CN106046247A - CO 2 responsive hyperbranched polymer and preparation method and application thereof - Google Patents
CO 2 responsive hyperbranched polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN106046247A CN106046247A CN201610546496.1A CN201610546496A CN106046247A CN 106046247 A CN106046247 A CN 106046247A CN 201610546496 A CN201610546496 A CN 201610546496A CN 106046247 A CN106046247 A CN 106046247A
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- Prior art keywords
- response
- methyl
- monomer
- dissaving polymer
- acrylamide
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- Granted
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- 229920000587 hyperbranched polymer Polymers 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 12
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000009792 diffusion process Methods 0.000 claims abstract description 15
- 230000002441 reversible effect Effects 0.000 claims abstract description 15
- 238000012546 transfer Methods 0.000 claims abstract description 13
- 239000013535 sea water Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000004044 response Effects 0.000 claims description 26
- 238000001556 precipitation Methods 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 (methyl) dimethylaminoethyl Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000035515 penetration Effects 0.000 claims description 12
- 239000012466 permeate Substances 0.000 claims description 12
- 239000002552 dosage form Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- QXDYJUSFCUKOQD-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-bromo-2-methylpropanoate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)(C)Br QXDYJUSFCUKOQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012988 Dithioester Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 2
- ZHBOFZNNPZNWGB-UHFFFAOYSA-N 9,10-bis(phenylethynyl)anthracene Chemical compound C1=CC=CC=C1C#CC(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C#CC1=CC=CC=C1 ZHBOFZNNPZNWGB-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 125000005022 dithioester group Chemical group 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229940117958 vinyl acetate Drugs 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims 2
- 238000011017 operating method Methods 0.000 claims 2
- XYNOUFAWYQMLKS-UHFFFAOYSA-N CC(=O)C.OC1(C(C(=O)O)(C=CC=C1C(=O)O)C1=CC=C(C=C1)O)C Chemical compound CC(=O)C.OC1(C(C(=O)O)(C=CC=C1C(=O)O)C1=CC=C(C=C1)O)C XYNOUFAWYQMLKS-UHFFFAOYSA-N 0.000 claims 1
- 125000004414 alkyl thio group Chemical group 0.000 claims 1
- 238000011033 desalting Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003204 osmotic effect Effects 0.000 abstract description 11
- 230000004907 flux Effects 0.000 abstract description 10
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 238000009292 forward osmosis Methods 0.000 abstract 3
- 101710141544 Allatotropin-related peptide Proteins 0.000 abstract 1
- 239000012986 chain transfer agent Substances 0.000 abstract 1
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 229920001513 poly[2-(diethylamino)ethyl methacrylate] polymer Polymers 0.000 description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SEHSOTXNSWXFQG-UHFFFAOYSA-N N.N=NC=NN.N=NC=NN.C(C(=C)C)(=O)O Chemical compound N.N=NC=NN.N=NC=NN.C(C(=C)C)(=O)O SEHSOTXNSWXFQG-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940067621 aminobutyrate Drugs 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- NOUPIZNZZWSTBI-UHFFFAOYSA-N n-butyl-n',n'-diethylprop-2-enehydrazide Chemical compound CCCCN(N(CC)CC)C(=O)C=C NOUPIZNZZWSTBI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides CO2A responsive hyperbranched polymer prepared by one of the following methods: (1) to have CO2Using responsive monomer, catalyst, ligand, initiator monomer and solvent as raw materials, and adopting ATRP method to prepare target product; (2) to have CO2Preparing a target product by taking a responsive monomer, a chain transfer agent type monomer, an initiator and a solvent as raw materials and adopting an RAFT (reversible addition-fragmentation chain transfer) method; CO of the invention2The responsive hyperbranched polymer can be used as a forward osmosis draw solute and is particularly applied to the forward osmosis seawater desalination process: introducing CO into the drawing liquid2The polymer is dissolved in water to form a high osmotic pressure drawing liquid, the water flux is large, the reverse diffusion is small, and N is introduced into the drawing liquid after the diffusion is stopped2The polymer can be precipitated and recycled by filtration for the next forward osmosis, and the recycling operation of the draw solute is simple and convenient, the energy consumption is low, and the draw solute can be reused.
