CN113801317B - Low molecular weight poly (arylene ether) and method of making the same - Google Patents
Low molecular weight poly (arylene ether) and method of making the same Download PDFInfo
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- CN113801317B CN113801317B CN202010531652.3A CN202010531652A CN113801317B CN 113801317 B CN113801317 B CN 113801317B CN 202010531652 A CN202010531652 A CN 202010531652A CN 113801317 B CN113801317 B CN 113801317B
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- arylene ether
- molecular weight
- low molecular
- poly
- weight poly
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- -1 poly (arylene ether Chemical compound 0.000 title claims abstract description 242
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 16
- 229910001431 copper ion Inorganic materials 0.000 claims description 16
- 239000002738 chelating agent Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000577 2,6-xylenyl group Chemical group [H]C1=C([H])C(=C(O*)C(=C1[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- IDFANOPDMXWIOP-UHFFFAOYSA-N n,n-dimethylpentan-1-amine Chemical compound CCCCCN(C)C IDFANOPDMXWIOP-UHFFFAOYSA-N 0.000 claims description 2
- AMJIVVJFADZSNZ-UHFFFAOYSA-N n-butylpentan-1-amine Chemical compound CCCCCNCCCC AMJIVVJFADZSNZ-UHFFFAOYSA-N 0.000 claims description 2
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 claims description 2
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 30
- 238000009826 distribution Methods 0.000 abstract description 10
- 230000009477 glass transition Effects 0.000 abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 235000013824 polyphenols Nutrition 0.000 description 8
- 238000004891 communication Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005691 oxidative coupling reaction Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- VJXIZXJHJXDYGJ-UHFFFAOYSA-N 2,6-dimethylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC(C)=C1O VJXIZXJHJXDYGJ-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 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
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
Abstract
The invention provides a low molecular weight poly (arylene ether) and a method of making the same, the method of making comprising: (1) Oxidizing and polymerizing a phenol monomer in a poly (arylene ether) good solvent in the presence of an oxidizing agent and a catalyst to obtain a mixed solution of low molecular weight poly (arylene ether) having an intrinsic viscosity of 0.05 to 0.3dl/g in a chloroform solution at 25 ℃; (2) washing with water; (3) Adding the water-washed mixed solution into a poly (arylene ether) poor solvent under stirring and in an inert atmosphere to form slurry, and filtering to obtain a wet material; wherein the solid content of the low molecular weight poly (arylene ether) in the mixed solution after water washing is controlled to be 30-80 wt%, and the weight ratio of the poly (arylene ether) poor solvent to the poly (arylene ether) mixed solution after water washing is 3 or more; (4) The wet mass is dried to give a low molecular weight poly (arylene ether). The low molecular weight poly (arylene ether) prepared by the invention has low quinone content, narrow molecular weight distribution and high glass transition temperature.
Description
Technical Field
The invention belongs to the technical field of poly (arylene ether) resin, and particularly relates to low molecular weight poly (arylene ether) and a preparation method thereof.
Background
Poly (arylene ether) is one of five general engineering plastics and has wide application in electronics, automobiles, household appliances, office equipment, industrial machinery, and the like. In recent years, with rapid development of communication technology, the 5 th generation (5G) communication technology has been popularized and used in the global scope, and 5G communication is a high-frequency communication technology, and has high requirements on electrical properties, particularly dielectric properties, of materials, and has high requirements on dielectric loss factors of base materials, particularly copper-clad plates, of communication equipment, and the smaller the dielectric loss factors are in favor of signal transmission in a certain range. In the copper-clad plate application field, the electrical performance of the traditional epoxy resin-based copper-clad plate cannot meet the requirements of the current communication technology.
Poly (arylene ether) resins have excellent electrical properties, relatively low dielectric loss factors, and relatively small and stable dielectric constants due to their high symmetry and low polarity of the molecular chains themselves. Thus, the poly (arylene ether) resin is advantageously used in 5G communications. However, the high molecular weight poly (arylene ether) (having a number average molecular weight of more than 10000 g/mol) has the disadvantages of high melt viscosity, high solution viscosity, etc., and is difficult to be directly applied to the fields of copper-clad plates, etc., which requires a reduction in molecular weight to obtain a low molecular weight poly (arylene ether). The preparation technology of the low molecular weight poly (arylene ether) mainly comprises a redistribution method and a direct monomer synthesis method.
The reassignment method is as follows: the preparation method comprises the steps of taking high molecular weight poly (arylene ether) (with the number average molecular weight of more than 10000 g/mol) as a raw material, adding bisphenol or polyphenol redistribution monomers, dissolving the bisphenol or polyphenol redistribution monomers in a good solvent of the poly (arylene ether) to form a solution, adding a free radical initiator, and initiating a reaction at a certain temperature to form the low molecular weight poly (arylene ether). For example, chinese patent CN101389691a discloses a method for producing a low molecular weight poly (arylene ether) by using a poly (arylene ether) having a number average molecular weight of 10000g/mol or more, a polyphenol compound, and a radical initiator to perform a redistribution reaction, thereby producing a low molecular weight poly (arylene ether) having a number average molecular weight of 4000g/mol or less. Also, a high molecular weight poly (arylene ether) resin is first synthesized by a monomer synthesis method, and then a redistribution reaction is performed in the synthesized solution by adding a redistribution phenol monomer to form a low molecular weight poly (arylene ether) resin. For another example, chinese patent CN1140565C discloses a method for producing low molecular weight poly (arylene ether) resins by redistribution, first synthesizing a high molecular weight poly (arylene ether) by oxidative coupling to form a poly (arylene ether) solution, and then adding a functionalized phenolic monomer to the solution, without the need for further redistribution catalyst, to produce a low molecular weight poly (arylene ether). In addition, chinese patent CN1188450C also discloses a method for preparing low molecular weight poly (arylene ether) using a redistribution method. However, when the redistribution method is used to prepare the low molecular weight poly (arylene ether), it is difficult to control the chain scission length of the molecular chain during the reaction, and an oil-soluble free radical catalyst is introduced, which is difficult to remove during the subsequent processing, and the processing is complicated. Thus, the use of redistribution processes to prepare low molecular weight poly (arylene ether) s is not commercially available.
