CN105295026A - Preparation method and device of ten-thousand-ton aryloxy polymer - Google Patents
Preparation method and device of ten-thousand-ton aryloxy polymer Download PDFInfo
- Publication number
- CN105295026A CN105295026A CN201510622177.XA CN201510622177A CN105295026A CN 105295026 A CN105295026 A CN 105295026A CN 201510622177 A CN201510622177 A CN 201510622177A CN 105295026 A CN105295026 A CN 105295026A
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- China
- Prior art keywords
- aryloxy
- polymkeric substance
- amine
- ton
- preparation
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- 125000004104 aryloxy group Chemical group 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 239000003960 organic solvent Substances 0.000 claims abstract description 79
- 238000001556 precipitation Methods 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 150000001412 amines Chemical class 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000004094 preconcentration Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- -1 alkyl disubstituted phenol Chemical class 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000003141 primary amines Chemical class 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 126
- 239000003795 chemical substances by application Substances 0.000 claims description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 32
- 238000000605 extraction Methods 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 29
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 26
- 238000000746 purification Methods 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- 239000003352 sequestering agent Substances 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 11
- 150000003512 tertiary amines Chemical class 0.000 claims description 11
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 10
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000009434 installation Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 150000003335 secondary amines Chemical class 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 235000012054 meals Nutrition 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- KNCHDRLWPAKSII-UHFFFAOYSA-N 4-ethyl-2-methylpyridine Chemical compound CCC1=CC=NC(C)=C1 KNCHDRLWPAKSII-UHFFFAOYSA-N 0.000 claims description 5
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 5
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 5
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002780 morpholines Chemical class 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- AILVYPLQKCQNJC-UHFFFAOYSA-N 2,6-dimethylcyclohexan-1-one Chemical compound CC1CCCC(C)C1=O AILVYPLQKCQNJC-UHFFFAOYSA-N 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 3
- KVZJDSFEPWQXTF-UHFFFAOYSA-N 7-methyl-2,3-dihydro-1-benzofuran Chemical class CC1=CC=CC2=C1OCC2 KVZJDSFEPWQXTF-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 150000001896 cresols Chemical class 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 150000003739 xylenols Chemical class 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 230000009920 chelation Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007791 dehumidification Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004200 deflagration Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 17
- 229920000090 poly(aryl ether) Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 5
- 229940100198 alkylating agent Drugs 0.000 description 5
- 239000012296 anti-solvent Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- GZKAUWVJFVHDNV-UHFFFAOYSA-N CC=1C(=C(C(=C(C1)C=1C(C(C=CC1)=O)=O)C)C)C Chemical compound CC=1C(=C(C(=C(C1)C=1C(C(C=CC1)=O)=O)C)C)C GZKAUWVJFVHDNV-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 241000545067 Venus Species 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001616 alkaline earth metal bromide Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- BWLYQXJZLBBGCK-UHFFFAOYSA-N copper;dodecanoic acid Chemical compound [Cu].CCCCCCCCCCCC(O)=O BWLYQXJZLBBGCK-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method and a device of a ten-thousand-ton aryloxy polymer, wherein the method at least comprises the following steps: a. carrying out oxidative coupling reaction on alkyl disubstituted phenol, oxygen and a catalyst in an organic solvent; b. removing the catalyst; c. pre-concentration; d. precipitating and filtering the resin; e. washing and purifying the product; f. drying; the device at least comprises a reaction kettle, a catalyst removing device, a pre-concentration device, a resin precipitation device, a washing and purifying device and a drying device. The preparation method and the device of the ten-thousand-ton aryloxy polymer have the following beneficial technical effects: 1) the deflagration of the core section in the process can be safely prevented; 2) the fresh supplementary amount of primary amine in the amine mixture is reduced by 50 percent; 3) the recycling rate of the organic solvent and the precipitator is more than 95 percent, and the product quality meets the high-level standard requirement.
Description
Technical field
The present invention relates to a kind of preparation method and device thereof of aryloxy polymkeric substance, be specifically related to a kind of preparation method and device thereof of ton aryloxy polymkeric substance.
Background technology
Aryloxy polymkeric substance aryloxy polymkeric substance, also claim polyarylether (being called for short PAE), industrialization for a long time.US Patent No. 3,733,299 (people such as Cooper).US Patent No. 3,988,297 (people such as Bennett) and US Patent No. 3,306,874 and 3,306,875 (Hay) have description.At present, safety in production, environment protection, and the requirement of the aspect such as product application proposes requirements at the higher level to prior art.In safety in production, be embodied in the precise controlling of polymerization process, in whole process, fire protection; Environment protection aspect is embodied in: " zero release " of waste catalyst metal, the total system reuse that chemically non-reactive is reinforced.These require that producing line to the industrialization producing ton per year especially proposes new demand.。
Summary of the invention
For solving above new problem, the invention provides a kind of preparation method and device thereof of ton aryloxy polymkeric substance, PAE polymkeric substance is by alkyl phenesic acid and O
2produced by semi-batch, oxidative coupling reaction, O
2enter reactor, heating and cooling are completed by chuck and outer circulating tube shell heat exchanger, and form loop by installation pump.Basic material (2,6-xylenol and O
2) with semicontinuous batch fed, other components are all added in reactor prior to basic material in full batch mode.During reaction, 2,6-xylenol converts PAE and water to by consuming certain oxygen, and heat release.Unreacted oxygen is overflowed from fluid surface, by the nitrogen dilution of reactor head.A kind of chemical equilibrium process of complexity controls the running of reactor, initial reaction device inside is filled with: organic solvent organic reaction solvent, Cu/ organic amine mixture catalyzer, through the reaction of 2 hours, polymerizable molecular is formed gradually along with the consumption of oxygen, and corresponding stickiness reduces along with the rising of temperature.
After oxidative coupling reaction completes, add a kind of copper chelator in the reactive mixture, in continuous separating machine, light phase (organic copper) can be separated with heavy phase (hydration copper).By vacuum flashing system, the water ratio of liquid is down to 60%, the organic solvent reuse that flasher top distillates, in the polymers soln increasing concentration, constantly add precipitation agent, forms polymkeric substance precipitation and solid-liquid mud.Mud is sent to liquid-solid filter, constantly carries out multistagely rinsing with precipitation agent again, then enters drying centrifuge.Polymer powder is sent into warehouse style, and the mixture of organic solvent/precipitation agent enters recovery system precipitation agent organic solvent purifying and is separated, and reuse is to whole flow process.
The present invention is to monomer purity in ton flow process, and polymerization technique controling parameters, reclaims catalyst metal, whole process reuse solvent and precipitation agent, and product separation washing, purifying such as to improve the quality of products at the aspect synthetic innovation, propose fully integrated industry and produce linear flow journey.The following technical scheme of concrete employing:
(1) preparation method for ton aryloxy polymkeric substance, comprises the following steps:
A. under the condition of organic solvent, oxidative coupling polymerization reaction is carried out by alkyl phenesic acid monomer, oxygen and catalyzer;
B. catalyzer is removed;
C. pre-concentration;
D. precipitate, filter;
E. product washing, purifying;
F. dry.
(2) preparation method of the ton aryloxy polymkeric substance Gen Ju (1), described alkyl phenesic acid monomer meets the combination of following arbitrary index or any two and above index:
The purity > 99.5% of 2,6-xylenol;
Total methyl-phenoxide < 0.15%;
Total cresols < 0.15%;
Other xylenols < 0.010%;
Phenol < 0.010%;
Other alkylphenols < 0.15%;
Other organic impuritys < 0.10%;
Colourity < 110;
Moisture < 1500ppm.
(3) according to the preparation method of (1) or the ton aryloxy polymkeric substance described in (2), preferably, described alkyl phenesic acid monomer meets the combination of following arbitrary index or any two and above index:
The purity > 99.8% of 2,6-xylenol;
Total methyl-phenoxide < 0.010%;
Total cresols < 0.10%;
Other xylenols < 0.055%;
Phenol < 0.005%;
Other alkylphenols < 0.10%;
Other organic impuritys < 0.05%;
Colourity < 85;
Moisture < 500ppm.
(4) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(3), described catalyzer is copper-amine mixture, wherein: amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
(5) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(4), preferably, described amine mixture is the 10%-40% of alkyl phenesic acid monomer weight.
