CN108080039A - A kind of manufacturing method of alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin - Google Patents
A kind of manufacturing method of alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin Download PDFInfo
- Publication number
- CN108080039A CN108080039A CN201710559026.3A CN201710559026A CN108080039A CN 108080039 A CN108080039 A CN 108080039A CN 201710559026 A CN201710559026 A CN 201710559026A CN 108080039 A CN108080039 A CN 108080039A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- exchange resin
- anion exchange
- tertiary amine
- type
- 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.)
- Granted
Links
- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 125000003277 amino group Chemical group 0.000 title abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 43
- 150000001412 amines Chemical class 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000010935 stainless steel Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 239000004793 Polystyrene Substances 0.000 claims description 38
- 229920002223 polystyrene Polymers 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 21
- -1 dimethyl n butylamine Chemical compound 0.000 claims description 15
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000243 solution Substances 0.000 abstract description 22
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 235000019441 ethanol Nutrition 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 10
- 238000005349 anion exchange Methods 0.000 description 10
- 238000006482 condensation reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000007689 inspection Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 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 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012718 coordination polymerization Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000003196 chaotropic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920000891 common polymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08F8/44—Preparation of metal salts or ammonium salts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of alcohol-soluble quaternary amine type or the manufacturing methods of tertiary amine-type anion exchange resin, raw material is made using poly- (styrene ethylene) alternate copolymer of line style, it is allowed to be dissolved completely among halogenated alkane, then the industrial chloromethane ethereal solution dissolved with catalyst is added in, implements homogeneous chloromethylation；Then reaction product is squeezed out into the water containing dispersant and sodium hydroxide by stainless steel high pressure nozzle, suspension system is quickly dispersed as with the agitating paddle with cutting function；It is evaporated under reduced pressure to recycle halogenated alkane, and clean, addition organic amine reactant aqueous solution is washed with water after suspended particulate is filtered dry；Residual reaction liquid is filtered dry, dilute hydrochloric acid is added in and neutralizes, be washed with deionized several times after being filtered dry；Finally it is filtered dry again, by solid particle forced air drying, i.e., the obtained alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin product.Interiors of products quaternary amine or tertiary amine group are evenly distributed made from the method for the present invention, can be completely dissolved in the Organic Alcohol of hypotoxicity.
Description
Technical field
It is more particularly to a kind of to be based on poly- (styrene-ethylene) alternating copolymerization the invention belongs to functional high polymer material field
It is object, being completely dissolved in alcohol organic solvent, with strong alkaline quaternary ammonium base or alkalescent tertiary amine functional, can send out
The functional resin material and its manufacturing method of raw anion exchange.
Background technology
Polymer material (the alternatively referred to as amino polystyrene containing quaternary ammoniated or tertiary-aminated polystyrene component of line style
Based polyalcohol), due to possess can highly be swollen in water, appropriateness dissolving, strong hydrophilic, anion exchange in organic solvent
Physicochemical properties are waited, are widely used in the every field such as hydrophilic film preparation, water process, the energy.For example, at as hydrophilic water
The reason material of main part of Positively charged membrane (such as microfiltration membranes, ultrafiltration membrane, NF membrane, amberplex etc.) or auxiliary addition material
Material, to improve the hydrophily of film, pollution resistance or ion-selective permeability；For making alkaline fuel cell membrane；As water
The flocculant or dispersant of solution, play corresponding industrial use.
This kind of material, generally by the polystyrene based polymers to line style, implement successively chloromethylation and amination it
Obtained from afterwards.For chloromethylation, generally the chloromethyl ether of high activity is used to be added dropwise to and gather dissolved with line style as reaction reagent
Among the polymer solution of styrene content, under the effect of the catalyst, chloromethylation slowly occurs and (belongs to friedel-craft
Reaction mechanism).If catalyst activity too high (such as anhydrous Aluminum chloride), chloromethyl ether concentration is too dilute, reaction temperature is excessively high or
Reaction time is too long, it is most likely that causes self-crosslinking side reaction occurs between the chloromethylated polystyrene component of line style, be formed
The insoluble matter of gelatinous net structure.Even if after amination (quaternary ammoniated or tertiary-aminated), hydrophily is increased this insoluble matter
Add, but cross-linked structure still remains, alcohol-soluble or water-soluble all bad.At the same time, the tool of linear polystyrene base
Body configuration can also influence the result of chloromethylation.If the polystyrene component in macromolecule link is excessively intensive,
The possibility of self-crosslinking side reaction can be increased.Presently commercially available linear polystyrene based polyalcohol, except simple line style polyphenyl
Outside ethylene (being the polymer of single block in structure), polystyrene and polyethylene, polyisobutene, polypropylene, poly- fourth are further included
Two blocks or triblock copolymer of the compound composition of the components such as diene.For example, " A-B " configuration by the production of Ke Teng companies of the U.S.