The direct synthesis method is a method of synthesizing in a solvent of poly (arylene ether) under the catalysis of a copper amine complex catalyst using monomeric phenol. For example, chinese patent CN1142965C discloses a method for preparing a low molecular weight poly (arylene ether) resin having an intrinsic viscosity of 0.08dl/g to 0.16dl/g, preparing a low molecular weight poly (arylene ether) resin solution by oxidative coupling of at least one monovalent phenol in the reaction solution using an oxygen-containing gas and a complex metal catalyst, washing the catalyst with water, devolatilizing the reaction solution to remove an organic solvent, and obtaining a low molecular weight poly (arylene ether) resin. For example, chinese patent CN100352848C discloses a method for producing difunctional phenylene ether oligomers, wherein diphenol and monophenol 2, 6-dimethylphenol monomers are added, oligomeric poly (arylene ether) prepared by an oxidative polymerization process. For another example, chinese patent CN101305030B discloses the preparation of poly (arylene ether) having a polyfunctional property with an intrinsic viscosity of 0.04 to 0.3dl/g, which is purified by water washing to remove catalyst impurities, and then solvent is removed by a complete separation method such as degassing extrusion, spray drying, film evaporation, etc., to prepare a low molecular weight poly (arylene ether) product. In addition, WO2017105682A1, CN101479319B and CN1125107C disclose similar methods of preparing low molecular weight poly (arylene ether) s. However, for the preparation of low molecular weight poly (arylene ether) by the direct synthesis method disclosed, the low molecular weight poly (arylene ether) is mostly obtained by a complete detachment method, which has the characteristics of short preparation process, easy production and the like, but the complete detachment method retains impurities (for example, red quinone) in the polymerization process, and has the defects of wide molecular weight distribution, poor pyrolysis resistance and the like.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a low molecular weight poly (arylene ether) and a method for preparing the same, which have low quinone content, narrow molecular weight distribution, and high glass transition temperature, in view of the drawbacks of the prior art.
The aim of the invention is achieved by the following technical scheme.
In one aspect, the present invention provides a method of preparing a low molecular weight poly (arylene ether), wherein the method of preparing comprises the steps of:
(1) Oxidizing and polymerizing a phenol monomer in a poly (arylene ether) good solvent in the presence of an oxidizing agent and a catalyst to obtain a mixed solution of low molecular weight poly (arylene ether) having an intrinsic viscosity of 0.05 to 0.3dl/g in a chloroform solution at 25 ℃;
(2) Washing the mixed solution of the low molecular weight poly (arylene ether) to obtain a washed mixed solution of the low molecular weight poly (arylene ether);
(3) Adding the mixed solution of the low molecular weight poly (arylene ether) after water washing into a poor poly (arylene ether) solvent under stirring and in an inert atmosphere to form a low molecular weight poly (arylene ether) slurry, and filtering to obtain a low molecular weight poly (arylene ether) wet material; wherein the solid content of the low molecular weight poly (arylene ether) in the mixed solution of the low molecular weight poly (arylene ether) after water washing is controlled to be 30-80 wt%, and the weight ratio of the poor poly (arylene ether) solvent to the mixed solution of the poly (arylene ether) after water washing is 3 or more;
(4) The wet mass of low molecular weight poly (arylene ether) is dried to provide a low molecular weight poly (arylene ether).
When the low molecular weight poly (arylene ether) mixture prepared by the oxidative coupling method is treated by a complete detachment method such as spray drying or devolatilization, the obtained low molecular weight poly (arylene ether) product has high quinone impurity content, reddish color, broad molecular weight distribution and poor pyrolysis resistance. The present inventors have found that the quinone content in the low molecular weight poly (arylene ether) can be effectively reduced by controlling the concentration thereof, the amount of the poly (arylene ether) poor solvent, and the specific precipitation conditions, while the molecular weight distribution of the low molecular weight poly (arylene ether) is narrow and the glass transition temperature is high, with respect to the mixed solution of the low molecular weight poly (arylene ether) after washing with water to remove the residual catalyst. Without wishing to be bound by theory, it is believed that during formation of the slurry, the quinone is at least partially reduced to phenol soluble in the poly (arylene ether) good solvent and/or the poly (arylene ether) poor solvent under the protection of an inert gas such as nitrogen to be removed, whereby the low molecular weight poly (arylene ether) produced by the method of the present invention has a reduced quinone content.
According to the production method provided by the present invention, wherein a mixed solution of low molecular weight poly (arylene ether) having an intrinsic viscosity of 0.05 to 0.3dl/g in a chloroform solution at 25℃can be produced using a raw material and an oxidative polymerization method (oxidative coupling method) known in the art.
According to the preparation method provided by the invention, the phenolic monomer in the step (1) can be monohydric phenol, polyhydric phenol or a mixture thereof.
In the present invention, a monohydric phenol represented by formula (I):
wherein M is 1 、M 2 、M 3 And M 4 Each independently is a hydrogen atom, an alkyl (e.g., C1-6 alkyl), a halogen, a haloalkyl, or an alkoxy. Specifically, examples of monohydric phenols include, but are not limited to: 2, 6-dimethylphenol and 2,3, 6-trimethylphenol.