Description
(1) technical field
The present invention relates to a kind of CO2Response dissaving polymer, and preparation method thereof, and as just permeating draw molten
The application of matter.
(2) background technology
Along with population increases and the acceleration of process of industrialization, the problem that World Freshwater Resources is deficient seems further serious, this
Threaten the survival and development of the mankind to a certain extent.The growing tension of freshwater resources makes increasing countries and regions
Greatly develop desalination technology, seawater desalination is obtained fresh water.Just permeating is that one is not required to impressed pressure and does driving force, and only
Relying on the membrane separating process that osmotic pressure drives, and fouling membrane situation is the lightest, it is possible to operation for a long time without
Clean, have good application prospect in the field such as desalinization, sewage purification.But, draw solute reverse diffusion and
Subsequent process draws the separation process of solute and water is loaded down with trivial details and the application that needs the shortcomings such as energy consumption to limit positive infiltration technology with
Development.
Drawing liquid and need to provide sufficiently high osmotic pressure, the most properity and pure water quality to film do not impact,
Additionally, simpler method also should be able to be used therefrom to isolate pure water, to obtain fresh water.Draw the solute in liquid be called draw molten
Matter, preferably draws solute and should possess following condition: 1. can produce higher osmotic pressure, i.e. should have higher in water
Dissolubility, thus should have less molecular mass；2. avirulence, can security presence in producing water；3. can stable existence,
I.e. can not be with film generation chemical reaction；4. during preparing pure water, it should can facilitate and liquid and pure water will be drawn economically
Carry out separating and can reusing.Select suitably to draw the important topic during liquid is always positive penetration study.
The solute that draws reported includes: salt such as NaCl, MgCl2、Al2(SO4)3、NH4HCO3；Saccharide such as glucose, really
Sugar etc..Jeffrey R.McCutcheon etc. (J.Membr.Sci., 2006,278,114 123.) report with NH4HCO3Solution is
Draw liquid, be applied to positive penetration sea water desalinization.Draw solute to separate by heat resolve NH with water4HCO3Reach to separate purpose,
Draw solute can not reuse.
It is the positive osmosis system drawing liquid that CN 203668144U discloses with hydrogel, and the hydrogel of employing is temperature sensitive water
Gel, utilizes solar energy equal energy source heating hydrogel to make it be dehydrated to water-purifying container.Solar energy needs sizable daylighting thermal-arrest
Face could meet use requirement, and device ground area is big, and materials are many, and cost increases；Atmospheric effect is relatively big, and solar energy has certain
Limitation.
Yufeng Cai etc. (Chem.Commun., 2013,49,8377) propose with having CO2The line answered with temperature double-bang firecracker
Type polymethylacrylic acid dimethylaminoethyl (PDMAEMA) is as drawing solute for desalinization.Line style PDMAEMA is drawn
Solute, is applied to positive penetration sea water desalinization.It is high that the PDMAEMA that molecular weight is high draws liquid osmotic pressure, but high molecular
PDMAEMA dissolubility in water is low and draws solute and can inversely be diffused into material liquid side, causes drawing solute loss.
(3) summary of the invention
For defect present in prior art, the present invention method by ATRP or RAFT, design and be prepared for one
There is CO2The dissaving polymer of response, and draw solute be applied to positive penetration sea water desalinization as just permeating.Polymerization
Thing dissaving structure has the characteristic such as highly dissoluble, low viscosity, and branched structure can efficiently reduce the reverse expansion of polymer
Dissipate.To drawing, liquid is passed through CO2, what polymer was dissolved in that water forms hyperosmosis draws liquid, and water flux is big, and reverse diffusion is little.Stop
Only after diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation, it is recovered by filtration polymer, just permeates for next time.