(6) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(5), described copper-amine mixture comprises copper and is selected from following arbitrary organic amine and arbitrary combination thereof: primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein the mol ratio of amine mixture and copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
(7) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(6), preferably, the mol ratio of amine mixture and copper is 5-40, and amine mixture is the 10-40% of organic solvent weight.
(8) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(7), described amine mixture comprises aliphatic amine, described aliphatic amine comprises aliphatic list and diamines, and wherein aliphatic group can be straight or branched hydrocarbon or alicyclic compound.Preferred described aliphatic amine is aliphatic primary, secondary and tertiary monoamine or tertiary diamine.Preferred described aliphatic amine is single, two and three (rudimentary) alkylamine, and wherein alkyl has 1 ~ 6 carbon atom.Most preferred described aliphatic amine be single, two and the amine that replaces of trimethylammonium, ethyl, n-propyl, sec.-propyl, normal-butyl, or described aliphatic amine is single and dicyclohexylamine, ethylmethylamine, morpholine class, N-(rudimentary) alkyl cycloaliphatic amine such as N-methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propylene diamine, N, N, N '-trialkyl pentamethylene diamine; Or described aliphatic amine is cyclic tertiary amine, described cyclic tertiary amine is pyridine, α-collidine, γ-picoline.
(9) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(8), in oxidative coupling reaction, basic material is with semicontinuous batch fed, described basic material is alkyl phenesic acid and oxygen, and other components are all added in reactor prior to basic material in full batch mode.
(10) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(9), the reaction conditions of described oxidative coupling reaction meets the combination of following arbitrary index or any two and above index: temperature 5-70 DEG C, pressure 0-5psi above reactor, oxygen partial pressure 0-25%, oxygen feeding 0-425m above reactor
3/ hr, reactor outer circulation pumping head 10-100psi, reaction times 0-250 minute.
(11) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(10), described b step catalyzer is removed and is comprised chelating, de-organic phase, extraction and/or catalyst metal recycling step.
(12) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(11), sequestrant is added to remove the catalyst metal being polymerized and adding in described chelation step, wherein sequestrant comprises: sodium-potassium tartrate, nitrilotriacetic acid(NTA), citric acid, Padil, polyalkylene polyamine poly carboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, poly carboxylic acid and their basic metal, basic metal-the alkaline earth salt of alkaline-earth metal or mixing, preferably comprise: ethylenediamine tetraacetic acid (EDTA) (EDTA), HEDTA, diethylene triaminepentaacetic acid(DTPA) and their salt.
(13) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(12), by described de-organic phase step by the organic solution containing reaction product polymer and the aqueous phase separation containing catalyzer, sequestrant.
(14) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(13), described extraction step, for extracting described catalyzer, water and chelant mix in extraction tower, by organic solvent and organic amine from above-mentioned aqueous phase separation out and reuse organic phase is organic solvent is light phase, all the other aqueous phases become heavy phase.
(15) according to the preparation method of the ton aryloxy polymkeric substance described in any one of (1)-(14), copper to be precipitated out then to deliver to pressure filter for adding metallic sulfide by described copper recycling step from heavy phase.
(16) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(15), described step c pre-concentration carries out in pre-concentration flashing tower, organic solvent in part removal product polymer solution and water, obtain the concentrated polymer solution that weight concentration is 20-60%, wherein, the operation of flash distillation carries out between temperature 200 DEG C and 45 DEG C.
(17) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(16), in described steps d precipitation, cross in press filtration, become the polymkeric substance of liquid pulpous state state by precipitating described concentrated polymer, and obtain polymer powder filter cake by the polymkeric substance of continuous overvoltage filtrate pulpous state state.
(18) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(17), described step e product washing, purifying is the impurity removed by the washing of one or more levels precipitation agent and centrifugation in product, wherein, washing, purifying operation carries out between temperature 15 DEG C to 110 DEG C.
(19) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(18), by described step f dry aryloxy polymer powder and liquid carried out being separated obtain the finished product aryloxy polymkeric substance, wherein, the combination that drying process meets at least following arbitrary or any two and above condition is as follows: drying temperature is between 15 DEG C to 100 DEG C, total system carries out in the inert gas environment of circulation closed, and flow process reuse directly sent into by the volatile matter phlegma of generation.
(20) according to the preparation method of the ton aryloxy polymkeric substance described in any one of (1)-(19), the combination that described aryloxy polymkeric substance meets following arbitrary or any two and above standard is as follows:
Inherent viscosity and product summary maximum deviation < 5.0ml/g, preferred < 4.0ml/g;
After heat treatment inherent viscosity increases < 208ml/g, preferred < 180ml/g, and described thermal treatment temp is 285 DEG C, and the time is 4 minutes;
Organic amine residual concentration < 5%, preferred < 4%;
Copper ion concentration < 15ppm, preferred < 10ppm;
Fugitive constituent < 1.5%, preferred < 1%;
Polymerization organic solvent residual concentration < 300ppm, preferred < 200ppm;
Other organic impurity summation < 500ppm, preferred < 250ppm, other organic impurity described comprises 2,4,6-tri-cresols, Dihydrobenzofuranes, 2,6-dimethylcyclohexanon and 7-methyl-2,3-Dihydrobenzofuranes;
Bulk powder density > 0.25kg/L, preferred > 0.30kg/L;
Fine powder content < 35%, preferred < 10%, particle diameter < 38 order of described fine powder;
Meal content < 70%, preferred < 50%, particle diameter > 710 order of described meal;
Powder flowing index > 50, preferred > 60, powder flowing index is after gas is risen and initially piles up the volume ratio of powder.
(21) according to the preparation method of the ton aryloxy polymkeric substance described in any one of (1)-(20), preferred, the combination that described aryloxy polymkeric substance meets following arbitrary or any two and above standard is as follows:
Inherent viscosity and product summary maximum deviation < 1.5ml/g,
After heat treatment inherent viscosity increases < 12.5ml/g, and described thermal treatment temp is 285 DEG C, and the time is 4 minutes;
Organic amine residual concentration < 1.18%;
Copper ion concentration < 5ppm;
Fugitive constituent < 0.29%;
Toluene concentration < 1200ppm;
Other organic impurity summation < 284ppm, other organic impurity described comprises 2,4,6-tri-cresols, Dihydrobenzofuranes, 2,6-dimethylcyclohexanon and 7-methyl-2,3-Dihydrobenzofuranes;
Bulk powder density > 0.36kg/L;
Fine powder content < 7%, particle diameter < 38 order of described fine powder;
Meal content < 52%, particle diameter > 710 order of described meal;
Powder flowing index > 70, powder flowing index is after gas is risen and initially piles up the volume ratio of powder.
(22) preparation method of the ton aryloxy polymkeric substance according to any one of (1)-(21), also comprise solvent and precipitation agent purification reuse step, described purification reuse step comprise by extraction organic solvent is separated with precipitation agent, by organic solvent purification system reuse organic solvent, by precipitation agent purification system reuse precipitation agent.
(23) preparation facilities for ton aryloxy polymkeric substance, comprises polymeric kettle, catalyzer removal device, pre-concentration device, precipitation, filtration unit, product washing purifying device, drying installation.
(24) preparation facilities of the ton aryloxy polymkeric substance Gen Ju (23), in described polymeric kettle, carries out oxidative coupling polymerization reaction by alkyl phenesic acid monomer, oxygen and catalyzer under the condition of organic solvent.
(25) preparation facilities of basis (23) or the ton aryloxy polymkeric substance described in (24), catalyzer is copper-amine mixture, wherein: amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
(26) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(25), preferably, described amine mixture is the 10%-40% of alkyl phenesic acid monomer weight.
(27) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(26), described copper-amine mixture comprises copper and is selected from following arbitrary organic amine and arbitrary combination thereof: primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein the mol ratio of amine mixture and copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
(28) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(27), preferably, the mol ratio of amine mixture and copper is 5-40, and amine mixture is the 10-40% of organic solvent weight.
