CN105263971B - 用于制造包括脂族氨基官能团的阴离子交换和螯合剂树脂的方法 - Google Patents
用于制造包括脂族氨基官能团的阴离子交换和螯合剂树脂的方法 Download PDFInfo
- Publication number
- CN105263971B CN105263971B CN201480032274.7A CN201480032274A CN105263971B CN 105263971 B CN105263971 B CN 105263971B CN 201480032274 A CN201480032274 A CN 201480032274A CN 105263971 B CN105263971 B CN 105263971B
- Authority
- CN
- China
- Prior art keywords
- polymer
- nitro
- nitro compound
- method described
- vinylaromatic 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 title claims abstract description 15
- 239000013522 chelant Substances 0.000 title claims abstract description 8
- 238000005349 anion exchange Methods 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 230000003252 repetitive effect Effects 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 35
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 4
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical class CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 claims description 3
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical class CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007265 chloromethylation reaction Methods 0.000 description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- -1 alkylidene Ester Chemical class 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical group COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 238000007871 hydride transfer reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- 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
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
-
- 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
-
- 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
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明涉及用于制造包含乙烯基芳族聚合物的阴离子交换或螯合剂树脂的方法,所述乙烯基芳族聚合物包括重复单元,所述重复单元包含经脂族氨基取代的芳环,其中所述方法包含使乙烯基芳族聚合物与包含1到12个碳原子的硝基化合物反应的步骤,其条件是α碳包括至少一个氢。
Description
技术领域
本发明大体上涉及用于制造阴离子交换和螯合剂树脂的方法,其包括乙烯基芳族共聚物的胺化。
背景技术
已在至少六十年前就通过多步骤方法制备来阴离子交换和螯合剂树脂,所述多步骤方法包括乙烯基芳族聚合物的氯甲基化,接着进行胺化。参见例如:US 5134169、US6756462、US 6924317、US 7282153和US 8273799。氯甲基化的初始步骤涉及使乙烯基芳族聚合物与氯甲基化试剂在催化剂存在下、在高温下反应。一种最常见的氯甲基化反应剂是氯甲基甲基醚(CMME),一种需要特殊处理的已知致癌物。氯甲基化过程产生废料流,其含有额外需要特殊处理的挥发性有机物。参见例如US 8163138。鉴于与氯甲基化相关的问题和成本,长期感到需要用于在无氯甲基化步骤的情况下胺化乙烯基芳族的替代性、工业上可行的途径。一种这类技术描述于US 4952608和US 6329435中,由此通过在酸性条件下与羟基甲基酞亚胺反应,接着进行水解来胺化乙烯基芳族聚合物。仍需要其它途径。