Draw the reclaimer operation simplicity of solute, energy consumption is low and can reuse.
Therefore, it is an object of the invention to provide a kind of CO2Response dissaving polymer and preparation method thereof and conduct
Just permeating the application drawing solute.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of CO2Response dissaving polymer, its preparation method has two kinds:
The first preparation method:
To have CO2The monomer of response, catalyst, part, inimers, solvent are raw material, use ATRP (former
Sub-transferring free-radical polymerization) method, prepare described CO2Response dissaving polymer.
In the first described preparation method,
Described have CO2The monomer of response and inimers, catalyst, the ratio of amount of material of part are 1:
0.01～0.5:0.01～0.1:0.01～0.1；The amount of the material of described solvent has CO with described2The monomer of response and drawing
The ratio of the amount sum sending out the material of dosage form monomer is 1～10:1；
The concrete operation step of described ATRP method is: adds inimers in reaction vessel I, have CO2Response
The monomer of property, part, solvent, obtain liquid mixture, under the conditions of room temperature (20～30 DEG C), stir and lead to N2Except O215～
60min；Catalyst, at ambient temperature, logical N is added in reaction vessel II2Except O215～60min；Under anaerobic, will
Liquid mixture in reaction vessel I adds in reaction vessel II, and then reaction vessel II is placed in the thermostatical oil of 40～80 DEG C
Bath reacts 6～12h；After completion of the reaction, reactant liquor is post-treated, obtains described CO2Response dissaving polymer；
The method of described reactant liquor post processing is: after completion of the reaction, and reactant liquor adds the normal hexane of 5～30 times of volumes
In (0 DEG C), Precipitation, incline except supernatant liquid, precipitation oxolane carried out post (to remove catalyst) after dissolving, described
The method crossing post is: with neutral Al2O3For column packing, oxolane is eluant, with reactant liquor volume 3～the tetrahydrochysene furan of 10 times
Muttering eluting, the eluent of collection is dialysed with the bag filter of 3500～12000 molecular weight again, and last lyophilization i.e. obtains described
CO2Response dissaving polymer；
Described " reaction vessel I ", " reaction vessel II " does not has special implication, is labeled as " I ", " II " is only intended to district
Divide the reaction vessel used in different operating step；
Described catalyst is transition metal halide, the most such as: CuBr, CuCl or CuI；
Described part is bipyridyl, N, N, N, N, N-five methyl diethylentriamine (PMDTETA) or 1,1,4,7,10,
10-hexamethyl trien (HMTETA)；
Described solvent be ethyl acetate, dichloromethane, oxolane, acetone, normal hexane, petroleum ether, methanol, ethanol or
Chloroform；
Described inimers is BPEA, BIEM, BPEM or BIEA, and its structural formula is as follows:
Described has CO2The monomer of response is selected from one of following:
(methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) acrylic acid diformazan ammonia
Base butyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid diethylamino propyl ester, (methyl) acrylic acid diethyl
Base aminobutyrate, (methyl) acrylamide dimethylaminoethyl, (methyl) acrylamide dimethylamino propyl ester, (methyl) acryloyl
Amine dimethylamino butyl ester, (methyl) acrylamide diethylamino ethyl ester, (methyl) acrylamide diethylamino propyl ester or (first
Base) acrylamide diethylamino butyl ester；
The second preparation method:
To have CO2The monomer of response, chain tra nsfer dosage form monomer, initiator, solvent are raw material, use RAFT (reversible
Addition-fracture chain tra nsfer) method, prepare described CO2Response dissaving polymer；
In described the second preparation method,
Described have CO2The monomer of response is 1:0.02 with the ratio of chain tra nsfer dosage form monomer, the amount of the material of initiator