(29) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(28), described amine mixture comprises aliphatic amine, described aliphatic amine comprises aliphatic list and diamines, and wherein aliphatic group can be straight or branched hydrocarbon or alicyclic compound.Preferred described aliphatic amine is aliphatic primary, secondary and tertiary monoamine or tertiary diamine.Preferred described aliphatic amine is single, two and three (rudimentary) alkylamine, and wherein alkyl has 1 ~ 6 carbon atom.Most preferred described aliphatic amine be single, two and the amine that replaces of trimethylammonium, ethyl, n-propyl, sec.-propyl, normal-butyl, or described aliphatic amine is single and dicyclohexylamine, ethylmethylamine, morpholine class, N-(rudimentary) alkyl cycloaliphatic amine such as N-methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propylene diamine, N, N, N '-trialkyl pentamethylene diamine; Or described aliphatic amine is cyclic tertiary amine, described cyclic tertiary amine is pyridine, α-collidine, γ-picoline.
(30) according to (23)-(preparation facilities of the ton aryloxy polymkeric substance described in 29 any one, in oxidative coupling reaction, basic material is with semicontinuous batch fed, described basic material is alkyl phenesic acid and oxygen, and other components are all added in reactor in full batch mode prior to basic material; The reaction conditions of described oxidative coupling reaction meets the combination of following arbitrary index or any two and above index: temperature 5-70 DEG C, pressure 0-5psi above reactor, oxygen partial pressure 0-25%, oxygen feeding 0-425m above reactor
3/ hr, reactor outer circulation pumping head 10-100psi, reaction times 0-250 minute.
(31) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(30), the volume of described reactor is 15 to 100m
3be provided with oxygen intake, the heat-exchange system of agitator, tube and shell heat exchanger and outer circulation pump composition.
(32) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(31), described removal catalyst-assembly comprises storage tank, continuous centrifuge and catalyst metal recovery system.
(33) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(32), adds sequestrant and removes unreacted catalyzer in described storage tank; By described whizzer, the organic solution of polymkeric substance is separated with catalyzer, water, sequestrant; Described copper recovery system comprises pressure filter, by being provided with filter plate in described pressure filter, collects copper mud.
(34) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(33), described pre-concentration device comprises concentrated flashing tower, and described concentrated flashing tower is provided with heat exchanger and pre-concentration vacuum unit.
(35) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(34), described precipitation, filtration unit comprise stirring settler and continuous filter, and described continuous filter is provided with vacuum extractor.
(36) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(35), described washing purifying device comprises one or more levels agitator treating and solid-liquid continuous separation device.
(37) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(36), described drying installation comprises successive drying system, described dehumidification system is provided with following arbitrary heat-exchanger rig or arbitrary combination: chuck, internal circulation heat-exchanging, and external circulation heat exchanging.
(38) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(37), the combination that drying process in described drying installation meets at least following arbitrary or any two and above condition is as follows: drying temperature is between 15 DEG C to 100 DEG C, total system carries out in the inert gas environment of circulation closed, and flow process reuse directly sent into by the volatile matter phlegma of generation.
(39) preparation facilities of the ton aryloxy polymkeric substance according to any one of (23)-(38), the preparation facilities of described ton aryloxy polymkeric substance also comprises solvent, precipitation agent purification reclaiming system, described system comprises extraction tower, organic solvent purification tower and precipitation agent purification tower.
Phenoxy group base polymer of the present invention has diversified chemical structure.In some embodiments, aryloxy polymkeric substance is made up of following aryloxy repeated structural unit:
Wherein, for each structural unit, each Q
1be the one in following group all independently: halogen, the C of non-tertiary hydrocarbon base not replacing or replace
1-C
12alkyl, C
1-C
12sulfenyl, C
1-C
12-oxyl, C
2-C
12halo-oxyl and at least two, interval carbon atom between halogen and Sauerstoffatom.Each Q
2be the one in following group all independently: hydrogen atom, halogen, the C of non-tertiary hydrocarbon base not replacing or replace
1-C
12alkyl, C
1-C
12sulfenyl, C
1-C
12-oxyl, C
2-C
12halo-oxyl and at least two, interval carbon atom between halogen and Sauerstoffatom.Wherein, above-mentioned " alkyl " refers to all chemical structures be only made up of carbon and hydrogen.These chemical structures can be aliphatics or aromatic series, straight chain, side chain, ring, dicyclo, saturated and undersaturated structure.Meanwhile, also can be the combination of aliphatics, aromatic series, straight chain, straight chain, side chain, ring, dicyclo, saturated and unsaturation.But when " alkyl " refers in particular to the alkyl into replacing, the carbon on substituting group and hydrogen can be replaced arbitrarily by heteroatoms.Therefore, when specific be described as substituting group time, " alkyl " residue also can be one or more in carbonyl, amino, hydroxyl or similar group, or containing heteroatomic hydrocarbyl residue on skeleton.Give an example, Q
1can be di-n-butyl amino methyl, this group can be formed by di-n-butyl amine component reaction in 3,5-dimethyl-Isosorbide-5-Nitrae-phenylene end group and oxidative polymerization catalyst.
Aryloxy polymkeric substance is the monomer polymkeric substance that oxypolymerization obtains in polymer solvent under catalyst action.Monomer whose is at least a kind of monohydric phenol, may also be the combination with at least one binary or polyphenol.Catalyzer is made up of a metal ion species, amino ligands, can be obtained by metal ion and amino ligands reaction in－situ.Polymer solvent can be benzene, organic solvent, two organic solvents, three organic solvents, chlorobenzene, dichlorobenzene, chloroform or their mixture.In some case study on implementation, in polymer solvent, comprise organic solvent.Oxygen source can be purity oxygen or air.
The metal ion prepared in the catalyzer of aryloxy polymkeric substance is at least made up of a kind of heavy metal ion, as copper, manganese or cobalt.The source of catalyst metal ion is metal-salt, comprise cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, copper sulfate, sulfuric acid four ammino is cuprous, cupric tetramminosulfate, cuprous acetate, neutralized verdigris, propionic acid are cuprous, copper butyrate, lauric acid copper, hexadecanoic acid is cuprous and phenylformic acid is cuprous, and similar manganese salt and cobalt salt.Amino ligands suitable in catalyzer comprises dialkylamine (such as Di-n-Butyl Amine, DBA), trialkylamine (as N, N-dimethyl butylamine, DMBA), and alkyl diamine (as N, N '-di-tert-butyl quadrol, DBEDA).Directly add except the method for metal-salt except above-mentioned, another kind of feasible alternative method is reacted with mineral acid, organic acid or these aqueous acids at metal or metal oxide, and original position forms the metal-salt of correspondence or the hydrate of salt.
In some instances: aryloxy polymkeric substance (also can be described as herein " PAE ") comprises multiple aryloxy repeating units, preferably has the repeating unit of at least 50 formulas (I):
Wherein in each separate unit of described unit, each Z
1be hydrogen, halogen, alkyl (preferably containing reaching the primary of 7 carbon atoms or secondary alkyl), aryl (preferred phenyl), the halo alkyl (preferred haloalkyl) between halogen atom and the benzene nucleus of formula (I) with at least two carbon, aminoalkyl group,-oxyl or halo-oxyl independently, there are at least two carbon atoms to separate halogen and Sauerstoffatom in described halo-oxyl, and have at least two carbon atoms to separate the benzene nucleus of halogen atom and formula (I).
Each Z
2be hydrogen, halogen, alkyl (preferably containing reaching the primary of 7 carbon atoms or secondary alkyl), aryl (preferred phenyl), the halo alkyl (preferred haloalkyl) between halogen atom and the benzene nucleus of formula (I) with at least two carbon,-oxyl or halo-oxyl independently, there are at least two carbon atoms to separate halogen and Sauerstoffatom in described halo-oxyl, and have at least two carbon atoms to separate the benzene nucleus of halogen atom and formula (I).Each Z
1and Z
2aptly containing reaching 12 carbon atoms, modal, each Z
1for alkyl or phenyl, particularly C
1-C
4alkyl, and each Z
2hydrogen.