发明内容
在一个实施例中,本发明包括用于制造阴离子交换或螯合剂树脂的方法,其包含以下步骤:i)使乙烯基芳族聚合物与硝基化合物反应以形成聚合物,所述聚合物具有包含经硝基取代的芳环的重复单元,和ii)还原硝基以形成脂族氨基。硝基化合物优选包含1到12个碳原子,其条件是alpha(α)碳包括至少一个氢。在优选实施例中,硝基化合物是具有1到12个碳原子的硝基烷烃。描述许多其它实施例。通过本发明方法制得的树脂在多种应用中具有效用,包括水脱矿化和采矿。
具体实施方式
本发明包括用于制造阴离子交换树脂(包括弱碱和强碱树脂)和螯合剂树脂的方法。在优选实施例中,所述方法包括以下步骤:i)使乙烯基芳族聚合物与硝基化合物反应以形成聚合物,所述聚合物具有包含经硝基取代的芳环的重复单元,和ii)还原硝基以形成脂族氨基。硝基化合物优选包含1到12个碳原子,其条件是alpha(α)碳包括至少一个氢。在优选实施例中,硝基化合物是具有1到12个碳原子的硝基烷烃。代表性反应方案提供如下。
反应方案:
其中R1和R2独立地选自氢或具有1到12个碳原子的含碳部分(烃),例如脂族和芳族烃基。如所展示,乙烯基芳族聚合物包括重复单元,其包括芳族基,其在与硝基化合物反应时变成经硝基官能团(硝基产物)取代,并且在随后还原时变成位于芳环上的间位、邻位或对位处的脂族氨基(氨基产物)。优选硝基化合物包括硝基烷烃,例如硝基甲烷、硝基乙烷、1-硝基丙烷和2-硝基丙烷。在其它实施例中,“R1和R2”可包括含碳部分,其包括不饱和烃,例如乙烯基、芳族基等。
术语“乙烯基芳族聚合物”指一种聚合物,其在本领域中有时也称为“聚(芳乙烯)聚合物”。出于本说明书的目的,术语“乙烯基芳族聚合物”指来源于单亚乙烯单体和交联单体的聚合物。这类乙烯基芳族聚合物可使用众所周知的聚合技术制备,如单阶段聚合方法,如赫尔菲里希(F.Helfferich),《离子交换(Ion Exchange)》(麦格劳(McGraw)-希尔(Hill)1962),第35-36页中所描述,其中单一单体混合物悬浮聚合以产生共聚物珠粒;或“接种”或多阶段聚合方法,如US 4419245和4564644中所描述。适合的单亚乙烯单体是众所周知的并且参考由卡尔文E.席尔德克内希特(Calvin E.Schildknecht)编辑的《聚合物制程(Polymer Processes)》,由纽约国际科学出版社有限公司(Interscience Publishers,Inc.,New York)在1956年出版,席尔德克内希特的第III章,“悬浮液中的聚合”,第69-109页表II(第78-81页)描述适用于实践本发明的多种单亚乙烯单体。在所列举的单体中,优选包括单亚乙烯芳族化合物(如苯乙烯和经取代的苯乙烯)的不溶于水的单亚乙烯单体。术语“经取代的苯乙烯”包括苯乙烯的亚乙烯基和苯基中的任一个/或两个的取代基,并且包括:乙烯基萘、经α烷基取代的苯乙烯(例如α甲基苯乙烯)、经亚烷基取代的苯乙烯(尤其是经单烷基取代的苯乙烯,如乙烯基甲苯和乙基乙烯基苯)以及经卤基取代的苯乙烯,如溴代苯乙烯或氯代苯乙烯以及乙烯基苯甲基氯。其他可适用的单体包括单亚乙烯非苯乙烯类,如:α,β-烯系不饱和羧酸(尤其丙烯酸或甲基丙烯酸)酯;甲基丙烯酸甲酯;甲基丙烯酸异冰片酯;丙烯酸乙酯;以及丁二烯、乙烯、丙烯、丙烯腈以及氯乙烯;以及所述单体中的一个或多个的混合物。优选单亚乙烯单体包括苯乙烯和经取代的苯乙烯,如乙基乙烯基苯。术语“单亚乙烯单体”意欲包括均质单体混合物和不同类型单体(例如苯乙烯和甲基丙烯酸异冰片酯)的混合物。适合的交联单体(即聚亚二乙烯化合物)的实例包括聚亚二乙烯芳族化合物,如二乙烯基苯、二乙烯基甲苯、二乙烯基二甲苯、二氧化二乙烯基萘、三乙烯基苯、二(乙烯基)(二苯基)醚、二(乙烯基)(二苯基)砜,以及不同二丙烯酸亚烷基酯和二甲基丙烯酸亚烷基酯。优选交联单体是二乙烯基苯、三乙烯基苯和乙二醇二甲基丙烯酸酯。本文所使用的术语“交联剂(crosslinking agent)”、“交联剂(crosslinker)”和“交联单体”是同义词并且意图包括单种交联剂以及不同类型交联剂的组合。
标的乙烯基芳族聚合物典型地由包含超过50摩尔百分比并且优选超过75摩尔百分比以下物质的单体混合物制备:苯乙烯、经取代的苯乙烯或其组合;其中优选苯乙烯和乙基乙烯基苯。换句话说,所得乙烯基芳族聚合物的苯乙烯含量大于50摩尔百分比,并且更优选大于75摩尔百分比(以总摩尔含量计)。术语“苯乙烯含量”是指用于形成聚合物的苯乙烯和/或经取代的苯乙烯的单亚乙烯单体单元的数量。单体混合物进一步包括适量交联剂单体,其通常占全部单体混合物的0.01到20摩尔百分比,但优选是1到15摩尔百分比。