～0.1:0.002～0.01；The volumetric usage of described solvent is to have CO2The amount of the material of the monomer of response be calculated as 0.5～
5L/mol；
The concrete operation step of described RAFT method is: adds in reaction vessel and has CO2The monomer of response, chain tra nsfer
Dosage form monomer, initiator, solvent, logical N after sealing2Except O215～60min, then reaction vessel is placed in the constant temperature of 40～90 DEG C
Oil bath pan reacts 12～24h, reacts with liquid nitrogen cancellation afterwards, add chloroform dilute reaction solution (generally dilution 1～5 times), will
Reactant liquor after dilution adds in the normal hexane (0 DEG C) of 5～30 times of volumes, and Precipitation inclines except supernatant liquid, lower sediment
Vacuum drying, prepares described CO2Response dissaving polymer；
Described have CO2The monomer of response is identical with the definition in the first preparation method；
Described initiator is chemical initiator or photochemical initiators；Described chemical initiator includes that peroxide causes
Agent, azo-initiator, described peroxide initiator is concrete such as: Ammonium persulfate., potassium peroxydisulfate etc., described azo draws
Send out agent concrete such as: 4,4 '-azo double (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorate, azo diisopropyl imidazoline
Hydrochlorate, azo diisopropyl imidazoline etc.；Described photochemical initiators is concrete such as: 2-hydroxyl-1-[4-(hydroxyl) benzene
Base]-2-methyl isophthalic acid-acetone etc.；
Described solvent be ethyl acetate, dichloromethane, oxolane, acetone, normal hexane, petroleum ether, methanol, ethanol,
Chloroform, 1,4-dioxane, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, Methanamide or isopropanol；
Described chain tra nsfer dosage form monomer is containing dithio or the vinyl of trithio, phenylethylene or acrylic compounds
Compound, the most such as: (2-ethyoxyl dithioester base) vinylacetate (A), 2-[(2-{ [(dodecyl sulfur generation) carbonyl]
Sulfur generation }-2-methylpropionyl) epoxide]-ethyl acrylate (B), propyl group (4-vinyl benzyl) carbodithioic acid (C), (2-second
Thiazolinyl dithioester base) acetate (D), its structural formula is as follows:
The CO that the inventive method prepares2Response dissaving polymer can draw solute application, particularly as just permeating
During being applied to positive penetration sea water desalinization.
As just permeate draw solute be applied to during positive penetration sea water desalinization time,
Just permeating and drawing the compound method of liquid and be: taking CO of the present invention2Response dissaving polymer is added to the water, and is passed through
CO2, CO of the present invention2Liquid is drawn in the formation soluble in water of response dissaving polymer；Described CO2Response dissaving polymer with
The mass ratio of water controls 0.1～0.8:1；Described it is passed through CO2Rate controlled 20～500ml/min, the time controls
30min～6h；
The recovery method drawing solute is: after stopping diffusion, be passed through N to drawing in liquid2, CO of the present invention2Response is hyperbranched
Polymer meeting Precipitation, is recovered by filtration, just permeates for next time；Described it is passed through N2Rate controlled 20～500ml/min,
Time controls at 30min～6h.
The beneficial effects of the present invention is: the present invention is by atom transfer radical polymerization (ATRP) or reversible addition-disconnected
The method preparation splitting chain tra nsfer (RAFT) has CO2The dissaving polymer of response, and be applied to as drawing solute
Positive penetration sea water desalinization.To drawing, liquid is passed through CO2, what polymer was dissolved in that water forms hyperosmosis draws liquid, and water flux is big, inverse
Little to diffusion.After stopping diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation, it is recovered by filtration polymer, is used for
Next time just permeates.Draw the reclaimer operation simplicity of solute, energy consumption is low and can reuse.