In the present invention, the polyhydric phenol may be a polyhydric phenol having a phenol hydroxyl number of 2 to 7, and preferably a dihydric phenol.
Dihydric phenols suitable for use in the present invention may be those of formula (II):
wherein N is 1 、N 2 、N 3 And N 4 Each independently is a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, allyl; w is an alkyl group having 1 to 4C atoms such as ethyl, isopropyl or methylene. In addition, those dihydric phenols in which the W group is deleted from the dihydric phenols of the formula (II) may also be used in the present invention. Specifically, examples of the dihydric phenol include, but are not limited to: tetramethyl bisphenol a, and tetramethyl biphenol.
In some preferred embodiments, the phenolic monomer is 2, 6-dimethylphenol or a mixture of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol. The invention has no special requirement on the proportion of 2, 6-dimethylphenol to 2,3, 6-trimethylphenol in the mixture of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol. In some embodiments, the ratio of the amounts of the 2, 6-dimethylphenol to the 2,3, 6-trimethylphenol may be from 1:0.00001 to 0.1; in some embodiments from 1:0.0001 to 0.01; and in some embodiments from 1:0.0005 to 0.003.
According to the preparation method provided by the invention, low molecular weight poly (arylene ether) with different main chain structures can be obtained by selecting different phenol monomer types and/or proportions thereof.
In some embodiments, the low molecular weight poly (arylene ether) has the structure of formula (IV):
wherein K is 1 And K 2 Each independently is a C1-C8 hydrocarbyl group, preferably methyl; n is an integer of 5 to 100.
In other embodiments, the low molecular weight poly (arylene ether) has the structure of formula (V):
wherein n and m can be independently 0 or integers greater than 1, and n+m is an integer ranging from 5 to 100; x is X 1 、X 2 、X 3 And X 4 Each independently is a hydrogen atom, alkyl, halogen, haloalkyl or alkoxy, X 1 、X 2 、X 3 And X 4 The same or different; y is Y 1 And Y 2 Each independently is a hydrogen atom, alkyl, halogen, haloalkyl, phenolic hydroxyl or alkoxy, Y 1 And Y 2 The same or different.
In some preferred embodiments, X 1 And X 2 Each independently is hydrogen or methyl, X 3 And X 4 Each independently is methyl, Y 1 And Y 2 Is methyl.
The preparation method provided by the invention, wherein the intrinsic viscosity of the low molecular weight poly (arylene ether) in a chloroform solution at 25 ℃ is 0.07-0.15 dl/g. In particular, the inventors have found that by controlling the solids content and the poly (arylene ether) poor solvent ratio, the yield of low molecular weight poly (arylene ether) having an intrinsic viscosity in the range of 0.07 to 0.15dl/g during precipitation can be increased to 90% or more.
According to the preparation method provided by the invention, the oxidant is oxygen. Typically, oxygen is produced by purifying air, which typically contains components contained in air such as nitrogen. The oxygen may be oxygen produced by other methods such as electrolysis of water. In some embodiments, the concentration of oxygen is 5% to 100% by volume; and in some embodiments, 80% to 100% by volume.
The preparation method provided by the invention is characterized in that the catalyst is a metal amine composite catalyst. The metal amine composite catalyst contains a complexing agent formed by complexing a metal salt and an amine compound. The metal ions of the metal salt include chromium, manganese, cobalt, or copper ions, preferably copper ions. Examples of metal salts (copper salts) suitable for use in the present invention include, but are not limited to: cuprous chloride, cuprous bromide, cuprous sulfate, cuprous tetramine sulfate, cuprous acetate, cupric chloride, cupric bromide, cupric sulfate, cupric tetramine sulfate, and cupric acetate. In some embodiments, the ratio of the amount of the metal salt to the material of the phenolic monomer may be 0.005 to 2:100.
Typically, the amine compound may be a monoamine compound, for example, a primary amine, a tertiary amine, a secondary amine, or the like; a diamine compound; or mixtures thereof. Examples of primary amines suitable for use in the present invention include, but are not limited to: n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine and cyclohexylamine. Examples of secondary amines suitable for use in the present invention include, but are not limited to: di-n-propylamine, di-n-butylamine, di-t-butylamine, n-butyl-n-pentylamine and di-n-hexylamine. Examples of tertiary amines suitable for use in the present invention include, but are not limited to: triethylamine, tri-n-propylamine, tri-n-butylamine, dimethyl-n-butylamine and dimethyl-n-pentylamine.
The diamine compound suitable for use in the present invention has a structure represented by formula (III):
wherein R is 1 、R 2 、R 4 And R is 5 Each independently is a hydrogen atom, a C1-6 straight chain alkyl group, or a C3-6 branched alkyl group; r is R 3 Is a saturated alkyl group having 2 or more carbon atoms. Specifically, examples of diamine compounds suitable for use in the present invention include, but are not limited to: n, N '-tetramethyl-1, 3-diaminopropane and N, N' -di-tert-butylethylenediamine.
In some embodiments, the ratio of the amount of amine compound to the metal salt is 1 to 100:1, preferably 10 to 60:1.
In some embodiments, the catalyst is a copper amine catalyst comprising a complexing agent formed from a copper metal salt and an amine compound.
In some embodiments, the copper amine catalyst comprises cuprous bromide, N-dimethylbutylamine, di-N-butylamine, and N, N' -tetramethyl-1, 3-diaminopropane in a ratio of amounts of materials of 1:20:10:5.