Diblock copolymer, including polystyrene-polybutadiene (SB), polystyrene-ethylene/butene random copolymer (SEB) etc.；Also
The triblock copolymer of " A-B-A " configuration is provided, including polystyrene-polybutadiene-poly styrene polymer (SBS), polyphenyl
Ethylene-polyisoprene-polystrene polymer (SIS), hydrogenated polystyrene-ethylene/butylene random copolymer-polystyrene
Polymer (SEBS), polystyrene-ethylene/propylene copolymer-poly styrene polymer (SEPS) etc..These two blocks and three embedding
The copolymer of section, can serve as polystyrene based polymers, for implementing homogeneous chloromethylation (bibliography：Li Li
Deng, the indirect chloromethylation research of SEBS, chemical journal, 2007,65 (20):2331-2335).
Noncrosslinking list block linear polystyrene polymer (polystyrene component content close to 100%) and two embedding
The linear polystyrene base co-polymer of section or three block, all there are intensive polystyrene component (i.e. polyphenyl during macromolecule chains
Ethylene link is longer), it is easy to cause self-crosslinking side reaction occurs in chloromethylation.Meanwhile carried in block polymer
The polyolefin component of equivalent length so that the resin product after amination is difficult to be dissolved in alcohols solvent (such as ethyl alcohol, isopropanol)
Or solubility can be very low, generally will use highly toxic solvent (such as toluene, dimethylbenzene, tetrahydrofuran, dimethyl sulfoxide (DMSO),
Chloroform etc. or the cosolvent system being made of them) it could realize and be completely dissolved, cause the needs foundation in application more multiple
Miscellaneous solvent-treatment system.Meanwhile these block polymers are generally by the polymerization based on luxuriant titanium class catalyst
Obtained from (such as anionic polymerisation), therefore molecular weight distribution relatively wide (the ratio between weight average molecular weight and number-average molecular weight
More than 2.2), causing, the dissolving gender gap of aminate is larger.In addition, the polymerization activity being limited between styrene and ethylene is poor
Different, generally than relatively low, mass percent is difficult to more than 70% the polystyrene component content in these block polymers, therefore difficult
To obtain the anion exchange resin product compared with high-exchange-capacity after amination.
On the other hand, to the homogeneous chloromethane of above-mentioned polystyrene based polymers (including single block, two blocks and three block)
Glycosylation reaction generally requires and reaction solution is added to substantial amounts of intensive polar solvent (such as methanol, second after chloromethylation terminates
Alcohol) in rapid precipitation, block-like solid product is precipitated.A large amount of solvents are (such as halogenated used by this will cause chloromethylation
Alkane, industrial chloromethyl ether) it is mutually immiscible with a greater amount of precipitation solvents, further resulting in subsequent solvent separation process becomes numerous
It is trivial, time-consuming, laborious.Meanwhile block-like chloromethylation solid product, it is also necessary to could continue to implement aminating reaction after crushing.
This i other words, due to solvent post-treating process and wordy and efficient, cause being manufactured into for entire anion exchange resin product
This is high.
In view of the foregoing, it is necessary to select segmented structure more rationally, polystyrene component content higher, molecular weight distribution
Narrower polystyrene-based alternating polymer to replace the polystyrene based polymers of above-mentioned block structure, is implementing homogeneous chlorine
Alcohol-soluble more preferably anion exchange resin product is obtained after methylation reaction and aminating reaction, to meet some occasions (such as
Anion-exchange membrane cast liquid) use.Simultaneously, it is necessary to simplify the aftertreatment technology of chloromethylation, obtain smaller
While the chloromethylation midbody particle of granularity, make every effort to avoid the use of a large amount of precipitation solvents, to realize higher efficiency and more
Large-scale manufactures this kind of anion exchange resin product at low cost.
The content of the invention
The purpose of the invention is to improve the structure of amino polystyrene base product, solubility property and manufacturing method, carry
Go out a kind of quaternary amine type of alcohol-soluble or inexpensive, the efficient manufacturing method of tertiary amine-type anion exchange resin, to meet phase
Close the application demand of industrial circle.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of alcohol-soluble quaternary amine type or tertiary amine-type anion
The manufacturing method of exchanger resin, includes the following steps：1) poly- (styrene-ethylene) alternate copolymer of line style is put into alkyl halide
Hydrocarbon, heating, stirring are allowed to be completely dissolved, and form homogeneous Polymer Solution；2) rapidly join in advance dissolved with the industrial chlorine of catalyst
Methyl ether solution implements homogeneous chloromethylation；3) by reaction product by stainless steel high pressure nozzle, squeeze out to containing dispersant
In the water of sodium hydroxide, suspension system is quickly dispersed as with the agitating paddle with cutting function；4) after system stably dispersing
Halogenated alkane is recycled in vacuum distillation；Moisture content is filtered dry, obtains fluffy chloromethylation solid particle；5) it is washed with water several times, adds in
Organic amine/water solution implements aminating reaction；Be filtered dry reaction solution, add in dilute hydrochloric acid neutralize, transition, be washed with deionized to connecing
Weakly acidic pH；6) solid particle being filtered dry is sent into blast drier and dried, that is, the alcohol-soluble quaternary amine type or tertiary amine is made
Type anion exchange resin product.
