg, ethenyl, 1-propenyl, 2-propenyl), alkynyl groups (eg, ethynyl, 1-propynyl, 2-propynyl) , Aralkyl groups (for example, benzyl, phenethyl), alkoxy groups (for example, methoxy, ethoxy) and the like.
フェノール化合物（Ａ）としては、ｏ−クレゾール、２，６−ジメチルフェノール、２−エチルフェノール、２−メチル−６−エチルフェノール、２，６−ジエチルフェノール、２−ｎ−プロピルフェノール、２−エチル−６−ｎ−プロピルフェノール、２−メチル−６−クロルフェノール、２−メチル−６−ブロモフェノール、２−メチル−６−イソプロピルフェノール、２−メチル−６−ｎ−プロピルフェノール、２−エチル−６−ブロモフェノール、２−メチル−６−ｎ−ブチルフェノール、２，６−ジ−ｎ−プロピルフェノール、２−エチル−６−クロルフェノール、２−メチル−６−フェニルフェノール、２−フェニルフェノール、２，６−ジフェニルフェノール、２，６−ビス−（４−フルオロフェニル）フェノール、２−メチル−６−トリルフェノール、２，６−ジトリルフェノール、等が挙げられ、なかでも、安価であり入手が容易であるため、２，６−ジメチルフェノール、２，６−ジエチルフェノール、２，６−ジフェニルフェノールが好ましく、２，６−ジメチルフェノールがより好ましい。上記フェノール化合物（Ａ）は単独で用いても、２種以上を組み合わせて用いてもよい。例えば、２，６−ジメチルフェノールと２，６−ジエチルフェノールを組み合わせて使用する方法、２，６−ジメチルフェノールと２，６−ジフェニルフェノールを組み合わせて用いる方法などが挙げられ、その際の混合比は任意に選択できる。また使用するフェノール化合物（Ａ）の中には、製造の際の副産物として含まれている少量のｍ−クレゾール、ｐ−クレゾール、２，４−ジメチルフェノール、２，４，６−トリメチルフェノール等が含まれていてもかまわない。 As the phenolic compound (A), o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, 2-ethyl -6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl- 6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2 , 6-diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol, 2-methyl -6-tolylphenol, 2,6-ditolylphenol, etc. Among them, since it is inexpensive and easily available, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6- Diphenylphenol is preferred, and 2,6-dimethylphenol is more preferred. The said phenol compound (A) may be used independently, or may be used in combination of 2 or more type. For example, a method using a combination of 2,6-dimethylphenol and 2,6-diethylphenol, a method using a combination of 2,6-dimethylphenol and 2,6-diphenylphenol, etc., and the mixing ratio at that time Can be chosen arbitrarily. In addition, among the phenolic compounds (A) used, there are a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol and the like contained as by-products during production. It may be included.
フェノール化合物（Ｂ）としては、２、５−ジメチルフェノール、２，３，６−トリメチルフェノール、２，５−ジエチルフェノール、２−メチル−５−エチルフェノール、２−エチル−５−メチルフェノール、２−アリル−５−メチルフェノール、２、５−ジアリルフェノール、２,３−ジエチル−６−ｎ―プロピルフェノール、２−メチル−５−クロルフェノール、２−メチル−５−ブロモフェノール、２−メチル−５−イソプロピルフェノール、２−メチル−５−ｎ−プロピルフェノール、２−エチル−５−ブロモフェノール、２−メチル−５−ｎ−ブチルフェノール、２，５−ジ−ｎ−プロピルフェノール、２−エチル−５−クロルフェノール、２−メチル−５−フェニルフェノール、２，５−ジフェニルフェノール、２，５−ビス−（４−フルオロフェニル）フェノール、２−メチル−５−トリルフェノール、２，５−ジトリルフェノール、２，６−ジメチル−３−アリルフェノール、２，３，６−トリアリルフェノール、２，３，６−トリブチルフェノール、２，６−ジーｎ−ブチル−３−メチルフェノール、２，６−ジ−ｔ−ブチル−３−メチルフェノール、２,６−ジメチル−３―ｎ−ブチルフェノール、２，６−ジメチル−３―ｔ―ブチルフェノール、等が挙げられ、なかでも、安価であり入手が容易であるため、２,３,６−トリメチルフェノール、２，５−ジメチルフェノールが好ましく、２,３,６−トリメチルフェノールがより好ましい。上記フェノール化合物（Ｂ）は単独で用いても、２種以上を組み合わせて用いてもよい。例えば、２，３，６−トリメチルフェノールと２，５−ジメチルフェノールを組み合わせて使用する方法などが挙げられ、その際の混合比は任意に選択できる。また使用するフェノール化合物（Ｂ）の中に、製造の際の副産物として含まれている少量のｏ−クレゾール、ｐ−クレゾール、２，４−ジメチルフェノール、２，４，６−トリメチルフェノール等が含まれていても全くかまわない。 Examples of the phenol compound (B) include 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl-5-methylphenol, 2 -Allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2-methyl- 5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propylphenol, 2-ethyl- 5-chlorophenol, 2-methyl-5-phenylphenol, 2,5-diphenylphenol, 2,5-bis- (4-fluorophenyl) phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6-triallylphenol, 2,3, 6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-di-t-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6- Dimethyl-3-t-butylphenol and the like. Among them, 2,3,6-trimethylphenol and 2,5-dimethylphenol are preferable because they are inexpensive and easily available. Trimethylphenol is more preferred. The said phenol compound (B) may be used independently, or may be used in combination of 2 or more type. For example, a method of using a combination of 2,3,6-trimethylphenol and 2,5-dimethylphenol can be used, and the mixing ratio can be arbitrarily selected. In addition, the phenol compound (B) used contains a small amount of o-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., contained as by-products during production. It does not matter at all.
フェノール化合物（Ａ）とフェノール化合物（Ｂ）の割合は特に限定されないが、好ましくは、単量体混合物全体に対して、フェノール化合物（Ａ）が６０質量％〜９５質量％、フェノール化合物（Ｂ）が４０質量％〜５質量％、より好ましくは、フェノール化合物（Ａ）が７０質量％〜９０質量％、フェノール化合物（Ｂ）が３０〜１０質量％、さらに好ましくは、フェノール化合物（Ａ）が７０〜８５質量％、フェノール化合物（Ｂ）が３０〜１５質量％である。各フェノール化合物の割合が上記範囲外であると、ガラス転移温度（Ｔｇ）が低くなり充分な耐熱性が得られない、あるいは、微粉が発生する等の問題が生じるおそれがある。 The ratio of the phenolic compound (A) to the phenolic compound (B) is not particularly limited, but preferably, the phenolic compound (A) is 60% by mass to 95% by mass, and the phenolic compound (B) with respect to the entire monomer mixture. Is 40% by mass to 5% by mass, more preferably 70% by mass to 90% by mass of the phenol compound (A), 30% by mass to 10% by mass of the phenol compound (B), and more preferably 70% by mass of the phenol compound (A). -85 mass% and a phenolic compound (B) are 30-15 mass%. If the ratio of each phenol compound is outside the above range, the glass transition temperature (Tg) may be low and sufficient heat resistance may not be obtained, or problems such as generation of fine powder may occur.
