CN1101303A - 弱碱性阴离子交换剂的制备方法和适于这种用途的试剂 - Google Patents
弱碱性阴离子交换剂的制备方法和适于这种用途的试剂 Download PDFInfo
- Publication number
- CN1101303A CN1101303A CN94109572A CN94109572A CN1101303A CN 1101303 A CN1101303 A CN 1101303A CN 94109572 A CN94109572 A CN 94109572A CN 94109572 A CN94109572 A CN 94109572A CN 1101303 A CN1101303 A CN 1101303A
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- Prior art keywords
- reaction
- vinyl aromatic
- contain
- methyl
- anionite
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- 150000001450 anions Chemical class 0.000 title claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims description 38
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 2-methylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C)C(=O)C2=C1 ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 1
- -1 imide compound Chemical class 0.000 description 10
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005902 aminomethylation reaction Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- OAJRKNFPHGSOSX-UHFFFAOYSA-N 1-n,2-n-dimethylbenzene-1,2-dicarboxamide Chemical compound CNC(=O)C1=CC=CC=C1C(=O)NC OAJRKNFPHGSOSX-UHFFFAOYSA-N 0.000 description 5
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical group C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical class CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NVAYQMLMOYYYQE-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-dicarboxamide Chemical compound CC1=CC=C(C(N)=O)C(C(N)=O)=C1C NVAYQMLMOYYYQE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- YKKDJUGGSDWUKX-UHFFFAOYSA-N 1,2-bis(ethenyl)-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1C=C YKKDJUGGSDWUKX-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- YCBKMWAUQKGKBB-UHFFFAOYSA-N 1-(aziridin-1-yl)-2-methylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CC1 YCBKMWAUQKGKBB-UHFFFAOYSA-N 0.000 description 1