Term aryloxy polymkeric substance (polyarylether PAE) used in the present specification and claims comprises polyarylether polymer, polyarylether copolymer and their blend that unsubstituted polyarylether polymer, wherein aromatic ring are substituted.Also comprise and comprise in a known manner by the polyarylether polymer of the grafting materials of such as vinyl monomer or such as polystyrene and elastomeric polymkeric substance and so on prepared part to polyarylether, this is licensing to the U.S. Patent No. 5 of S.BruceBrown, 089, there is description in 566.In addition, also comprise the polyarylether polymer of coupling, coupling agent wherein such as low-molecular polycarbonate, quinones, heterocyclic and formal class to define the polymkeric substance of high molecular by the hydroxyl reaction in known method and two phenylate chains.Polyarylether polymer used in composition also can have multiple end group, and as contained end group and the 4-hydroxy diphenyl end group of aminoalkyl, these end groups are special introducing by oxidative coupling reaction.Polyarylether polymer can with terminal group functional or end-blocking, these end groups are that polymkeric substance adds larger reactivity, and additionally provide the consistency with other polymeric system in some cases, this polymeric system may be used for mixing mutually to form alloy or blend with polyphenylene ether polymer.Such as, polyarylether can with epoxy-terminated, phosphate end group or ortho ester (orthoester) terminal group functional, functionalized is by by functionalized reagent, as chloro-in 2-4 (2-diethyl phosphorus epoxy) 6-(2,4,6-trimethyl-phenoxy) (i.e. terminal hydroxy group) in-1,3,5-triazines (trizene) and polyarylether polymer end group carry out having reacted.
Obviously, according to foregoing, for the personnel understanding thoroughly art technology, can consider that the polyarylether polymer used comprises current all known polyarylethers, although its structural unit is diversified.Spendable suitable polyarylether polymer includes, but are not limited to gather (2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether); Poly-(2,3,6-trimethylammonium-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-diethyl-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2-methyl-6-propyl group-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-dipropyl-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2-ethyl-6-propyl group-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-dilauryl-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-phenylbenzene-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-dimethoxy-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2,6-diethoxy-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2-methoxyl group-6-oxyethyl group-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2-ethyl-6-octadecane Oxy-1,4-phenylene) ether; Poly-(the chloro-Isosorbide-5-Nitrae-phenylene of 2,6-bis-) ether; Poly-(2-methyl-6-phenyl-Isosorbide-5-Nitrae-phenylene) ether; Poly-(2-oxyethyl group-Isosorbide-5-Nitrae-phenylene) ether; Poly-(the chloro-Isosorbide-5-Nitrae-phenylene of 2-) ether; Poly-(the bromo-Isosorbide-5-Nitrae-phenylene of 2,6-bis-) ether; Poly-(bromo-2, the 6-dimethyl of 3--Isosorbide-5-Nitrae-phenylene) ether; Their mixture etc.Suitable multipolymer comprises the random copolymers containing 2,6-dimethyl-Isosorbide-5-Nitrae-phenylene ether units and 2,3,6-trimethylammonium-Isosorbide-5-Nitrae-phenylene ether units.
The limiting viscosity measured in the chloroform of 25 DEG C at aryloxy polymkeric substance disclosed by the invention is about be greater than 0.2-1.2dl/g, and its number-average molecular weight scope is about 3,000-60 usually, 000, the scope of weight-average molecular weight is 20,000-100,000, use gel permeation chromatography measurement.
The polyreaction of alkyl phenesic acid monomer by adding one or more phenol monomers and preferred copper-amine catalyst and carrying out in suitable reaction solvent.Preferably under cupric or cuprous salt-secondary amine catalyst such as cupric chloride and di-n-butyl amine exist, carry out polyreaction.Polyreaction is carried out ideally under inorganic base metal bromide or alkaline earth metal bromide exist.The consumption of inorganic bromide is every 100 mole of phenolic monomer is about 0.1 mole ~ about 150 moles.These catalystic materials are described in US Patent No. 3,733,299 (people such as Cooper).If needed, tetraalkylammonium salt also can be used as promotor.These promotors are disclosed in US Patent No. 3,988,297 (people such as Bennett).
The primary, secondary or tertiary amine component of catalyst complexes generally corresponds to US Patent No. 3,306,874 and 3,306,875 (Hay).Exemplary material comprises aliphatic amine, comprises aliphatic list and diamines, and wherein aliphatic group can be straight or branched hydrocarbon or alicyclic compound.Preferably aliphatic primary, secondary and tertiary monoamine and tertiary diamine.Especially preferred is single, two and three (rudimentary) alkylamine, and wherein alkyl has 1 ~ 6 carbon atom.Typically, can use list, two and trimethylammonium, ethyl, n-propyl, sec.-propyl, normal-butyl replace amine, list and dicyclohexylamine, ethylmethylamine, morpholine class, N-(rudimentary) alkyl cycloaliphatic amine such as N-methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propylene diamine, N, N, N '-trialkyl pentamethylene diamine etc.In addition, cyclic tertiary amine such as pyridine, α-collidine, γ-picoline etc. can be used.Be particularly useful be N, N, N ', N '-tetraalkyl quadrol, butanediamine etc.
The mixture of this type of primary, secondary and tertiary amine can be used.Preferred monoalkylamine is n-Butyl Amine 99; Preferred dialkylamine is Di-n-Butyl Amine; And preferred trialkylamine is triethylamine.Preferred cyclic tertiary amine is pyridine.In reaction mixture, the concentration of primary and secondary amine can change in wide region, but needs to add with lower concentration.The preferable range of non-tertiary amine is about 2.0 ~ about 25.0 moles/100 moles unit price phenol.When tertiary amine, preferred scope is wide in the extreme, and is about 0.2 ~ about 1500 mole/100 moles unit price phenol.In tertiary amine situation, if do not removed from reaction mixture by water, preferably use amine/100 moles of phenol of about 500 ~ about 1500 moles.If by water removing from reaction, the tertiary amine such as triethylamine or triethylamine/100 moles of phenol of about 10 moles is so only needed to be used as lower limit.Even can use tertiary diamine such as N, N, the N of small amount ', N '-tetraalkyl butanediamine, is low to moderate about 0.2 mole/100 moles of phenol downwards.
The exemplary being suitable for cuprous salt in described method and mantoquita is shown in Hay patent.These salt comprise that such as cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitride, cuprous sulfate tetramine, cuprous acetate, butyric acid are cuprous, organic solvent cuprous formate, cupric chloride, cupric bromide, copper sulfate, copper nitride, copper sulfate tetramine, venus crystals, copper butyrate, organic solvent Tubercuprose etc.Preferred cuprous salt and mantoquita comprise halogenide, alkanoate or vitriol, such as cuprous bromide and cuprous chloride, cupric bromide and cupric chloride, copper sulfate, cupric fluoride, cuprous acetate and venus crystals.When primary and secondary amine, the concentration of mantoquita needs to remain in low-level, preferably about 0.2 ~ 2.5mol/100mol unit price phenol.In tertiary amine situation, the preferable amount of mantoquita is about 0.2 ~ about 15mol/100mol unit price phenol.
For the preparation of copper-amine mixture catalyzer, copper halide is generally preferred than cuprous halide, this is because their lower costs.The use of copper (I) class also substantially increases the utilization ratio of oxygen in polyreaction commitment, and oxygen concn lower in reactor head space contributes to reducing the danger of catching fire or exploding in reactor.Preparation method and the use of suitable copper-amine catalyst appear at US Patent No. 3,900, in 445 (people such as Cooper).
Catalyst based the obtained very fast initial reaction rate of copper (I) is used also to cause the minimizing of the amount of the unwanted tetramethyl-phenylbenzene quinone of the less Cumulate Sum gained of unreacted monomer.Tetramethyl-phenylbenzene quinone (reverse dimer) be it is believed that and to be incorporated in PAE by balanced reaction.Balanced reaction causes the decline of the limiting viscosity of PAE, and this is because dimeric introducing makes the molecular weight and molecular weight of PAE.In oxidative coupling process, minimizing of tetramethyl-phenylbenzene quinone is needs, to avoid the decline of molecular weight and adjoint difficulty, described difficulty is to need to set up the molecular weight higher than molecular weight, to make up the loss in reverse dimeric equilibrium process.Unexpectedly find, the invention provides a kind of method, in the equilibrium step process wherein after the oxypolymerization of phenol monomer, limiting viscosity (I.V.) that the PAE in reaction mixture shows reduce be less than 10% low, preferably be less than 5%, be most preferably less than 3%.
Polyreaction is preferably carried out in a solvent.Suitable solvent is disclosed in above-mentioned Hay patent.Aromatic solvent such as benzene, organic solvent, ethylbenzene, two organic solvents and o-dichlorobenzene are especially preferred, although also can use tetrachloromethane, trichloromethane, methylene dichloride, 1,2-ethylene dichloride and trieline.The weight ratio of solvent and monomer normally 1: 1 ~ 20: 1, is namely up to 20 times of excessive solvents at the most.Solvent is preferably 1: 1 ~ 10: 1 (weight) with the ratio of monomer.
