CN105295026B - A kind of preparation method and its device of 10,000 tons aryloxy group polymer - Google Patents
A kind of preparation method and its device of 10,000 tons aryloxy group polymer Download PDFInfo
- Publication number
- CN105295026B CN105295026B CN201510622177.XA CN201510622177A CN105295026B CN 105295026 B CN105295026 B CN 105295026B CN 201510622177 A CN201510622177 A CN 201510622177A CN 105295026 B CN105295026 B CN 105295026B
- Authority
- CN
- China
- Prior art keywords
- amine
- aryloxy group
- tons
- organic solvent
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 136
- 125000004104 aryloxy group Chemical group 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 239000003960 organic solvent Substances 0.000 claims abstract description 72
- 230000001376 precipitating effect Effects 0.000 claims abstract description 53
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 150000001412 amines Chemical class 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 238000004094 preconcentration Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 14
- 150000003141 primary amines Chemical class 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- -1 alkyl phenols Chemical class 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 239000002738 chelating agent Substances 0.000 claims description 21
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 125000001931 aliphatic group Chemical group 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000000345 2,6-xylenols Chemical class 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 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
- 150000004985 diamines Chemical class 0.000 claims description 9
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003335 secondary amines Chemical class 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- KNCHDRLWPAKSII-UHFFFAOYSA-N 4-ethyl-2-methylpyridine Chemical compound CCC1=CC=NC(C)=C1 KNCHDRLWPAKSII-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
- JHIDGGPPGFZMES-UHFFFAOYSA-N acetic acid;n-(2-aminoethyl)hydroxylamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNO JHIDGGPPGFZMES-UHFFFAOYSA-N 0.000 claims description 3
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001342 alkaline earth 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007701 flash-distillation Methods 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 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
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- 150000003739 xylenols Chemical class 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 238000005474 detonation Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 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 18
- 238000011084 recovery Methods 0.000 description 14
- 229920000090 poly(aryl ether) Polymers 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 210000002966 serum Anatomy 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 239000006227 byproduct Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001816 cooling Methods 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
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000470 constituent Substances 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-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
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 2
- 150000000342 2,4-xylenols Chemical class 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- 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 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 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
- 239000000539 dimer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 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 class ClCCCl WSLDOOZREJYCGB-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
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 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
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 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
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 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
- 239000007810 chemical reaction solvent Substances 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
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-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
- 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
- BJYLNGGDLHKELP-UHFFFAOYSA-N copper;formic acid Chemical compound [Cu].OC=O BJYLNGGDLHKELP-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal 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
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 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
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 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
- 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- KGHYGBGIWLNFAV-UHFFFAOYSA-N n,n'-ditert-butylethane-1,2-diamine Chemical compound CC(C)(C)NCCNC(C)(C)C KGHYGBGIWLNFAV-UHFFFAOYSA-N 0.000 description 1
- 150000003941 n-butylamines Chemical group 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
- 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
- 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
- 238000000710 polymer precipitation Methods 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
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000005086 pumping Methods 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
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 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
- 230000007115 recruitment Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 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
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-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
Abstract
The present invention relates to a kind of preparation method and its device of 10,000 tons aryloxy group polymer, the method at least includes the following steps：A. oxidative coupling reaction is carried out in organic solvent by alkyl phenesic acid, oxygen and catalyst；B. catalyst removes；C. pre-concentration；D. resin precipitated filters；E. product washing, purifying；F. it dries；Described device includes at least reaction kettle, removes catalyst-assembly, pre-concentration device, resin precipitated device, washing purifying device, drying device.The preparation method and its device of a kind of 10,000 tons aryloxy group polymer aryloxy group polymer provided by the invention have following advantageous effects：It 1) can be with the detonation of core workshop section in safety precaution flow；2) the primary amine fresh supplemented amount in amine mixture reduces by 50%；3) up to 95% or more, product quality reaches high-level standard requirement for organic solvent and precipitating reagent reuse.
Description
Technical field
The present invention relates to a kind of preparation methods and its device of aryloxy group polymer, and in particular to a kind of 10,000 tons aryloxy group
The preparation method and its device of polymer.
Background technology
Aryloxy group polymer aryloxy group polymer, also referred to as polyarylether (abbreviation PAE) have industrialized for a long time.The U.S.
Patent US3,733,299 (Cooper et al.).United States Patent (USP) US3,988,297 (Bennett et al.) and United States Patent (USP) US3,
306,874 and 3,306,875 (Hay) are described.Currently, the requirement of safety in production, environmental protection and products application etc.
Requirements at the higher level are proposed to the prior art.The precise controlling of polymerization process, firing in whole process are embodied in terms of safety in production
Protection；It is embodied in terms of environmental protection：" zero-emission " of waste catalyst metal, the total system reuse of chemically non-reactive charging.
These requirements especially propose new demand to the industrialization producing line for producing 10,000 tons per year..
Invention content
To solve the above new problem, the present invention provides a kind of preparation method and its device of 10,000 tons aryloxy group polymer,
PAE polymer is by alkyl phenesic acid and O2It is produced by semi-batch, oxidative coupling reaction, O2Into reactor, heating and cooling
It is to be completed by chuck and outer circulating tube shell heat exchanger, and be formed into a loop by installing pump.Basic material (2,6- xylenols and
O2) with semicontinuous batch fed, other components are added to prior to basic material in reactor in a manner of full batch.In the reaction phase
Between, 2,6- xylenols are converted into PAE and water, and heat release by consuming certain oxygen.Unreacted oxygen is escaped from liquid surface,
It is diluted by the nitrogen of reactor head.A kind of chemical balance process of complexity controls the operating of reactor, in initially reactor
Portion is filled with：Organic solvent organic reaction solvent, Cu/ organic amine mixture catalyst, by the reaction of 2 hours, polymerizable molecular
It is gradually formed with the consumption of oxygen, corresponding stickiness is reduced with the raising of temperature.
After oxidative coupling reaction is completed, a kind of copper chelator is added in the reactive mixture, you can in continuous separating machine
It is middle to detach light phase (organic copper) and heavy phase (hydration copper).By vacuum flashing system, the moisture content of liquid is down to 60%, flash distillation
The organic solvent reuse distillated at the top of device is continuously added precipitating reagent in the polymer solution by increasing concentration, forms polymer
Precipitation and solid-liquid mud.Mud is sent to liquid-solid filter, and constantly carry out multistage with precipitating reagent rinses again, subsequently into drying
Centrifuge.Polymer powder feeding is warehouse style, and the mixture of organic solvent/precipitating reagent enters recovery system precipitating reagent organic solvent
Purifies and separates, reuse to whole flow process.
The present invention recycles catalyst metals, whole process in 10,000 tons flow to monomer purity, polymerization technique control parameter
Reuse solvent and precipitating reagent, separation product and washing, purifying improve product quality etc. synthetic innovation, propose fully integrated
Industrial producing line flow.Specifically adopt the following technical scheme that：
(1) a kind of preparation method of 10,000 tons aryloxy group polymer, includes the following steps：
A. it is anti-that oxidative coupling polymerization is carried out under conditions of organic solvent by alkyl phenesic acid monomer, oxygen and catalyst
It answers；
B. catalyst is removed；
C. pre-concentration；
D. it precipitates, filter；
E. product washing, purifying；
F. it dries.
(2) according to the preparation method of the 10,000 tons aryloxy group polymer described in (1), the alkyl phenesic acid monomer meets
The combination of following any index or any two and the above index：
The purity ＞ 99.5% of 2,6- xylenols；
Total methyl phenyl ethers anisole ＜ 0.15%；
Total cresols ＜ 0.15%；
Other xylenols ＜ 0.010%；
Phenol ＜ 0.010%；
Other alkyl phenols ＜ 0.15%；
Other organic impurities ＜ 0.10%；
Coloration ＜ 110；
Moisture ＜ 1500ppm.
(3) according to the preparation method of the 10,000 tons aryloxy group polymer described in (1) or (2), it is preferred that the alkyl two takes
Meet the combination of following any index or any two and the above index for phenol monomer：
The purity ＞ 99.8% of 2,6- xylenols；
Total methyl phenyl ethers anisole ＜ 0.010%；
Total cresols ＜ 0.10%；
Other xylenols ＜ 0.055%；
Phenol ＜ 0.005%；
Other alkyl phenols ＜ 0.10%；
Other organic impurities ＜ 0.05%；
Coloration ＜ 85；
Moisture ＜ 500ppm.
(4) according to the preparation method of (1)-(3) any one of them 10,000 tons aryloxy group polymer, the catalyst is
Copper-amine mixture, wherein：Amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
(5) according to the preparation method of (1)-(4) any one of them 10,000 tons aryloxy group polymer, it is preferred that the amine
Mixture is the 10%-40% of alkyl phenesic acid monomer weight.
(6) according to the preparation method of (1)-(5) any one of them 10,000 tons aryloxy group polymer, the copper-amine mixture
Including copper and selected from following any organic amine and its arbitrary combination：Primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein amine mixture and
The molar ratio of copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
(7) according to the preparation method of (1)-(6) any one of them 10,000 tons aryloxy group polymer, it is preferred that amine mixture
Molar ratio with copper is 5-40, and amine mixture is the 10-40% of organic solvent weight.