The beneficial effects of the invention are as follows：The alcohol-soluble quaternary amine type made from the method for the invention or tertiary amine-type anion are handed over
Naval stores is changed, because it is poly- (styrene-ethylene) to employ the narrower line style of polystyrene component content higher, molecular weight distribution
Alternate copolymer, instead of the linear polystyrene base block copolymerization that polystyrene component content is relatively low, molecular weight distribution is wider
Object, the Nomenclature Composition and Structure of Complexes of macromolecule link is more uniform, causes dissolubility of the chloromethylation before in halogenated alkane more preferably, i.e.,
Homogeneous chloromethylation can more effectively be implemented；And after height chloromethylation and abundant amination, anion exchange resin
The ion exchange capacity higher of product, and alcohol organic solvent can be rapidly dissolved completely in, it is high so as to obtain clear function
Molecular solution.Meanwhile the present invention proposes by high pressure nozzle to squeeze out chloromethylation system to Compound Water phase (containing dispersant
With the aqueous solution of sodium hydroxide) among, and suspension system is quickly dispersed as with the agitating paddle with cutting function, causing can be real
Now vacuum distillation recycling reaction dissolvent (halogenated alkane), obtains the smaller and relatively uniform product particle of granularity, this not only facilitates
Subsequent aminating reaction and improve product appearance, it is thus also avoided that use traditional " alcohol deposition method ", it is anti-to realize halogenated alkane
The timely recycling of solvent is answered, therefore greatly simplifies production process and reduces production cost.
Specific embodiment
The manufacturing method of alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin of the present invention, including walking as follows
Suddenly：1) poly- (styrene-ethylene) alternate copolymer of line style is put into halogenated alkane, heating, stirring are allowed to be completely dissolved, and are formed equal
Phase Polymer Solution；2) rapidly join in advance dissolved with the industrial chloromethane ethereal solution of catalyst, implement homogeneous chloromethylation；3)
By reaction product by stainless steel high pressure nozzle, squeeze out into the water containing dispersant and sodium hydroxide, with cutting function
Agitating paddle be quickly dispersed as suspension system；4) it is evaporated under reduced pressure after system stably dispersing, recycles halogenated alkane；It is filtered dry moisture content,
Obtain fluffy chloromethylation solid particle；5) it is washed with water several times, adds in organic amine/water solution, implements aminating reaction；It is filtered dry
Reaction solution adds in dilute hydrochloric acid and neutralizes, makes the transition, and is washed with deionized to close neutrality；6) solid particle being filtered dry is sent into and roused
It is dried in wind drying machine, i.e., the obtained alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin product.
Poly- (styrene-ethylene) alternate copolymer of line style described in step 1, number-average molecular weight 30,000~50,000
Dalton.If molecular weight is too small, the water-soluble of product after amination (particularly quaternary ammoniated) can be caused to increase or even understood
It is complete soluble in water；If molecular weight is too big, alcohol-soluble can be caused insufficient, it is molten to cannot get completely soluble clear macromolecule
Liquid, while can also increase the possibility that self-crosslinking side reaction occurs for chloromethylation process.Line style poly- (styrene-ethylene) is alternately common
The ratio between weight average molecular weight and number-average molecular weight of polymers are 1.8~2.2.It is general to be difficult to obtain molecular weight narrower (ratio is less than
1.8) copolymer, and too wide molecular weight distribution (ratio is more than 2.2) can cause anion exchange resin product solubility,
It is separated in the physicochemical properties such as film forming, ionic conduction there are apparent difference, influences subsequent applications.This kind of line style it is poly- (styrene-
Ethylene) alternate copolymer, macromolecule chains can generally be represented simply as "~S with structural formulam-En~" (in formula：S refers to single
Styrene molecules, E refer to single ethylene molecule, m=1~2, n=2~5), it may be referred to Chinese invention patent application number
A kind of 201110083107.3 described methods, using rare earth being made of rare earth amido complex/alkyl aluminum/organic boron salt
Catalyst system and catalyzing is obtained with coordination polymerization process.Wherein, the mass percentage content of polystyrene component is 65~80%.
If content is less than 65%, the ion exchange capacity deficiency of anion exchange resin obtained, while polyethylene segment can be caused
It is long, the alcohol-soluble of resin can be influenced；If content is higher than 80%, chloromethylation process can be easily lead to, self-crosslinking occurs
Side reaction.Halogenated alkane described in step 1, including dichloromethane, chloroform and dichloroethanes, preferably dichloroethanes.Chlorine
Addition quality for alkane is added in 12~20 times of poly- (styrene-ethylene) alternate copolymer of line style.If alkyl halide
Hydrocarbon adds in very little, it is difficult to be completely dissolved alternating polymer, also be easy to cause during chloromethylation because of the dense of linear polymer
Du Taigao and the probability for increasing self-crosslinking side reaction.If halogenated alkane dosage is too big, reactant concentration can be caused relatively low, therefore
Chloromethylation speed reduces and the reaction time significantly extends, while causes unnecessary waste of solvent.