另一种可适用的乙烯基芳族聚合物包括互穿聚合物网状物(IPN)。术语“互穿聚合物网状物”意图描述含有至少两种聚合物的材料,每种都呈网状物形式,其中至少一种聚合物在另一种聚合物存在情况下合成和/或交联。聚合物网状物以物理方式彼此缠结并且在一些实施例中还可以共价键结。在特征上,IPN膨胀但既不溶解于溶剂中也不在加热时流动。包括IPN的离子交换树脂已市售多年并且可以通过涉及制备多聚合物组分的已知技术来制备。这类树脂以及其制备技术的实例提供于US 4419245、US 4564644、US 4582859、US5834524、US 6251996、US 6924317和US 2002/0042450中。如本文所使用,术语“聚合物组分”是指由独特的聚合步骤产生的聚合材料。举例来说,在本发明的优选实施例中,标的IPN离子交换树脂是“种子”树脂;即,树脂经由接种过程形成,其中首先形成聚合物(优选是交联的)晶种并且随后,渗吸单体并且随后聚合。可随后在聚合过程期间添加额外的单体(即,“连续添加”(continuous addition/con-add))。晶种粒子的形成构成了独特的聚合物组分。类似地,渗吸和使单体混合物聚合成晶种的过程步骤构成了另一种聚合物组分。若使用,通常用于“生长”晶种的单体混合物的后续连续添加步骤也构成了独特的聚合物组分。除非本文中明确描述,否则各种聚合物组分的成分可以相同或不同。此外,在聚合步骤期间所使用的单体混合物无需是均匀的;即,单体的比率和类型可以改变。术语“聚合物组分”并不打算意指所得树脂具有除互穿聚合物网状物以外的任何特定形态;然而,树脂可以具有“核-壳”型结构,如US Re34112中所描述。本发明的每种聚合物组分优选占最终IPN聚合粒子的超过约5重量百分比,并且更优选占至少10重量百分比。典型地,树脂包含两种或三种聚合物组分,例如晶种组分、渗吸组分和/或连续添加组分。所属领域的技术人员将理解,可以使用聚合物组分的不同或额外组合,例如可以利用多种连续添加组分。第一聚合物组分、第二聚合物组分、第三聚合物组分等不一定与添加顺序相对应。即,“第一聚合物组分”不一定与首先聚合的聚合物组分(例如晶种粒子)相对应。仅使用术语“第一”、“第二”等来将一种组分与另一种组分进行区分,并不表示添加顺序。
如先前所指示,本发明的聚合物可借助于接种聚合来制得。接种聚合,也称为连续或半连续分阶段聚合,通常描述于US 4419245、US 4564644和US 5244926中。其它适合的聚合方法描述于US 4444961、US 4623706、US 4,666673和US 5244926中。尽管交联聚合物可以是大孔型或凝胶型,优选凝胶型聚合物。术语“凝胶型”和“大孔型”是本领域中众所周知的并且一般描述聚合粒子孔隙度的性质。如本领域中常用的,术语“大孔型”意指聚合物同时具有大孔和中孔。术语“微孔型”、“蜂窝状”、“凝胶”和“凝胶型”是同义词,其描述孔径小于约20埃的聚合物粒子,而大孔型聚合物粒子具有约到约的中孔和大于约的大孔。凝胶型和大孔型聚合物粒子以及其制备进一步描述于US 4256840和US5244926中。成品聚合物粒子优选具有中值粒径是150到800微米的珠粒结构。交联聚合物粒子可以具有高斯粒径分布(Gaussian particle size distribution)或相对均匀粒径分布,也就是说,至少90体积%的珠粒的粒径是体积平均粒径的约0.9倍到约1.1倍。
乙烯基芳族聚合物与硝基化合物的反应优选通过组合某一化学计量比的成分来进行(例如硝基化合物与乙烯基芳族聚合物中的芳族部分是15∶1到1∶1摩尔比)。组合优选在适合的溶剂中,在惰性气氛(例如氮气)和温和温度(例如约20℃到140℃)下回流约20分钟到20小时。适合的溶剂能够使自由基稳定,例如乙酸、硝基烷烃(如硝基甲烷)、卤化溶剂(如二氯甲烷和EDC)。乙酸是优选溶剂。反应可视情况通过包括金属试剂(优选具有1.0到2.5V的还原电位,例如Mn+3或Ce+4)催化。优选试剂是乙酸锰(III)。接着可以从反应混合物分离(例如过滤)试剂并且通过阳极氧化以电化学方式再生。对于Mn2+经由电化学途径转化成Mn3+,这一再生也可以现场实现,引起Mn3+中的过程催化。通常在以下参考文献中关于非聚合物描述锰(III)催化的硝基烷基化的使用:库茨(Kurz)等人,使用硝基甲烷-乙酸锰(III)的芳族烃的硝基甲基化(Nitromethylation ofAromatic Hydrocarbons withNitromethane-Manganese(III)Acetate),化学通讯杂志(J.C.S.Chem.Comm.),(1976),968-969;库茨等人,由乙酸锰(III)促进芳族烃的硝基甲基化(Nitroalkylation ofAromatic Hydrocarbons Promoted by Manganese(III)Acetate),有机化学杂志(J.Org.Chem)(1981),46,4668-4672;和使用以电化学方式产生的锰(III)进行苯的硝基甲基化(Nitromethylation of Benzene Using Electrochemically Generated Manganese(III)),斯堪的纳维亚化学学报,系列B(Acta Chemica Scandinavica B),33(1979),208-212。
实例
实例1:乙酸锰(III)(10.0mmol)、苯乙烯-DVB共聚物(2.0mmol)、乙酸(10.0mL)、二氯甲烷(5.0mL)和硝基烷烃(以下中的一种:1-硝基丙烷、2-硝基丙烷、硝基乙烷或硝基甲烷,10.0mL)可共同在氮气气氛下回流,同时连续搅拌直到乙酸锰(II)沉淀并且反应混合物呈现白色。向反应混合物中添加水,接着过滤反应混合物并且用水(3×15.0mL)洗涤,并且在真空中干燥。IR(纯)3025,2922,2848,1547(NO2vas),1492,1451,1369(NO2vs)cm-1。