A beyond thought advantage of producing present method of low limiting viscosity PAE is, compared with producing the method for higher (i.e. > 0.28I.V.) PAE, high solid content is possible.(improve soltion viscosity simultaneous high-molecular weight polymer) when not improving soltion viscosity, final solids concn can improve at least 20%, and raising 30% or more is possible.So, when not improving reactor size and number, process provides a kind of method improving reactor utilization ratio and productive rate.Polymerization process and reaction conditions such as reaction times, temperature, oxygen flow velocity etc. are changed based on required accurate target molecular weight.Polymerization terminal uses online viscometer determining easily.Although other method also can be used such as to carry out molecular weight test, predetermined reaction time, the oxygen concn controlled in specified end group concentration or solution.
The temperature completing polymerization stage of the present invention is generally from about 0 DEG C ~ about 95 DEG C.More preferably, temperature range is from about 35 DEG C ~ about 45 DEG C, higher close to temperature of reaction during reaction end.At very high temperatures, side reaction occurs, and produces byproduct of reaction, in very low temperatures, forms ice crystal in solution.
Many different extraction agents or sequestrant practice used in the present invention, so that after polyreaction terminal and catalyst complex.Such as can use sulfuric acid, acetic acid, ammonium salt, bisul-phate and various sequestrant.When these materials are added in PAE reaction soln, copper-amine catalyst is poisoning, cannot further be oxidized.Many differing materials can be used, but preferably use and be disclosed in US Patent No. 3,838, those sequestrants in 102 people such as () Bennett.
Useful sequestrant comprises the compound containing polyfunctional carboxylic acids, such as sodium-potassium tartrate, nitrilotriacetic acid(NTA) (NTA), citric acid, Padil etc., especially preferably they are selected from the basic metal-alkaline earth salt of polyalkylene polyamine poly carboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, poly carboxylic acid and their basic metal, alkaline-earth metal or mixing.Preferred reagent comprises ethylenediamine tetraacetic acid (EDTA) (EDTA), HEDTA, diethylene triaminepentaacetic acid(DTPA) and their salt.Especially preferred be ethylidene diaminetetracetic acid or it is single, two, three and tetra-na salt, gained copper complex can be called as copper carboxylate title complex.
By using liquid/liquid whizzer, the metallic catalyst constituents of chelating can with the water extraction produced in polyreaction.Preferred is the aqueous solution of low-level chain triacontanol for the extraction liquid in the inventive method, i.e. water and the mixture of alkanol with 1 ~ about 4 carbon atom.Alkanol or the glycol of general about 1vol% ~ about 80vol% can be used.These ratios of the volume parts of liquid, aqueous extraction agent and discontinuous organic phase can change from about 0.01: 1 ~ about 10: 1 parts by volume.
Reaction medium generally comprises aqueous environment.Also anti-solvent (anti-solvent) can be used in conjunction with water-bearing media, to help the precipitation promoting copper (I) class material.The selection of suitable anti-solvent is based in part on the solubility factor of precipitated copper (I) class material.Halogenide is very not easily water-soluble, for the logK of CuCl, CuBr and CuI when 25 DEG C
[sp]value is-4,49 ,-8.23 and-11.96 respectively.Due to such as CuCl
2, CuCl
3and CuCl
4formation and there is excessive halide ions and due to other title complex, solubleness in water is increased.The non-limitative example of anti-solvent comprises low molecular weight alkyl and aromatic hydrocarbons, ketone, alcohols etc., and they itself have certain solubility in aqueous.If necessary, one skilled in the art can select the anti-solvent of suitable type and amount.
After removing catalyzer, the solution containing PAE is concentrated into higher solids content, and the part as PAE is separated.Use and be generally used for the precipitation that there is I.V. and be greater than the standard non-solvent technique (non-solventtechniques) of the PAE of 0.28dl/g, as the total part be separated, preferably a part of solvent of removing to reduce solvent on total separating device.Preferably improved the temperature of the solution containing PAE by the pressure reduced in solvent flash vessel simultaneously, realize the concentrated of the solution containing PAE.The pressure of about 35 ~ 50 bar is needs, and temperature of reaction is elevated at least 200 DEG C, preferably at least 230 DEG C.At least 55%, preferably the solids content PAE of at least 65% or higher is needs.
The preparation method of a kind of ton aryloxy polymkeric substance aryloxy polymkeric substance provided by the invention and device thereof, have following Advantageous Effects: 1) be first can the detonation of core workshop section in safety precaution flow process; 2) the primary amine fresh supplemented amount in amine mixture reduces by 50%; 3) organic solvent and precipitation agent reuse reach more than 95%, and quality product reaches high-level standard-required.
Accompanying drawing explanation
Fig. 1 is PAE process flow diagram.
Embodiment
Embodiment 1:
The monomer of polyreaction of the present invention is prepared by following technique:
Substituted phenol monomer is generated through gas phase catalytic reaction by phenols and alcohols alkylating agent.Reaction is carried out at shell and tube-type reactor.Filling porous MgO in each reactor tube.Shell-side melting salt takes away alkylated reaction institute liberated heat, and the basic material of reaction comprises fresh and phenols that is that recycle, alcohols alkylating agent etc.Reactor adds nitrogen for maintaining the pressure of reaction and Distallation systm, and reaction conditions is: 400-550 DEG C, 10-60psi pressure.The output object of reaction is mainly 2,6-xylenol and other alkylation phenolic product.
Reactor connects conventional distil-lation tower and realizes product separation.These liquid starting materials are by hot salt, deep fat heating evaporation, and product enters liquid condenser after leaving reactor, cooling, and (major part is 2 to phenolic, 6-xylenol, ortho-cresol, unreacted phenol), water and the unreacted precipitation agent of major part are condensed and enter product still.The gas produced in condenser mainly comprises CO, CO
2, methane, water vapor, H
2, sub-fraction alcohols alkylating agent.These gases be not condensed enter water suction tower to remove precipitation agent, and remaining tail gas is burnt (residual exhaust results from the incomplete decomposing of alcohols alkylating agent, represents the invalid rate of utilization of precipitation agent).The material of product still enters precipitation agent tower, and alcohols alkylating agent and water distillate from tower top, reuse.Phenols gas enters decanting vessel at the bottom of tower, and the inside mixed organic solvents is distinguished with the density improving water and organic solvent.Light phase (organic solvent and phenols) enters dehydration tower, and heavy phase realizes organic solvent and is separated after entering extraction tower, and reuse is to decanting vessel, and this part draining produced enters Sewage treatment systems.
Dehydration tower overhead contains the organic solvent (being used for extracting moisture) recycled, and bottom output object mainly phenols, for the charging of ortho-cresol tower, in this tower, light phase (ortho-cresol and phenol) is separated with heavy phase.Gently enter next distillation tower through a little storage tank.
Material enters phenol tower, and phenol distillates from tower top, and reuse is to phenol storage tank, and bottom materials is as the charging of ortho position tower, and ortho-cresol is sold as byproduct after obtaining purification here.Bottom ejecta is heavy phenols (2,6-xylenol, 2,4 mainly, 6-tri-cresols, 2,4-xylenol etc.), it is as 2, the charging of 6-xylenol purification column, 2,6-xylenol (more than 99.7%) distillates the resin raw material as polymerization technique from tower top.Bottom ejecta can distill further to reclaim 2,4,6-tri-cresols or 2,4-xylenol is sold as byproduct, or is used as the fuel of hot oil furnace.
The substituted phenol monomer obtained by this flow process can meet standard as following table:
Embodiment 2:
As shown in Figure 1, a kind of preparation method of ton aryloxy polymkeric substance aryloxy polymkeric substance, each technique detailed step is as follows.
(1) polyreaction
The preparation feedback of PAE is carry out under the condition of solvent at organic solvent by 2,6-xylenol, oxygen and catalyzer, and in the presence of oxygen, catalyzer can accelerate the coupling of monomer-polymer, and this process is called that oxidation coupling reacts.Amine mixture comprises: dialkylamine, Dialkylaminoethylamine, dialkyl group butylamine, morpholine.By the measurement of viscosity apparatus, when polymkeric substance has reached required molecular weight, stop oxygen supply.Obtain the organic solvent solution of PAE.Reacting amines mixture concentration is in organic solvent 20-40%, and the reaction times is 60-200 minute, and temperature of reaction is 10-95 DEG C.