- SCMVPOVMOHQFKU-UHFFFAOYSA-N 1-(aziridin-1-yl)prop-2-en-1-one Chemical compound C=CC(=O)N1CC1 SCMVPOVMOHQFKU-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- YHCVYAHUIMOIGE-UHFFFAOYSA-N 2,3-dihydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCC(O)CO YHCVYAHUIMOIGE-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JKGLRGGCGUQNEX-UHFFFAOYSA-N 2-(chloromethyl)isoindole-1,3-dione Chemical class C1=CC=C2C(=O)N(CCl)C(=O)C2=C1 JKGLRGGCGUQNEX-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- SJQITXILEOCXGI-UHFFFAOYSA-N 3,3,6,6-tetramethyl-1,2,4,5-tetraoxane Chemical compound CC1(C)OOC(C)(C)OO1 SJQITXILEOCXGI-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SKEYBVJYVVGWPE-UHFFFAOYSA-N C(=C)OCC(=S)OCCO Chemical compound C(=C)OCC(=S)OCCO SKEYBVJYVVGWPE-UHFFFAOYSA-N 0.000 description 1
- ZGHNHKVUNFYLAY-UHFFFAOYSA-N CC=NC(=O)N(C=C)C=C Chemical compound CC=NC(=O)N(C=C)C=C ZGHNHKVUNFYLAY-UHFFFAOYSA-N 0.000 description 1
- OEHHAMWXJLEVFW-UHFFFAOYSA-N CCC=NC(=O)N(C=C)C=C Chemical compound CCC=NC(=O)N(C=C)C=C OEHHAMWXJLEVFW-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- AGINPOJWTDKORT-UHFFFAOYSA-N [H]OP(=O)OC([H])([H])N Chemical group [H]OP(=O)OC([H])([H])N AGINPOJWTDKORT-UHFFFAOYSA-N 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
一种改进的合理制备弱碱性阴离子交换剂的氨
甲基化方法,在该方法中,得到的副产物能够容易地
转化成一种适当的原料。
Description
本发明涉及一种通过氨甲基化方法制备交联的乙烯基芳香族聚合物类的弱碱性阴离子交换剂的低废方法以及制备适合于这种用途的N-氯甲基邻苯二甲酰亚胺类化合物的方法。
弱碱性阴离子交换剂为含有伯氨基和/或仲氨基和/或叔氨基的水不溶性聚合物,含有伯氨基的阴离子交换剂用作制备含有仲氨基、叔氨基或季铵基团的阴离子交换剂的原料。
有两种工艺成熟的制备弱碱性阴离子交换剂的方法:1.氯甲基化随后氨基化的方法,2.氨甲基化方法。
氯甲基化包括制备含有氯甲基的交联的乙烯基芳香族聚合物,然后使其与胺或多胺反应,下面的交联聚苯乙烯与一氯二甲醚反应、随后与二甲胺反应的实例说明了这一方法。
该方法的缺点是不可避免副反应,其中碱性氮与一个以上卤素基反应,结果发生交联,生成具有不合要求的强碱性离子交换剂性质的四价结构(R.L. Gustafson,Ind.Eng.Chem.Fundam.,Vol.9,No.2,1970),交换能力降低。
与此不同,氨甲基化包括使乙烯基芳香族聚合物与邻苯二甲酰亚胺衍生物反应并将得到的酰亚胺化合物水合,其过程如下面反应式所示。
其中n=在每种情况下为0.3~1.5。
更为严格的环境保护要求采用一种合理的邻苯二甲酸二钠的处理方法。由此制备氨甲基化试剂需要许多步骤:
由邻苯二甲酸盐中释出邻苯二甲酸,从水相中分离出邻苯二甲酸,成酐,将邻苯二甲酸酐转化成酰亚胺,最后将邻苯二甲酰亚胺转化成所需的氨甲基化试剂。这种处理方法过于复杂,因而迫切需要一种能够在明晰、简短的反应程序中将得到的副产物转化成原料之一的一流方法。
令人惊奇的是,这个问题已通过包括下述步骤的方法得到解决:
a)将交联的乙烯基芳香族聚合物与N-氯甲基邻苯二甲酰亚胺反应,
b)用甲胺将得到的反应物分解成弱碱性阴离子交换剂和N,N′-二甲基邻苯二甲酰胺,