(8) according to the preparation method of (1)-(7) any one of them 10,000 tons aryloxy group polymer, the amine mixture includes
Aliphatic amine, the aliphatic amine include aliphatic list and diamines, and wherein aliphatic group can be linear chain or branched chain hydrocarbon or alicyclic chemical combination
Object.The preferred aliphatic amine is aliphatic primary, secondary and tertiary monoamine or tertiary diamine.The preferred aliphatic amine be mono-, di- and
Three (rudimentary) alkylamines, wherein alkyl have 1~6 carbon atom.The most preferred aliphatic amine is mono-, di- and trimethyl, second
Base, n-propyl, isopropyl, the amine of normal-butyl substitution or the aliphatic amine be single and dicyclohexylamine, ethylmethylamine,
Quinoline class, N- (rudimentary) alkyl cycloaliphatic amine such as N- methylcyclohexyls amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group the third two
Amine, N, N, N '-trialkyl pentanediamine；Or the aliphatic amine be cyclic tertiary amine, the cyclic tertiary amine be pyridine, α-collidine,
γ-picoline.
(9) according to the preparation method of (1)-(8) any one of them 10,000 tons aryloxy group polymer, in oxidative coupling reaction
Middle basic material is alkyl phenesic acid and oxygen with semicontinuous batch fed, the basic material, and other components to criticize entirely
Formula mode is added to prior to basic material in reactor.
(10) according to the preparation method of (1)-(9) any one of them 10,000 tons aryloxy group polymer, the oxidative coupling
The reaction condition of reaction meets the combination of following any index or any two and the above index：5-70 DEG C of temperature, on reaction kettle
Square pressure 0-5psi, reaction kettle top oxygen partial pressure 0-25%, oxygen feeding 0-425m3/ hr, reaction kettle outer circulation pump head
10-100psi, reaction time 0-250 minute.
(11) according to the preparation method of (1)-(10) any one of them 10,000 tons aryloxy group polymer, the b step is urged
Agent removal includes chelating, de- organic phase, extraction and/or catalyst metals recycling step.
(12) it according to the preparation method of (1)-(11) any one of them 10,000 tons aryloxy group polymer, is walked in the chelating
Chelating agent is added in rapid to remove the catalyst metals that polymerization is added, wherein chelating agent includes：Potassium sodium tartrate, three second of nitrilo-
Acid, citric acid, amion acetic acid, polyalkylene polyamine polycarboxylic acid, aminopolycanboxylic acid, amino carboxylic acid, aminopolycanboxylic acid, aminocarboxylic
Acid, polycarboxylic acid and their alkali metal, alkaline-earth metal or mixed alkali metal-alkali salt include preferably：Ethylenediamine tetraacetic
Acetic acid (EDTA), hydroxyethylenediamine triacetic acid, diethylene-triamine pentaacetic acid and their salt.
(13) according to the preparation method of (1)-(12) any one of them 10,000 tons aryloxy group polymer, have by described take off
Machine phase step is by the organic solution containing reaction product polymer and the aqueous phase separation containing catalyst, chelating agent.
(14) according to the preparation method of (1)-(13) any one of them 10,000 tons aryloxy group polymer, the extraction step
Suddenly, it is to be extracted to the catalyst, water and chelant mix in extraction tower, by organic solvent and organic amine from upper
It states aqueous phase separation out and reuse organic phase be organic solvent is light phase, remaining water phase becomes heavy phase.
(15) according to the preparation method of (1)-(14) any one of them 10,000 tons aryloxy group polymer, the copper recycling step
Rapid be precipitated out copper from heavy phase for addition metal sulfide is then sent to filter press.
(16) according to the preparation method of (1)-(15) any one of them 10,000 tons aryloxy group polymer, the step c is pre-
It is concentrated in pre-concentration flash column and carries out, part removes the organic solvent and water in product polymer solution, obtains weight concentration
For the concentrated polymer solution of 20-60%, wherein the operation of flash distillation is carried out between 200 DEG C and 45 DEG C of temperature.
(17) according to the preparation method of (1)-(16) any one of them 10,000 tons aryloxy group polymer, in the step d
Precipitation is crossed in press filtration, becomes the polymer of slurry state by precipitating the concentrated polymer, and starch by continuous overvoltage filtrate
The polymer of state obtains polymer powder filter cake.
(18) according to the preparation method of (1)-(17) any one of them 10,000 tons aryloxy group polymer, the step e production
Product washing, purifying is the impurity for washing and centrifuging by one or more levels precipitating reagent in removal product, wherein washing, purifying
Operation is carried out between 15 DEG C to 110 DEG C of temperature.
(19) according to the preparation method of (1)-(18) any one of them 10,000 tons aryloxy group polymer, pass through the step
Aryloxy group polymer powder and liquid are carried out isolated final products aryloxy group polymer by f dryings, wherein drying process is full
Foot is at least following any or the combination of any two and conditions above is as follows：Drying temperature is between 15 DEG C to 100 DEG C, total system
It is carried out in the inert gas environment of circulation closed, the volatile matter condensate liquid of generation is sent directly into flow reuse.
(20) according to the preparation method of (1)-(19) any one of them 10,000 tons aryloxy group polymer, the aryloxy group is poly-
Close object meet following any or any two and the above standard combination it is as follows：
Inherent viscosity and product objective maximum deviation ＜ 5.0ml/g, preferred ＜ 4.0ml/g；
After heat treatment inherent viscosity increases ＜ 208ml/g, preferred ＜ 180ml/g, and the heat treatment temperature is 285
DEG C, 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 impurities summation ＜ 500ppm, preferred ＜ 250ppm, other organic impurities include 2,4,6- tri-
Cresols, Dihydrobenzofuranes, 2,6- dimethylcyclohexanons and 7- methyl -2,3- Dihydrobenzofuranes；
Bulk powder density ＞ 0.25kg/L, preferred ＞ 0.30kg/L；
Fine powder content ＜ 35%, preferred ＜ 10%, 38 mesh of grain size ＜ of the fine powder；
Coarse powder content ＜ 70%, preferred ＜ 50%, 710 mesh of grain size ＞ of the coarse powder；
Powder flowing index ＞ 50, preferred ＞ 60, powder flowing index are that gas rises the rear volume with initial accumulation powder
Than.
(21) according to the preparation method of (1)-(20) any one of them 10,000 tons aryloxy group polymer, it is furthermore preferred that institute
State aryloxy group polymer meet following any or any two and the above standard combination it is as follows：
Inherent viscosity and product objective maximum deviation ＜ 1.5ml/g,
After heat treatment inherent viscosity increases ＜ 12.5ml/g, and the heat treatment temperature 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 impurities summation ＜ 284ppm, other organic impurities include 2,4,6- tri- cresols, dihydrobenzo furan
It mutters, 2,6- dimethylcyclohexanons and 7- methyl -2,3- Dihydrobenzofuranes；
Bulk powder density ＞ 0.36kg/L；
Fine powder content ＜ 7%, 38 mesh of grain size ＜ of the fine powder；
Coarse powder content ＜ 52%, 710 mesh of grain size ＞ of the coarse powder；
Powder flowing index ＞ 70, powder flowing index are that gas rises the rear volume ratio with initial accumulation powder.
(22) according to the preparation method of (1)-(21) any one of them 10,000 tons aryloxy group polymer, further include solvent and
Precipitating reagent purifies reuse step, and the purification reuse step includes being detached organic solvent and precipitating reagent by extraction, by having
Solvent purification system reuse organic solvent passes through precipitating reagent purification system reuse precipitating reagent.
(23) a kind of preparation facilities of 10,000 tons aryloxy group polymer, including polymeric kettle, catalyst removal device, pre-concentration
Device, precipitation, filter device, product washing purifying device, drying device.
(24) according to the preparation facilities of the 10,000 tons aryloxy group polymer described in (23), in the polymeric kettle, by alkyl
Phenesic acid monomer, oxygen and catalyst carry out oxidative coupling polymerization reaction under conditions of organic solvent.
(25) according to the preparation facilities of the 10,000 tons aryloxy group polymer described in (23) or (24), catalyst is mixed for copper-amine
Agent, wherein：Amine mixture is the 1%-50% of alkyl phenesic acid monomer weight.
(26) according to the preparation facilities of (23)-(25) any one of them 10,000 tons aryloxy group polymer, it is preferred that described
Amine mixture is the 10%-40% of alkyl phenesic acid monomer weight.
(27) according to the preparation facilities of (23)-(26) any one of them 10,000 tons aryloxy group polymer, the copper-amine is mixed
Agent includes copper and is selected from following any organic amine and its arbitrarily combines：Primary amine, secondary amine and tertiary amine, consisting of phase-transferring agent, wherein amine mixture
Molar ratio with copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
(28) according to the preparation facilities of (23)-(27) any one of them 10,000 tons aryloxy group polymer, it is preferred that amine is mixed
The molar ratio of agent and copper is 5-40, and amine mixture is the 10-40% of organic solvent weight.