According to the preparation method provided by the invention, the poly (arylene ether) good solvent refers to an organic solvent capable of dissolving poly (arylene ether), particularly low molecular weight poly (arylene ether) with a number average molecular weight of 10000g/mol or less. Examples of good poly (arylene ether) solvents suitable for use in the present invention include, but are not limited to: benzene, toluene, xylene, chloroform and tetrahydrofuran. In the present invention, the poly (arylene ether) good solvent may be one of the solvents described above, or may be a mixed solvent of these solvents. In a preferred embodiment, the poly (arylene ether) good solvent is toluene.
According to the preparation method provided by the invention, the mass ratio of the poly (arylene ether) good solvent to the phenol monomer is 1-10:1, preferably 2-7:1.
According to the preparation method provided by the invention, the oxidative polymerization in the step (1) is carried out at a temperature of 15-80 ℃. In some embodiments, the oxidative polymerization in step (1) is performed at a temperature of 25 to 45 ℃.
According to the preparation method provided by the invention, in the step (2), the mixed solution of the low molecular weight poly (arylene ether) is washed by adopting an aqueous solution containing a copper ion chelating agent.
Examples of copper ion chelating agents suitable for use in the present invention include, but are not limited to: EDTA, EDTA-2Na, EDTA-3Na, EDTA-4Na, sodium citrate and trisodium nitrilotriacetate.
In the present invention, there is no particular requirement for the aqueous solution containing the copper ion chelating agent, as long as the metal ion of the catalyst can be effectively chelated. In some embodiments, the ratio of the copper ion chelating agent to the amount of metal ion species in the metal salt is 1.1 to 3:1.
The preparation method provided by the invention, wherein the water washing operation in the step (2) is as follows: adding an aqueous solution containing a copper ion chelating agent to the mixed solution of the low molecular weight poly (arylene ether), separating the phases, and separating the liquid from the liquid.
In the present invention, the liquid-liquid separation can be performed by centrifugal separation. Of course, any other known oil-water separation method in the art may be used for the liquid-liquid separation.
According to the preparation method provided by the invention, the inert atmosphere in the step (3) is a nitrogen atmosphere, a helium atmosphere or an argon atmosphere.
According to the preparation method provided by the invention, the solid content range of the low molecular weight poly (arylene ether) in the mixed solution of the low molecular weight poly (arylene ether) after water washing in the step (3) is controlled to be 30-80 wt%. The solids content range of the mixed solution may vary for low molecular weight poly (arylene ether) s having different intrinsic viscosities. Typically, for low molecular weight poly (arylene ether) s having a relatively low intrinsic viscosity, the solids content of the mixed solution may be relatively high. For example, for low molecular weight poly (arylene ether) having an intrinsic viscosity of 0.07 to 0.15dl/g in chloroform at 25 ℃, the solid content of the low molecular weight poly (arylene ether) in the mixed solution of low molecular weight poly (arylene ether) after water washing in step (3) may be 60 to 80 weight percent.
According to the production method provided by the present invention, wherein the solid content of the low molecular weight poly (arylene ether) in the mixed solution of the low molecular weight poly (arylene ether) after washing with water can be increased in step (3) by a method such as reduced pressure distillation, atmospheric pressure distillation, flash evaporation, or wiped film evaporation. Of course, the concentration may be reduced by adding a poly (arylene ether) good solvent to the mixed solution of the low molecular weight poly (arylene ether) after washing, and the solid content may be controlled to fall within the target range.
According to the preparation method provided by the invention, the poor poly (arylene ether) solvent is C1-C5 alcohol or a mixture thereof. Examples of poly (arylene ether) poor solvents suitable for use in the present invention include, but are not limited to: methanol, ethanol, n-propanol, n-butanol and n-pentanol. In some preferred embodiments, the poly (arylene ether) poor solvent is methanol.
According to the preparation method provided by the invention, when the proportion of the poor solvent of the poly (arylene ether) is lower than 3:1, the post-precipitation rate of the product is very low; on the contrary, if the ratio is high, the consumption is large, and the post-treatment cost is high. In some embodiments, the weight ratio of the poly (arylene ether) poor solvent to the mixed solution of the low molecular weight poly (arylene ether) after washing is 3 to 10:1; and in some embodiments 5 to 8:1.
According to the preparation method provided by the invention, in the step (3), the mixed solution of the low molecular weight poly (arylene ether) after water washing is added into the poor poly (arylene ether) solvent at a constant speed within 10-30 min, preferably within 20-30 min. The adding speed is too high, and large-block polymer precipitation which is difficult to stir easily occurs, and impurities possibly contained in the precipitation can influence the quality of the product; otherwise, the adding speed is too slow, and the production efficiency is low.
The preparation method provided in accordance with the present invention, wherein the operation of forming the low molecular weight poly (arylene ether) slurry in step (3) is conducted at a temperature of 0 to 65 ℃, preferably 30 to 55 ℃, more preferably 35 to 45 ℃.
In some embodiments, the low molecular weight poly (arylene ether) preferably has an intrinsic viscosity of 0.05 to 0.3dl/g, preferably 0.07 to 0.15dl/g, in chloroform solution at 25 ℃; the solid content of the low molecular weight poly (arylene ether) in the mixed solution of the low molecular weight poly (arylene ether) after washing in the step (3) is 60 to 80 weight percent, the weight ratio of the poor poly (arylene ether) solvent to the mixed solution of the low molecular weight poly (arylene ether) after washing in the step (3) is 3 to 10:1, preferably 5 to 8:1, and the operation of forming the low molecular weight poly (arylene ether) slurry in the step (3) is performed at a temperature of 35 to 45 ℃.