本発明におけるポリフェニレンエーテルの製造方法において、重合に用いる混合フェノール化合物の濃度は特に限定されないが、溶液全体に対して、好ましくは１０〜５０重量％であり、より好ましくは１５〜３０質量％である。混合フェノール化合物の濃度が上記範囲内であると、沈殿析出重合の特徴が発揮され易いため好ましい。 In the method for producing polyphenylene ether in the present invention, the concentration of the mixed phenol compound used for the polymerization is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 30% by weight, based on the entire solution. . It is preferable that the concentration of the mixed phenol compound is within the above range because the characteristics of precipitation and precipitation polymerization are easily exhibited.
本発明におけるポリフェニレンエーテルの製造方法は、反応溶媒中に重合体が粒子として析出する沈殿析出重合である。重合体の析出を観察する方法としては、特に限定されず、例えば、反応器の覗き窓から重合体の析出を目視観察する、或いはサンプリング口からガラス等の透明容器に重合液を抜き出し重合体の析出を目視観察する等の方法により観察することが可能である。目視観察を始める目安としては、重合系内に含まれるフェノール化合物の量やポリフェニレンエーテルに対する良溶媒または貧溶媒の量にもよるが、好ましくは、重合率が８０％に達した以降から、より好ましくは、重合率が７０％に達した以降から、さらに好ましくは、重合率が５０％に達した以降から重合系内における重合体の析出に注意し観察を始める。 The method for producing polyphenylene ether in the present invention is precipitation polymerization in which a polymer is precipitated as particles in a reaction solvent. The method for observing the polymer precipitation is not particularly limited. For example, the polymer precipitation is visually observed from the observation window of the reactor, or the polymer solution is taken out from the sampling port into a transparent container such as glass. The precipitation can be observed by a method such as visual observation. As a guideline for starting visual observation, although it depends on the amount of the phenol compound contained in the polymerization system and the amount of the good solvent or the poor solvent relative to the polyphenylene ether, preferably, after the polymerization rate reaches 80%, more preferably Starts observation after paying attention to the precipitation of the polymer in the polymerization system after the polymerization rate reaches 70%, and more preferably after the polymerization rate reaches 50%.
本発明におけるポリフェニレンエーテルの製造方法において、重合に用いるフェノール化合物は重合初期から重合槽内に全量存在させてもよいし、重合中に逐次添加してもよい。その際、単量体として使用するフェノール化合物の全量を、沈殿析出を開始しスラリー状態を呈し始める以前に重合槽内に全て添加し終えると、微粉の発生が抑制される傾向があるため好ましい。沈殿析出を開始しスラリー状態を呈し始めた後にフェノール化合物を添加すると、添加されたフェノール化合物の成長により粒子核が発生し、１０６μｍ以下の微粉の発生を誘発するおそれがある。 In the method for producing polyphenylene ether in the present invention, the phenolic compound used for the polymerization may be present in the polymerization tank from the beginning of the polymerization or may be added successively during the polymerization. At that time, it is preferable to add all of the phenolic compound used as the monomer in the polymerization tank before starting precipitation and starting to exhibit a slurry state, because generation of fine powder tends to be suppressed. When a phenol compound is added after starting precipitation and starting to exhibit a slurry state, particle nuclei are generated due to the growth of the added phenol compound, which may induce generation of fine powder of 106 μm or less.
本発明におけるポリフェニレンエーテルの製造方法においては、重合体が沈殿析出した後、重合温度を上昇させることが重要である。重合温度を上昇させることで、微粉の発生を抑制することができ、得られるポリフェニレンエーテルに優れた耐溶剤性を付与することが可能となる。沈殿析出前の重合温度としては、好ましくは０℃〜４４℃、より好ましくは１０℃〜４０℃、さらに好ましくは２０℃〜４０℃である。沈殿析出前の温度が低すぎると、反応が進行しにくい場合がある。また、沈殿析出後の重合温度としては、好ましくは４５℃〜１００℃、より好ましくは５０℃〜８０℃、さらに好ましくは５５℃〜７０℃である。沈殿析出後の温度が高すぎると、重合に用いる溶媒の揮発が激しくなり、冷却還流設備への負荷が大きくなるおそれがある。さらに、沈殿析出前と沈殿析出後の温度差としては、好ましくは１０℃以上、より好ましくは１２℃以上、さらに好ましくは１５℃以上である。 In the method for producing polyphenylene ether in the present invention, it is important to raise the polymerization temperature after the polymer is precipitated. By raising the polymerization temperature, the generation of fine powder can be suppressed, and excellent solvent resistance can be imparted to the resulting polyphenylene ether. The polymerization temperature before precipitation is preferably 0 ° C to 44 ° C, more preferably 10 ° C to 40 ° C, and further preferably 20 ° C to 40 ° C. If the temperature before precipitation is too low, the reaction may not proceed easily. Moreover, as polymerization temperature after precipitation, it becomes like this. Preferably it is 45 to 100 degreeC, More preferably, it is 50 to 80 degreeC, More preferably, it is 55 to 70 degreeC. If the temperature after precipitation is too high, volatilization of the solvent used for the polymerization becomes violent, which may increase the load on the cooling reflux facility. Further, the temperature difference before and after precipitation is preferably 10 ° C. or higher, more preferably 12 ° C. or higher, and further preferably 15 ° C. or higher.
重合体が沈殿析出した後、重合温度を上昇させる時期としては、酸素含有ガスの供給量にもよるが、好ましくは３０分以内、より好ましくは１０分以内、さらに好ましくは５分以内、最も好ましくは２分以内である。重合温度を上昇させる時期が上記範囲内であると、微粉の発生が抑制され、耐溶剤性に優れたポリフェニレンエーテルが得られる傾向にある。また、温度を上昇させている間、酸素含有ガスの供給を一次停止させ、所望の温度に達した後に酸素含有ガスの供給を再開し重合を継続してもよく、酸素含有ガスの供給量、ジャケットに流す熱媒、ジャケットの伝熱係数などにより適宜選択することができる。 The time for raising the polymerization temperature after precipitation of the polymer is preferably within 30 minutes, more preferably within 10 minutes, even more preferably within 5 minutes, most preferably, depending on the supply amount of the oxygen-containing gas. Is within 2 minutes. When the time for raising the polymerization temperature is within the above range, generation of fine powder is suppressed, and polyphenylene ether excellent in solvent resistance tends to be obtained. Further, while the temperature is raised, the supply of the oxygen-containing gas is temporarily stopped, and after reaching the desired temperature, the supply of the oxygen-containing gas may be resumed to continue the polymerization. It can be appropriately selected depending on the heat medium flowing through the jacket, the heat transfer coefficient of the jacket, and the like.