随后用于形成氨基产物的硝基(参见以上说明的反应方案中的硝基产物)还原可通过在压力(例如2到25kPa)下,在温和温度(例如约20℃到100℃)下组合硝基产物与氢气来进行。反应可通过包括经典还原反应剂(诸如钯、铂和镍)来催化。也可以使用催化剂调节剂,如砜、亚砜、硫酸盐、胺和多元胺。还原反应优选在溶剂(如水、醇、醚或烃)中进行。在另一个实施例中,硝基还原成胺可使用氢化物转移反应剂进行。一个实例是在四氢呋喃溶剂中,在0℃到60℃的温度下使用氢化锂铝历时1到6小时。举例来说,在0℃下,向硝基烷基化聚苯乙烯-共-DVB(0.30mmol于NO2基团中)于THF(10.0mL)中的混合物中缓慢添加LAH(1.0mmol)。反应物的内部温度应保持低于20℃。在室温下搅拌混合物4小时。接着将反应物冷却到0℃并且通过相继缓慢添加水(10.0mL)和NaOH的50%饱和溶液(10.0mL)来淬灭。可过滤聚合物珠粒并且用水(3×15.0mL)洗涤,并且在真空中干燥。IR(纯)3419(NH搅拌),3025,2920,2848,1601,1493,1451,1366,1003,744cm-1
实例2:硝酸铈铵(10.0mmol)、直链聚苯乙烯或苯乙烯-DVB共聚物(2.0mmol)、(10.0mL)乙酸(10.0mL)、二氯甲烷(5.0mL)和硝基烷烃(以下中的一种:1-硝基丙烷、2-硝基丙烷、硝基乙烷或硝基甲烷,10.0mL)共同在氮气气氛下回流,同时连续搅拌8小时。添加水,并且接着过滤反应混合物且用水(3×15.0mL)洗涤,并且在真空中干燥。IR(纯)3025,2922,2848,1547(NO2nas),1492,1451,1369(NO2ns)cm-1。
实例3:将乙酸锰(II)(1.47g,6mmol)和LiBF4(560mg,0.1M)添加到乙酸(60mL)、硝基甲烷(50mL)和直链聚苯乙烯或苯乙烯-DVB共聚物(2.0mmol)的混合物中。将混合物加热到85℃并且在10V下电解2.5小时。添加水,并且接着过滤反应混合物且用水(3×15.0mL)洗涤,并且在真空中干燥。IR(纯)3025,2922,2848,1547(NO2nas),1492,1451,1369(NO2ns)cm-1。
已经描述了本发明的多个实施例并且在一些情况下,已将某些实施例、选择、范围、成分或其它特征表征为“优选的”。“优选”特征的表征决不应解释为将这类特征视为对本发明来说所需的、必需的或至关重要的。应理解,某些特征和子组合具有效用,并且可以在不参考其它特征和子组合的情况下使用。数值范围的参考明确地包括这类范围的端点。应了解,除本文中所描述的胺化反应以外,本文中所描述的乙烯基芳族聚合物可进一步官能化。
Claims (7)
1.一种用于制造阴离子交换或螯合剂树脂的方法,其包含以下步骤:
i)在金属试剂存在下,使乙烯基芳族聚合物与硝基化合物反应以形成聚合物,所述聚合物具有重复单元,所述重复单元包含经硝基取代的芳环,其中所述硝基化合物包含1到12个碳原子,其条件是α碳包括至少一个氢,和
ii)还原所述硝基以形成脂族氨基。
2.根据权利要求1所述的方法,其中所述硝基化合物是硝基烷烃。
3.根据权利要求1所述的方法,其中所述硝基化合物是选自以下各项中的至少一个:硝基甲烷、硝基乙烷、1-硝基丙烷和2-硝基丙烷。
4.根据权利要求1所述的方法,其中所述乙烯基芳族聚合物与硝基化合物之间的反应是在具有1.0到2.5V的还原电位的金属试剂存在下进行。
5.根据权利要求1所述的方法,其中所述乙烯基芳族聚合物与硝基化合物之间的反应是在选自以下各项中的至少一个的金属试剂存在下进行:Mn+3和Ce+4。
6.根据权利要求1所述的方法,其中所述金属试剂通过阳极氧化以电化学方式再生。
7.根据权利要求1所述的方法,其中所述乙烯基芳族聚合物包含来源于包含苯乙烯和二乙烯基苯的反应混合物的聚合物。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361836769P | 2013-06-19 | 2013-06-19 | |
US61/836769 | 2013-06-19 | ||
PCT/US2014/041458 WO2014204686A1 (en) | 2013-06-19 | 2014-06-09 | Method for making anion exchange and chelant resins including aliphatic amino functional groups |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105263971A CN105263971A (zh) | 2016-01-20 |
CN105263971B true CN105263971B (zh) | 2018-04-27 |
Family
ID=51062993
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480032274.7A Expired - Fee Related CN105263971B (zh) | 2013-06-19 | 2014-06-09 | 用于制造包括脂族氨基官能团的阴离子交换和螯合剂树脂的方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9486798B2 (zh) |
EP (1) | EP2986651B1 (zh) |
JP (1) | JP6185663B2 (zh) |
KR (1) | KR102167236B1 (zh) |
CN (1) | CN105263971B (zh) |