(29) according to the preparation facilities of (23)-(28) any one of them 10,000 tons aryloxy group polymer, the amine mixture
Including aliphatic amine, the aliphatic amine includes aliphatic list and diamines, and wherein aliphatic group can be linear chain or branched chain hydrocarbon or alicyclic
Compound.The preferred aliphatic amine is aliphatic primary, secondary and tertiary monoamine or tertiary diamine.The preferred aliphatic amine be it is single,
Two and three (rudimentary) alkylamines, wherein alkyl have 1~6 carbon atom.The most preferred aliphatic amine is mono-, di- and front three
Base, ethyl, n-propyl, isopropyl, the amine of normal-butyl substitution or the aliphatic amine are single and dicyclohexylamine, ethyl-methyl
Amine, morpholine class, N- (rudimentary) alkyl cycloaliphatic amine such as N- methylcyclohexyls amine, N, N '-Dialkylaminoethylamine, N, N '-dioxane
Base propane diamine, N, N, N '-trialkyl pentanediamine；Or the aliphatic amine is cyclic tertiary amine, the cyclic tertiary amine is that pyridine, α-can
Power fourth, γ-picoline.
(30) according to (23)-(preparation facilities of 29 any one of them 10,000 tons aryloxy group polymer, it is anti-in oxidative coupling
Answer middle basic material with semicontinuous batch fed, the basic material is alkyl phenesic acid and oxygen, and other components are with complete
Batch mode is added to prior to basic material in reactor；The reaction condition of the oxidative coupling reaction meets following any index
Or the combination of any two and the above index：5-70 DEG C of temperature, reaction kettle top pressure 0-5psi, reaction kettle top oxygen partial pressure
0-25%, oxygen feeding 0-425m3/ hr, reaction kettle outer circulation pump head 10-100psi, reaction time 0-250 minute.
(31) according to the preparation facilities of (23)-(30) any one of them 10,000 tons aryloxy group polymer, the reaction kettle
Volume be 15 to 100m3Be equipped with oxygen intake, blender, shell-and-tube heat exchanger and outer circulation pump group at heat-exchange system.
(32) according to the preparation facilities of (23)-(31) any one of them 10,000 tons aryloxy group polymer, the removal is urged
Agent device includes storage tank, continuous centrifuge and catalyst metals recovery system.
(33) according to the preparation facilities of (23)-(32) any one of them 10,000 tons aryloxy group polymer, in the storing
Chelating agent is added in tank and removes unreacted catalyst；By the centrifuge by the organic solution of polymer and catalyst, water,
Chelating agent detaches；The copper recovery system includes filter press, by being equipped with filter plate in the filter press, collects copper sludge.
(34) according to the preparation facilities of (23)-(33) any one of them 10,000 tons aryloxy group polymer, the pre-concentration
Device includes concentration flash column, and the concentration flash column is equipped with heat exchanger and pre-concentration vacuum plant.
(35) according to the preparation facilities of (23)-(34) any one of them 10,000 tons aryloxy group polymer, the precipitation, mistake
It includes stirring settler and continuous filter to filter device, and the continuous filter is equipped with vacuum extractor.
(36) according to the preparation facilities of (23)-(35) any one of them 10,000 tons aryloxy group polymer, the washing is net
Makeup is set including one or more levels agitator treating and solid-liquid continuous separation device.
(37) according to the preparation facilities of (23)-(36) any one of them 10,000 tons aryloxy group polymer, the dry dress
It sets including continuous drying system, following any heat-exchanger rig or arbitrary combination is equipped on the drying system：Chuck, interior cycle
Heat exchange and external circulation heat exchanging.
(38) according to the preparation facilities of (23)-(37) any one of them 10,000 tons aryloxy group polymer, the dry dress
The combination that drying process in setting meets at least following any or any two and conditions above is as follows：Drying temperature at 15 DEG C extremely
Between 100 DEG C, total system carries out in the inert gas environment of circulation closed, and the volatile matter condensate liquid of generation is sent directly into flow
Reuse.
(39) according to the preparation facilities of (23)-(38) any one of them 10,000 tons aryloxy group polymer, the 10,000 tons
The preparation facilities of aryloxy group polymer further includes solvent, and precipitating reagent purifies reclaiming system, and the system comprises extraction tower, You Jirong
Agent purifying column and precipitating reagent purifying column.
The phenoxy group Type of Collective object of the present invention has diversified chemical constitution.In some embodiments, aryloxy group
Polymer is made of following aryloxy group constitutional repeating unit：
Wherein, for each structural unit, each Q1The one kind independently being in following group：Halogen, it is unsubstituted or
The C of the non-tertiary hydrocarbon base of substitution1-C12Alkyl, C1-C12Sulfenyl, C1-C12Oxyl, C2-C12Halogenated oxyl and halogen and oxygen
Two carbon atoms are at least spaced between atom.Each Q2The one kind independently being in following group：It is hydrogen atom, halogen, unsubstituted
Or the C of the non-tertiary hydrocarbon base of substitution1-C12Alkyl, C1-C12Sulfenyl, C1-C12Oxyl, C2-C12Halogenated oxyl and halogen and
Two carbon atoms are at least spaced between oxygen atom.Wherein, above-mentioned " alkyl " refers to all chemical constitutions being only made of carbon and hydrogen.This
A little chemical constitutions can be aliphatic or aromatic series, straight chain, branch, ring, bicyclic, saturation and undersaturated structure.Meanwhile also may be used
To be aliphatic, aromatic series, straight chain, straight chain, branch, ring, bicyclic, saturation and unsaturated structure combination.However, when " alkyl "
Refer in particular to for substituted alkyl when, carbon and hydrogen on substituent group can arbitrarily be replaced by hetero atom.Therefore, when being specifically described as replacing
When base, " alkyl " residue can also be on the one or more or skeleton in carbonyl, amino, hydroxyl or similar group
Contain heteroatomic hydrocarbyl residue.For example, Q1Can be di-n-butyl amino methyl, this group can be by 3,5- dimethyl-
1,4- phenylenes end group is formed with di-n-butyl amine component reaction in oxidative polymerization catalyst.
Aryloxy group polymer is the monomer polymer that the oxidation polymerization in polymer solvent obtains under the action of catalyst.Its list
Body is at least a kind of monohydric phenol, can also be the combination at least one binary or polyphenol.Catalyst is by a metal ion species, ammonia
Ylidene ligands form, and can be made by metal ion and amino ligands reaction in-situ.Polymer solvent can be benzene, organic solvent, two have
Solvent, three organic solvents, chlorobenzene, dichloro-benzenes, chloroform or their mixture.In some case study on implementation, polymer solvent
In include organic solvent.Oxygen source can be purity oxygen or air.
It prepares the metal ion in the catalyst of aryloxy group polymer to be at least made of a kind of heavy metal ion, such as copper, manganese
Or cobalt.The source of catalyst metal ion is metal salt, including stannous chloride, copper chloride, cuprous bromide, copper bromide, iodate Asia
Copper, cupric iodide, cuprous sulfate, copper sulphate, four ammino of sulfuric acid be cuprous, cupric tetramminosulfate, cuprous acetate, copper acetate, propionic acid are sub-
The manganese salt and cobalt salt that copper, copper butyrate, lauric acid copper, hexadecanoic acid are cuprous and benzoic acid is cuprous and similar.It is suitable in catalyst
Amino ligands include dialkylamine (such as di-n-butylamine, DBA), trialkylamine (such as N, N- dimethyl butylamine, DMBA), and
Alkyl diamine (such as N, N '-di-tert-butyl ethylenediamine, DBEDA).In addition to it is above-mentioned be directly added into the method for metal salt other than, another kind can
Capable alternative is to react metal or metal oxide with the aqueous solution of inorganic acid, organic acid or these acid, in situ
Form the hydrate of corresponding metal salt or salt.
In some instances：Aryloxy group polymer includes (herein alternatively referred to as " PAE ") multiple aryloxy repeating units,
It is preferred that the repetitive unit at least 50 formulas (I)：
Wherein in each separate unit of the unit, each Z1Hydrogen, halogen, alkyl independently is (to preferably comprise more
Up to the primary or secondary alkyl of 7 carbon atoms), aryl (preferably phenyl), have between halogen atom and the benzene nucleus of formula (I)
Halohydrocarbyl (preferably halogenated alkyl), aminoalkyl, oxyl or the halogenated oxyl of at least two carbon, the halogenated oxyl
In there are at least two carbon atoms to separate halogen and oxygen atom, and the benzene for thering are at least two carbon atoms to separate halogen atom and formula (I)
Core.
Each Z2It independently is hydrogen, halogen, alkyl and (preferably comprises the primary of up to 7 carbon atoms or secondary alkane
Base), aryl (preferably phenyl), between halogen atom and the benzene nucleus of formula (I) at least two carbon halohydrocarbyl it is (preferably halogenated
Alkyl), oxyl or halogenated oxyl, there are at least two carbon atoms to separate halogen and oxygen atom in the halogenated oxyl, with
And the benzene nucleus for thering are at least two carbon atoms to separate halogen atom and formula (I).Each Z1And Z2Suitably contain up to 12 carbon atoms,
It is most common, each Z1For alkyl or phenyl, especially C1-C4Alkyl and each Z2It is hydrogen.
Term aryloxy polymer (polyarylether PAE) used includes unsubstituted in the present specification and claims
The substituted polyarylether polymer of polyarylether polymer, wherein aromatic ring, polyarylether copolymer and their blend.It further include packet
Containing in a known manner by the grafting materials of the polymer of such as vinyl monomer or such as polystyrene and elastomer etc to poly- virtue
The polyarylether polymer of prepared part on ether, this is in the United States Patent (USP) No.5 for having licensed to S.Bruce Brown, and 089,566
In be described.In addition, further include the polyarylether polymer of coupling, coupling agent therein such as low-molecular polycarbonate, quinones, miscellaneous
Ring class and formal class form the polymer of high molecular weight by the hydroxyl reaction in known method and two phenylate chains.