Catalyst described in step 2, including anhydrous zinc chloride and anhydrous ferric chloride.The chloromethyl of polystyrene component
Change, can also use anhydrous stannic chloride, anhydrous titanium tetrachloride and anhydrous Aluminum chloride and implement to be catalyzed；But these three catalyst
Activity is too high, it is easy to cause poly- (styrene-ethylene) alternate copolymer of the line style that self-crosslinking side reaction occurs.It is and anhydrous
The catalytic activity of zinc chloride and anhydrous ferric chloride is relatively low, and it (is not slow to be rapidly joined again after industrial chloromethyl ether is dissolved in advance
Slowly it is added dropwise), self-crosslinking side reaction can be effectively prevented.The addition quality of anhydrous zinc chloride and anhydrous ferric chloride, to be added in
0.2~0.6 times of poly- (styrene-ethylene) alternate copolymer of line style, specific addition is (anhydrous according to the species of catalyst
The catalytic activity of iron chloride is more slightly higher than anhydrous zinc chloride), in alternate copolymer polystyrene component content (content is higher,
Catalyst needs more), required chloromethylation degree etc. is because usually determining.It adds in very little, institute is not achieved in chloromethylation
The extent of reaction needed, i.e. benzyl chloride group content deficiency；It adds in too many, it will make reaction too fast, increase self-crosslinking side reaction
Probability.In addition, the industrial chloromethyl ether described in step 2, the effective content of general chloromethyl ether is 40~45%, remaining is organic molten
Agent component (such as dichlormethyl ether, chlorohydrocarbon) has no effect on use.The addition quality of industrial chloromethyl ether, the line style to be added in are gathered
3~6 times of (styrene-ethylene) alternate copolymer.Addition is very little, can cause the effective concentration deficiency of chloromethyl ether, so as to hold
Easily cause self-crosslinking side reaction；Addition is too big, not only wastes, and also results in and occurs to swash play when squeezing out to water phase by nozzle
Chloromethyl ether hydrolysis and acid-base neutralization reaction, be unfavorable for chlorinated paraffin solvent recycling use.
Dispersant described in step 3 is polyvinyl alcohol, hydroxyethyl cellulose and gelatin, preferably polyvinyl alcohol.Depending on specific
Dispersion effect, the addition of dispersant can adjust suitably, be usually no more than the 0.5% of water quality.The hydroxide added in
The amount of sodium, the amount of the chloromethyl ether added in when need to be according to chloromethylation are calculated and obtain, are preferably ensured water-soluble after neutralization
Liquid meta-alkalescence (pH is 10~12), to be mutually connected with subsequent aminating reaction.But it if sodium hydroxide adds in excessively, can lead
It causes that violent chloromethyl ether degradation and acid-base neutralization reaction occur when chloromethylation product is expressed into water phase, makes alkyl halide
Hydrocarbon overflows too fast.Used stainless steel nozzle, most handy 316L stainless steels manufacture, to ensure to resist the acidity of high intensity
Liquid corrosion；Nozzle can be the multi-port structure of " shower nozzle " formula, but the spacing between spout and spout is more preferably greater than 2 lis
Rice, to prevent that it is agglomerating that spinneret from mutually bonding；Nozzle diameter is more preferably less than 1 millimeter, to ensure that spinneret is sufficiently fine；By chloromethylation
When reaction product is squeezed out to water phase, nozzle should be installed on container bottom, and be totally submerged among Yu Shuixiang, pass through high-pressure pump (example
Such as plunger pump) squeeze out when, radially spray.The used agitating paddle with cutting function, structure are stirring slurry main shaft
On densely horizontal slurry of the dispersed placement with the sharp keen knife edge, cause agitating paddle that will can progressively be precipitated in quick rotation
Soft particle cut, spread out immediately.The position of stainless steel nozzle, preferably apart from agitating paddle lower half (the 1/3 of lowermost end
To between 1/5) those cutting paddles periphery it is not far, shearing force during ensureing to cut is maximum.
In step 4, after treating system stably dispersing, vacuum distillation, you can recycling halogenated alkane is obtained containing chloromethylation
The suspension system of intermediate solid particle；By being installed on the strainer of reactor bottom, it is filtered dry after water phase, you can obtain granularity
Uniform cottony solid particle, stock size are 3~8 millimeters；Tap water is added in, agitator treating is filtered dry 2~3 times；It adds in immediately
Organic amine aqueous solution implements aminating reaction.Organic amine described in step 5, including trimethylamine, dimethylethanolamine, diformazan
Base n-propylamine, dimethyl n butylamine, dimethylamine, diethylamine and tetramethylethylenediamine.Wherein, chloromethylation intermediate solid
Grain, the aqueous solution with trimethylamine, dimethylethanolamine, dimethyl n propylamine, dimethyl n butylamine or tetramethylethylenediamine, reaction
Generate the strong-base anion-exchange resin product of quaternary amine type；With dimethylamine or the aqueous solution of diethylamine, then generation uncle can be reacted
The weak-base anion-exchange resin product of amine type.If the organic amine (such as dimethyl n butylamine) added in, incomplete with water
It is miscible, suitable methanol, ethyl alcohol or acetone can be added in, the aminating reaction system of complete miscibility is formed to promote, to ensure amine
Change abundant.But this kind of chaotropic agent cannot add in and (add in quality too much and be generally no greater than line style poly- (styrene-ethylene) alternately
The quality of copolymer), it is otherwise easy to cause aminate and is partially dissolved among aminating reaction liquid, cause loss of product.With pure
The addition quality for the organic amine that product calculate, for 0.5~2.0 times of poly- (styrene-ethylene) alternate copolymer of line style added in.