RU (1) | RU2658003C2 (zh) |
WO (1) | WO2014204686A1 (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5134169A (en) * | 1988-12-19 | 1992-07-28 | Mintek | Gold selective ion exchange resins |
CN102317325A (zh) * | 2009-02-13 | 2012-01-11 | 陶氏环球技术有限责任公司 | 使用叔胺的乙烯基芳族聚合物的胺化 |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL241315A (zh) | 1958-07-18 | |||
US3791996A (en) * | 1971-11-01 | 1974-02-12 | Rohm & Haas | Direct acylaminomethylation of aromatic polymers |
JPS5326889A (en) * | 1976-08-25 | 1978-03-13 | Kanebo Ltd | Preparation of adsorbent for heavy metals |
CA1166413A (en) | 1980-10-30 | 1984-05-01 | Edward E. Timm | Process and apparatus for preparing uniform size polymer beads |
US4666673A (en) | 1980-10-30 | 1987-05-19 | The Dow Chemical Company | Apparatus for preparing large quantities of uniform size drops |
US4419245A (en) | 1982-06-30 | 1983-12-06 | Rohm And Haas Company | Copolymer process and product therefrom consisting of crosslinked seed bead swollen by styrene monomer |
US4564644A (en) | 1982-08-02 | 1986-01-14 | The Dow Chemical Company | Ion exchange resins prepared by sequential monomer addition |
US4582859A (en) | 1983-12-02 | 1986-04-15 | Rohm And Haas Company | Process for producing an expanded seed copolymer and product therefrom |
US4623706A (en) | 1984-08-23 | 1986-11-18 | The Dow Chemical Company | Process for preparing uniformly sized polymer particles by suspension polymerization of vibratorily excited monomers in a gaseous or liquid stream |
DE3704307A1 (de) | 1987-02-12 | 1988-08-25 | Dow Chemical Gmbh | Komplexbildendes harz des geltyps und seine verwendung zur verringerung der konzentration mehrwertiger erdalkali- und/oder schwermetallionen in loesungen |
DE3733033A1 (de) | 1987-09-30 | 1989-04-13 | Bayer Ag | Verfahren zur herstellung von kunstharzen mit anionenaustauschenden eigenschaften |
USRE34112E (en) | 1989-10-17 | 1992-10-27 | The Dow Chemical Company | Condensate purification process |
JP2846390B2 (ja) * | 1990-02-14 | 1999-01-13 | 株式会社バイオマテリアル研究所 | 表面にアミノ基を有する光透過性芳香族ビニル系重合体成型品およびその製造方法 |
US5244926A (en) | 1992-06-16 | 1993-09-14 | The Dow Chemical Company | Preparation of ion exchange and adsorbent copolymers |
JPH06287221A (ja) * | 1993-03-30 | 1994-10-11 | Maruzen Petrochem Co Ltd | ビニルフェノール系重合体のアミノ化物の製造方法 |