Polyarylether polymer used in composition can also have a variety of end groups, such as end group containing aminoalkyl and 4- hydroxy diphenyls end
Base, these end groups are by the special introducing of oxidative coupling reaction.Polyarylether polymer can use terminal group functional or sealing end,
These end groups are that polymer increases the reactivity of bigger, and additionally provides in some cases and other polymeric systems
Compatibility, the polymeric system can be used for mixing with polyphenylene ether polymer to form alloy or blend.For example, polyarylether
Can be by that will be functionalized with epoxy-terminated, phosphate end group or ortho esters (ortho ester) terminal group functional, functionalization
Reagent, such as (2- diethyl phosphorus epoxy) 6- (2,4,6- the trimethyl-phenoxy) -1,3,5-triazines (trizene) of 2- chloro- 4 with it is poly-
One (i.e. terminal hydroxy group) in aryl oxide polymer terminal group carries out reaction completion.
Obviously, according to the above, for understanding thoroughly person skilled in the art, it is contemplated that the polyarylether polymerization used
Object includes known polyarylethers all at present, although its structural unit is diversified.Workable suitable polyarylether is poly-
Object is closed to include, but are not limited to poly- (2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether)；Poly- (2,3,6- trimethyls-Isosorbide-5-Nitrae-phenylene) ether；
Poly- (2,6- diethyl-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2- methyl -6- propyl-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2,6- dipropyl-Isosorbide-5-Nitrae-
Phenylene) ether；Poly- (2- ethyls -6- propyl-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2,6- dilauryls-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2,
6- diphenyl-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2,6- dimethoxys-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2,6- diethoxies-Isosorbide-5-Nitrae-Asia benzene
Base) ether；Poly- (2- methoxyl groups -6- ethyoxyls-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2- ethyls -6- octadecane epoxides-Isosorbide-5-Nitrae-phenylene)
Ether；Poly- (2,6- bis- chloro- Isosorbide-5-Nitrae-phenylene) ether；Poly- (2- methyl -6- phenyl-Isosorbide-5-Nitrae-phenylene) ether；Poly- (2- ethyoxyls-Isosorbide-5-Nitrae-
Phenylene) ether；Poly- (the chloro- Isosorbide-5-Nitrae-phenylenes of 2-) ether；Poly- (2,6- bis- bromo- Isosorbide-5-Nitrae-phenylene) ether；Poly- (bromo- 2, the 6- dimethyl-of 3-
Isosorbide-5-Nitrae-phenylene) ether；Their mixture etc..Suitable copolymer includes containing 2,6- dimethyl-Isosorbide-5-Nitrae-phenylene ether units
With 2, the random copolymer of 3,6- trimethyls-Isosorbide-5-Nitrae-phenylene ether units.
It is to be approximately more than 0.2- in the inherent viscosity that aryloxy group polymer disclosed by the invention measures in 25 DEG C of chloroform
1.2dl/g's, its usual range of number-average molecular weight is about 3,000-60,000, ranging from the 20,000-100 of weight average molecular weight,
000, it is measured with gel permeation chromatography.
The polymerisation of alkyl phenesic acid monomer can be by the way that one or more phenol lists be added into suitable reaction dissolvent
Body and preferred copper-amine catalyst and carry out.It is preferred that in cupric or cuprous salt-secondary amine catalyst such as copper chloride and two positive fourths
Polymerisation is carried out in the presence of base amine.Ideally it is polymerize in the presence of inorganic base metal bromide or alkaline earth metal bromide
Reaction.The dosage of inorganic bromide is that every 100 mole of phenolic monomer is about 0.1 mole~about 150 moles.These catalyst materials are retouched
It is set forth in United States Patent (USP) US3,733,299 (Cooper et al.).If desired, tetraalkylammonium salt may also used as co-catalyst.This
A little co-catalysts are disclosed in United States Patent (USP) US3,988,297 (Bennett et al.).
The primary, secondary or tertiary amine component of catalyst complexes corresponds generally to United States Patent (USP) US3,306,874 and 3,306,875
(Hay).Exemplary substance includes aliphatic amine, including aliphatic list and diamines, wherein aliphatic group can be linear chain or branched chain hydrocarbon or
Alicyclic compound.Preferably aliphatic primary, secondary and tertiary monoamine and tertiary diamine.Especially preferably mono-, di- and three (rudimentary)
Alkylamine, wherein alkyl have 1~6 carbon atom.Typically, mono-, di- and trimethyl, ethyl, n-propyl, isopropyl can be used
The amine that base, normal-butyl replace, single and dicyclohexylamine, ethylmethylamine, morpholine class, N- (rudimentary) alkyl cycloaliphatic amines such as N-
Methylcyclohexyl amine, N, N '-Dialkylaminoethylamine, N, N '-dialkyl group propane diamine, N, N, N '-trialkyl pentanediamine etc..Separately
Outside, cyclic tertiary amine such as pyridine, α-collidine, γ-picoline etc. can be used.It is especially useful that N, N, N ', N '-four
Alkylethylene diamines, butanediamine etc..
The mixture of such primary, secondary and tertiary amine can be used.Preferred monoalkylamine is n-butylamine；Preferred dialkylamine
It is di-n-butylamine；And preferred trialkylamine is triethylamine.Preferred cyclic tertiary amine is pyridine.Primary and secondary amines in reaction mixture
Concentration can change in a wide range, but need be added with low concentration.The preferred scope of non-tertiary amine is about 2.0~about 25.0 to rub
You/100 moles of monovalent phenol.In the case of tertiary amine, preferred range is wide in the extreme, and is about 0.2~about 1500 mole/100
Mole monovalent phenol.In tertiary amine, if water not removed from reaction mixture, it is preferable to use about 500~about 1500 rub
The moles of phenol of your amine/100.If water removed from reaction, about 10 moles of tertiary amine such as triethylamine or three is only needed
The moles of phenol of ethamine/100 is used as lower limit.Or even less amount of tertiary diamine such as N, N, N ' can be used, N '-tetraalkyl butanediamine, to
Under down to about 0.2 mole/100 moles of phenol.
Exemplary suitable for cuprous salt and mantoquita in the method is shown in Hay patents.These salt include
Such as stannous chloride, cuprous bromide, cuprous sulfate, cuprous nitride, cuprous sulfate tetramine, cuprous acetate, butyric acid are cuprous, You Jirong
Agent cuprous formate, copper chloride, copper bromide, copper sulphate, copper nitride, copper sulphate tetramine, copper acetate, copper butyrate, organic solvent formic acid
Copper etc..Preferred cuprous salt and mantoquita include halide, alkanoate or sulfate, such as cuprous bromide and stannous chloride,
Copper bromide and copper chloride, copper sulphate, copper fluoride, cuprous acetate and copper acetate.In the case of primary and secondary amines, the concentration of mantoquita needs
It is maintained in low-level, preferably from about 0.2~2.5mol/100mol unit price phenol.Preferable amount in tertiary amine, mantoquita is
About 0.2~about 15mol/100mol unit price phenol.
For the preparation of copper-amine mixture catalyst, copper halide is generally more preferred than cuprous halide, this is because they are more
Low cost.The use of copper (I) class also substantially increases the utilization rate of oxygen in polymerisation early stage, and on reactor liquid level
Lower oxygen concentration helps to reduce the danger caught fire or exploded in reactor in space.The preparation of suitable copper-amine catalyst
Method and use appear in United States Patent (USP) US3,900,445 (Cooper et al.).
The very fast initial reaction rate obtained using copper (I) base catalyst also cause unreacted monomer less accumulation and
The reduction of the amount of the unwanted tetramethyl diphenyl quinone of gained.Tetramethyl diphenyl quinone (reverse dimer) is it is believed that pass through balance
Reaction is introduced into PAE.Balanced reaction leads to the decline of the inherent viscosity of PAE, this is because the introducing of dimer makes PAE's
Molecular weight and molecular weight.The minimum of tetramethyl diphenyl quinone is needed during oxidative coupling, to avoid under molecular weight
Drop and adjoint difficulty, the difficulty is to need to establish molecular weight more higher than required molecular weight, to make up reverse two
Loss in the equilibrium process of aggressiveness.It has been unexpectedly found that the present invention provides a kind of methods, wherein in the oxidation of phenol monomer
During equilibrium step after polymerization, inherent viscosity (I.V.) reduction that the PAE in reaction mixture is shown is low less than 10%,
Preferably smaller than 5%, more preferably less than 3%.
Polymerisation preferably carries out in a solvent.Suitable solvent is disclosed in above-mentioned Hay patents.Arsol is for example
Benzene, organic solvent, ethylbenzene, two organic solvents and o-dichlorobenzene are especially preferred, although tetrachloromethane, trichlorine can also be used
Methane, dichloromethane, 1,2- dichloroethanes and trichloro ethylene.The weight ratio of solvent and monomer is typically 1: 1~20: 1, i.e., at most
Up to 20 times of excessive solvents.The ratio between solvent and monomer are preferably 1: 1~10: 1 (weight).