(2) purification of polymkeric substance
1. chelating
Polymers soln in retort is added chelating agent solution in proportion to remove unreacted catalyzer.Mixing need flow process to provide the time to complete process that sequestrant (NTA, EDTA and composition thereof) consumes unreacted catalyzer.The ratio of sequestrant and solution is at 5-100 than 10000, and mixing time 5-100 minute, temperature is 20-95 DEG C
Polymkeric substance in storage tank is sent to continuous centrifuge and dewaters, and according to the density difference of catalyzer, water, sequestrant and polymkeric substance, is separated by centrifugal force.Polymers soln through purification is called as light phase, and catalyzer, water, sequestrant (NTA) are called as heavy phase.Gently enter pre-concentration storage tank mutually, heavy phase enters mud storage tank and is admitted to extraction tower.
2. extraction tower and mud storage tank
Extraction tower and mud storage tank are used to reclaim the organic amine heavy phase be separated the heavy phase produced from continuous centrifuge and enter extraction tower from mud storage tanks, heavy phase is deposited to bottom, and the solution containing organic solvent and organic amine organic solvent rises to top, spills into light phase storage tank.The light centrifuge that is back to mutually is in order to purification, and heavy phase enters heavy phase storage tank by gravitational settling.
3. copper recovery system
Heavy phase promotes and delivers to pressure filter from heavy phase storage tank, then adds NaSH and be precipitated out from heavy phase by copper, and filtering under pressure storage tank is used for storing heavy phase, progressively sends into pressure filter.Filter plate is in order to collect the copper mud of liquid, and filtrate (mainly water) enters Sewage treatment systems by strainer.The temperature of this step controls at 25-75 DEG C
4. pre-concentration
Preconcentration technique mainly removes organic solvent in centrifuge dehydration operation post-consumer polymer and water.Polymkeric substance enters pressurized heat interchanger from pre-concentration storage tank, and polymeric liquid is warming up to concrete temperature under a certain pressure.When liquid enters concentrated flashing tower, pressure reduces rapidly liquid is seethed with excitement again, and the top that now organic solvent and water rise to flashing tower in gaseous form enters cooling system, and remaining polymeric liquid is back to heat exchanger.Wholely operate in temperature 35-130 DEG C, carry out between 5-45PSI positive pressure and 100-600mmHG vacuum.
The light of flashing tower effusion carries out condensation by condenser, and phlegma enters into concentrated solution extraction tower, and in order to Separation of Water and organic solvent, organic solvent cyclically utilizing is to organic solvent storage tank, and water is promoted to mud storage tank.Pre-concentration vacuum unit provides vacuum to dodge the vapour pressure reducing polymers soln.This makes preconcentration technique to operate at low temperatures, to reduce corrosion.
(3) polymkeric substance extraction and isolation
1. storage tank is precipitated
The concentrated polymer that pre-concentration flashing tower produces enters and stirs precipitation storage tank.Concentrated polymer mixes liquid at precipitation storage tank and precipitation agent and carries out mixing and make polymkeric substance be precipitated as particulate polymers precipitating in storage tank to overflow, and enters continuous vacuum filter storage tank by gravitational settling.In this operation, charging maintains 150-1000L/min, and temperature at 15-65 DEG C, and maintains suitable positive pressure.
2. continous vacuum filters
Charging stock tank supply liquid/slurry polymkeric substance is to continuous vacuum filter.When being full of liquid slurry in continuous vacuum filter, by vacuumizing separated powder and all the other fluid operated temperature 20-65 DEG C, vacuum tightness 300-700mmHg.
3. product washing, purifying
Through the polymer powder of continuous vacuum filter by one or more levels agitator treating and being continuously separated.Mainly remove and run introducing and secondary multiple organic and inorganic impurity from monomer and polymerization, improve quality.First with No. 3 masterbatch enter No. 1 serum storage tank in the lump and form circulation loop.The slurries carrying out self circular loop enter two-stage centrifugal.Two-stage centrifugal utilizes PAE powder to be separated with the difference of fluid density.PAE pruinescence reclaims precipitation agent flushing and enters No. 2 serum pots to a skewed slot.Parting liquid, No. 2 materials enter No. 2 material pots by gravity settling so that carry out reuse in No. 1 precipitation storage tank.Precipitation agent PAE slurries in No. 2 serum pots enter circulation loop by pump, and the raw material of each centrifugal drying system is all from No. 2 serum recycle loops.Powder enters drying machine finally by skewed slot and carries out drying.Whole operation holding temperature 15-65 DEG C,
4. drying machine feeding system and drying machine
Product wet feed powder is delivered to the import of drying machine feeding system by worm conveyor by the feed of drying machine, and PAE powder is separated with liquid with chuck heating by using the dry axle of the spiral of band blade by drying machine.The blade of screw shaft is by product to the conveying of drying machine bottom, and dried product is transported to drying machine front portion by a rotation lock, then enters through the whole service temperature of gas delivery system at 45-250 DEG C, charging 10-800L/min..
5. drying machine exhaust system
The steam of moisture eliminator and rare gas element are sent to drying machine washer, and the particulate matter in steam removed by precipitation agent, and then precipitation agent and PAE powder deliver to serum pot.From the nitrogen of drying machine washer through drying machine condenser, phlegma enters drying machine condensate tank, No. 2 material pots of then pumping.
Enter water wash column by gas remaining after drying machine condenser, gas enters first step washing tower, by water condensation.Any remaining gas enters second stage washing tower, and phlegma enters extraction tower by washing tower by pumping.
Remaining gas is admitted to by glycol condenser, and enter drying machine condensate tank after precipitation agent organic solvent is condensed, after passing through from glycol condenser, gas is sent to mist eliminator, forms drop and enters drying machine condensate tank.Last gas and steam enter isolation washing tower and nitrogen recycling system respectively.
6. PAE delivery system
PAE is delivered to feed bin from drying machine outlet by PAE dry powder transmission system.The product powder that drying machine is discharged delivers to sack cleaner by powder cooler.Nitrogen is separated with product powder by sack cleaner, and nitrogen is back to gas blower, and powder falls bottom, rotates locking-valve enter little funnel by one.Product powder enters into product feed bin by a similar rotation locking-valve by blast system.
(4) solvent recuperation
1. extract
The mixed solution produced from precipitation and washing unit enters primary separation tower, and adds water at organic solvent and precipitant mix thing, and the density of the precipitation agent aqueous solution is comparatively large, and bottom extraction tower, and organic solvent is on top.The aqueous solution of precipitation agent is promoted to precipitation agent purification precipitation agent recovery system by pump bottom extraction tower, and organic solvent delivers to its recovery system of organic solvent from top of tower.
2. organic solvent purification reclaiming system
The main material of recovery system for organic solvent is the organic solvent containing microprecipitation agent, water and oligodynamical PAE, from the material of extraction tower by entering the near top of organic solvent tower after the heat exchanger of a group, rise to organic solvent top of tower after the mixture evaporation of precipitation agent and water, and organic solvent flows at the bottom of tower through column plate.
The mixing steam of precipitation agent and water enters inner storage tank through condenser, and being then pumped can extraction tower, and organic solvent at the bottom of organic solvent tower and solid substance are sent to vaporizer.Circulation loop is formed after organic solvent in vaporizer and solid substance are heated by reboiler.
Organic solvent in organic solvent storage tank through supercooler laggard enter organic solvent withdrawing can.
Solid substance in vaporizer and impurity remove organic solvent by enrichment, and the solid substance after enrichment and impurity are sent to fuel reservoir.Organic solvent purification system runs under 0-90 DEG C and high vacuum condition.
3. precipitation agent purification reclaiming system
The main material of precipitation agent recovery system is precipitation agent and water.Material is sent to precipitation agent tower from extraction tower, needs through one group of heat exchanger before entering precipitation agent tower.The material of precipitation agent tower forms circulation loop by reboiler, and precipitation agent forms steam and rises to precipitation agent top of tower in tower, is condensed after effusion, and phlegma enters precipitation agent storage tank.Part precipitation agent phlegma returns to precipitation agent tower with temperature in adjusting tower, and remaining precipitation agent is delivered to precipitation agent and reclaimed storage tank.