According to the preparation method provided by the invention, in the step (3), the stirring is shearing stirring, and the rotating speed is 50-1000 rpm, preferably 400-800 rpm. In addition, the stirring mode can be spiral, blade or paddle type.
The preparation method provided by the invention, wherein the operation of forming the low molecular weight poly (arylene ether) slurry in the step (3) is as follows:
(301) Adding a poly (arylene ether) poor solvent into the precipitation kettle, and introducing nitrogen to discharge air;
(302) Adding the washed mixed solution of the low molecular weight poly (arylene ether) into a precipitation kettle filled with the poly (arylene ether) poor solvent at a constant speed within 20-30 min under spiral shearing and stirring at a rotating speed of 400-800 rpm, and continuously stirring for 5-10 min to form low molecular weight poly (arylene ether) slurry;
(303) The low molecular weight poly (arylene ether) slurry is filtered to provide a low molecular weight poly (arylene ether) wet mass.
According to the preparation method provided by the invention, the filtration is performed in a solid-liquid two-phase filter. Examples of solid-liquid two-phase filters suitable for use in the present invention include, but are not limited to: suction filtration bucket, washing filtration all-in-one, centrifugal filter and rotary drum filter.
According to the preparation method provided by the invention, the drying in the step (4) is performed under a negative pressure at a temperature ranging from 30 ℃ to 120 ℃. In some embodiments, the drying may be performed in a stepwise elevated temperature, e.g., a first stage, elevated to 40-50 ℃ for 1-5 hours; in the second stage, heating to 70-80 ℃ and keeping for 1-3 h; and in the third stage, heating to 100-120 ℃ until the volatile components are reduced to below 0.5 wt%. More specifically, the temperature rise rate may be 5 to 20 ℃/h.
According to the production method provided by the present invention, wherein the drying in step (4) may be performed in an industrial dryer or dryer such as a vacuum dryer, a rake dryer, and a drum dryer.
In another aspect, the present invention also provides a low molecular weight poly (arylene ether) prepared by the above method.
The invention has the following advantages:
(1) The low molecular weight poly (arylene ether) prepared by the preparation method has low quinone content, narrow molecular weight distribution and high glass transition temperature;
(2) By controlling parameters such as the intrinsic viscosity of the low molecular weight poly (arylene ether), the solids content, the poly (arylene ether) poor solvent ratio, and the temperature at which the low molecular weight poly (arylene ether) slurry is formed, the low molecular weight poly (arylene ether) yield can be improved, while having a low quinone content, a narrow molecular weight distribution, and a high glass transition temperature.
(3) The preparation method has short working procedures, is easy to produce and is easy to popularize and apply.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. No specific technique or condition is identified in the examples, which follow the techniques or conditions described in the literature in this field, or follow the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Intrinsic viscosity
A poly (arylene ether) sample was dissolved in chloroform to form a solution having a concentration of 0.5g/dl, which was measured at 25℃using an Ubbelohde viscometer in dl/g.
Molecular weight distribution
The molecular weight distribution of the low molecular weight poly (arylene ether) was analyzed using a Showa Denko K.K. company under the trade name "SHODEX GPC system" gel permeation chromatograph. Wherein the eluent is chloroform, the flow is 1.0ml/min, and the temperature of the tower column is 40 ℃.
Glass transition temperature
Glass transition temperature was measured using a Pyrisl differential scanning calorimeter. Wherein, the atmosphere is nitrogen atmosphere, and the temperature rising speed is 20 ℃/min.
Poly (arylene ether) yield
The poly (arylene ether) yield is expressed as weight percent of the final product obtained to the phenol monomer used.
Quinone content
The difference of electron absorption spectra of poly (arylene ether) and quinone is utilized, chloroform is used as a solvent to prepare a solution of 0.3g/100ml of poly (arylene ether) sample and a reference sample respectively, the solution is kept stand at 25 ℃ for 2 hours, then the reference sample is used as a reference, the absorbance with the wavelength of 421nm is measured in a visible ultraviolet spectrophotometer, and the content is calculated.
The main raw materials used in the following examples are as follows:
phenol monomer: 2, 6-dimethylphenol; tetramethyl bisphenol a;
poly (arylene ether) good solvent: toluene;
oxidizing agent: 99.99% oxygen;
copper ion chelating agent: EDTA-2Na;
copper ammonium composite catalyst composition: cuprous bromide, N, N-dimethylbutylamine, di-N-butylamine, and N, N, N ', N' -tetramethyl-1, 3-diaminopropane in a mass ratio of 1:20:10:5;
poly (arylene ether) poor solvent: methanol.
Example 1
(1) Preparing 10Kg of 2, 6-dimethylphenol monomer, 150Kg of toluene and 2Kg of copper-ammonium composite catalyst into a reaction kettle, injecting the solution into the reaction kettle, starting stirring, introducing 99.99% oxygen into the reaction kettle within the temperature range of 20+/-5 ℃, starting the oxidative polymerization reaction at 40+/-2 ℃, then uniformly adding 40Kg of 2, 6-dimethylphenol into the reaction kettle within 60 minutes, continuing the reaction after the dripping is finished, sampling and detecting on line until the intrinsic viscosity of a polymerization product reaches 0.12dl/g, and stopping polymerization.
(2) Adding an aqueous solution of a copper ion chelating agent into the mixed solution of the low molecular weight poly (arylene ether), stirring and extracting for 15 minutes, then standing for 20-30 minutes, and separating off the lower aqueous phase. Wherein the concentration of the aqueous solution of the copper ion chelating agent is 0.1mol/L, and the dosage is 35L.