(4) detailed description of the invention
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Embodiment 1
BIEM 0.8g (2.75mmol), diethylaminoethyl methacrylate is added in the single port flask I of 25ml
(DEAEMA) 5.1g (27.5mmol), ethyl acetate 5mL (51.1mmol), PMDTETA 54mg (0.3mmol), magnetic agitation,
At ambient temperature, logical N2Except O2.Separately take the CuBr that 25ml flask II adds 43.5mg (0.3mmol), at ambient temperature, logical
N2Except O2.After 30min, under anaerobic, the liquid mixture in flask I is added flask II, then flask II is put into 60
DEG C thermostatical oil bath in, react 12h.After completion of the reaction, reactant liquor is added in 90mL normal hexane (0 DEG C), Precipitation, will
The supernatant is outwelled, and after precipitation is dissolved with 10ml oxolane, crosses post, with neutral Al2O3For column packing, 45mL oxolane is
Eluant, the eluent of collection is dialysed with the bag filter of 3500 molecular weight, the reservation liquid lyophilization in bag filter is prepared
Hyperbranched PDEAEMA (polymethylacrylic acid lignocaine ethyl ester) 4.01g；
In this example, the conversion ratio of polymerization system is 67%, its number-average molecular weight is 6800, molecular weight distribution is 2.1.Take
4.01g PDEAEMA puts in 10mL water, is passed through CO2, PDEAEMA be dissolved in water formed concentration be 0.4g/g draw liquid (raw material
Liquid is 0.5M NaCl solution), osmotic pressure reaches 1.306osmol/kg, and water flux is 0.8L/ (m2H), the reverse diffusing capacity of solute is
15mg/(m2*h).After stopping diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation, it is recovered by filtration polymer, uses
Just permeate next time.Showing that PDEAEMA draws liquid and has good osmotic effect, and reclaimer operation is simple, polymer loss is few.
Embodiment 2
BIEM 0.8g (2.75mmol), diethylaminoethyl methacrylate is added in the single port flask I of 25ml
(DEAEMA) 10.2g (55mmol), ethyl acetate 10mL (102.3mmol), PMDTETA 100mg (0.58mmol), magnetic force stirs
Mix, at ambient temperature, logical N2Except O2.Separately take the CuBr that 25ml flask II adds 83.4mg (0.58mol), at ambient temperature,
Logical N2Except O2.After 30min, under anaerobic, the liquid mixture in flask I is added flask II, then flask II is put into
In the thermostatical oil bath of 60 DEG C, react 12h.After completion of the reaction, reactant liquor is added in 160mL normal hexane (0 DEG C), precipitation analysis
Go out, the supernatant is outwelled, after precipitation is dissolved with 20ml oxolane, cross post, with neutral Al2O3For column packing, 80mL tetrahydrochysene furan
Mutter as eluant, collect eluent again with the bag filter dialysis of 8000 molecular weight, by the reservation liquid lyophilization system in bag filter
Obtain hyperbranched PDEAEMA 7.8g；
In this example, the conversion ratio of polymerization system is 74%, its number-average molecular weight is 13600, molecular weight distribution is 1.88.
Take 3g PDEAEMA to put in 10mL water, be passed through CO2, PDEAEMA be dissolved in water formed concentration be 0.3g/g draw liquid (material liquid
For 0.5M NaCl solution), osmotic pressure the highest (exceed permeability manometer and detect the 2osmol/kg that reaches the standard grade), water flux is 2.6L/ (m2*
H), the reverse diffusing capacity of solute is 52mg/ (m2*h).After stopping diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation is logical
Polymer is recovered by filtration, just permeates for next time.Show that the PDEAEMA that number-average molecular weight is high draws solute penetration effect
Good, and reclaimer operation is simple.
Embodiment 3
DEAEMA 5.6g (30mmol), 2-[(2-{ [(dodecyl sulfur generation) carbonyl is added in the round-bottomed flask of 100ml
Base] sulfur generation-2-methylpropionyl) epoxide]-ethyl acrylate 0.46g (1mmol), AIBN 18mg (0.1mmol), 1,4-bis-
Oxygen six ring 30ml, and use rubber closure sealed flask.With syringe needle logical N in flask2Except O2After 30min, flask is placed in 70 DEG C
Oil bath pan reacts 24h.React with liquid nitrogen cancellation, add the dilution of 10mL chloroform, then the reactant liquor after dilution is just being added 300mL
In hexane (0 DEG C), Precipitation, the supernatant being outwelled, lower sediment vacuum drying prepares dissaving polymer
PDEAEMA6.6g。
In this example, the conversion ratio of polymerization system is 82%, its number-average molecular weight is 8000, molecular weight distribution is 1.7.Take
4g PDEAEMA puts in 10mL water, is passed through CO2, PDEAEMA is dissolved in the liquid that draws that water formation concentration is 0.4g/g, and (material liquid is
0.5MNaCl solution), osmotic pressure is 1.204osmol/kg, and water flux is 0.6L/ (m2H), the reverse diffusing capacity of solute is 22mg/
(m2*h).After stopping diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation, it is recovered by filtration polymer, under being used for
Secondary just permeate.Show that the PDEAEMA that number-average molecular weight is high draws solute penetration effective, and reclaimer operation is simple.