c)将N,N′-二甲基邻苯二甲酰胺环化成N-甲基邻苯二甲酰亚胺,
d)在自由基存在下用氯将N-甲基邻苯二甲酰亚胺氯化得到N-氯甲基邻苯二甲酰亚胺。
乙烯基芳香族聚合物优选用每个分子含有一个以上、优选含有二或三个可共聚的C=C双键的交联单体通过共聚交联。这种交联单体包括(例如)多官能乙烯基芳香族化合物,如二和三乙烯基苯、二乙烯基乙苯、二乙烯基甲苯、二乙烯基二甲苯、二乙烯基萘;多官能烯丙基芳香族化合物,如二或三烯丙基苯;多官能乙烯基和烯丙基杂环化合物,如三乙烯基和三烯丙基氰脲酸酯和异氰脲酸酯;N,N′-C1-C6亚烷基二丙烯酰胺类和N,N′-C1-C6亚烷基二甲基丙烯酰胺类,如N,N′-亚甲基二丙烯酰胺和N,N′-亚甲基二甲基丙烯酰胺、N,N′-亚乙基二丙烯酰胺和N,N′-亚乙基二甲基丙烯酰胺;每个分子含有2至4个羟基的饱和C2-C20多元醇的多乙烯基醚或多烯丙基醚,如乙二醇二乙烯基醚和乙二醇二烯丙基醚、二甘醇二乙烯基醚和二甘醇二烯丙基醚;不饱和的C3-C12醇或每个分子含有2至4个羟基的饱和C2-C20多元醇的酯,如甲基丙烯酸烯丙酯、二(甲基)丙烯酸乙二醇酯、三(甲基)丙烯酸甘油酯、季戊四醇四(甲基)丙烯酸酯;二乙烯基亚乙基脲、二乙烯基亚丙基脲;已二酸二乙烯酯;含有二或三个孤立的C=C双键的脂族或脂环族烯烃,如1,5-已二烯、2,5-二甲基-1,5-已二烯、1,7-辛二烯、1,2,4-三乙烯基环已烷。经证明特别适用的交联单体为二乙烯基苯(异构体混合物)和二乙烯基苯与含有二或三个C=C双键的脂族C6-C12烃类的混合物。交联单体的用量通常为所用的可聚合单体的总重量的2~20%、优选2~12%。
交联单体不必以纯化合物的形式使用,也可以市售低纯度工业混合物(如二乙烯基苯和乙基苯乙烯的混合物)的形式使用。
氨甲基化反应a)可按如下方法进行:在交联乙烯基芳香族聚合物的溶胀剂和Friedel-Crafts催化剂存在下(DE-B1054715),将交联的乙烯基芳香族聚合物与N-氯甲基邻苯二甲酰亚胺反应,其中邻苯二甲酰亚胺衍生物的用量为使得交联乙烯基芳香族聚合物中芳环达到所需取代度(每个芳环的取代度为0.3至2.0)的合适用量(或最高过量至20%,优选最高至10%)。
适用的溶胀剂包括卤代烃类,优选氯代C1-C4烃类。最优选的溶胀剂为1,2-二氯乙烷。
优选的Friedel-Crafts催化剂包括(例如)AlCl3、BF3、FeCl3、ZnCl2、TiCl4、ZrCl4、SnCl4、H3PO4、HF和HBF4。每摩尔N-氯甲基邻苯二甲酰亚胺的催化剂用量可以从0.01至0.1摩尔。
例如,该反应可如下进行:将交联乙烯基芳香族聚合物加入N-氯甲基邻苯二甲酰亚胺在溶胀剂中的溶液中,并在催化剂存在下,在加热下(通常为50℃至100℃,优选50℃至75℃)使反应物反应,直至氯化氢基本上完全放出。反应通常需2至20小时。在将取代的乙烯基芳香族聚合物、液体反应介质和无机产物分离之后,应将乙烯基芳香族聚合物溶于氯化钠水溶液并通过蒸馏除去残留的溶胀剂。
在甲胺存在下的取代的乙烯基芳香族聚合物的分解反应(b)中,每摩尔邻苯二甲酰亚氨基甲基需要至少2摩尔,优选至少3摩尔甲胺。反应温度优选为110℃至150℃,压力优选为10至100巴。根据一个优选的实施方案,反应在过量甲胺(作为反应介质)中进行。反应进程可用分析法监测,例如用稀盐酸滴定形成的伯氨基的方法。通常2至20小时后反应进行完全。除去过量的甲胺后,可将生成的N,N′-二甲基邻苯二甲酰胺溶于适当的有机溶剂中并与弱碱性阴离子交换剂分离。适用的溶剂的例子有沸点为40℃至130℃的有机液体;优选的溶剂为脂族单羟基C1~C4醇类,如甲醇、乙醇、异丙醇和各种丁醇。
在将二甲基邻苯二甲酰胺用于反应c)之前应除去溶剂。反应c)的原理是已知的,可参见Spring,Woods,J.Chem.Soc.1945,625-628页。该反应可在加热条件下进行或在水存在下进行。热环化优选在100℃至250℃温度下进行,特别优选在150℃至220℃下进行。该反应可在有机溶剂中进行;优选在熔体中进行,释出的甲胺由其中蒸出。甲胺的释出一停止,便可认为反应已进行完全。残余物可通过(例如)重结晶法或升华法等纯化。
采用至少等摩尔量的氯进行N-甲基邻苯二甲酰亚胺的氯化反应d);优选采用至多20%过量的氯。自由基形成剂的存在可加速反应。这类化合物的适用的例子有过氧化二酰,如过氧化二乙酰、过氧化二苯甲酰、过氧化二对氯苯甲酰;过氧酯,如过乙酸叔丁酯、过苯甲酸叔丁酯、过二碳酸二环已酯;烷基过氧化物,如二(叔丁基过氧丁烷)、过氧化二枯基、过氧化叔丁基枯基;氢过氧化物,如氢过氧化枯烯、叔丁基过氧化氢;酮过氧化物,如氢过氧化环已酮、氢过氧化甲乙酮、过氧化乙酰丙酮,或优选偶氮二异丁腈。