If molecular weight is smaller or water-soluble good amine, such as trimethylamine and dimethylamine, it can add in less, you can ensure
Aminating reaction is abundant；If the molecular weight of amination reagent is larger or water-soluble bad, such as dimethyl n propylamine and dimethyl
N-butylamine should then increase addition, while add in chaotropic agent, improve reaction temperature and extend the reaction time, to promote amination
Reaction is smoothed out.
After aminating reaction, residual reaction liquid is filtered dry, dilute hydrochloric acid solution (concentration is 4~5%) is added in and neutralizes, after being filtered dry
It is washed with deionized to close to neutral (pH is 6~7), chlorine type is converted by hydrogen-oxygen type to complete anion exchange resin.It will
The solid particle being filtered dry is sent into blast drier, is dried at 75~85 DEG C, that is, the alcohol-soluble quaternary amine type or tertiary amine-type is made
Anion exchange resin product.With reference to the method for inspection of anion exchange resin, the anion-exchange capacity measured should be 1.8
~3.2mmol/g siccatives；If exchange capacity be less than 1.8mmol/g, explanation may be chloromethylation or aminating reaction degree not
Foot, it is also possible in poly- (styrene-ethylene) alternate copolymer of line style caused by the content deficiency of polystyrene component, then can cause
The alcohol-soluble of product is bad, cannot get qualified product；And exchange capacity is higher than 3.2mmol/g, then not only line style is required to gather
The content of polystyrene component is sufficiently high in (styrene-ethylene) alternate copolymer, but also requires chloromethylation degree
It is sufficiently high, but both of which can increase considerably the chance of the self-crosslinking side reaction of chloromethylation process, should strongly avoid, it is real
It is also difficult to reach on border.
The present invention is further explained below by way of specific embodiment.
Embodiment 1：
First according to Chinese invention patent application (application number：201110083107.3) No. 8 examinations corresponding to embodiment 1-3
The experimental condition and method are tested, coordination polymerization prepares poly- (styrene-ethylene) alternate copolymer of line style, surveyed with GPC method
(using polystyrene as standard specimen, mobile phase 1,2-C6D4Cl2, temperature is 145 DEG C)：MnFor 42,000, molecular weight distribution index
(Mw/Mn) it is 2.07, it uses1HNMR methods measure (solvent C2D2Cl4, temperature is 120 DEG C, PS mol%=4Aar/(5Aal+
Aar), wherein AarRepresent the number of proton in the phenyl ring of polystyrene component, AalAliphatic chain is represented (including polyethylene component and to gather
The ethylene of styrenic component) in proton number)：The content of polystyrene component is 47mol% (molar percentage), is converted into
Mass content was 76.7% (being equal to 104.15 × 47/ (104.15 × 47+28.06 × 53) × 100%).
The preparation process of alcohol-soluble anion exchange resin is as follows：1) it is 500g line styles poly- (styrene-ethylene) is alternately common
Polymers (383.5g containing polystyrene component counts 3.68mol), puts among 20L glass reaction kettles, adds in 7.5L (about
9260g) dichloroethanes is stirred at room temperature 80 minutes, is completely dissolved, and forms clarified solution；2) will be stirred in advance in 5.0L three-necked flasks
The industrial chloromethyl ethers (purity 42%) of 2800g (about 2600mL) for having dissolved 250 grams of anhydrous zinc chloride powder are mixed, it is disposable, quick
It puts among glass reaction kettle, is warming up to 40~45 DEG C, when reaction 4.5 is small, terminates chloromethylation；3) reaction product is led to
Stainless steel high pressure nozzle is crossed, is squeezed out to containing 400g polyvinyl alcohol, 2000g sodium hydroxides (50mol), the 200L of 100L tap water
Among glassed steel reaction vessels, suspension system is dispersed as with the agitating paddle with cutting function quick (220~250 revs/min)；Control
System squeezed out within 30 minutes, breaks up and finish；4) using about 20 minutes, treat that suspension/dispersion is stablized, progressively heat up, in 60
~80 DEG C are implemented vacuum distillation, dichloroethanes are recycled, about in completion in 100 minutes or so；Moisture content, kettle are filtered dry by bottom screen
Interior residual faint yellow solid particle；5) 80L tap water is added in every time, stirring is filtered dry after 30 minutes, is released after washing 3 times,
It is filtered dry in filter wash bucket；The solid particle that chloromethylation is finished is put into again in 20L glass reaction kettles, and it is about 30% to add in content
Trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L, it is air-cooled solidifying in 36~40 DEG C of decentralizations
React 10 it is small when；Remaining reaction solution is filtered dry by bottom screen, the dilute hydrochloric acid that 8L concentration is 4% is added in and neutralizes, stirring 1 is small
When；Acid solution is filtered dry, adds in deionized water washing, adds in 10L deionized waters every time, stirring is filtered dry after 30 minutes, washing 6~8
Time, until washing lotion pH is 6~7；6) it is discharged among polypropylene filter wash bucket, is filtered dry, discharges, fluffy solid particle is sent in batches
It among entering air dry oven, stirs frequently, when drying 4 is small at 80 DEG C, collection obtains the slice that about 700g is faint yellow, solid
Shape particle is the quaternary amine type anion exchange resin product.