The polymkeric substance prepared by above-mentioned ton PAE technique meets listed in Table:
Embodiment 3
A preparation facilities for ton aryloxy polymkeric substance aryloxy polymkeric substance, comprises reactor, except catalyst-assembly, and pre-concentration device, precipitation, filtration unit, washing purifying device, drying installation.
1) described reactor is provided with oxygen intake and oxygen level monitor, and whipping appts, outer circulating tube shell heat exchanger and recycle pump etc., described tube and shell heat exchanger has the effect of heating and cooling, wherein: the volume of reactor is 20-75m
3, design pressure is less than 50kg/cm
2, the total heat interchanging area 100-800m of outer circulating tube shell heat exchanger
2, the flow of recycle pump be 100-1000 ton/hour
2) described catalyzer removal device comprises sequestrant charging system, continuous centrifuge, extraction tower and catalyst metal recovery system.Polymers soln is separated with catalyzer, water, sequestrant by described continuous centrifuge; Described catalyst metal recovery system comprises pressure filter, by being provided with filter plate in described pressure filter, and collection catalyst metal sludge.Wherein: continuous centrifuge maximum temperature 250 DEG C, maximum speed of revolution lower than 8000rpm, flow 1-100m
3/ hr
3) described pre-concentration device comprises concentrated flashing tower, and described concentrated flashing tower is provided with heat exchanger and pre-concentration vacuum unit.Wherein, concentrated flashing tower volume 1-15m
3, temperature is lower than 300 DEG C, and pressure is at vacuum and 20kg/cm
2between heat exchanger heat interchanging area 50-350m
2, temperature 100-350 DEG C.
4) described precipitation, filtration unit comprise stirring stillpot and continuous filter, and described filter is provided with vacuum extractor, wherein stir stillpot volume at 1-10m
3, mixing speed at 25-350rpm, continuous filter flow 10-100m
3/ hr, temperature 10-200 DEG C.
5) described product washing purifying device comprises agitator treating still, continuous centrifuge takes off liquid device.Wherein agitator treating kettle amasss at 1-10m
3, mixing speed is at 25-350rpm, and continuous centrifuge takes off liquid device flow 5-200m
3/ hr, temperature 10-200 DEG C.
6) described drying installation comprises moisture eliminator, and described moisture eliminator is provided with the dry axle of spiral of band blade.Temperature 50-250 DEG C, flow 1-20 ton/hour
7) preparation facilities of described ton aryloxy polymkeric substance aryloxy polymkeric substance also comprises solvent, precipitation agent purification reclaiming system, described system comprises initial gross separation (extraction) tower, organic solvent purification tower recovery system and precipitation agent purification tower recovery system, by initial gross separation (extraction) tower, organic solvent is separated with precipitation agent, reclaim organic solvent by recovery system for organic solvent, reclaim precipitation agent by precipitation agent recovery system.Wherein: initial gross separation (extraction) tower body amasss 50-250M
3, temperature 80-200 DEG C.
Above-described embodiment is not the exhaustive of embodiment; also can there is other embodiment; above-described embodiment object is the present invention is described, but not limits the scope of the invention, and all application come by simple change of the present invention all drop in protection scope of the present invention.
This patent specification use-case goes to show the present invention, comprising optimal mode, and those of ordinary skill in the art is manufactured and uses the present invention.This invents the content that delegatable scope comprises embodiment in the content of claims and specification sheets and other embodiment.These other examples also should belong to the scope of claims of the present invention, as long as they contain the technical characteristic described by the identical written language of claim, or they include with claim without essence difference similar literal language described by technical characteristic.
All patents, the full content of patent application and other reference should be incorporated to present specification by reference.But if a term in the application conflicts mutually with the term including reference in, preferential with the term of the application.
All scopes disclosed herein all comprise end points, and are combine independently of one another between end points.
It should be noted that " first ", " second " or similar vocabulary do not represent any order, quality or importance, are only used to distinguish different technical characteristics.The qualifier " approximately " used in conjunction with quantity comprises the implication that described value and content context are specified.(such as: it includes error when measuring specific quantity).
Claims (31)
1. a preparation method for ton aryloxy polymkeric substance, is characterized in that, comprises the following steps:
A. under the condition of organic solvent, oxidative coupling polymerization reaction is carried out by alkyl phenesic acid monomer, oxygen and catalyzer;
B. catalyzer is removed;
C. pre-concentration;
D. precipitate, filter;
E. product washing, purifying;
F. dry.
2. the preparation method of ton aryloxy polymkeric substance according to claim 1, is characterized in that, described alkyl phenesic acid monomer meets the combination of following arbitrary index or any two and above index:
The purity > 99.5% of 2,6-xylenol;
Total methyl-phenoxide < 0.15%;
Total cresols < 0.15%;
Other xylenols < 0.010%;
Phenol < 0.010%;
Other alkylphenols < 0.15%;
Other organic impuritys < 0.10%;
Colourity < 110;
Moisture < 1500ppm.
3. the preparation method of ton aryloxy polymkeric substance according to claim 1, is characterized in that, described catalyzer is copper-amine mixture, wherein: amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
4. the preparation method of ton aryloxy polymkeric substance according to claim 3, it is characterized in that, described copper-amine mixture comprises copper and is selected from following arbitrary organic amine and arbitrary combination thereof: primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein the mol ratio of amine mixture and copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
5. the preparation method of ton aryloxy polymkeric substance according to claim 4, it is characterized in that, amine mixture comprises aliphatic amine, and described aliphatic amine comprises aliphatic list and diamines, and wherein aliphatic group is straight or branched hydrocarbon or alicyclic compound; Described aliphatic amine is aliphatic series uncle monoamine, aliphatic secondary monoamine, aliphatic tertiary monoamine or aliphatic tertiary diamine; Or described aliphatic amine is single, two and three (rudimentary) alkylamine, and wherein alkyl has 1 ~ 6 carbon atom; Or described aliphatic amine be can use list, two and trimethylammonium, ethyl, n-propyl, sec.-propyl, normal-butyl replace amine; Or described aliphatic amine is single and dicyclohexylamine, ethylmethylamine, morpholine class, N-(rudimentary) alkyl cycloaliphatic amine such as N-methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propylene diamine, N, N, N '-trialkyl pentamethylene diamine; Or described aliphatic amine is cyclic tertiary amine, described cyclic tertiary amine is pyridine, α-collidine, γ-picoline.
6. the preparation method of ton aryloxy polymkeric substance according to claim 1, it is characterized in that, in oxidative coupling reaction, basic material is with semicontinuous batch fed, described basic material is alkyl phenesic acid and oxygen, and other components are all added in reactor in full batch mode prior to basic material; The reaction conditions of described oxidative coupling reaction meets the combination of following arbitrary index or any two and above index: temperature 5-70 DEG C, pressure 0-5psi above reactor, oxygen partial pressure 0-25%, oxygen feeding 0-425m above reactor
3/ hr, reactor outer circulation pumping head 10-100psi, reaction times 0-250 minute.
7. the preparation method of ton aryloxy polymkeric substance according to claim 1, is characterized in that, described b step is removed catalyzer and comprised chelating, de-organic phase, extraction and/or catalyst metal recycling step.
8. the preparation method of ton aryloxy polymkeric substance according to claim 7, it is characterized in that, sequestrant is added to remove the catalyst metal being polymerized and adding in described chelation step, wherein sequestrant comprises: sodium-potassium tartrate, nitrilotriacetic acid(NTA), citric acid, Padil, the basic metal-alkaline earth salt of polyalkylene polyamine poly carboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, aminopolycanboxylic acid, aminocarboxylic acid, poly carboxylic acid and their basic metal, alkaline-earth metal or mixing; Or sequestrant comprises: ethylenediamine tetraacetic acid (EDTA), HEDTA, diethylene triaminepentaacetic acid(DTPA) and their salt.
9. the preparation method of ton aryloxy polymkeric substance according to claim 7, is characterized in that, by described de-organic phase step by the organic solution containing reaction product polymer and the aqueous phase separation containing catalyzer, sequestrant.
10. the preparation method of ton aryloxy polymkeric substance according to claim 7, it is characterized in that, described extraction step, for extracting described catalyzer, water and chelant mix in extraction tower, by organic solvent and organic amine from above-mentioned aqueous phase separation out and reuse, organic phase is organic solvent is light phase, and all the other aqueous phases become heavy phase.