自由基形成剂可以催化量使用,即优选为N-甲基邻苯二甲酰亚胺的重量的0.01~2%。
反应d)优选在加热条件下进行,通常在45℃至180℃下进行。该反应可在有机溶剂中进行,优选在熔体中进行。一旦不再吸收氯,反应便进行完全。通常2至8小时后反应进行完全。生成的N-氯甲基邻苯二甲酰亚胺可不经进一步纯化而直接用于反应步骤a)。
下面以聚苯乙烯为例说明整个反应方案。
因此,本发明提供了一种通过(ⅰ)含有环上键合的邻苯二甲酰亚氨基甲基的交联乙烯基芳香族聚合物与(ⅱ)甲胺在加热和加压条件下反应制备含有环上键合的伯氨甲基的交联乙烯基芳香族聚合物类的弱碱性阴离子交换剂的方法。
本发明还提供了一种在自由基形成剂存在和加热条件下用氯将N-甲基邻苯二甲酰亚胺氯化制备N-氯甲基邻苯二甲酰亚胺的方法。
最后,本发明提供了一种制备含有环上键合的伯氨甲基的交联乙烯基芳香族聚合物类的弱碱性阴离子交换剂的方法,该方法包括:
a)将交联的乙烯基芳香族聚合物与N-氯甲基邻苯二甲酰亚胺反应,
b)用甲胺将得到的反应产物分解成阴离子交换剂和N,N′-二甲基邻苯二甲酰胺,
c)将得到的N,N′-二甲基邻苯二甲酰胺环化成N-甲基邻苯二甲酰亚胺,
d)在自由基形成剂存在下用氯将N-甲基邻苯二甲酰亚胺氯化。
用本发明方法得到的弱碱性阴离子交换剂含有-CH2-NH2基团;它们可以原样用作离子交换剂,或与烷基化剂(如氯代甲烷)或甲醛/甲酸(Leuckart-Wallach试剂)反应得到季铵盐或叔胺,叔胺可根据需要与烷基化剂(如氯乙醇)反应得到季铵盐。
含-CH2NH2基的弱碱性阴离子交换剂可进一步与单氯代乙酸钠反应得到氨基双乙酸型螯合树脂,或与硫脲反应得到含硫脲官能基的树脂,或与HCHO/磷(Ⅲ)反应得到含氨甲基膦酸基的树脂。
本发明还提供了采用含有-CH2NH2基并可用本发明方法得到的阴离子交换剂制备含叔氨甲基和/或季铵基和/或亚氨基双乙酸基的树脂的方法。这些树脂可用作阴离子交换树脂或吸附树脂。
实施例
反应a)
在室温下,将97gN-氯甲基邻苯二甲酰亚胺(0.5mol)加入600ml 1,2-二氯乙烷中并使之溶解。然后加入60g(0.57mol)二乙烯基苯含量为4%(重量)的苯乙烯/二乙烯基苯的交联珠状聚合物。将该悬浮液在室温下搅拌1小时。然后在30分钟内计量加入0.05mol四氯化锡,将该混合物加热至回流温度并在该温度下再搅拌10小时。
冷却后,排掉反应液。加入氯化钠水溶液并蒸出残余的1,2-二氯乙烷。
反应b)
在1.3升的高压锅中,将100g由反应a)得到的干树脂在120℃下于400ml甲胺中搅拌8小时(压力为37~38巴)。冷却至室温后,将甲胺慢慢转移至另一个高压锅(残余压力为4.5巴)中并同时降压。随后按上述方法再将该树脂在120℃下与400ml甲胺反应8小时。将甲胺蒸发后的残余物在80℃下干燥以除去残余的甲胺。
第一次反应后得到的N,N′-二甲基邻苯二甲酰胺重55.7g(理论产量的84%)。
第二次反应后得到的N,N′-二甲基邻苯二甲酰胺重11.6g。
N,N′-二甲基邻苯二甲酰胺的总量为67.3g(产率为100%)。
得到的离子交换剂重54.5g(理论产量的99.2%)。
总生产能力为3.0mol/l。
取代度为每个芳环0.77。
将得到的弱碱性阴离子交换剂与氯代甲烷反应得到强碱性阴离子交换剂。
总生产能力为1.26mol/l。
反应c)
将19.7g N,N′-二甲基邻苯二甲酰胺加入100ml三颈瓶中并加热至183℃。将混合物在该温度下保持21小时。在加热期间有甲胺蒸出。
冷却后,烧瓶中得到棕色残余物,升华后得到白色固体。
根据HPLC分析结果,该固体具有下面组成:
9.1%(重量)N,N′-二甲基邻苯二甲酰胺,
1.1%(重量)4-甲基苄胺,
89.8%(重量)N-甲基邻苯二甲酰亚胺。
反应d)
在一个装有搅拌器、温度计、回流冷凝器和进气管的四颈瓶中将322g(2mol)N-甲基邻苯二甲酰亚胺在170℃下熔化。在150℃至155℃内温下,在4.5小时内加入160g(2.2mol)氯和1g偶氮二异丁腈(5%(重量)的二氯甲烷溶液)。将热熔体倾至铝箔上并使之固化。
产量:370g,其中含346g N-氯甲基邻苯二甲酰亚胺,相当于理论产量的88.5%。
Claims (8)
1、一种通过(i)含有环上键合的邻苯二甲酰亚氨基甲基的交联乙烯基芳香族聚合物与(ii)甲胺在加热和加压下反应制备含有环上键合的伯氨甲基的交联乙烯基芳香族聚合物类的弱碱性阴离子交换剂的方法。
2、根据权利要求1的方法,其中每摩尔邻苯二甲酰亚氨基甲基与至少2摩尔甲胺反应。
3、根据权利要求1的方法,其中反应温度为110℃至150℃。