(3) The mixed solution of the low molecular weight poly (arylene ether) after water washing is transferred into a benzene removal kettle, heated to remove benzene under the negative pressure condition, and concentrated to the solid content of 65 weight percent at the temperature of 80 ℃.
(4) 450Kg of methanol was injected into the precipitation tank, heated to 45℃and nitrogen was introduced to expel air, and the concentrated mixed solution of low molecular weight poly (arylene ether) was added at constant speed over 30 minutes by a pump under stirring with blade shear at 500rpm, followed by continued stirring for 10 minutes to form a low molecular weight poly (arylene ether) slurry.
(5) And (3) carrying out suction filtration on the low molecular weight poly (arylene ether) slurry by using a suction filtration barrel to obtain a low molecular weight poly (arylene ether) wet material.
(6) Transferring the low molecular weight poly (arylene ether) wet material into a drum dryer, and drying by adopting a gradual heating mode under the negative pressure condition, wherein in the first stage, the temperature is raised to 45 ℃ and maintained for 1h; in the second stage, heating to 80 ℃ and keeping for 2 hours; and in the third stage, the temperature is increased to 110 ℃ until the volatile component is reduced to below 0.5wt%, wherein the temperature increasing speed is 20 ℃/h. An off-white low molecular weight poly (arylene ether) product is obtained.
Comparative example 1
The concentrated poly (arylene ether) solution having a solids content of 65 weight percent was prepared according to the methods described in steps (1) - (3) of example 1, and the toluene was removed by placing the concentrated poly (arylene ether) solution in a vacuum wiped film evaporator and cooling to provide a reddish brown low molecular weight poly (arylene ether) product.
Example 2
(1) 10Kg of the mixture was taken as a molar ratio of 1: preparing 0.8 of mixed monomer of 2, 6-dimethylphenol monomer and tetramethyl bisphenol A, 150Kg of toluene and 2Kg of copper-ammonium composite catalyst into a reaction kettle, injecting into the reaction kettle, starting stirring, introducing 99.99% oxygen into the reaction kettle within the temperature range of 20+/-5 ℃, starting the oxidative polymerization reaction at 40+/-2 ℃, then adding 40Kg of 2, 6-dimethylphenol into the reaction kettle at a constant speed within 60 minutes, continuing the reaction after the dripping is finished, sampling and detecting on line until the intrinsic viscosity of a polymerized product reaches 0.09dl/g, and stopping polymerization.
(2) Adding an aqueous solution of a copper ion chelating agent into the mixed solution of the low molecular weight poly (arylene ether), stirring and extracting for 15 minutes, then standing for 20-30 minutes, and separating off the lower aqueous phase. Wherein the concentration of the aqueous solution of the copper ion chelating agent is 0.1mol/L, and the dosage is 35L.
(3) The mixed solution of the low molecular weight poly (arylene ether) after water washing is transferred into a benzene removal kettle, heated to remove benzene under the negative pressure condition, and concentrated to 70 weight percent of solid content at 80 ℃.
(4) 450Kg of methanol was injected into the precipitation tank, heated to 45℃and nitrogen was introduced to expel air, and the concentrated mixed solution of low molecular weight poly (arylene ether) was added at constant speed over 30 minutes by a pump under stirring with blade shear at 500rpm, followed by continued stirring for 5 minutes to form a low molecular weight poly (arylene ether) slurry.
(5) And (3) carrying out suction filtration on the low molecular weight poly (arylene ether) slurry by using a suction filtration barrel to obtain a low molecular weight poly (arylene ether) wet material.
(6) Transferring the low molecular weight poly (arylene ether) wet material into a drum dryer, and drying by adopting a gradual heating mode under the negative pressure condition, wherein in the first stage, the temperature is raised to 45 ℃ and maintained for 1h; in the second stage, heating to 80 ℃ and keeping for 2 hours; and in the third stage, the temperature is increased to 110 ℃ until the volatile component is reduced to below 0.5wt%, wherein the temperature increasing speed is 10 ℃/h. An off-white low molecular weight poly (arylene ether) product is obtained.
Comparative example 2
The concentrated poly (arylene ether) solution having a solids content of 70 weight percent was prepared according to the methods described in steps (1) - (3) of example 2, and the toluene was removed by placing the concentrated poly (arylene ether) solution in a vacuum wiped film evaporator, and the temperature was reduced to provide a reddish brown low molecular weight poly (arylene ether) product.
Example 3
(1) Preparing 10Kg of 2, 6-dimethylphenol monomer, 150Kg of toluene and 3Kg of copper ammonium composite catalyst into a reaction kettle, injecting the solution into the reaction kettle, starting stirring, introducing 99.99% oxygen into the reaction kettle within the temperature range of 20+/-5 ℃, carrying out oxidative polymerization reaction at 40+/-2 ℃, then uniformly adding 40Kg of 2, 6-dimethylphenol into the reaction kettle within 60 minutes, continuing the reaction after the dripping is finished, sampling and detecting on line until the intrinsic viscosity of a polymerization product reaches 0.28dl/g, and stopping polymerization.
(2) Adding an aqueous solution of a copper ion chelating agent into the mixed solution of the low molecular weight poly (arylene ether), stirring and extracting for 15 minutes, then standing for 20-30 minutes, and separating off the lower aqueous phase. Wherein the concentration of the aqueous solution of the copper ion chelating agent is 0.1mol/L and the dosage is 52.5L.
(3) The mixed solution of the low molecular weight poly (arylene ether) after water washing is transferred into a benzene removal kettle, heated to remove benzene under the negative pressure condition, and concentrated to the solid content of 40 weight percent at the temperature of 80 ℃.