DE19634393A1 (de) | 1996-08-26 | 1998-03-05 | Bayer Ag | Verfahren zur Herstellung vernetzter Polymerisate |
US6251996B1 (en) | 1998-12-09 | 2001-06-26 | The Dow Chemical Company | Gel-type copolymer bead and ion-exchange resins made therefrom |
DE50014560D1 (de) | 1999-08-27 | 2007-09-27 | Lanxess Deutschland Gmbh | Verfahren zur Herstellung von monodispersen, vernetzten Perlpolymerisaten mit Thioharnstoffgruppen und ihre Verwendung zur Adsorption von Metallverbindungen |
DE10010002A1 (de) * | 2000-03-02 | 2001-09-06 | Celanese Ventures Gmbh | Verfahren zur Nitrierung und Aminierung von Arylpolymer |
JP4635162B2 (ja) | 2000-04-27 | 2011-02-16 | 独立行政法人理化学研究所 | 芳香族ジアミンの製造方法及び芳香族ジアミン化合物 |
DE10049807A1 (de) | 2000-10-09 | 2002-04-18 | Bayer Ag | Verwendung monodisperser Ionenaustauscher zur Arsen-/Antimonentfernung |
US6756462B2 (en) | 2001-07-03 | 2004-06-29 | Rohm And Haas Company | Method for preparation of anion exchange resins |
DE10214844A1 (de) | 2002-04-04 | 2003-10-16 | Bayer Ag | Verfahren zur Herstellung von grobkörnigen gelförmigen Anionenaustauschern |
EP1568660B1 (en) | 2004-02-24 | 2010-12-15 | Rohm And Haas Company | Method for removal of arsenic from water |
US8163138B2 (en) | 2007-05-23 | 2012-04-24 | Dow Global Technologies Llc | Method for processing effluent from chloromethylation of vinyl aromatic polymers |
RU2429070C1 (ru) * | 2010-02-17 | 2011-09-20 | Олег Алексеевич Шпигун | Анионообменный сорбент для одновременного ионохроматографического определения поляризуемых и неполяризуемых неорганических анионов и способ его изготовления |
-
2014
- 2014-06-09 KR KR1020167000629A patent/KR102167236B1/ko active IP Right Grant
- 2014-06-09 EP EP14735061.5A patent/EP2986651B1/en not_active Not-in-force
- 2014-06-09 JP JP2016519567A patent/JP6185663B2/ja not_active Expired - Fee Related
- 2014-06-09 US US14/384,101 patent/US9486798B2/en active Active
- 2014-06-09 RU RU2015155269A patent/RU2658003C2/ru active
- 2014-06-09 CN CN201480032274.7A patent/CN105263971B/zh not_active Expired - Fee Related
- 2014-06-09 WO PCT/US2014/041458 patent/WO2014204686A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5134169A (en) * | 1988-12-19 | 1992-07-28 | Mintek | Gold selective ion exchange resins |
CN102317325A (zh) * | 2009-02-13 | 2012-01-11 | 陶氏环球技术有限责任公司 | 使用叔胺的乙烯基芳族聚合物的胺化 |
Also Published As