The preparation method of 11. ton aryloxy polymkeric substance according to claim 7, is characterized in that, copper to be precipitated out then to deliver to pressure filter for adding metallic sulfide by described copper recycling step from heavy phase.
The preparation method of 12. ton aryloxy polymkeric substance according to claim 1, it is characterized in that, described step c pre-concentration carries out in pre-concentration flashing tower, organic solvent in part removal product polymer solution and water, obtain the concentrated polymer solution that weight concentration is 20-60%, wherein, the operation of flash distillation carries out between temperature 200 DEG C and 45 DEG C.
The preparation method of 13. ton aryloxy polymkeric substance according to claim 1, it is characterized in that, in described steps d precipitation, filtration, become the polymkeric substance of liquid pulpous state state by precipitating described concentrated polymer, and obtain polymer powder filter cake by the polymkeric substance of continuous filtration liquid pulpous state state.
The preparation method of 14. ton aryloxy polymkeric substance according to claim 1, it is characterized in that, described step e product washing, purifying is the impurity removed by the washing of one or more levels precipitation agent and centrifugation in product, wherein, washing, purifying operation carries out between temperature 15 DEG C to 110 DEG C.
The preparation method of 15. ton aryloxy polymkeric substance according to claim 1, it is characterized in that, by described step f dry aryloxy polymer powder and liquid carried out being separated obtain the finished product aryloxy polymkeric substance, wherein, the combination that drying process meets at least following arbitrary or any two and above condition is as follows: drying temperature is between 15 DEG C to 100 DEG C, total system carries out in the inert gas environment of circulation closed, and flow process reuse sent into by the volatile matter phlegma of generation.
The preparation method of 16. ton aryloxy polymkeric substance according to claim 15, is characterized in that, the combination that described aryloxy polymkeric substance meets following arbitrary or any two and above standard is as follows:
Inherent viscosity and product summary maximum deviation < 5.0ml/g,
After heat treatment inherent viscosity increases < 208ml/g, and described thermal treatment temp is 285 DEG C, and the time is 4 minutes;
Organic amine residual concentration < 5%;
Copper ion concentration < 15ppm;
Fugitive constituent < 1.5%;
Polymerization organic solvent residual concentration < 300ppm;
Other organic impurity summation < 500ppm, other organic impurity described comprises 2,4,6-tri-cresols, Dihydrobenzofuranes, 2,6-dimethylcyclohexanon and 7-methyl-2,3-Dihydrobenzofuranes;
Bulk powder density > 0.25kg/L;
Fine powder content < 35%, particle diameter < 38 order of described fine powder;
Meal content < 70%, particle diameter > 710 order of described meal;
Powder flowing index > 50, powder flowing index is after gas is risen and initially piles up the volume ratio of powder.
The preparation method of 17. ton aryloxy polymkeric substance according to any one of claim 1-16, it is characterized in that, also comprise solvent and precipitation agent purification reuse step, described purification reuse step comprise by extraction organic solvent is separated with precipitation agent, by organic solvent purification system reuse organic solvent, by precipitation agent purification system reuse precipitation agent.
The preparation facilities of 18. 1 kinds of ton aryloxy polymkeric substance, is characterized in that, comprise polymeric kettle, catalyzer removal device, pre-concentration device, precipitation, filtration unit, product washing purifying device, drying installation.
The preparation facilities of 19. ton aryloxy polymkeric substance according to claim 18, is characterized in that, in described polymeric kettle, carries out oxidative coupling polymerization reaction by alkyl phenesic acid monomer, oxygen and catalyzer under the condition of organic solvent.
The preparation facilities of 20. ton aryloxy polymkeric substance according to claim 19, is characterized in that, catalyzer is copper-amine mixture, wherein: amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
The preparation facilities of 21. ton aryloxy polymkeric substance according to claim 20, it is characterized in that, described copper-amine mixture comprises copper and is selected from following arbitrary organic amine and arbitrary combination thereof: primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein the mol ratio of amine mixture and copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
The preparation facilities of 22. ton aryloxy polymkeric substance according to claim 21, it is characterized in that, amine mixture comprises aliphatic amine, and described aliphatic amine comprises aliphatic list and diamines, and wherein aliphatic group is straight or branched hydrocarbon or alicyclic compound; Described aliphatic amine is aliphatic series uncle monoamine, aliphatic secondary monoamine, aliphatic tertiary monoamine or aliphatic tertiary diamine; Or described aliphatic amine is single, two and three (rudimentary) alkylamine, and wherein alkyl has 1 ~ 6 carbon atom; Or described aliphatic amine be can use list, two and trimethylammonium, ethyl, n-propyl, sec.-propyl, normal-butyl replace amine; Or described aliphatic amine is single and dicyclohexylamine, ethylmethylamine, morpholine class, N-(rudimentary) alkyl cycloaliphatic amine such as N-methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propylene diamine, N, N, N '-trialkyl pentamethylene diamine; Or described aliphatic amine is cyclic tertiary amine, described cyclic tertiary amine is pyridine, α-collidine, γ-picoline.
The preparation facilities of 23. ton aryloxy polymkeric substance according to claim 19, it is characterized in that, in oxidative coupling reaction, basic material is with semicontinuous batch fed, described basic material is alkyl phenesic acid and oxygen, and other components are all added in reactor in full batch mode prior to basic material; The reaction conditions of described oxidative coupling reaction meets the combination of following arbitrary index or any two and above index: temperature 5-70 DEG C, pressure 0-5psi above reactor, oxygen partial pressure 0-25%, oxygen feeding 0-425m above reactor
3/ hr, reactor outer circulation pumping head 10-100psi, reaction times 0-250 minute.
The preparation facilities of 24. ton aryloxy polymkeric substance according to claim 18, it is characterized in that, the volume of described reactor is 15 to 100m
3be provided with oxygen intake, the heat-exchange system of agitator, tube and shell heat exchanger and outer circulation pump composition.
The preparation facilities of 25. ton aryloxy polymkeric substance according to claim 18, it is characterized in that, described catalyzer removal device comprises storage tank, continuous centrifuge and catalyst metal recovery system; In described storage tank, add sequestrant remove unreacted catalyzer; By described whizzer, the organic solution of polymkeric substance is separated with catalyzer, water, sequestrant; Described copper recovery system comprises pressure filter, by being provided with filter plate in described pressure filter, collects copper mud.
The preparation facilities of 26. ton aryloxy polymkeric substance according to claim 18, it is characterized in that, described pre-concentration device comprises concentrated flashing tower, and described concentrated flashing tower is provided with heat exchanger and pre-concentration vacuum unit.
The preparation facilities of 27. ton aryloxy polymkeric substance according to claim 18, is characterized in that, described precipitation, filtration unit comprise stirring settler and continuous filter, and described continuous filter is provided with vacuum extractor.
The preparation facilities of 28. ton aryloxy polymkeric substance according to claim 18, it is characterized in that, described washing purifying device comprises one or more levels agitator treating and solid-liquid continuous separation device.
The preparation facilities of 29. ton aryloxy polymkeric substance according to claim 18, it is characterized in that, described drying installation comprises successive drying system, described dehumidification system is provided with following arbitrary heat-exchanger rig or arbitrary combination: chuck, internal circulation heat-exchanging, and external circulation heat exchanging.
The preparation facilities of 30. ton aryloxy polymkeric substance according to claim 29, it is characterized in that, the combination that drying process in described drying installation meets at least following arbitrary or any two and above condition is as follows: drying temperature is between 15 DEG C to 100 DEG C, total system carries out in the inert gas environment of circulation closed, and flow process reuse directly sent into by the volatile matter phlegma of generation.
The preparation facilities of 31. ton aryloxy polymkeric substance according to any one of claim 18-30, it is characterized in that, the preparation facilities of described ton aryloxy polymkeric substance also comprises solvent, precipitation agent purification reclaiming system, described system comprises extraction tower, organic solvent purification tower and precipitation agent purification tower.
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| CN112111057A (en) * | 2019-06-20 | 2020-12-22 | 南通星辰合成材料有限公司 | Polyphenylene ether and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113493565B (en) * | 2020-04-02 | 2024-01-26 | 上海孛柯博科技有限公司 | Polyphenylene oxide, preparation method thereof and device for producing polyphenylene oxide |
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| CN105295026B (en) | 2018-09-18 |
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