また、本発明のポリフェニレンエーテルの製造方法においては、酸素含有ガスの供給量にもよるが、重合体が沈殿析出した後、温度を上昇させた状態で、好ましくは１分以上、より好ましくは１０分以上、さらに好ましくは３０分以上重合を継続させると、耐溶剤性に優れ、かつガラス転移温度の高い（耐熱性に優れた）ポリフェニレンエーテルが得られる傾向にあるため好ましい。 In the method for producing polyphenylene ether of the present invention, although depending on the supply amount of the oxygen-containing gas, the polymer is preferably precipitated for 1 minute or more, more preferably 10 minutes or more after precipitation. It is preferable to continue the polymerization for at least 30 minutes, more preferably for at least 30 minutes, because a polyphenylene ether having excellent solvent resistance and a high glass transition temperature (excellent heat resistance) tends to be obtained.
本発明の製造方法においては、フェノール化合物を酸化重合させて得られる重合体であるポリフェニレンエーテルに対する良溶媒と貧溶媒の比率を変化させ、貧溶媒の比率を大きくすることで反応の進行とともに重合体が反応溶媒中に粒子として析出する沈殿重合法になる。良溶媒：貧溶媒の割合としては、重量比で３５：６５〜９５：５であるのが好ましく、４５：５５〜８５：１５であるのがより好ましく、５５：４５〜７５：２５であるのがさらに好ましい。各溶媒の割合が上記範囲内であると、析出した粒子の反応器へのスケールが極めて少なく、安定な重合体が生成する。良溶媒の割合が上記範囲よりも少ないと、所望の重合度のポリフェニレンエーテルを得るために重合時間が著しく長期化する可能性がある、重合中に外部からの加熱が必要となることがある等、効率的にポリフェニレンエーテルを得られなくなる場合がある。また、良溶媒の割合が上記範囲を超えると、重合体が反応溶媒中に粒子として析出しなくなることがある。 In the production method of the present invention, the ratio of the good solvent and the poor solvent with respect to polyphenylene ether, which is a polymer obtained by oxidative polymerization of a phenol compound, is changed, and the ratio of the poor solvent is increased to increase the polymer as the reaction proceeds. Is a precipitation polymerization method in which particles are precipitated as particles in the reaction solvent. The ratio of good solvent: poor solvent is preferably 35:65 to 95: 5 by weight, more preferably 45:55 to 85:15, and 55:45 to 75:25. Is more preferable. When the ratio of each solvent is within the above range, the scale of precipitated particles into the reactor is extremely small, and a stable polymer is formed. If the proportion of the good solvent is less than the above range, the polymerization time may be remarkably prolonged in order to obtain a polyphenylene ether having a desired polymerization degree, and external heating may be required during the polymerization. In some cases, polyphenylene ether cannot be obtained efficiently. When the proportion of the good solvent exceeds the above range, the polymer may not be precipitated as particles in the reaction solvent.
本発明のポリフェニレンエーテルの製造方法において、ポリフェニレンエーテルの良溶媒とは、従来の方法で得られるポリ（２，６―ジメチルフェニレン）エーテルを溶解させることができる溶媒である。このような溶媒を例示すると、ベンゼン、トルエン、キシレン（ｏ−、ｍ−、ｐ−の各異性体を含む）、エチルベンゼン、スチレンなどの芳香族炭化水素、クロロホルム、塩化メチレン、１,２−ジクロロエタン、クロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素、ニトロベンゼンのようなニトロ化合物が挙げられる。また、その他の良溶媒に分類されるものとしては、ペンタン、ヘキサン、へプタン、シクロヘキサン、シクロへプタン等の脂肪族炭化水素類、酢酸エチル、ギ酸エチル等のエステル類、テトラヒドロフラン、ジエチルエーテルなどのエーテル類、ジメチルスルホキシド等が例示される。これらの良溶媒は、単独でも用いても、２種以上を組み合わせて用いてもよい。これらの中でも好ましい良溶媒はベンゼン、トルエン、キシレン、エチルベンゼン、スチレン等の芳香族炭化水素やクロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素である。 In the method for producing polyphenylene ether of the present invention, the good solvent for polyphenylene ether is a solvent capable of dissolving poly (2,6-dimethylphenylene) ether obtained by a conventional method. Examples of such solvents include benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, styrene and other aromatic hydrocarbons, chloroform, methylene chloride, and 1,2-dichloroethane. , Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and nitro compounds such as nitrobenzene. In addition, those classified as other good solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and cycloheptane, esters such as ethyl acetate and ethyl formate, tetrahydrofuran, diethyl ether and the like. Examples include ethers and dimethyl sulfoxide. These good solvents may be used alone or in combination of two or more. Among these, preferred good solvents are aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and styrene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene.
本発明のポリフェニレンエーテルの製造方法において、ポリフェニレンエーテルの貧溶媒とは、従来の方法で得られるポリ（２，６―ジメチルフェニレン）エーテルを全く溶解しないか、わずかに溶解できる溶媒である。例えば、ケトン類、アルコール類である。好ましくは貧溶媒として炭素数１〜１０のアルコールを用いる方法である。このような貧溶媒としては例えば、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、エチレングリコール等を挙げることができ、このような貧溶媒に、更に水が含まれていてもよい。これらの貧溶媒は単独でも用いられるし、２種以上を組み合わせて用いてもよい。特に好ましい貧溶媒はメタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、２−ブタノール、ｔｅｒｔ−ブタノールである。 In the method for producing polyphenylene ether of the present invention, the poor solvent for polyphenylene ether is a solvent that does not dissolve or slightly dissolves poly (2,6-dimethylphenylene) ether obtained by a conventional method. For example, ketones and alcohols. A method using an alcohol having 1 to 10 carbon atoms as a poor solvent is preferred. Examples of such a poor solvent include methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol and the like, and water may be further contained in such a poor solvent. These poor solvents may be used alone or in combination of two or more. Particularly preferred poor solvents are methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and tert-butanol.
しばしば用いられる溶媒の例としてはトルエンやキシレン等の芳香族炭化水素溶媒に、メタノール、エタノール等のアルコール類を含有させた混合溶媒である。 An example of a frequently used solvent is a mixed solvent in which an aromatic hydrocarbon solvent such as toluene or xylene contains an alcohol such as methanol or ethanol.
本発明で用いられる触媒は、一般的にポリフェニレンエーテルの製造に用いることができる公知の触媒系が全て使用できる。一般的に知られている触媒系は酸化還元能を有する遷移金属イオンとこの金属イオンと錯形成可能なアミン化合物からなるものが知られており、例えば銅化合物とアミンからなる触媒系、マンガン化合物とアミンからなる触媒系、コバルト化合物とアミンからなる触媒系、等である。重合反応は若干のアルカリ性条件下で効率よく進行するため、ここに若干のアルカリもしくは更なるアミンを加えることもある。 As the catalyst used in the present invention, any known catalyst system that can be generally used for production of polyphenylene ether can be used. Known catalyst systems are known to be composed of transition metal ions having redox ability and amine compounds capable of complexing with the metal ions. For example, catalyst systems consisting of copper compounds and amines, manganese compounds And a catalyst system comprising an amine, a catalyst system comprising a cobalt compound and an amine, and the like. Since the polymerization reaction proceeds efficiently under some alkaline conditions, some alkali or further amine may be added thereto.