Chloromethylation faint yellow solid particle obtained by 4th step is sampled into 1~2g, is shredded, with methanol washes clean, is used
Volhard methods analyze chlorinty, and measuring benzyl chloride base content, (such as all phenyl ring are by chloromethylation, most Dali for 3.21mmol/g
It is 5.42mmol/g by value)；With reference to the method for inspection of conventional strong basic ion exchange resin (such as 201 × 7 resins), survey
：Anion-exchange capacity is 2.61mmol/g siccatives, and water absorption rate is 190% (i.e. every gram of dryed product can absorb 1.9 grams of moisture).
The solubility (35 DEG C) in different alcohols solvents is further measured, the result is that：It is to be in methanol in 7.2g/100mL, ethyl alcohol
It is 20.6g/100mL in 12.8g/100mL, isopropanol, is 18.3g/100mL in n-butanol.
Embodiment 2：
By in the 5th step of " preparation process of alcohol-soluble anion exchange resin " of embodiment 1 " add in content be about
30% trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L is vented at 36~40 DEG C
When condensation reaction 10 is small ", with " addition dimethylethanolamine 600mL (about 530g), deionized water 7L are vented at 40~43 DEG C
When condensation reaction 12 is small " it replaces, remaining raw material, formula and operating condition are constant, and the flaxen quaternary amine types of about 710g are made
Anion exchange resin product.
With reference to the conventional strong basic ion exchange resin method of inspection, measure anion-exchange capacity and done for 2.54mmol/g
Material, water absorption rate 180%.Further the solubility (35 DEG C) in measure alcohol is：It is to be in methanol in 6.8g/100mL, ethyl alcohol
It is 21.1g/100mL in 11.4g/100mL, isopropanol, is 19.3g/100mL in n-butanol.
Embodiment 3：
By in the 5th step of " preparation process of alcohol-soluble anion exchange resin " of embodiment 1 " add in content be about
30% trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L is vented at 36~40 DEG C
When condensation reaction 10 is small ", with " addition dimethyl n butylamine 1L (about 750g), acetone 500mL, deionized water 5.5L, in 45~50
When DEG C empty condensation reaction 15 of decentralization is small " it replaces, remaining raw material, formula and operating condition are constant, and it is faint yellow that about 700g is made
Quaternary amine type anion exchange resin product.
With reference to the conventional strong basic ion exchange resin method of inspection, measure anion-exchange capacity and done for 2.43mmol/g
Material, water absorption rate 160%.Further the solubility (35 DEG C) in measure alcohol is：It is to be in methanol in 6.6g/100mL, ethyl alcohol
It is 18.9g/100mL in 9.3g/100mL, isopropanol, is 17.2g/100mL in n-butanol.
Embodiment 4：
By in the 5th step of " preparation process of alcohol-soluble anion exchange resin " of embodiment 1 " add in content be about
30% trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L is vented at 36~40 DEG C
When condensation reaction 10 is small ", with " add in content be about 40% dimethylamine agueous solution 1.5L (about 1350g, containing dimethylamine about
540g), deionized water 6.5L, when the empty condensation reaction 12 of 36~40 DEG C of decentralizations is small " is replaced, remaining raw material, formula and operation
Condition is constant, and the flaxen tertiary amine-type anion exchange resin products of about 680g are made.
With reference to conventional weak-base ion-exchange resin (such as D301) method of inspection, measuring anion-exchange capacity is
2.36mmol/g siccatives, water absorption rate 120%.Further the solubility (35 DEG C) in measure alcohol is：It is 5.6g/ in methanol
It is 16.9g/100mL in 8.4g/100mL, isopropanol to be in 100mL, ethyl alcohol, is 17.0g/100mL in n-butanol.
Embodiment 5：
Referring initially to Chinese invention patent application (application number：201110083107.3) No. 9 examinations corresponding to embodiment 1-3
The experimental condition and method are tested, coordination polymerization prepares poly- (styrene-ethylene) alternate copolymer of line style, surveyed with GPC method
：MnFor 35,000, molecular weight distribution index (Mw/Mn) it is 2.16, it uses1HNMR methods measure：The content of polystyrene component is
37mol% is converted into mass content as 68.6%.