(4) 450Kg of methanol was injected into the precipitation tank, heated to 45℃and nitrogen was introduced to expel air, and the concentrated mixed solution of low molecular weight poly (arylene ether) was added at a constant speed over 30 minutes by a pump under stirring with blade shear at 500rpm, followed by continuing stirring for 3 minutes to form a low molecular weight poly (arylene ether) slurry.
(5) And (3) carrying out suction filtration on the low molecular weight poly (arylene ether) slurry by using a suction filtration barrel to obtain a low molecular weight poly (arylene ether) wet material.
(6) Transferring the low molecular weight poly (arylene ether) wet material into a drum dryer, and drying by adopting a gradual heating mode under the negative pressure condition, wherein in the first stage, the temperature is raised to 45 ℃ and maintained for 1h; in the second stage, heating to 80 ℃ and keeping for 2 hours; and in the third stage, the temperature is increased to 110 ℃ until the volatile component is reduced to below 0.5wt%, wherein the temperature increasing speed is 10 ℃/h. A pale yellow low molecular weight poly (arylene ether) product is obtained.
Comparative example 3
The concentrated poly (arylene ether) solution having a solids content of 65 weight percent was prepared by the method of steps (1) - (3) of example 3, toluene was removed by placing the concentrated poly (arylene ether) solution in a vacuum wiped film evaporator, and the temperature was reduced to provide a reddish brown low molecular weight poly (arylene ether) product.
Example 4
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: the mixed solution of the low molecular weight poly (arylene ether) after washing with water is concentrated in step (3) to a poly (arylene ether) solids content of 60 weight percent.
Finally obtaining the off-white low molecular weight poly (arylene ether) product.
Example 5
A low molecular weight poly (arylene ether) was prepared substantially as in example 2, except that: concentrating the water-washed mixed solution of the low molecular weight poly (arylene ether) in the step (3) until the solid content of the poly (arylene ether) is 80 weight percent; the amount of methanol added in the step (4) was 400Kg.
Finally obtaining the off-white low molecular weight poly (arylene ether) product.
Example 6
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: step (4) is carried out at a temperature of 35 ℃.
Finally obtaining the off-white low molecular weight poly (arylene ether) product.
Example 7
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: step (4) is carried out at a temperature of 25 ℃.
Finally obtaining the brown yellow low molecular weight poly (arylene ether) product.
Example 8
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: the mixed solution of the low molecular weight poly (arylene ether) after washing with water is concentrated in step (3) to a poly (arylene ether) solids content of 35 weight percent.
Finally obtaining the off-white low molecular weight poly (arylene ether) product.
Example 9
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: step (4) employs ethanol as the poor solvent for the low molecular weight poly (arylene ether).
Finally obtaining the brown yellow low molecular weight poly (arylene ether) product.
Comparative example 4
A low molecular weight poly (arylene ether) was prepared substantially as in example 1, except that: in the step (4), the concentrated mixed solution of low molecular weight poly (arylene ether) is added in an air atmosphere, and then stirring is continued for 3 minutes.
Finally obtaining the brown yellow low molecular weight poly (arylene ether) product.
Comparative example 5
A low molecular weight poly (arylene ether) was prepared substantially as in example 2, except that: in the step (4), 200Kg of methanol was added, and stirring was continued for 5 minutes.
Finally obtaining the off-white low molecular weight poly (arylene ether) product.
The properties of the low molecular weight poly (arylene ether) s prepared in examples 1-7 and comparative examples 1-5 are shown in Table 1.
TABLE 1 Low molecular weight Poly (arylene ether) Properties
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As can be seen from Table 1, the low molecular weight poly (arylene ether) product prepared according to the present invention has a relatively lower quinone content, a relatively narrower molecular weight distribution, a relatively higher glass transition temperature, and a high yield. In particular, as can be seen from a comparison of example 1 with comparative example 1, adding the water-washed mixed solution of low molecular weight poly (arylene ether) to a poly (arylene ether) poor solvent under stirring and under an inert atmosphere forms a low molecular weight poly (arylene ether) slurry and then removing toluene, having a reduced quinone content as compared to toluene removal in a vacuum wiped film evaporator; from example 1 and comparative example 4, it is seen that the low molecular weight poly (arylene ether) prepared by the method of the present invention has a reduced quinone content during formation of the slurry under protection with nitrogen as an inert gas. As can be seen from a comparison of examples 1, 6 and 7, the temperature of the system during formation of the slurry also has a greater effect on the quinone content, which is more advantageous at 35-45 ℃.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A method of preparing a low molecular weight poly (arylene ether), wherein the method comprises the steps of:
(1) Oxidizing and polymerizing a phenol monomer in a poly (arylene ether) good solvent in the presence of an oxidant and a catalyst to obtain a mixed solution of low molecular weight poly (arylene ether) with an intrinsic viscosity of 0.07-0.15 dl/g in a chloroform solution at 25 ℃;
(2) Washing the mixed solution of the low molecular weight poly (arylene ether) to obtain a washed mixed solution of the low molecular weight poly (arylene ether);
(3) Adding the mixed solution of the low molecular weight poly (arylene ether) after water washing into a poor poly (arylene ether) solvent under stirring and in an inert atmosphere to form a low molecular weight poly (arylene ether) slurry, and filtering to obtain a low molecular weight poly (arylene ether) wet material; the solid content of the low molecular weight poly (arylene ether) in the mixed solution of the low molecular weight poly (arylene ether) after water washing is controlled to be 60-80 wt%, and the weight ratio of the poor poly (arylene ether) solvent to the mixed solution of the poly (arylene ether) after water washing is 5-8:1; the operation of forming the low molecular weight poly (arylene ether) slurry is conducted at a temperature of 35 to 45 ℃;
(4) The wet mass of low molecular weight poly (arylene ether) is dried to provide a low molecular weight poly (arylene ether).