本発明で好適に使用される触媒は、触媒の構成成分として銅化合物、ハロゲン化合物および上記式（３）で表されるジアミン化合物を含む触媒である。 The catalyst suitably used in the present invention is a catalyst containing a copper compound, a halogen compound and a diamine compound represented by the above formula (3) as constituent components of the catalyst.
ここで述べられた触媒成分の銅化合物の例を列挙する。好適な銅化合物としては第一銅化合物、第二銅化合物またはそれらの混合物を使用することができる。第二銅化合物としては、例えば、塩化第二銅、臭化第二銅、硫酸第二銅、硝酸第二銅等を例示することができる。また第一銅化合物としては、例えば塩化第一銅、臭化第一銅、硫酸第一銅、硝酸第一銅等を例示することができる。これらの中で特に好ましい金属化合物は塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅である。またこれらの銅塩は酸化物（例えば酸化第一銅）、炭酸塩、水酸化物等と対応するハロゲンまたは酸から使用時に合成してもよい。しばしば用いられる方法は先に例示の酸化第一銅とハロゲン化水素（またはハロゲン化水素の溶液）を混合して作成する方法である。 Examples of the copper compounds of the catalyst component described here are listed. As a suitable copper compound, a cuprous compound, a cupric compound or a mixture thereof can be used. Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide and cupric bromide. In addition, these copper salts may be synthesized at the time of use from oxides (for example, cuprous oxide), carbonates, hydroxides, and the corresponding halogens or acids. A method often used is a method in which cuprous oxide and hydrogen halide (or a solution of hydrogen halide) exemplified above are mixed and prepared.
ハロゲン化合物としては、例えば、塩化水素、臭化水素、ヨウ化水素、塩化ナトリウム、臭化ナトリウム、ヨウ化ナトリウム、塩化カリウム、臭化カリウム、ヨウ化カリウム、塩化テトラメチルアンモニウム、臭化テトラメチルアンモニウム、ヨウ化テトラメチルアンモニウム、塩化テトラエチルアンモニウム、臭化テトラエチルアンモニウム、ヨウ化テトラエチルアンモニウム等である。またこれらは水溶液や適当な溶媒を用いた溶液として使用できる。これらのハロゲン化合物は、単独でも用いられるし、２種類以上組み合わせて用いてもよい。好ましいハロゲン化合物は、塩化水素の水溶液、臭化水素の水溶液である。 Examples of the halogen compound include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, and tetramethylammonium bromide. Tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and the like. These can be used as an aqueous solution or a solution using an appropriate solvent. These halogen compounds may be used alone or in combination of two or more. Preferred halogen compounds are an aqueous solution of hydrogen chloride and an aqueous solution of hydrogen bromide.
これらの化合物の使用量は特に限定されないが、銅原子のモル量に対してハロゲン原子として２倍以上２０倍以下が好ましく、使用されるフェノール化合物の１００モルに対して好ましい銅原子の使用量としては０．０２モルから０．６モルの範囲である。 Although the usage-amount of these compounds is not specifically limited, As a halogen atom with respect to the molar amount of a copper atom, 2 times or more and 20 times or less are preferable, As a preferable usage-amount of a copper atom with respect to 100 mol of the phenolic compound used. Is in the range of 0.02 to 0.6 mol.
次に触媒成分のジアミン化合物の例を列挙する。例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリメチルエチレンジアミン、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ−メチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラエチルエチレンジアミン、Ｎ，Ｎ，Ｎ’−トリエチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ−エチルエチレンジアミン、Ｎ，Ｎ−ジメチル−Ｎ’−エチルエチレンジアミン、Ｎ，Ｎ’−ジメチル−Ｎ−エチルエチレンジアミン、Ｎ−ｎ−プロピルエチレンジアミン、Ｎ，Ｎ’−ジーｎ−プロピルエチレンジアミン、Ｎ−ｉ−プロピルエチレンジアミン、Ｎ，Ｎ’−ジーｉ−プロピルエチレンジアミン、Ｎ−ｎ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｎ−ブチルエチレンジアミン、Ｎ−ｉ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｉ−ブチルエチレンジアミン、Ｎ−ｔ−ブチルエチレンジアミン、Ｎ，Ｎ’−ジーｔ−ブチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノプロパン、Ｎ，Ｎ，Ｎ’−トリメチル−１，３−ジアミノプロパン、Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパン、Ｎ−メチル−１，３−ジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノ−１−メチルプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ジアミノ−２−メチルプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，４−ジアミノブタン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，５−ジアミノペンタン等が挙げられる。 Next, the example of the diamine compound of a catalyst component is enumerated. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-dimethylethylenediamine, N-methylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N′-triethylethylenediamine, N, N′-diethylethylenediamine, N, N-diethylethylenediamine, N-ethylethylenediamine, N, N-dimethyl-N′-ethylethylenediamine N, N'-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N, N'-di-n-propylethylenediamine, Ni-propylethylenediamine, N, N'-di-propylethylenediamine, N -N-Butylethylenedia N, N'-di-n-butylethylenediamine, Ni-butylethylenediamine, N, N'-di-butylethylenediamine, Nt-butylethylenediamine, N, N'-di-t-butylethylenediamine, N , N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N′-trimethyl-1,3-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N -Methyl-1,3-diaminopropane, N, N, N ', N'-tetramethyl-1,3-diamino-1-methylpropane, N, N, N', N'-tetramethyl-1,3 -Diamino-2-methylpropane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N, N ′, N′-tetramethyl-1,5-diaminopentane, etc. Be
本発明にとって好ましいジアミン化合物は２つの窒素原子をつなぐアルキレン基（Ｒ10）の炭素数が２又は３のものである。これらのジアミン化合物の使用量は特に限定されないが、通常使用されるフェノール化合物１００モルに対して０．０１モル〜１０モルの範囲で用いられる。 Preferred diamine compounds for the present invention are those in which the alkylene group (R 10 ) connecting two nitrogen atoms has 2 or 3 carbon atoms. Although the usage-amount of these diamine compounds is not specifically limited, It is used in 0.01 mol-10 mol with respect to 100 mol of phenol compounds used normally.
本発明において触媒の構成成分として、更に３級モノアミン化合物または２級モノアミン化合物をそれぞれ単独で、またはこれらを組み合わせて含ませることは好ましい。３級モノアミン化合物とは、脂環式３級アミンを含めた脂肪族３級アミンである。例えばトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリイソブチルアミン、ジメチルエチルアミン、ジメチルプロピルアミン、アリルジエチルアミン、ジメチル−ｎ−ブチルアミン、ジエチルイソプロピルアミン、Ｎ−メチルシクロヘキシルアミン等が挙げられる。これらの第３級モノアミンは単独でも用いられるし、２種類以上組み合わせて用いてもよい。これらの使用量は特に限定されないが、通常使用されるフェノール１００モルに対して１５モル以下の範囲が好ましい。 In the present invention, it is preferable to further include a tertiary monoamine compound or a secondary monoamine compound alone or in combination as a constituent component of the catalyst. The tertiary monoamine compound is an aliphatic tertiary amine including an alicyclic tertiary amine. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine and the like. These tertiary monoamines may be used alone or in combination of two or more. Although the usage-amount of these is not specifically limited, The range of 15 mol or less is preferable with respect to 100 mol of phenol normally used.