Publication number | Publication date |
---|---|
US9486798B2 (en) | 2016-11-08 |
EP2986651A1 (en) | 2016-02-24 |
JP2016521800A (ja) | 2016-07-25 |
KR102167236B1 (ko) | 2020-10-20 |
JP6185663B2 (ja) | 2017-08-23 |
KR20160037881A (ko) | 2016-04-06 |
CN105263971A (zh) | 2016-01-20 |
US20160236187A1 (en) | 2016-08-18 |
RU2015155269A (ru) | 2017-07-24 |
EP2986651B1 (en) | 2017-02-22 |
RU2658003C2 (ru) | 2018-06-19 |
WO2014204686A1 (en) | 2014-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9234082B2 (en) | Polymer material having high capacity for hydrogen storage and preparation method thereof | |
KR20110126672A (ko) | 3급 아민을 사용하는 비닐 방향족 중합체의 아민화 | |
MX2010012594A (es) | Composicion de catalizador de aleacion de metales. | |
CN105504128A (zh) | 一种用于处理含酚废水的吸附树脂及其制备方法和应用 | |
HU225306B1 (en) | Functionalized polymeric media for separation analytes | |
US4207398A (en) | Process for preparing physically stable quaternary ammonium anion exchange resins by chloromethylation and amination in the absence of additional organic solvent | |
US20090057231A1 (en) | Monodisperse boron-selective resins | |
JP5443682B2 (ja) | ヒドロキシ基又は第1級アミノ基を有する多孔質樹脂粒子とその製造方法 | |
CN105263971B (zh) | 用于制造包括脂族氨基官能团的阴离子交换和螯合剂树脂的方法 | |
CN100523055C (zh) | 双酚a的制造方法 | |
EP0455628A1 (en) | Method for preparation of anion exchange resins having very low chlorine content | |
JP4744494B2 (ja) | 熱安定性アニオン交換体 | |
CN104704008B (zh) | 包括侧位芳基环氧基团的水不溶性共聚物 | |
Da Costa et al. | Influence of the matrix porosity on the synthesis and adsorption behavior of dithiocarbamate styrenic resins toward zinc (II) and cadmium (II) ions | |
US7399792B2 (en) | Solid reagents | |
CN108367213A (zh) | 使用强碱阴离子交换树脂层析分离丙酸 | |
EP0045824A1 (en) | Ion exchange material, its preparation and use | |
KR20160056676A (ko) | 인 제거용 키토산-멜라민 복합체 및 이의 제조방법 | |
JP2013512980A (ja) | メチレンアミノエチルスルホン酸キレート樹脂 | |
JP2019519652A (ja) | アミドメチル化ビニル芳香族粒状ポリマーを製造するための方法 | |
RU2387673C1 (ru) | Способ получения пористых слабоосновных анионитов | |
JPH0549951A (ja) | 糖液精製用架橋アニオン交換体 | |
Sun et al. | Synthesis and separation properties for Cu (II)‐Ni (II) of macroporous crosslinked polystyrene‐supported triethylenetetramine resin using Cu (II) as template | |
JP2002030112A (ja) | アニオン交換樹脂、その製法及びこれを用いるクランピング防止方法 | |
JPH0645654B2 (ja) | キレ−ト樹脂及びその製法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180427 |