The preparation process of alcohol-soluble anion exchange resin is as follows：1) it is 500g line styles poly- (styrene-ethylene) is alternately common
Polymers (343g containing polystyrene component counts 3.3mol), puts among 20L glass reaction kettles, adds in 6L (about 7900g) dichloro
Methane is stirred at room temperature 90 minutes, is completely dissolved, and forms clarified solution；It 2) will the stirring and dissolving 120 in the 5.0L three-necked flasks in advance
The industrial chloromethyl ethers (purity 42%) of the 1800g (about 1650mL) of gram anhydrous ferric chloride powder, disposable, quick input glass reaction
Among kettle, 38~41 DEG C, when reaction 5 is small are warming up to, terminates chloromethylation；3) reaction product is passed through into stainless steel high pressure spray
Mouth, squeeze out to containing 300g polyvinyl alcohol, 1600g sodium hydroxides (40mol), 90L tap water 200L glassed steel reaction vessels it
In, quickly it is dispersed as suspension system with the agitating paddle with cutting function；4) treat that suspension/dispersion is stablized, progressively heat up, in
30~50 DEG C are implemented vacuum distillation, dichloromethane are recycled, about in completion in 90 minutes or so；Moisture content is filtered dry by bottom screen,
Residual faint yellow solid particle in kettle；5) 80L tap water is added in every time, stirring is filtered dry after 30 minutes, is released after washing 3 times,
It is filtered dry in filter wash bucket；Solid particle is put into again in 20L glass reaction kettles, it is water-soluble to add in the trimethylamine that content is about 30%
Liquid 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L, when the empty condensation reaction 10 of 36~40 DEG C of decentralizations is small；It is logical
It crosses bottom screen and is filtered dry remaining reaction solution, add in the dilute hydrochloric acid that 8L concentration is 4% and neutralize, when stirring 1 is small；Acid solution is filtered dry, is added
Enter deionized water washing, add in 10L deionized waters every time, stirring is filtered dry after 30 minutes, is washed 7 times；6) it is discharged to polypropylene
It among filter wash bucket, is filtered dry, discharges, among fluffy solid particle is sent into air dry oven in batches, stir frequently, at 80 DEG C
Dry 3.5 it is small when, collection obtains the faint yellow noodle granules of about 680g, is the quaternary amine type anion exchange resin production
Product.
Chloromethylation faint yellow solid particle obtained by 4th step is sampled into 1~2g, is shredded, with methanol washes clean, is used
Volhard methods analyze chlorinty, measure benzyl chloride base content as 3.07mmol/g (maximum theoretical 5.0mmol/g)；Reference
The method of inspection of conventional strong basic ion exchange resin, measures：Anion-exchange capacity be 2.42mmol/g siccatives, water absorption rate
For 180%.The solubility (35 DEG C) in different alcohols solvents is further measured, the result is that：It is 7.0g/100mL in methanol, second
It is 19.5g/100mL in 11.3g/100mL, isopropanol to be in alcohol, is 18.0g/100mL in n-butanol.
Embodiment 6：
By in the 5th step of " preparation process of alcohol-soluble anion exchange resin " of embodiment 5 " add in content be about
30% trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L is vented at 36~40 DEG C
When condensation reaction 10 is small ", with " addition tetramethylethylenediamine 1.0L (about 780g), deionized water 6L are air-cooled in 42~45 DEG C of decentralizations
When solidifying reaction 12 is small " it replaces, remaining raw material, formula and operating condition are constant, and it is cloudy that the flaxen quaternary amine types of about 680g are made
Amberlite fat prod.
With reference to the conventional strong basic ion exchange resin method of inspection, measure anion-exchange capacity and done for 2.19mmol/g
Material, water absorption rate 160%.Further the solubility (35 DEG C) in measure alcohol is：It is to be in methanol in 6.8g/100mL, ethyl alcohol
It is 19.1g/100mL in 10.7g/100mL, isopropanol, is 17.7g/100mL in n-butanol.
Embodiment 7：
By in the 5th step of " preparation process of alcohol-soluble anion exchange resin " of embodiment 5 " add in content be about
30% trimethylamine aqueous solution 1.2L (about 1100g, containing trimethylamine about 330g), deionized water 6.8L is vented at 36~40 DEG C
When condensation reaction 10 is small ", with " addition diethylamine 1.2L (about 850g), deionized water 6L, in the empty condensation reactions of 40~42 DEG C of decentralizations
12 it is small when " replace, remaining raw material, formula and operating condition are constant, and the flaxen tertiary amine-type anion of about 680g are made and hand over
Change naval stores.
With reference to the conventional weak-base ion-exchange resin method of inspection, measure anion-exchange capacity and done for 1.96mmol/g
Material, water absorption rate 110%.Further the solubility (35 DEG C) in measure alcohol is：It is to be in methanol in 5.2g/100mL, ethyl alcohol
It is 15.4g/100mL in 7.7g/100mL, isopropanol, is 14.3g/100mL in n-butanol.
Above-described embodiment is for the explanation and illustration present invention rather than limits the invention.The present invention's
Within spirit and scope of the claims, as made by those of ordinary skill in the art to any modification of the present invention and
Change, all without departing from protection scope of the present invention.