２級モノアミン化合物の例として、第２級脂肪族アミンとしては例えば、ジメチルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジ−ｉ−プロピルアミン、ジ−ｎ−ブチルアミン、ジ−ｉ−ブチルアミン、ジ−ｔ−ブチルアミン、ジペンチルアミン類、ジヘキシルアミン類、ジオクチルアミン類、ジデシルアミン類、ジベンジルアミン類、メチルエチルアミン、メチルプロピルアミン、メチルブチルアミン、シクロヘキシルアミンが挙げられる。芳香族を含む２級モノアミン化合物の例としては、Ｎ−フェニルメタノールアミン、Ｎ−フェニルエタノールアミン、Ｎ−フェニルプロパノールアミン、Ｎ−（ｍ−メチルフェニル）エタノールアミン、Ｎ−（ｐ−メチルフェニル）エタノールアミン、Ｎ−（２’，６’−ジメチルフェニル）エタノールアミン、Ｎ−（ｐ−クロロフェニル）エタノールアミン、Ｎ−エチルアニリン、Ｎ−ブチルアニリン、Ｎ−メチル−２−メチルアニリン、Ｎ−メチル−２，６−ジメチルアニリン、ジフェニルアミン等が挙げられるがこれらの例には限定されない。これらの２級モノアミン化合物は単独でも用いられるし、２種類以上組み合わせて用いてもよい。使用量は特に限定されないが、通常使用されるフェノール１００モルに対し１５モル以下の範囲が好ましい。 Examples of secondary monoamine compounds include secondary aliphatic amines such as dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- -T-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine. Examples of secondary monoamine compounds containing aromatics include N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N- (m-methylphenyl) ethanolamine, N- (p-methylphenyl). Ethanolamine, N- (2 ′, 6′-dimethylphenyl) ethanolamine, N- (p-chlorophenyl) ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl Examples include -2,6-dimethylaniline and diphenylamine, but are not limited to these examples. These secondary monoamine compounds may be used alone or in combination of two or more. Although the usage-amount is not specifically limited, The range of 15 mol or less is preferable with respect to 100 mol of phenol normally used.
本発明には従来から活性に向上効果を有することが知られている界面活性剤を添加することについて何ら制限されない。例えば、Ａｌｉｑｕａｔ３３６やＣａｐｒｉｑｕａｔの商品名で知られるトリオクチルメチルアンモニウムクロライドである。使用量は重合反応混合物の全量に対して０．１質量％を超えない範囲が好ましい。 In the present invention, there is no limitation on adding a surfactant that has been conventionally known to have an effect of improving activity. For example, trioctylmethylammonium chloride known under the trade names of Aliquat 336 and Capriquat. The amount used is preferably within a range not exceeding 0.1% by mass relative to the total amount of the polymerization reaction mixture.
本発明の重合における酸素含有ガスは純酸素の他、酸素と窒素等の不活性ガスとを任意の割合で混合したもの、空気、更には空気と窒素、希ガス等の不活性ガスとを任意の割合で混合したもの等が使用できる。重合反応中の系内圧力は常圧で充分であるが必要に応じて減圧でも加圧でも使用できる。酸素含有ガスの供給速度は、除熱や重合速度等を考慮して任意に選択できるが、重合に用いるフェノール化合物１モル当たりの純酸素として５Ｎｍｌ／分以上が好ましく、１０Ｎｍｌ／分以上がさらに好ましい。 The oxygen-containing gas in the polymerization of the present invention is pure oxygen, oxygen and an inert gas such as nitrogen mixed at an arbitrary ratio, air, and optionally an inert gas such as air and nitrogen or a rare gas. The thing etc. which were mixed in the ratio of can be used. The system pressure during the polymerization reaction is normal pressure, but it can be used under reduced pressure or increased pressure as necessary. The supply rate of the oxygen-containing gas can be arbitrarily selected in consideration of heat removal, polymerization rate, etc., but it is preferably 5 Nml / min or more, and more preferably 10 Nml / min or more, as pure oxygen per mole of phenol compound used for polymerization. .
本発明の重合反応系に、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物、アルカリ金属のアルコキサイド、硫酸マグネシウム、塩化カルシウム等の中性塩、ゼオライト等も添加することができる。 Alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, neutral salts such as magnesium sulfate and calcium chloride, zeolite, and the like can also be added to the polymerization reaction system of the present invention.
重合反応終了後の後処理方法については特に制限はない。通常、塩酸や酢酸等の酸、またはエチレンジアミン４酢酸（ＥＤＴＡ）及びその塩、ニトリロトリ酢酸及びその塩等を反応液に加えて触媒を失活させる。その後重合終結時の重合溶液の形状がスラリーであるため、触媒の洗浄除去を目的として、重合に用いたポリフェニレンエーテルの溶解能が低い溶媒を主成分とする溶液を用いて繰り返し洗浄を実施することがより好ましい。その後、各種乾燥機を用いた乾燥工程において乾燥するという操作でポリフェニレンエーテルが回収できる。 There is no particular limitation on the post-treatment method after completion of the polymerization reaction. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and its salt, nitrilotriacetic acid and its salt or the like is added to the reaction solution to deactivate the catalyst. Since the shape of the polymerization solution at the end of the polymerization is a slurry after that, for the purpose of washing and removing the catalyst, repeated washing with a solution mainly composed of a solvent having low solubility of polyphenylene ether used for polymerization is performed. Is more preferable. Thereafter, polyphenylene ether can be recovered by an operation of drying in a drying process using various dryers.
本発明のポリフェニレンエーテルを重合するにあたり、重合に用いる重合方式は特に限定されないが、多種類のポリフェニレンエーテルを製造する場合には、様々なガラス転移温度を有するポリフェニレンエーテルの造り分けが容易なバッチ方式が好ましい。 In the polymerization of the polyphenylene ether of the present invention, the polymerization method used for the polymerization is not particularly limited. However, in the case of producing various types of polyphenylene ether, a batch method that makes it easy to separately produce polyphenylene ethers having various glass transition temperatures. Is preferred.
本発明の方法で得られたポリフェニレンエーテルは、従来既知の熱可塑性樹脂及び熱硬化性樹脂と溶融混練することができる。次に熱可塑性樹脂及び熱硬化性樹脂の例を列挙する。例えば、ポリエチレン、ポリプロピレン、ポリスチレン、アクリロニトリル／スチレン樹脂、アクリロニトリル／ブタジエン／スチレン樹脂、メタクリル樹脂、塩化ビニル、ポリアミド、ポリアセタール、超高分子量ポリエチレン、ポリブチレンテレフタレート、ポリメチルペンテン、ポリカーボネート、ポリフェニレンサルファイド、ポリエーテルエーテルエーテルケトン、液晶ポリマー、ポリテトラフロロエチレン、ポリエーテルイミド、ポリアリレート、ポリサルフォン、ポリエーテルサルフォン、ポリアミドイミド、フェノール、尿素、メラミン、不飽和ポリエステル、アルキッド、エポキシ、ジアリルフタレート等の樹脂が挙げられる。また溶融混練時に、導電性、難燃性、耐衝撃性等の効果を付与する目的で従来既知の添加剤や熱可塑性エラストマーを加えることがより好ましい。 The polyphenylene ether obtained by the method of the present invention can be melt-kneaded with conventionally known thermoplastic resins and thermosetting resins. Next, examples of the thermoplastic resin and the thermosetting resin are listed. For example, polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methacrylic resin, vinyl chloride, polyamide, polyacetal, ultrahigh molecular weight polyethylene, polybutylene terephthalate, polymethylpentene, polycarbonate, polyphenylene sulfide, polyether Examples include ether ether ketone, liquid crystal polymer, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, phenol, urea, melamine, unsaturated polyester, alkyd, epoxy, diallyl phthalate, etc. It is done. Moreover, it is more preferable to add conventionally known additives and thermoplastic elastomers for the purpose of imparting effects such as conductivity, flame retardancy and impact resistance during melt kneading.