2. The process of claim 1, wherein the phenolic monomer in step (1) is a monohydric phenol, a polyhydric phenol, or a mixture thereof;
wherein the structure of the monohydric phenol is shown as a formula (I):
（I）
wherein M is 1 、M 2 、M 3 And M 4 Each independently is a hydrogen atom, alkyl, halogen, haloalkyl or alkoxy.
3. The production method according to claim 2, wherein the monohydric phenol is 2, 6-dimethylphenol or 2,3, 6-trimethylphenol.
4. The production method according to claim 2, wherein the polyhydric phenol is a polyhydric phenol having a phenol hydroxyl number of 2 to 7.
5. The process according to claim 4, wherein the polyhydric phenol has a structure represented by formula (II):
（II）
wherein N is 1 、N 2 、N 3 And N 4 Each independently represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 8 carbon atoms; w is an alkylene group having 1 to 4 carbon atoms.
6. The production method according to claim 2, wherein the phenol monomer is 2, 6-dimethylphenol or a mixture of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol; the ratio of the amount of 2, 6-dimethylphenol to 2,3, 6-trimethylphenol in the mixture of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol is 1:0.0001-0.01.
7. The production method according to any one of claims 1 to 5, wherein the oxidizing agent is oxygen; the catalyst is a metal amine composite catalyst.
8. The preparation method of claim 7, wherein the metal salt in the metal amine composite catalyst is one or more selected from cuprous chloride, cuprous bromide, cuprous sulfate, cuprous tetramine sulfate, cuprous acetate, cupric chloride, cupric bromide, cupric sulfate, cupric tetramine sulfate and cupric acetate; the ratio of the amount of the metal salt to the amount of the phenol monomer is 0.005-2:100;
the amine compound in the metal amine composite catalyst is a monoamine compound and a diamine compound; or mixtures thereof.
9. The production process according to claim 8, wherein the amine compound is one or more selected from the group consisting of N-propylamine, isopropylamine, N-butylamine, sec-butylamine, t-butylamine, N-pentylamine, N-hexylamine, cyclohexylamine, di-N-propylamine, di-N-butylamine, di-t-butylamine, N-butyl-N-pentylamine, di-N-hexylamine, triethylamine, tri-N-propylamine, tri-N-butylamine, dimethyl-N-pentylamine, N '-tetramethyl-1, 3-diaminopropane and N, N' -di-t-butylethylenediamine;
the ratio of the amount of the amine compound to the amount of the metal salt is 1-100:1.
10. The production method according to any one of claims 1 to 6, wherein the poly (arylene ether) good solvent is one or more of benzene, toluene, xylene, chloroform, and tetrahydrofuran;
the mass ratio of the poly (arylene ether) good solvent to the phenol monomer is 1-10:1.
11. The preparation method of claim 8, wherein the oxidative polymerization in step (1) is performed at 15-80 ℃;
washing the mixed solution of the low molecular weight poly (arylene ether) with an aqueous solution comprising a copper ion chelating agent in step (2); the ratio of the copper ion chelating agent to the amount of metal ion substances in the metal salt is 1.1-3:1;
the inert atmosphere in the step (3) is nitrogen atmosphere, helium atmosphere or argon atmosphere.
12. The method of any one of claims 1 to 6, wherein the poly (arylene ether) poor solvent is a C1-C5 alcohol or mixture thereof;
and (3) in the step (3), adding the mixed solution of the low molecular weight poly (arylene ether) after washing into the poly (arylene ether) poor solvent at a constant speed for 10-30 min.
13. The production method according to any one of claims 1 to 6, wherein the stirring in the step (3) is shear stirring at a rotation speed of 50 to 1000 rpm.
14. The production method according to any one of claims 1 to 6, wherein the operation of forming the low molecular weight poly (arylene ether) slurry in step (3) is as follows:
(301) Adding a poly (arylene ether) poor solvent into the precipitation kettle, and introducing nitrogen to discharge air;
(302) Adding the washed mixed solution of the low molecular weight poly (arylene ether) into a precipitation kettle filled with the poly (arylene ether) poor solvent at a constant speed within 20-30 min under spiral shearing and stirring at a rotating speed of 400-800 rpm, and continuously stirring for 5-10 min to form low molecular weight poly (arylene ether) slurry;
(303) The low molecular weight poly (arylene ether) slurry is filtered to provide a low molecular weight poly (arylene ether) wet mass.
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| GB1333511A (en) * | 1971-08-17 | 1973-10-10 | Asahi Dow Ltd | Process for producing aromatic polyethers |
| JP2001040087A (en) * | 1999-07-27 | 2001-02-13 | Mitsubishi Gas Chem Co Inc | Production of polyphenylene ether |
| KR20020071050A (en) * | 2001-03-02 | 2002-09-12 | 송원산업 주식회사 | Method of preparing 4,4'-biphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1333511A (en) * | 1971-08-17 | 1973-10-10 | Asahi Dow Ltd | Process for producing aromatic polyethers |
| JP2001040087A (en) * | 1999-07-27 | 2001-02-13 | Mitsubishi Gas Chem Co Inc | Production of polyphenylene ether |
| KR20020071050A (en) * | 2001-03-02 | 2002-09-12 | 송원산업 주식회사 | Method of preparing 4,4'-biphenol |
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