Embodiment 4
DEAEMA5.6g (30mmol), 2-[(2-{ [(dodecyl sulfur generation) carbonyl] is added in the round-bottomed flask of 100ml
Sulfur generation }-2-methylpropionyl) epoxide]-ethyl acrylate 0.46g (1mmol), AIBN18mg (0.1mmol), 1,4-dioxy six
Ring 30ml, and use rubber closure sealed flask.With syringe needle logical N in flask2Except O230min, is placed in flask in the oil bath pan of 70 DEG C
Reaction 24h.React with liquid nitrogen cancellation, after adding the dilution of 10mL chloroform, then the reactant liquor after dilution is added 300mL normal hexane (0
DEG C) in, Precipitation, the supernatant to be outwelled, lower sediment vacuum drying prepares dissaving polymer PDEAEMA6.2g.
In this example, the conversion ratio of polymerization system is 82%, its number-average molecular weight is 8000, molecular weight distribution is 1.7.Take
6g PDEAEMA puts in 10mL water, is passed through CO2, PDEAEMA is dissolved in the liquid that draws that water formation concentration is 0.6g/g, and (material liquid is
0.5MNaCl solution), osmotic pressure the highest (exceed permeability manometer and detect the 2osmol/kg that reaches the standard grade), water flux is 2.4L/ (m2H),
The reverse diffusing capacity of solute is 31mg/ (m2*h).After stopping diffusion, to drawing, liquid is passed through N2, polymer meeting Precipitation, passes through
Polymer is recovered by filtration, just permeates for next time.Show that PDEAEMA concentration of aqueous solution more Thief zone effect is the best, and reclaim behaviour
Making simple, polymer loss is few.
Comparative example 1
2-isobutyl ethyl bromide 0.11g (0.54mmol), DEAEMA 5.0g is added in the single port flask I of 25ml
(27mmol), PMDTETA 94mg (0.54mmol), magnetic agitation, at ambient temperature, logical N2Except O2.Separately take 25ml flask II
Add the CuBr (I) of 77.5mg (0.54mmol), at ambient temperature, logical N2Except O2.After 30min, under anaerobic, will burn
Liquid mixture in bottle I adds flask II, is then put into by flask II in the thermostatical oil bath of 60 DEG C, reacts 0.2h.Reaction
After, reactant liquor is added in 90mL normal hexane (0 DEG C), Precipitation, the supernatant is outwelled, precipitation 10ml tetrahydrochysene furan
Mutter after dissolving, cross post, with neutral Al2O3For column packing, 35mL oxolane is eluant, collects eluent and uses 3500 molecules again
The bag filter dialysis of amount, prepares linear PDEAEMA 4.1g by the liquid lyophilization that retains in bag filter；
In this example, the conversion ratio of polymerization system is 89%, its weight average molecular weight is 8400, molecular weight distribution is 1.12.
Take the linear PDEAEMA of 3g to put in 10mL water, be passed through CO2, PDEAEMA be dissolved in water formed concentration be 0.3g/g draw liquid, ooze
Pressure reaches 1.14osmol/kg thoroughly, and water flux is 0.4L/ (m2H), the reverse diffusing capacity of solute is 47mg/ (m2*h).Show hyperbranched
PDEAEMA draws liquor ratio line style PDEAEMA and draws liquid and have more preferable osmotic effect, and solute inversely spreads less.