以下に実施例を示して、本発明をより詳細に説明するが、本発明は以下に記載の実施例によって限定されるものではない。なお、以下において％とは、重量％を意味する。
［測定方法］
本明細書中の物性、特性等の測定方法は以下の通りである。
（１）重合率の測定
重合に供するフェノール化合物の重量より、理論上重合に必要な酸素体積（リットル）を下式により求めた。
理論酸素量＝フェノール化合物の重量／フェノールの分子量×２２．４／２
重合に要した酸素量は下式により求めた。
重合に要した酸素量＝（重合に供した酸素量）−（排出ガス中の酸素量）
重合率は上述した理論酸素量及び重合に要した酸素量を用い、下式により求めた。
重合率（％）＝重合に要した酸素量／理論酸素量×１００
（２）収率の測定
重合に供したモノマー質量に対する乾燥ポリフェニレンエーテルの質量割合を１００分率で測定した。
（３）ガラス転移温度の測定
得られたポリフェニレンエーテルのガラス転移温度は示差走査熱量計ＤＳＣ（ＰｅｒｋｉｎＥｌｍｅｒ製−Ｐｙｒｉｓ１）を用いて測定した。窒素雰囲気中毎分２０℃の昇温速度で室温から２８０℃まで加熱後５０℃まで毎分４０℃で降温し、その後毎分２０℃の昇温速度でガラス転移温度を測定した。
（４）反応器へのスケ−ル付着の確認
重合液を反応器から抜き出した後、反応器内に付着しているスケールの量を目視にて確認した。
（５）微粉発生量の確認
得られたポリフェニレンエーテルのスラリーをろ別し、１４０℃で２時間真空乾燥した後、目開き１０６μｍのふるいを用い、筒井理化器械株式会社製ミクロ型電磁振動ふるい器Ｍ−２型で１０分間振動し微粉の量を測定した。
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples described below. In the following, “%” means “% by weight”.
[Measuring method]
Measuring methods for physical properties, characteristics and the like in this specification are as follows.
(1) Measurement of polymerization rate From the weight of the phenolic compound to be subjected to polymerization, the oxygen volume (liter) theoretically required for polymerization was determined by the following equation.
Theoretical oxygen amount = weight of phenol compound / molecular weight of phenol × 22.4 / 2
The amount of oxygen required for polymerization was determined by the following formula.
Amount of oxygen required for polymerization = (amount of oxygen used for polymerization)-(amount of oxygen in exhaust gas)
The polymerization rate was determined by the following equation using the above theoretical oxygen amount and the oxygen amount required for the polymerization.
Polymerization rate (%) = oxygen amount required for polymerization / theoretical oxygen amount × 100
(2) Measurement of yield The mass ratio of the dry polyphenylene ether to the mass of the monomer subjected to polymerization was measured at 100 minutes.
(3) Measurement of glass transition temperature The glass transition temperature of the obtained polyphenylene ether was measured using a differential scanning calorimeter DSC (manufactured by PerkinElmer-Pyris 1). After heating from room temperature to 280 ° C. at a temperature rising rate of 20 ° C. in a nitrogen atmosphere, the temperature was lowered to 50 ° C. at 40 ° C. per minute, and then the glass transition temperature was measured at a temperature rising rate of 20 ° C. per minute.
(4) Confirmation of scale adhesion to reactor After the polymerization solution was extracted from the reactor, the amount of scale adhered in the reactor was visually confirmed.
(5) Confirmation of the amount of fine powder generated The obtained polyphenylene ether slurry was filtered and vacuum-dried at 140 ° C. for 2 hours, and then a sieve with an aperture of 106 μm was used to make a micro-type electromagnetic vibration sieve manufactured by Tsutsui Rika Instruments Co., Ltd. The amount of fine powder was measured by shaking for 10 minutes with M-2 type.
［ポリフェニレンエーテルの製造］
（実施例１）
重合槽底部に酸素含有ガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１リットルのジャケット付きガラス製重合槽に５０ｍｌ／分の流量で窒素ガスを吹き込みながら、０．０５４４ｇの塩化第二銅２水和物、０．２３３ｇの３５％塩酸、２．０７７ｇのＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミン、０．７８３ｇのジ−ｎ−ブチルアミン、６３．４ｇのｎ−ブタノール、６３．４ｇのメタノール、１９０．１ｇのキシレン、６０ｇの２，６−ジメチルフェノール、２０ｇの２，３，６−トリメチルフェノールを入れ、均一溶液となり、かつ反応器の内温が４０℃になるまで撹拌した。
激しく撹拌した重合槽へ、１２８Ｎｍｌ／分の速度で酸素ガスをスパージャーより導入を始め、反応器の内温が４０℃になるようコントロールし、槽内の様子を観察した。重合液は透明であった。
酸素ガス導入より４０分が経過した頃、槽内の様子に変化が見られ重合液に濁りが観察された。この時の重合率は７４％であった。そのまま観察を続けたところ重合率７８％となった時に、重合体の析出が確認されたため、酸素ガス導入を停止し、重合槽内の温度を５５℃に上昇させた。上昇後再度１２８Ｎｍｌ／分の速度で酸素ガスを導入し、１２０分沈殿析出状態で重合を継続した。
酸素含有ガスの通気をやめ、重合混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の５０％水溶液を０．３ｇ添加し６０分間重合混合物を撹拌し、次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで撹拌を続けた。
その後、濾過して湿潤ポリフェニレンエーテルを得た。湿潤ポリフェニレンエーテルをメタノール３２０ｇともに１Ｌ洗浄槽に入れ分散させ、３０分間撹拌した後再度ろ過した。洗浄槽の内温は４０℃になるようコントロールした。これを３回繰り返し、次いで１４０℃で１２０分真空乾燥し乾燥ポリフェニレンエーテルを得た。
得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られず溶解しない成分が確認された。この液を濾過後、濾残を乾燥させたところ重量は５．１ｇであった。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２３０℃、１０６μｍメッシュの篩を通過した微粉の量は１．０質量％未満であった。また、反応器等へのスケールは確認されなかった。
また、乾燥ポリフェニレンエーテルを用い、３３０℃、１０ＭＰａの条件下で１０分間加熱し、ポリフェニレンエーテルのフィルムサンプルを作製した。フィルムサンプルは透明であった。このフィルムサンプル１０ｇをｏ−ジクロロベンゼン１００ｍｌに溶解し、９０℃で１０分撹拌したところ、透明な溶液が得られず溶解しない成分が確認された。この液を濾過後、濾残を乾燥させたところ重量は５．１ｇであり、耐溶剤性が高いことがわかった。
[Production of polyphenylene ether]
Example 1
Nitrogen at a flow rate of 50 ml / min in a 1 liter jacketed glass polymerization tank equipped with a sparger for introducing oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a reflux gas cooler in the vent gas line at the top of the polymerization tank While blowing gas, 0.0544 g of cupric chloride dihydrate, 0.233 g of 35% hydrochloric acid, 2.077 g of N, N, N ′, N′-tetramethylpropanediamine, 0.783 g of dimethyl -Put n-butylamine, 63.4 g n-butanol, 63.4 g methanol, 190.1 g xylene, 60 g 2,6-dimethylphenol, 20 g 2,3,6-trimethylphenol into a homogeneous solution. And stirring until the internal temperature of the reactor reached 40 ° C.