Producing a unexpected advantage of this method of low inherent viscosity PAE is, with higher (the i.e. ＞ of production
0.28I.V.) method of PAE is compared, what high solid content was possible to.It (is improved molten in the case where not improving solution viscosity
Fluid viscosity simultaneous heavy polymer), final solid concentration can improve at least 20%, and improving 30% or more is
It is possible.Then, reactor size sum number purpose is not being improved, process provides a kind of utilizations of raising reactor
The method of rate and yield.Change polymerization and reaction condition such as reaction time, temperature based on required accurate target molecular weight
Degree, oxygen flow velocity etc..Polymerization terminal is advantageously used in line viscosimeter measurement.Although other methods can also be used for example to carry out molecular weight
Oxygen concentration in test, predetermined reaction time, control to specified end group concentration or solution.
The temperature for completing polymerization stage of the present invention is usually from about 0 DEG C~about 95 DEG C.It is highly preferred that temperature range is from about
35 DEG C~about 45 DEG C, reaction temperature is higher when close to reaction end.At very high temperatures, side reaction occurs, and generates anti-
Answer by-product, in very low temperatures, form ice crystal in solution.
Many different extractant or chelating agent practices for use in the present invention, so as to after polymerisation terminal with urge
Agent coordinates.Sulfuric acid, acetic acid, ammonium salt, bisulfate and various chelating agents can be used for example.When these materials are added into
When in PAE reaction solutions, copper-amine catalyst poisoning can not be aoxidized further.Many different materials can be used, but
It is that it is preferable to use those of be disclosed in United States Patent (USP) US3,838,102 (Bennett et al.) chelating agent.
Useful chelating agent includes the compound containing polyfunctional carboxylic acids, such as potassium sodium tartrate, nitrilotriacetic acid
(NTA), citric acid, amion acetic acid etc., particularly preferably they are selected from polyalkylene polyamine polycarboxylic acid, aminopolycanboxylic acid, amino
Carboxylic acid, aminopolycanboxylic acid, amino carboxylic acid, polycarboxylic acid and their alkali metal, alkaline-earth metal or mixed alkali metal-alkaline-earth metal
Salt.Preferred reagent include ethylenediamine tetra-acetic acid (EDTA), hydroxyethylenediamine triacetic acid, diethylene-triamine pentaacetic acid and they
Salt.Especially preferably ethylidene diaminetetracetic acid or its mono-, di-, three and tetrasodium salt, gained copper complex are referred to alternatively as
Carboxylic acid copper complex.
By using liquid liquid centrifuge, the metallic catalyst constituents of chelating can use generated water extraction in polymerisation
It takes.The extract liquor being preferably used in the method for the present invention is the aqueous solution of low-level chain triacontanol, i.e., water with have 1~about 4 carbon original
The mixture of the alkanol of son.The alkanol or glycol of general about 1vol%~about 80vol% can be used.Liquid, aqueous extractant
It can change from about 0.01: 1~about 10: 1 parts by volume with these ratios of the volume parts of discontinuous organic phase.
Reaction medium generally comprises aqueous environment.Also anti-solvent (anti-solvent) can be used in conjunction with water-bearing media,
To help to promote the precipitation of copper (I) substance.The selected section of suitable anti-solvent based on precipitated copper (I) substance
Solubility coefficient.Halide is to be not readily dissolved in very much water, for the log K of CuCl, CuBr and CuI at 25 DEG C[sp]Value is respectively-
4,49, -8.23 and -11.96.Due to such as CuCl2、CuCl3And CuCl4Formation and there are excessive halide ion and by
In other complexs so that solubility increases in water.The non-limitative example of anti-solvent includes low molecular weight alkyl and aromatic hydrocarbon
Class, ketone, alcohols etc., themselves has certain solubility in aqueous solution.If necessary, one skilled in the art
It can select the anti-solvent of suitable type and amount.
After removing catalyst, the solution containing PAE is concentrated into higher solid content, as being partially separated for PAE.Make
With the standard non-solvent technique (non-solvent techniques) for being generally used for the PAE for having I.V. more than 0.28dl/g
Precipitation, as the part detached totally, preferably removes a part of solvent to reduce solvent content on total separation equipment.It is logical
Crossing reduces the preferred temperature for improving the solution containing PAE simultaneously of the pressure in solvent flash vessel, realizes the solution containing PAE
Concentration.About 35~50 bars of pressure is needed, and reaction temperature is increased at least 200 DEG C, preferably at least 230 DEG C.At least 55%,
Preferably at least 65% or higher solid content PAE is needed.
The preparation method and its device of a kind of 10,000 tons aryloxy group polymer aryloxy group polymer provided by the invention, have
Following advantageous effects：1) being first can be with the detonation of core workshop section in safety precaution flow；2) primary amine in amine mixture is new
Fresh magnitude of recruitment reduces by 50%；3) up to 95% or more, product quality reaches high-level standard requirement for organic solvent and precipitating reagent reuse.
Description of the drawings
Fig. 1 is PAE process flow diagrams.
Specific implementation mode
Embodiment 1：
The monomer of polymerisation of the present invention is prepared by following process：
By phenols and alcohols alkylating agent substituted phenol monomer is generated through gas phase catalytic reaction.Reaction shell-and-tube reactor into
Row.The porous MgO of filling in each reactor tube.Shell-side takes away the heat that alkylated reaction is released with fuse salt, reaction
Basic material includes fresh and recycling phenols, alcohols alkylating agent etc..Reactor add nitrogen for maintain reaction with
The pressure of Distallation systm, reaction condition are：400-550 DEG C, 10-60psi pressure.The output object of reaction is mainly 2,6- xylenols
With other alkylation phenolic products.
Reactor connects conventional distil-lation tower to realize the separation of product.These liquid charging stocks are steamed by hot salt, deep fat heating
Hair, product leave reactor, it is cooling after enter liquid condenser, phenolic (be largely 2,6- xylenols, o-cresol, not instead
The phenol answered), water and most of unreacted precipitating reagent are condensed into product kettle.The gas generated in condenser includes mainly
CO、CO2, methane, water vapour, H2, sub-fraction alcohols alkylating agent.These gases not being condensed enter water suction tower to remove
Precipitating reagent, (residual exhaust results from the incomplete decomposing of alcohols alkylating agent, represents the invalid of precipitating reagent for remaining tail gas burn-up
Utilization rate).The material of product kettle enters precipitating reagent tower, and alcohols alkylating agent and water are distillated from tower top, reuse.Phenols gas is from tower
Bottom enters decanter, and the inside mixed organic solvents are distinguished with the density for improving water and organic solvent.Light phase (organic solvent and phenol
Class) enter dehydrating tower, heavy phase realizes organic solvent separation, reuse to decanter, the draining that this part generates after entering extraction tower
Into sewage disposal system.
The organic solvent (for extracting moisture) that dehydrating tower overhead contains recycling, bottom output object are mainly
Phenols is used for the charging of o-cresol tower, and in the tower, light phase (o-cresol and phenol) is detached with heavy phase.Light phase is by one small
Storage tank enters next destilling tower.
Material enters phenol tower, and phenol is distillated from tower top, reuse to phenol storage tank, bottom materials as ortho position tower into
Material, o-cresol are sold after being purified herein as byproduct.Bottom effluent mainly weight phenols (2,6- xylenols, 2,
4,6- tri- cresols, 2,4- xylenols etc.), its charging as 2,6- xylenol purification columns, 2,6- xylenols (99.7% or more)
The resin raw material as polymerization technique is distillated from tower top.Bottom effluent can further distill with recycle tri- cresols of 2,4,6- or
2,4- xylenols are sold as byproduct, or the fuel as hot oil furnace.
The substituted phenol monomer obtained by this flow can meet standard such as following table：
Embodiment 2：
As shown in Figure 1, a kind of preparation method of 10,000 tons aryloxy group polymer aryloxy group polymer, each technique detailed step
It is as follows.
(1) polymerisation
The preparation reaction of PAE is carried out under conditions of organic solvent is solvent by 2,6- xylenols, oxygen and catalyst
, in the presence of oxygen, catalyst can accelerate the coupling of monomer-polymer, and it is anti-that this process is known as oxidation coupling
It answers.Amine mixture includes：Dialkylamine, Dialkylaminoethylamine, dialkyl group butylamine, morpholine.By the measurement of viscosity apparatus, work as polymer
When having reached required molecular weight, stop oxygen supply.Obtain the organic solvent solution of PAE.Reacting amines mixture is organic molten
A concentration of 20-40% in agent, reaction time are 60-200 minutes, and reaction temperature is 10-95 DEG C.
(2) purification of polymer
1. chelating
Polymer solution in retort is proportionally added into chelating agent solution to remove unreacted catalyst.Mixing
Flow is needed to provide the time to complete the process that chelating agent (NTA, EDTA and its mixture) consumes unreacted catalyst.Chelating
The ratio of agent and solution is 20-95 DEG C in 5-100 ratios 10000, incorporation time 5-100 minutes, temperature
Polymer in storage tank is sent to continuous centrifuge and is dehydrated, according to catalyst, water, chelating agent and polymer
Density contrast, detached by centrifugal force.Polymer solution by purification is referred to as light phase, catalyst, water, chelating
Agent (NTA) is referred to as heavy phase.Light phase enters pre-concentration storage tank, and heavy phase enters sludge storage tank and is admitted to extraction tower.