Comparative example 2
Concentration be the magnesium chloride of 150g/L as drawing liquid, the NaCl of 35g/L is as material liquid, and water flux is 1.2L/
(m2*h).Magnesium chloride is loaded down with trivial details with the separation process of water, compares magnesium chloride as drawing solute, and hyperbranched PDEAEMA is as drawing
Solute, reclaimer operation is easy, energy consumption is low and can reuse.
Summary embodiment and comparative example are visible, and the inventive method has CO by preparation2The hyperbranched poly of response
Compound also draws solute be applied in positive penetration sea water desalinization as just permeating.During positive penetration sea water desalinization, to
Draw and liquid is passed through CO2, what polymer was dissolved in that water forms hyperosmosis draws liquid, and water flux is big, and reverse diffusion is little.Stop diffusion
After, to drawing, liquid is passed through N2, polymer meeting Precipitation, it is recovered by filtration polymer, just permeates for next time.Draw molten
The reclaimer operation of matter is easy, energy consumption is low and can reuse.The dissaving polymer that the present invention obtains is just to permeate sea water light
Change has and well applies effect.
Above-described embodiment be used for illustrate the present invention rather than limit the invention, the present invention spirit and
In scope of the claims, any modifications and changes that the present invention is made, both fall within protection scope of the present invention.
Claims (8)
1. a CO2Response dissaving polymer, it is characterised in that described CO2Response dissaving polymer is by such as lower section
Method prepares:
To have CO2The monomer of response, catalyst, part, inimers, solvent are raw material, use atom transfer freely
Base polymerization, prepares described CO2Response dissaving polymer；
Described have CO2The monomer of response and inimers, catalyst, the ratio of amount of material of part be 1:0.01～
0.5:0.01～0.1:0.01～0.1；The amount of the material of described solvent has CO with described2The monomer of response and initiation dosage form
The ratio of the amount sum of the material of monomer is 1～10:1；
Described catalyst is CuBr, CuCl or CuI；
Described part is bipyridyl, N, N, N, N, N-Five methyl diethylentriamineOr 1,1,4,7,10,10-hexamethyl Sanya
Tetramine；
Described solvent is ethyl acetate, dichloromethane, oxolane, acetone, normal hexane, petroleum ether, methanol, ethanol or trichlorine
Methane；
Described inimers is BPEA, BIEM, BPEM or BIEA, and its structural formula is as follows:
Described has CO2The monomer of response is selected from one of following:
(methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) acrylate fourth
Ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid diethylamino propyl ester, (methyl) acrylic acid diethyl amino
Base butyl ester, (methyl) acrylamide dimethylaminoethyl, (methyl) acrylamide dimethylamino propyl ester, (methyl) acrylamide two
Methylamino butyl ester, (methyl) acrylamide diethylamino ethyl ester, (methyl) acrylamide diethylamino propyl ester or (methyl)
Acrylamide diethylamino butyl ester.
2. CO as claimed in claim 12Response dissaving polymer, it is characterised in that described atom transferred free radical gathers
Legal operating procedure is:
In reaction vessel I, add inimers, there is CO2The monomer of response, part, solvent, obtain liquid mixing
Thing, at ambient temperature, stirs and leads to N2Except O215～60min；Addition catalyst in reaction vessel II, at ambient temperature,
Logical N2Except O215～60min；Under anaerobic, the liquid mixture in reaction vessel I is added in reaction vessel II, then
Reaction vessel II is placed in the thermostatical oil bath of 40～80 DEG C reaction 6～12h；After completion of the reaction, reactant liquor is post-treated,
To described CO2Response dissaving polymer.