Oxygen gas was introduced from a sparger into the vigorously stirred polymerization tank at a rate of 128 Nml / min, and the internal temperature of the reactor was controlled to be 40 ° C., and the inside of the tank was observed. The polymerization solution was transparent.
When 40 minutes had passed since the introduction of oxygen gas, the state in the tank was changed and turbidity was observed in the polymerization solution. The polymerization rate at this time was 74%. When observation was continued as it was, when the polymerization rate reached 78%, precipitation of the polymer was confirmed, so the introduction of oxygen gas was stopped and the temperature in the polymerization tank was raised to 55 ° C. After rising, oxygen gas was again introduced at a rate of 128 Nml / min, and polymerization was continued for 120 minutes in a precipitated state.
Stop the ventilation of the oxygen-containing gas, add 0.3 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.
Thereafter, filtration was performed to obtain wet polyphenylene ether. Wet polyphenylene ether and 320 g of methanol were both dispersed in a 1 L washing tank, stirred for 30 minutes, and then filtered again. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 120 minutes to obtain dry polyphenylene ether.
When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was not obtained and components that did not dissolve were confirmed. After filtering this liquid and drying the filter residue, the weight was 5.1 g.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 230 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was less than 1.0% by mass. Moreover, the scale to a reactor etc. was not confirmed.
Moreover, using polyphenylene ether, it heated for 10 minutes on 330 degreeC and 10 Mpa conditions, and produced the film sample of polyphenylene ether. The film sample was transparent. When 10 g of this film sample was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was not obtained and components that did not dissolve were confirmed. After filtering this liquid and drying the filter residue, the weight was 5.1 g, indicating that the solvent resistance was high.
（実施例２）
重合槽内に入れる２，６−ジメチルフェノールの量を５２ｇ、２，３，６−トリメチルフェノールの量を２８ｇとした以外は実施例１と同様に実施した。なお、重合率７１％で重合体の析出が確認された。得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られず溶解しない成分が確認された。この液を濾過後、濾残を乾燥させたところ重量は６.２ｇであり、耐溶剤性が高いことがわかった。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２３６℃、１０６μｍメッシュの篩を通過した微粉の量は１質量％未満であった。また、反応器等へのスケ−ルは確認されなかった。
(Example 2)
The same procedure as in Example 1 was performed except that the amount of 2,6-dimethylphenol placed in the polymerization tank was 52 g and the amount of 2,3,6-trimethylphenol was 28 g. In addition, precipitation of a polymer was confirmed at a polymerization rate of 71%. When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was not obtained and components that did not dissolve were confirmed. After filtering this liquid and drying the filter residue, the weight was 6.2 g, indicating that the solvent resistance was high.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 236 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was less than 1% by mass. Moreover, the scale to a reactor etc. was not confirmed.
（実施例３）
重合槽内に入れる２，６−ジメチルフェノールの量を６８ｇ、２，３，６−トリメチルフェノールの量を１２ｇとした以外は実施例１と同様に実施した。なお、重合率８５％で重合体の析出が確認された。得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られず溶解しない成分が確認された。この液を濾過後、濾残を乾燥させたところ重量は３.２ｇであり、耐溶剤性が高いことがわかった。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２２９℃、１０６μｍメッシュの篩を通過した微粉の量は１質量％未満であった。また、反応器等へのスケ−ルは確認されなかった。
(Example 3)
The same procedure as in Example 1 was carried out except that the amount of 2,6-dimethylphenol placed in the polymerization tank was 68 g and the amount of 2,3,6-trimethylphenol was 12 g. In addition, precipitation of a polymer was confirmed at a polymerization rate of 85%. When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was not obtained and components that did not dissolve were confirmed. After filtering this liquid and drying the filter residue, the weight was 3.2 g, indicating that the solvent resistance was high.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 229 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was less than 1% by mass. Moreover, the scale to a reactor etc. was not confirmed.
（比較例１）
実施例１と同様に重合を開始し、重合率７８％となり析出が確認された後も反応器の内温が４０℃になるようコントロールし、１２８Ｎｍｌ／分の速度で酸素ガスを導入し続け、１２０分沈殿析出状態で重合を継続した。
得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られ完全に溶解した。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２３０℃、１０６μｍメッシュの篩を通過した微粉の量は２５質量％であった。また、反応器へのスケールは微量確認された。
(Comparative Example 1)
Polymerization was started in the same manner as in Example 1, and after the polymerization rate was 78% and precipitation was confirmed, the internal temperature of the reactor was controlled to be 40 ° C., and oxygen gas was continuously introduced at a rate of 128 Nml / min. Polymerization was continued for 120 minutes in a precipitated state.
When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was obtained and completely dissolved.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 230 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was 25% by mass. In addition, a small amount of scale to the reactor was confirmed.