2. extraction tower and sludge storage tank
Extraction tower and sludge storage tank be for recycle from continuous centrifuge separation generate heavy phase in organic amine heavy phase from
Enter extraction tower in sludge storage tank, heavy phase is deposited to bottom, and rises containing the solution of organic solvent and organic amine organic solvent
To top, light phase storage tank is spilt into.Light phase is back to centrifugal dehydrator to purify, and heavy phase enters heavy phase by gravity precipitation
Storage tank.
3. copper recovery system
Heavy phase is promoted from heavy phase storage tank and is sent to filter press, is added NaSH and is precipitated out copper from heavy phase, pressure mistake
Filter storage tank is used for storing heavy phase, is gradually sent into filter press.For filter plate to collect the copper sludge of liquid, filtrate (mainly water) is logical
It crosses filter and enters sewage disposal system.The temperature of this step is controlled at 25-75 DEG C
4. pre-concentration
Preconcentration technique is mainly the organic solvent and water removed in centrifugal dehydration process post-consumer polymer.Polymer is from pre- dense
Contracting storage tank enters pressurization heat exchanger, and polymeric liquid is warming up to specific temperature under a certain pressure.When liquid enter it is dense
Pressure, which reduces rapidly, when contracting flash column makes liquid boil again, and organic solvent and water rise to flash column in gaseous form at this time
Top enters cooling system, and remaining polymeric liquid is back to heat exchanger.Whole operation is in 35-130 DEG C of temperature, 5-
It is carried out between 45PSI normal pressures and 100-600mmHG vacuum.
The light phase of flash column effusion is condensed by condenser, and condensate liquid enters concentrate extraction tower, to detach
Water and organic solvent, for organic solvent circulating and recovering to organic solvent storage tank, water is promoted to sludge storage tank.Pre-concentration vacuum plant
Vacuum is provided to dodge to reduce the vapour pressure of polymer solution.This enables preconcentration technique to operate at low temperature, to reduce corruption
Erosion.
(3) polymer extraction separation
1. precipitating storage tank
The concentrated polymer that pre-concentration flash column generates enters stirring precipitation storage tank.Concentrated polymer is in precipitation storage tank and sinks
Shallow lake agent, which mixes liquid and carries out mixing, to be made polymer be precipitated as particulate polymers to overflow in precipitate storage tank, and enters company by gravity precipitation
Continuous vacuum filter storage tank.In this operation, charging maintains 150-1000L/min, and temperature remains suitable at 15-65 DEG C
Work as normal pressure.
2. continuous vacuum filters
Head tank supplies liquid/slurry polymer to continuous vacuum filter.When being full of slurry in continuous vacuum filter, pass through
Vacuumize 20-65 DEG C of separated powder and remaining fluid body operation temperature, vacuum degree 300-700mmHg.
3. product washing, purifying
Pass through one or more levels agitator treating and continuous separation by the polymer powder of continuous vacuum filter.Mainly
It removes from monomer and polymerization operation introduces and secondary a variety of organic and inorganic impurity, improve quality.First together with No. 3 masterbatch
Circulation loop is formed into No. 1 serum storage tank.The slurries for carrying out self circular loop enter two-stage centrifugal.Two-stage centrifugal utilizes PAE powder
The difference of end and fluid density is detached.PAE powder, which is recovered precipitating reagent and rinses to a skewed slot, enters No. 2 serum pots.Separation
Liquid, No. 2 materials enter No. 2 material pots by gravitational settling and carry out reuse in order to be precipitated in storage tank at No. 1.In No. 2 serum pots
Precipitating reagent PAE slurries circulation loop is entered by pump, the raw material of each centrifugal drying system is all from No. 2 serum recycles and returns
Road.Powder enters drying machine finally by skewed slot and is dried.Whole operation maintains 15-65 DEG C of temperature,
4. drying machine feeding system and drying machine
The feed of drying machine is sent product wet feed powder to drying machine feeding system import by screw conveyor, and drying machine is logical
It crosses and is detached PAE powder and liquid using the spiral drying axis with blade and chuck heating.The blade of helical axis is by product
It is conveyed to drying machine lower part, drying machine front is transported to by a rotation lock by dry product, subsequently into passing through gas
Body conveying system whole operation temperature feeds 10-800L/min. at 45-250 DEG C.
5. drying machine exhaust system
The steam and inert gas of drier are sent to drying machine washer, and precipitating reagent removes the particulate matter in steam, so
Precipitating reagent and PAE powder are sent to serum pot afterwards.Nitrogen from drying machine washer passes through drying machine condenser, and condensate liquid enters
Drying machine condensate tank, then pumping No. 2 material pot.
Enter water scrubber by remaining gas after drying machine condenser, gas enters first order scrubbing tower, by water condensation.
Any remaining gas enters second level scrubbing tower, and condensate liquid is by scrubbing tower by being pumped into extraction tower.
Remaining gas is fed through glycol condenser, and precipitating reagent organic solvent enters drying machine after being condensed and condenses
Liquid storage tank, after glycol condenser passes through, gas is sent to demister, forms drop and enters drying machine condensate tank.Most
Gas and steam respectively enter isolation scrubbing tower and nitrogen recycling system afterwards.
6. PAE transport systems
PAE is delivered to feed bin by PAE dry powder Transmission system from drying machine outlet.The product powder of drying machine discharge is by powder
Cooler is sent to sack cleaner.Sack cleaner detaches nitrogen and product powder, and nitrogen is back to air blower, and powder is fallen
To bottom, small funnel is entered by a rotation locking-valve.Product powder passes through blast system by a similar rotation locking-valve
Enter product feed bin.
(4) solvent recovery
1. extracting
The mixed liquor generated from precipitation and washing unit enters primary separation tower, and in organic solvent and precipitant mix object
Water is added, the density of precipitating reagent aqueous solution is larger, and in extraction tower bottom, and organic solvent is on top.The aqueous solution of precipitating reagent from
Extraction tower bottom by pump be promoted to precipitating reagent purify precipitating reagent recovery system, and organic solvent be sent to from top of tower it is organic molten
Its recovery system of agent.
2. organic solvent purifies reclaiming system
The main material of recovery system for organic solvent is the organic solvent containing microprecipitation agent, water and oligodynamical PAE,
Material from extraction tower passes through the near top into organic solvent tower after one group of heat exchanger, the mixing of precipitating reagent and water
Organic solvent top of tower is risen to after object evaporation, and organic solvent passes through column plate to flow into bottom of tower.
The mixed vapour of precipitating reagent and water enters internal storage tank by condenser, is then pumped meeting extraction tower, and organic
The organic solvent and solid content at solvent column bottom are sent to evaporator.Organic solvent and solid content in evaporator are added by reboiler
Circulation loop is formed after heat.
Organic solvent in organic solvent storage tank enters organic solvent recycling can after subcooler.
Solid content and impurity in evaporator remove organic solvent, the solid content after enrichment and impurity quilt by enrichment
It send to fuel reservoir.Organic solvent purification system is run under 0-90 DEG C and high vacuum condition.
3. precipitating reagent purifies reclaiming system
The main material of precipitating reagent recovery system is precipitating reagent and water.Material is sent to precipitating reagent tower from extraction tower, into
It is needed by one group of heat exchanger before entering precipitating reagent tower.The material of precipitating reagent tower forms circulation loop, precipitation by reboiler
Agent forms steam in tower and rises to precipitating reagent top of tower, is condensed after effusion, and condensate liquid enters precipitating reagent storage tank.A part is heavy
Shallow lake agent condensate liquid returns to precipitating reagent tower with temperature in adjusting tower, and remaining precipitating reagent is sent to precipitating reagent recycling storage tank.
The polymer being prepared by above-mentioned 10,000 tons PAE techniques meets listed in Table：
Embodiment 3
A kind of preparation facilities of 10,000 tons aryloxy group polymer aryloxy group polymer, including reaction kettle remove catalyst-assembly,
Pre-concentration device, precipitation, filter device, washing purifying device, drying device.
1) reaction kettle is equipped with oxygen intake and oxygen content monitor, agitating device, outer circulating tube shell heat exchanger
With circulating pump etc., the shell-and-tube heat exchanger has the function of heating and cooling, wherein：The volume of reaction kettle is 20-75m3If
It counts pressure and is less than 50kg/cm2, the total heat exchange area 100-800m of outer circulating tube shell heat exchanger2, the flow of circulating pump is 100-
1000 ton hours
2) the catalyst removal device includes chelating agent charging system, continuous centrifuge, extraction tower and catalyst
Metal recovery system.The continuous centrifuge detaches polymer solution with catalyst, water, chelating agent；The catalyst
Metal recovery system includes filter press, by being equipped with filter plate, collection catalyst metal sludge in the filter press.Wherein：Continuously
250 DEG C of centrifugal separator maximum temperature, maximum (top) speed are less than 8000rpm, flow 1-100m3/hr
3) pre-concentration device includes concentration flash column, and the concentration flash column is equipped with heat exchanger and pre-concentration is true
Empty device.Wherein, concentration flash column volume 1-15m3, temperature is less than 300 DEG C, and pressure is in vacuum and 20kg/cm2Between heat exchange
Device heat exchange area 50-350m2, 100-350 DEG C of temperature.