4、根据权利要求1的方法,其中反应压力为10至100巴。
5、一种在自由基形成剂存在下于加热条件下用氯使N-甲基邻苯二甲酰亚胺氯化制备N-氯甲基邻苯二甲酰亚胺的方法。
6、根据权利要求5的方法,其中反应温度为45℃至180℃。
7、一种制备含有环上键合的伯氨甲基的交联乙烯基芳香族聚合物类的弱碱性离子交换剂的方法,该方法包括:
a)将交联的乙烯基芳香族聚合物与N-氯甲基邻苯二甲酰亚胺反应,
b)用权利要求1的方法将得到的反应产物分解成阴离子交换剂和N,N′-二甲基邻苯二甲酰胺,
c)将得到的N,N′-二甲基邻苯二甲酰胺环化成N-甲基邻苯二甲酰亚胺,
d)用权利要求1的方法将N-甲基邻苯二甲酰亚胺氯化。
8、含有-CH2NH2基并可用权利要求1和7的方法得到的阴离子交换剂在制备含有仲氨甲基和/或叔氨甲基和/或季铵基团的阴离子交换剂中的应用。
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CN104759299A (zh) * | 2015-04-23 | 2015-07-08 | 杜卫卫 | 单分散性碱型阴离子交换剂及其制备方法 |
CN104826671A (zh) * | 2015-04-30 | 2015-08-12 | 王英英 | 羟乙基二甲基氨基基团单分散性强碱型阴离子交换剂的制备方法 |
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BR9904682A (pt) * | 1999-02-24 | 2000-09-26 | Conselho Nacional De Desenvolv | Copolìmero de estireno e divinilbenzeno funcionalizado com elevado grau de grupamentos amino-metìlicos (epm-1) e sua utilização como novo tipo de resina trocadora aniÈnica |
EP1078689A3 (de) * | 1999-08-27 | 2003-02-26 | Bayer Ag | Verfahren zur Herstellung von monodispersen Anionenaustauschern mit stark basischen funktionellen Gruppen |
EP1078690B1 (de) * | 1999-08-27 | 2011-10-12 | LANXESS Deutschland GmbH | Verfahren zur Herstellung von monodispersen Ionenaustauschern mit chelatisierenden Gruppen |
JP3824153B2 (ja) * | 2002-03-26 | 2006-09-20 | 本田技研工業株式会社 | 電子パーツリストシステム |
GR1005716B (el) * | 2006-07-13 | 2007-11-07 | Βιομεντικα Λαϊφ Σαϊενσις Α.Ε. | Νεα βαθμιαιας υποκαταστασης αμινομεθυλιωμενα πολυμερη του πολυστυρενιου (βαμπ) για πεπτιδικη και οργανικη συνθεση σε στερεα φαση |
DE102006045504A1 (de) * | 2006-09-27 | 2008-04-03 | Lanxess Deutschland Gmbh | Wärmestabile Anionenaustauscher |
US20110020107A1 (en) * | 2007-03-23 | 2011-01-27 | Flodesign Wind Turbine Corporation | Molded wind turbine shroud segments and constructions for shrouds |
MX2017003774A (es) | 2014-09-29 | 2017-05-12 | Rennovia Inc | Preparacion y separacion de una mezcla que contiene acido dicarboxilico usando una forma dicarboxilada de una resina para cromatografia de intercambio anionico. |