（比較例２）
重合槽底部に酸素含有ガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１リットルのジャケット付ガラス重合槽に５０ｍｌ／分の流量で窒素ガスを吹き込みながら、０．１６４９ｇの酸化第二銅、１．２４０ｇの４７％臭化水素水溶液、０．３９７３ｇのジ−ｔ−ブチルエチレンジアミン、１．９２３ｇのジ−ｎ−ブチルアミン、５.８５４ｇのブチルジメチルアミン、６６０．２ｇのトルエン、８６．４ｇの２，６−ジメチルフェノール、２８．８ｇの２，３，６−トリメチルフェノールを入れ、均一溶液となり、かつ反応器の内温が４０℃になるまで撹拌した。
次いで、激しく撹拌した重合槽へ、重合槽へ８０Ｎｍｌ／分の速度で酸素ガスをスパージャーより導入した。２８０分通気し、反応器の内温が４０℃になるようコントロールした。重合途中に析出は確認されず、重合終結時の重合液は均一溶液状態であった。
酸素含有ガスの通気をやめ、重合混合物にエチレンジアミン四酢酸４ナトリウム塩（同仁化学研究所製試薬）の２．５％水溶液を８０ｇ添加し１００分間重合混合物を撹拌後静置し、液−液分離により有機相と水相を分離した。得られた有機相にメタノールを過剰に加えてポリフェニレンエーテルを析出後濾過し、濾残のポリフェニレンエーテルをメタノール５１２ｇに分散させた。
次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで撹拌を続けた。反応器の内温は４０℃になるようコントロールした。その後、濾過して濾残の湿潤ポリフェニレンエーテルをメタノール５１２ｇともに１Ｌ洗浄槽に入れ分散させ、３０分間撹拌した後再度ろ過した。洗浄槽の内温は４０℃になるようコントロールした。これを３回繰り返し、次いで１４０℃で１２０分真空乾燥し乾燥ポリフェニレンエーテルを得た。
得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られ完全に溶解した。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２３０℃、１０６μｍメッシュの篩を通過した微粉の量は２０質量％であった。
(Comparative Example 2)
Nitrogen gas at a flow rate of 50 ml / min in a 1 liter jacketed glass polymerization tank equipped with a sparger for introducing an oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a reflux gas cooler in the vent gas line at the top of the polymerization tank 0.1649 g of cupric oxide, 1.240 g of 47% aqueous hydrogen bromide, 0.3973 g of di-t-butylethylenediamine, 1.923 g of di-n-butylamine, 5.854 g of butyl Dimethylamine, 660.2 g of toluene, 86.4 g of 2,6-dimethylphenol and 28.8 g of 2,3,6-trimethylphenol are added to obtain a homogeneous solution, and the internal temperature of the reactor becomes 40 ° C. Until stirred.
Then, oxygen gas was introduced from the sparger into the polymerization tank vigorously stirred at a rate of 80 Nml / min. Aeration was performed for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. Precipitation was not confirmed during the polymerization, and the polymerization solution at the end of the polymerization was in a uniform solution state.
Stop the ventilation of the oxygen-containing gas, add 80g of 2.5% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 100 minutes, and leave it to stand for liquid-liquid separation Separated the organic and aqueous phases. Methanol was added to the obtained organic phase excessively to precipitate polyphenylene ether, followed by filtration. The polyphenylene ether remaining as a filter was dispersed in 512 g of methanol.
Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and stirring was continued until the slurry-like polyphenylene ether became white. The internal temperature of the reactor was controlled to 40 ° C. Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 1 L washing tank and dispersed together with 512 g of methanol, stirred for 30 minutes, and then filtered again. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 120 minutes to obtain dry polyphenylene ether.
When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was obtained and completely dissolved.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 230 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was 20% by mass.
（比較例３）
反応器の内温を５５℃とした以外は実施例２と同様に実施した。重合率８２％において析出が確認された後、１２０分沈殿析出状態で重合を継続した。得られた乾燥ポリフェニレンエーテル１０ｇを、ｏ−ジクロロベンゼン１００ｍｌに溶解し９０℃で１０分撹拌したところ、透明な溶液が得られ完全に溶解した。
乾燥ポリフェニレンエーテルを用いてガラス転移温度及び微粉発生量の測定を行なったところ、ガラス転移温度は２２９℃、１０６μｍメッシュの篩を通過した微粉の量は１０質量％であった。また、反応器等へのスケールは微量確認された。
(Comparative Example 3)
The same operation as in Example 2 was carried out except that the internal temperature of the reactor was changed to 55 ° C. After the precipitation was confirmed at a polymerization rate of 82%, the polymerization was continued for 120 minutes in the state of precipitation. When 10 g of the obtained dry polyphenylene ether was dissolved in 100 ml of o-dichlorobenzene and stirred at 90 ° C. for 10 minutes, a transparent solution was obtained and completely dissolved.
When the glass transition temperature and the amount of fine powder generated were measured using dry polyphenylene ether, the glass transition temperature was 229 ° C., and the amount of fine powder that passed through a 106 μm mesh sieve was 10% by mass. In addition, a small amount of scale to the reactor and the like was confirmed.
以上の結果から明らかなように、実施例１〜３では、沈殿析出後に温度を上昇させることによって、耐溶剤性に優れ、かつガラス転移温度の高い（耐熱性に優れた）ポリフェニレンエーテルを得ることができた。また、微粉の発生量も低減され、反応器へのスケールも確認されなかった。
一方、比較例１及び比較例３では、沈殿析出後も温度を上昇させることなく一定に保っていたため、ポリフェニレンエーテルに優れた耐溶剤性を付与することができず、また微粉やスケールの発生量も多かった。また、比較例２では、沈殿析出後も温度を上昇させることなく一定に保ち、さらに重合形態を溶液重合で行ったため、ポリフェニレンエーテルに優れた耐溶剤性を付与することができず、また微粉の発生量も多かった。
As is clear from the above results, in Examples 1 to 3, by increasing the temperature after precipitation, polyphenylene ether having excellent solvent resistance and high glass transition temperature (excellent heat resistance) is obtained. I was able to. Moreover, the generation amount of fine powder was reduced, and the scale to the reactor was not confirmed.
On the other hand, in Comparative Example 1 and Comparative Example 3, since the temperature was kept constant after precipitation, the excellent solvent resistance could not be imparted to polyphenylene ether, and the amount of fine powder and scale generated There were also many. Further, in Comparative Example 2, since the temperature was kept constant after precipitation and the polymerization was performed by solution polymerization, excellent solvent resistance could not be imparted to the polyphenylene ether, and fine powder The amount generated was also large.
ハロゲン溶剤、芳香族炭化水素溶剤などへの耐溶剤性に優れ、かつ高いガラス転移温度を有する耐熱性に優れたポリフェニレンエーテルを、微粉の発生やスケールの発生を抑制しながら、効率良く安定に製造することが可能となる。 Polyphenylene ether with excellent solvent resistance to halogen solvents, aromatic hydrocarbon solvents, etc., and high heat resistance with high glass transition temperature, efficiently and stably producing fine powder and scale. It becomes possible to do.
Claims (11)
で表されるフェノール化合物（Ａ）及び／又は、
下記式（２）
で表されるフェノール化合物（Ｂ）からなる混合フェノール化合物を、触媒の存在下、少なくとも１種以上のポリフェニレンエーテルの良溶媒及び少なくとも１種以上のポリフェニレンエーテルの貧溶媒からなる混合溶媒中で、酸素含有ガスを用いて酸化カップリングし、重合体を沈殿析出させるポリフェニレンエーテルの製造方法であって、沈殿析出後に重合温度を上昇させる、ポリフェニレンエーテルの製造方法。 Following formula (1)
A phenol compound (A) and / or
Following formula (2)
In the presence of a catalyst, a mixed phenol compound consisting of the phenol compound (B) represented by the formula (1) is mixed with a good solvent of at least one polyphenylene ether and a poor solvent of at least one polyphenylene ether. A method for producing polyphenylene ether, which comprises oxidative coupling using a contained gas to precipitate a polymer, wherein the polymerization temperature is increased after precipitation.
で表されるジアミン化合物を含む、請求項１〜７のいずれか１項に記載のポリフェニレンエーテルの製造方法。 The component of the catalyst is a copper compound, a halogen compound and the following formula (3)
The manufacturing method of the polyphenylene ether of any one of Claims 1-7 containing the diamine compound represented by these.
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