4) precipitation, filter device include stirring stillpot and continuous filter, and the filter is equipped with vacuum means
It sets, wherein stirring stillpot volume is in 1-10m3, speed of agitator is in 25-350rpm, continuous filter flow 10-100m3/ hr, temperature
10-200 DEG C of degree.
5) the product washing purifying device includes agitator treating kettle, the de- liquid device of continuous centrifuge.Wherein stirring is washed
Autoclave body product is washed in 1-10m3, speed of agitator is in 25-350rpm, the de- liquid device flow 5-200m of continuous centrifuge3/ hr, temperature
10-200℃。
6) drying device includes drier, and the spiral with blade is equipped on the drier and dries axis.Temperature 50-
250 DEG C, flow 1-20 ton hours
7) preparation facilities of the 10,000 tons aryloxy group polymer aryloxy group polymer further includes that solvent, precipitating reagent purify back
With system, the system comprises the recycling of initial gross separation (extraction) tower, organic solvent purifying column recovery system and precipitating reagent purifying column
Organic solvent and precipitating reagent are detached by initial gross separation (extraction) tower, are recycled by recovery system for organic solvent organic by system
Solvent recycles precipitating reagent by precipitating reagent recovery system.Wherein：Initial gross separation (extraction) tower body accumulates 50-250M3, temperature 80-
200℃。
Above-described embodiment is not the exhaustion of specific implementation mode, can also have other embodiments, above-described embodiment purpose to exist
In illustrating the present invention, the protection domain being not intended to limit the present invention, all applications from simple change of the present invention all fall within this
In the protection domain of invention.
This patent specification goes the displaying present invention using example, including optimal mode, and makes to be familiar with this field
Technical staff manufactures and uses the present invention.The delegatable range of the invention includes in the content and specification of claims
The content of specific implementation mode and other embodiments.These other examples should also belong to the range of claims of the present invention,
As long as it includes with claim without reality that they, which contain technical characteristic described in the identical written language of claim or they,
Technical characteristic described in the similar literal language of matter difference.
The full content of all patents, patent application and other bibliography should be incorporated by reference into present specification.But
Be if a term in the application mutually conflicts with the term for being included in bibliography, it is preferential with the term of the application.
All ranges disclosed herein all include endpoint, and are to combine independently of one another between endpoint.
It should be noted that " first ", " second " or similar vocabulary are not offered as any sequence, quality or importance,
It is used only to distinguish different technical characteristics.The qualifier " about " that combined amount uses includes that described value and content context refer to
Fixed meaning.(such as：It includes error when measuring specific quantity).
Claims (10)
1. a kind of preparation method of 10,000 tons aryloxy group polymer, which is characterized in that include the following steps：
A. oxidative coupling polymerization reaction is carried out under conditions of organic solvent by alkyl phenesic acid monomer, oxygen and catalyst；
Wherein：The volume of reaction kettle is 20-75m3, the total heat exchange area 100-800m of outer circulating tube shell heat exchanger2；The catalyst is
Copper-amine mixture, wherein：Amine mixture is the 1%-50% of alkyl phenesic acid monomer weight, and amine mixture is organic solvent weight
1-50%；The reaction condition of the oxidative coupling reaction meets the combination of following any index or any two and the above index：
5-70 DEG C of temperature, reaction kettle top pressure 0-5psi, reaction kettle top oxygen partial pressure 0-25%, oxygen feeding 0-425m3/ hr,
Reaction kettle outer circulation pump head 10-100psi, in reaction time 60-200 minute, the ratio between solvent and monomer weight are 1: 1~10: 1；
B. catalyst removes：Including chelating, organic phase, extraction and/or catalyst metals recycling step are taken off, passes through continuous centrifugal point
It disembarks de- organic phase, the continuous centrifuge maximum (top) speed is less than 8000rpm, flow 1-100m3/hr；Wherein chelating agent
Ratio with polymer solution is 5-100 ratios 1000, and incorporation time 5-100 minutes, temperature is 20-95 DEG C；The wherein described extraction
To be extracted to the catalyst, water and chelant mix in extraction tower, by organic solvent and organic amine from above-mentioned
Aqueous phase separation out simultaneously reuse, organic phase is that organic solvent is light phase, remaining water phase becomes heavy phase；
C. pre-concentration：It is carried out in pre-concentration flash column, part removes the organic solvent and water in product polymer solution, obtains
Weight concentration is the concentrated polymer solution of 20-60%, wherein flash column volume 1-15m3, heat exchanger heat exchange area 50-
350m2；Wherein, the operation of flash distillation is carried out between 200 DEG C and 45 DEG C of temperature；
D. it precipitates, filter：Become the polymer of slurry state by precipitating the concentrated polymer, and by continuously filtering slurry
The polymer of state obtains polymer powder filter cake, wherein stirring stillpot volume is in 1-10m3, speed of agitator is in 25-
350rpm, continuous filter flow 10-100m3/hr；In precipitation operation, temperature is at 15-65 DEG C, continuous filter operation temperature
20-65 DEG C, vacuum degree 300-700mmHg；
E. product washing, purifying：The impurity in removal product is washed and centrifuges by one or more levels precipitating reagent, wherein is stirred
Washing kettle volume is mixed in 1-10m3, speed of agitator is in 25-350rpm, the de- liquid device flow 5-200m of continuous centrifuge3/hr；It washes
Washing purification run is carried out between 15 DEG C to 110 DEG C of temperature；
F. it dries：Total system carries out in the inert gas environment of circulation closed, 50-250 DEG C of temperature, flow 1-20 ton hours；
The volatile matter condensate liquid of generation is sent directly into precipitation, filtration step and washing, purifying step reuse；
Further include have solvent and precipitating reagent purification reuse step, the purification reuse step include by extraction by organic solvent with
Precipitating reagent detaches, and adds water in organic solvent and precipitant mix object, the density of precipitating reagent aqueous solution is larger, at extraction tower bottom
Portion, and organic solvent is on top；It is heavy by precipitating reagent purification system reuse by organic solvent purification system reuse organic solvent
Shallow lake agent, organic solvent purification system are run under 0-90 DEG C and high vacuum condition, and a part of precipitant system overhead condensation liquid is sent
Precipitant system is back to adjust temperature；
Aryloxy group polymer prepared by the preparation method of the 10,000 tons aryloxy group polymer meets following at least one standard：
Inherent viscosity and product objective maximum deviation ＜ 4.0ml/g；
After heat treatment inherent viscosity increases ＜ 180ml/g, and the heat treatment temperature is 285 DEG C, and the time is 4 minutes；
Organic amine residual concentration ＜ 4%.
2. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that the alkyl two takes
Meet the combination of following any index or any two and the above index for phenol monomer：
The purity ＞ 99.5% of 2,6- xylenols；
Total methyl phenyl ethers anisole ＜ 0.15%；
Total cresols ＜ 0.15%；
Other xylenols ＜ 0.010%；
Phenol ＜ 0.010%；
Other alkyl phenols ＜ 0.15%；
Other organic impurities ＜ 0.10%；
Coloration ＜ 110；
Moisture ＜ 1500ppm.
3. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that the copper-amine is mixed
Agent includes copper, and selected from following any organic amine and its arbitrary combination：Primary amine, secondary amine and tertiary amine and consisting of phase-transferring agent；Wherein amine
The molar ratio of mixture and copper is 0.5-50, and amine mixture is the 1-50% of organic solvent weight.
4. the preparation method of 10,000 tons aryloxy group polymer according to claim 2, which is characterized in that amine mixture includes fat
Race's amine, the aliphatic amine include aliphatic list and diamines, and wherein aliphatic group is linear chain or branched chain hydrocarbon or alicyclic compound；It is described
Aliphatic amine is aliphatic primary monoamine, the secondary monoamine of aliphatic series, the tertiary monoamine of aliphatic series or aliphatic tertiary diamine；Or the aliphatic amine is
Mono-, di- and three (rudimentary) alkylamines, wherein alkyl have 1~6 carbon atom；Or the aliphatic amine is that can use mono-, di-
The amine replaced with trimethyl, ethyl, n-propyl, isopropyl, normal-butyl；Or the aliphatic amine is single and dicyclohexylamine, second
Ylmethyl amine, N- methylcyclohexyls amine, N, N '-Dialkylaminoethylamines, N, N '-dialkyl group propane diamine, N, N, N '-trialkyl penta 2
Amine；Or the aliphatic amine is cyclic tertiary amine, the cyclic tertiary amine is pyridine, α-collidine, γ-picoline.
5. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that anti-in oxidative coupling
Answer middle basic material with semicontinuous batch fed, the basic material is alkyl phenesic acid and oxygen, and other components are with complete
Batch mode is added to prior to basic material in reactor.
6. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that walked in the chelating
Chelating agent is added in rapid to remove the catalyst metals that polymerization is added, wherein chelating agent includes：Potassium sodium tartrate, three second of nitrilo-
Acid, citric acid, amion acetic acid, polyalkylene polyamine polycarboxylic acid, aminopolycanboxylic acid, amino carboxylic acid and their alkali metal, alkaline earth
Metal or mixed alkali metal-alkali salt；Or chelating agent includes：Ethylenediamine tetra-acetic acid, hydroxyethylenediamine triacetic acid, two
The salt of ethylenetriamine pentacetic acid and they.
7. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that have by described take off
Machine phase step is by the organic solution containing reaction product polymer and the aqueous phase separation containing catalyst, chelating agent.
8. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that the copper recycling step
Rapid be precipitated out copper from heavy phase for addition metal sulfide is then sent to filter press.
9. the preparation method of 10,000 tons aryloxy group polymer according to claim 1, which is characterized in that pass through the step
Aryloxy group polymer powder and liquid are carried out isolated final products aryloxy group polymer by f dryings, wherein drying process is full
Foot is at least following any or the combination of any two and conditions above is as follows：Drying temperature is between 15 DEG C to 100 DEG C, total system
It is carried out in the inert gas environment of circulation closed, the volatile matter condensate liquid of generation is sent into flow reuse.
10. the preparation method of 10,000 tons aryloxy group polymer according to claim 9, which is characterized in that the aryloxy group
The combination that polymer meets following any or any two and the above standard is as follows：
Copper ion concentration ＜ 15ppm；
Volatile matter ＜ 1.5%；
Polymerization organic solvent residual concentration ＜ 300ppm；
Other organic impurities summation ＜ 500ppm, other organic impurities include 2,4,6- tri- cresols, Dihydrobenzofuranes, 2,
6- dimethylcyclohexanons and 7- methyl -2,3- Dihydrobenzofuranes；
Bulk powder density ＞ 0.25kg/L；
Fine powder content ＜ 35%, 38 mesh of grain size ＜ of the fine powder；
Coarse powder content ＜ 70%, 710 mesh of grain size ＞ of the coarse powder；
Powder flowing index ＞ 50, powder flowing index are that gas rises the rear volume ratio with initial accumulation powder.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810273681.7A CN108383992B (en) | 2015-09-25 | 2015-09-25 | Preparation device of ten-thousand-ton-level aryloxy polymer |
| CN201510622177.XA CN105295026B (en) | 2015-09-25 | 2015-09-25 | A kind of preparation method and its device of 10,000 tons aryloxy group polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510622177.XA CN105295026B (en) | 2015-09-25 | 2015-09-25 | A kind of preparation method and its device of 10,000 tons aryloxy group polymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810273681.7A Division CN108383992B (en) | 2015-09-25 | 2015-09-25 | Preparation device of ten-thousand-ton-level aryloxy polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105295026A CN105295026A (en) | 2016-02-03 |
| CN105295026B true CN105295026B (en) | 2018-09-18 |
Family
ID=55192920
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810273681.7A Active CN108383992B (en) | 2015-09-25 | 2015-09-25 | Preparation device of ten-thousand-ton-level aryloxy polymer |
| CN201510622177.XA Active CN105295026B (en) | 2015-09-25 | 2015-09-25 | A kind of preparation method and its device of 10,000 tons aryloxy group polymer |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810273681.7A Active CN108383992B (en) | 2015-09-25 | 2015-09-25 | Preparation device of ten-thousand-ton-level aryloxy polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108383992B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046351B (en) * | 2016-06-30 | 2018-11-20 | 山东凯盛新材料股份有限公司 | The method for removing metal ion in polyether ketone ketone crude product |
| CN106046347A (en) * | 2016-06-30 | 2016-10-26 | 山东凯盛新材料股份有限公司 | Method for refining polyetherketone ketone crude product by using ethylenediamine tetramethylenephosphonic acid |
| CN112111057B (en) * | 2019-06-20 | 2023-07-14 | 南通星辰合成材料有限公司 | Polyphenylene ether and process for producing the same |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1531568A (en) * | 2001-06-21 | 2004-09-22 | ͨ�õ�����˾ | Method of preparing poly(arylene ether), and poly(arylene ether) prepared thereby |
| CN1798806A (en) * | 2003-08-26 | 2006-07-05 | 通用电气公司 | Methods of preparing a polymeric material composite |
| CN103443165A (en) * | 2011-03-15 | 2013-12-11 | 沙伯基础创新塑料知识产权有限公司 | Process for forming poly(arylene ethers) with lower content of fine particle |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4059466B2 (en) * | 2000-06-19 | 2008-03-12 | 三菱瓦斯化学株式会社 | Process for producing polyphenylene ether |
| US20040211657A1 (en) * | 2003-04-11 | 2004-10-28 | Ingelbrecht Hugo Gerard Eduard | Method of purifying 2,6-xylenol and method of producing poly(arylene ether) therefrom |
| JP2014031424A (en) * | 2012-08-02 | 2014-02-20 | Asahi Kasei Chemicals Corp | Process for producing polyphenylene ether |
-
2015
- 2015-09-25 CN CN201810273681.7A patent/CN108383992B/en active Active
- 2015-09-25 CN CN201510622177.XA patent/CN105295026B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1531568A (en) * | 2001-06-21 | 2004-09-22 | ͨ�õ�����˾ | Method of preparing poly(arylene ether), and poly(arylene ether) prepared thereby |
| CN1798806A (en) * | 2003-08-26 | 2006-07-05 | 通用电气公司 | Methods of preparing a polymeric material composite |
| CN103443165A (en) * | 2011-03-15 | 2013-12-11 | 沙伯基础创新塑料知识产权有限公司 | Process for forming poly(arylene ethers) with lower content of fine particle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105295026A (en) | 2016-02-03 |
| CN108383992A (en) | 2018-08-10 |
| CN108383992B (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105295026B (en) | A kind of preparation method and its device of 10,000 tons aryloxy group polymer | |
| US20040102583A1 (en) | Compositions comprising functionalized polyphenylene ether resins | |
| CN1164650C (en) | Process for preparation of polyphenylether | |
| CN105016360A (en) | Methods and apparatus for purifying solid salt compositions | |
| CN1612910A (en) | Method of preparing a poly(arylene ether) and a poly(arylene ether) prepared thereby | |
| US3630995A (en) | Removal of catalyst residue from polyphenylene ethers | |
| EP2686368A1 (en) | Process for formation of poly(arylene ethers) with lower fine particle content | |
| US4246398A (en) | Method for recovering polyphenylene oxides | |
| US4042564A (en) | Method for preparing polyphenylene ethers | |
| JP2002542324A (en) | Method and apparatus for separating solids from polymer solutions | |
| CN111662453A (en) | Method for preparing polysulfone resin material by adopting cooperative dehydration process | |
| US3733301A (en) | Separation and recovery of catalyst residue | |
| CN101351491B (en) | Method for preparing poly (arylidene aether) and relative combination | |
| CN1564839A (en) | Process and apparatus for preparing a poly(arylene ether) | |
| KR101276776B1 (en) | Method for Producing Phenylene Ether Oligomer | |
| CN111621012B (en) | Polysulfone series resin polymerization dehydration process | |
| CN205076993U (en) | Preparation facilities of ten thousand tonnes of aryloxy group polymer | |
| JP3810326B2 (en) | Solvent recovery method in polyphenylene ether production | |
| CN213085853U (en) | Production system of ten thousand ton level 2,6 alkyl disubstituted phenol polymer | |
| JPH03181423A (en) | Method for separating solvent | |
| EP1207175B1 (en) | Process for producing polyphenylene ether | |
| CN117624585A (en) | Method for water phase re-reaction in polyphenyl ether production | |
| JP4765144B2 (en) | Process for producing polyphenylene ether | |
| JP2000281781A (en) | Method for separating solvent in preparation of polyphenylene ether | |
| CN117777433A (en) | Polyphenylene ether, process for producing the same, and thermosetting resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160331 Address after: 222300, Jiangsu, Donghai County province Lianyungang hi tech Development Zone Kirin Road south side of the West Lake Road Applicant after: DONGHAI HAOHUA NEW MATERIAL TECHNOLOGY CO.,LTD. Applicant after: BEIJING TIANCHEN HAOHUA TECHNOLOGY CO.,LTD. Address before: Kylin Avenue South of Donghai County high tech Development Zone, Lianyungang City, Jiangsu province 222300 West Road on the eastern side. Applicant before: DONGHAI HAOHUA NEW MATERIAL TECHNOLOGY CO.,LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190415 Address after: 100085 Beijing Haidian District Shangdi Information Road 2 (Beijing Shichuang High-tech Development Corporation 2-2 D Building 1-8 Floor) 2nd Floor 208A-2 Patentee after: BEIJING TIANCHEN HAOHUA TECHNOLOGY CO.,LTD. Address before: 222300 High-tech Development Zone, Donghai County, Lianyungang City, Jiangsu Province, south of Qilin Avenue, east of Huxi Road Co-patentee before: BEIJING TIANCHEN HAOHUA TECHNOLOGY CO.,LTD. Patentee before: DONGHAI HAOHUA NEW MATERIAL TECHNOLOGY CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240123 Address after: No. 17 Zhabei Road, Taixing Economic Development Zone, Taizhou City, Jiangsu Province, 225442 Patentee after: Jiangsu Jingteng Haohua Technology Co.,Ltd. Guo jiahuodiqu after: Zhong Guo Address before: 100085 Beijing Haidian District Shangdi Information Road 2 (Beijing Shichuang High-tech Development Corporation 2-2 D Building 1-8 Floor) 2nd Floor 208A-2 Patentee before: BEIJING TIANCHEN HAOHUA TECHNOLOGY CO.,LTD. Guo jiahuodiqu before: Zhong Guo |
|
| TR01 | Transfer of patent right |