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NL113552C (zh) * | 1957-12-02 | |||
DE1495762B2 (de) * | 1963-12-05 | 1971-09-09 | Farbenfabriken Bayer Ag, 5090 Lever Kusen | Verfahren zur herstellung von polymerisaten mit anionenaustau schenden eigenschaften |
US3882053A (en) * | 1971-12-11 | 1975-05-06 | Bayer Ag | Anion exchange resins |
US4491586A (en) * | 1980-06-05 | 1985-01-01 | Glaxo Group Limited | Amine derivatives |
US4478984A (en) * | 1983-09-23 | 1984-10-23 | Smithkline Beckman Corporation | Synthesis of benzhydrylamine resins |
DE3733033A1 (de) * | 1987-09-30 | 1989-04-13 | Bayer Ag | Verfahren zur herstellung von kunstharzen mit anionenaustauschenden eigenschaften |
-
1993
- 1993-08-20 DE DE4328075A patent/DE4328075A1/de not_active Withdrawn
-
1994
- 1994-06-24 TW TW083105738A patent/TW332785B/zh active
- 1994-08-08 DE DE59404931T patent/DE59404931D1/de not_active Expired - Fee Related
- 1994-08-08 EP EP94112375A patent/EP0639588B1/de not_active Expired - Lifetime
- 1994-08-12 US US08/289,812 patent/US5464875A/en not_active Expired - Fee Related
- 1994-08-12 JP JP6210693A patent/JPH0797406A/ja active Pending
- 1994-08-18 RO RO94-01384A patent/RO115426B1/ro unknown
- 1994-08-19 CN CN94109572A patent/CN1101303A/zh active Pending
- 1994-08-19 KR KR1019940020463A patent/KR950005851A/ko not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102029201A (zh) * | 2009-09-30 | 2011-04-27 | 朗盛德国有限责任公司 | 通过螯合树脂改进阳离子去除的方法 |
CN104759299A (zh) * | 2015-04-23 | 2015-07-08 | 杜卫卫 | 单分散性碱型阴离子交换剂及其制备方法 |
CN104826671A (zh) * | 2015-04-30 | 2015-08-12 | 王英英 | 羟乙基二甲基氨基基团单分散性强碱型阴离子交换剂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR950005851A (ko) | 1995-03-20 |
US5464875A (en) | 1995-11-07 |
EP0639588A1 (de) | 1995-02-22 |
EP0639588B1 (de) | 1998-01-07 |
TW332785B (en) | 1998-06-01 |
JPH0797406A (ja) | 1995-04-11 |
RO115426B1 (ro) | 2000-02-28 |
DE4328075A1 (de) | 1995-02-23 |
DE59404931D1 (de) | 1998-02-12 |
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