Claims (9)
1. the manufacturing method of a kind of alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin, which is characterized in that this method includes
Following steps：1) poly- (styrene-ethylene) alternate copolymer of line style being put into halogenated alkane, heating, stirring are allowed to be completely dissolved,
Form homogeneous Polymer Solution；2) rapidly join in advance dissolved with the industrial chloromethane ethereal solution of catalyst, implement homogeneous chloromethylation
Reaction；3) by reaction product by stainless steel high pressure nozzle, squeeze out into the water containing dispersant and sodium hydroxide, with cutting
The agitating paddle for cutting function is quickly dispersed as suspension system；4) it is evaporated under reduced pressure after system stably dispersing, recycles halogenated alkane；It is filtered dry
Moisture content obtains fluffy chloromethylation solid particle；5) it is washed with water several times, adds in organic amine/water solution, it is anti-implements amination
It should；Reaction solution is filtered dry, dilute hydrochloric acid is added in and neutralizes, makes the transition, is washed with deionized to close neutrality；6) solid particle that will be filtered dry
It is sent into blast drier and dries, i.e., the obtained alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin product.
2. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, poly- (styrene-ethylene) alternate copolymer of the line style described in step 1, number-average molecular weight 30,000~50,000
Er Dun, the ratio between weight average molecular weight and number-average molecular weight are 1.8~2.2.
3. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, poly- (styrene-ethylene) alternate copolymer of the line style described in step 1, the mass content of polystyrene component therein
For 65~80%.
4. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, the halogenated alkane described in step 1, including dichloromethane, chloroform and dichloroethanes；The addition of chloro halogenated alkane
Quality is added in 12~20 times of poly- (styrene-ethylene) alternate copolymer of line style.
5. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, the catalyst described in step 2, including anhydrous zinc chloride and anhydrous ferric chloride, adds in quality as the line style that is added in
0.2~0.6 times of poly- (styrene-ethylene) alternate copolymer.
6. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, the industrial chloromethyl ether described in step 2, adds in quality as poly- (styrene-ethylene) alternate copolymer of line style that is added in
3~6 times.
7. the manufacturing method of alcohol-soluble quaternary amine type according to claim 1 or tertiary amine-type anion exchange resin, feature
It is, the organic amine described in step 5, including trimethylamine, dimethylethanolamine, dimethyl n propylamine, dimethyl n butylamine, two
Methylamine, diethylamine and tetramethylethylenediamine add in quality as poly- (styrene-ethylene) alternate copolymer of line style that is added in
0.5~2.0 times.
8. alcohol-soluble quaternary amine type or tertiary amine-type the moon that the method in claim 1~7 described in arbitrary claim is prepared from
Sub-exchange resin.
9. alcohol-soluble quaternary amine type according to claim 8 or tertiary amine-type anion exchange resin, it is characterised in that its ion
Exchange capacity is 1.8~3.2mmol/g siccatives.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227562A (en) * | 2019-05-24 | 2019-09-13 | 衢州蓝然新材料有限公司 | Using the flat perforated membrane of screen cloth enhancing as the anion-exchange membrane of matrix and its manufacturing method |
| CN113501901A (en) * | 2021-07-23 | 2021-10-15 | 核工业北京化工冶金研究院 | Preparation method of uranium-adsorbing strongly-basic resin with narrow distribution particle size |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4321331A (en) * | 1978-11-06 | 1982-03-23 | The Dow Chemical Company | High density ion exchange resins from haloalkylated aromatic polymer |
| US6323249B1 (en) * | 1988-09-26 | 2001-11-27 | Purolite International, Ltd. | Macroporous resins having large pores but with high crush strength |
| CN103223305A (en) * | 2013-04-24 | 2013-07-31 | 浙江大学宁波理工学院 | Polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method |
| CN105702970A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院大连化学物理研究所 | Preparation of three-dimensional resin solution for alkaline anion exchange membrane |
-
2017
- 2017-07-11 CN CN201710559026.3A patent/CN108080039B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4321331A (en) * | 1978-11-06 | 1982-03-23 | The Dow Chemical Company | High density ion exchange resins from haloalkylated aromatic polymer |
| US6323249B1 (en) * | 1988-09-26 | 2001-11-27 | Purolite International, Ltd. | Macroporous resins having large pores but with high crush strength |
| CN103223305A (en) * | 2013-04-24 | 2013-07-31 | 浙江大学宁波理工学院 | Polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method |
| CN105702970A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院大连化学物理研究所 | Preparation of three-dimensional resin solution for alkaline anion exchange membrane |
Non-Patent Citations (2)
| Title |
|---|
| 朱传涛等: ""可溶性聚苯乙烯系阴离子交换聚合物的制备及其均相成膜性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 潘玉鹏等: "新型限制几何构型稀土金属有机配合物", 《应用化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227562A (en) * | 2019-05-24 | 2019-09-13 | 衢州蓝然新材料有限公司 | Using the flat perforated membrane of screen cloth enhancing as the anion-exchange membrane of matrix and its manufacturing method |
| CN110227562B (en) * | 2019-05-24 | 2022-02-22 | 衢州蓝然新材料有限公司 | Anion exchange membrane using mesh cloth reinforced flat type porous membrane as substrate and manufacturing method thereof |
| CN113501901A (en) * | 2021-07-23 | 2021-10-15 | 核工业北京化工冶金研究院 | Preparation method of uranium-adsorbing strongly-basic resin with narrow distribution particle size |
| CN113501901B (en) * | 2021-07-23 | 2023-11-28 | 核工业北京化工冶金研究院 | Preparation method of strong alkaline resin with narrow-distribution particle size for adsorbing uranium |
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