3. CO as claimed in claim 22Response dissaving polymer, it is characterised in that the method for described reactant liquor post processing
For:
After completion of the reaction, being added by reactant liquor in normal hexane, Precipitation, incline except supernatant liquid, precipitation oxolane dissolves
After carried out post, described cross post method be: with neutral Al2O3For column packing, oxolane is eluant, the eluent of collection
Dialysing with the bag filter of 3500～12000 molecular weight, last lyophilization i.e. obtains described CO again2The hyperbranched polymerization of response
Thing.
4. a CO2Response dissaving polymer, it is characterised in that described CO2Response dissaving polymer is by such as lower section
Method prepares:
To have CO2The monomer of response, chain tra nsfer dosage form monomer, initiator, solvent are raw material, use reversible addition-fracture chain
Transfer method, prepares described CO2Response dissaving polymer；
Described have CO2The monomer of response is 1:0.02～0.1 with the ratio of chain tra nsfer dosage form monomer, the amount of the material of initiator:
0.002～0.01；The volumetric usage of described solvent is to have CO2The amount of the material of the monomer of response is calculated as 0.5～5L/mol；
Described initiator is Ammonium persulfate., potassium peroxydisulfate, 4,4 '-azo double (4-cyanopentanoic acid), azo diisobutyl amidine salt
Hydrochlorate, azo diisopropyl imidazoline hydrochloride, azo diisopropyl imidazoline or 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-
Methyl isophthalic acid-acetone；
Described solvent is ethyl acetate, dichloromethane, oxolane, acetone, normal hexane, petroleum ether, methanol, ethanol, trichlorine
Methane, 1,4-dioxane, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, Methanamide or isopropanol；
Described chain tra nsfer dosage form monomer is: (2-ethyoxyl dithioester base) vinylacetate (A), 2-[(2-{ [(12
Alkylthio) carbonyl] sulfur generation-2-methylpropionyl) epoxide]-ethyl acrylate (B), propyl group (4-vinyl benzyl) dithio
Carboxylic acid (C), (2-vinyl dithioester base) acetate (D), its structural formula is as follows:
Described has CO2The monomer of response is selected from one of following:
(methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) acrylate fourth
Ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid diethylamino propyl ester, (methyl) acrylic acid diethyl amino
Base butyl ester, (methyl) acrylamide dimethylaminoethyl, (methyl) acrylamide dimethylamino propyl ester, (methyl) acrylamide two
Methylamino butyl ester, (methyl) acrylamide diethylamino ethyl ester, (methyl) acrylamide diethylamino propyl ester or (methyl)
Acrylamide diethylamino butyl ester.
5. CO as claimed in claim 42Response dissaving polymer, it is characterised in that described reversible addition-fracture chain turns
The operating procedure of shifting method is:
Reaction vessel adds there is CO2The monomer of response, chain tra nsfer dosage form monomer, initiator, solvent, logical N after sealing2
Except O215～60min, then reaction vessel is placed in the thermostatical oil bath of 40～90 DEG C reaction 12～24h, uses liquid nitrogen afterwards
Cancellation is reacted, and adds chloroform dilute reaction solution, adds in normal hexane by the reactant liquor after dilution, and Precipitation inclines except upper liquid
Body, lower sediment is vacuum dried, and prepares described CO2Response dissaving polymer.
6. the CO as described in claim 1 or 42Response dissaving polymer draws solute application as just permeating.
7. the CO as described in claim 1 or 42Response dissaving polymer draws solute be applied to just permeate as just permeating
In desalting process.
Apply the most as claimed in claim 7, it is characterised in that described CO2Response dissaving polymer draws as just permeating
Take solute when being applied to during positive penetration sea water desalinization,
Just permeating and drawing the compound method of liquid and be: taking described CO2Response dissaving polymer is added to the water, and is passed through CO2, institute
The CO stated2Liquid is drawn in the formation soluble in water of response dissaving polymer；Described CO2Response dissaving polymer and the matter of water
Amount ratio controls 0.1～0.8:1；Described it is passed through CO2Rate controlled 20～500ml/min, the time control at 30min～
6h；
The recovery method drawing solute is: after stopping diffusion, be passed through N to drawing in liquid2, described CO2The hyperbranched polymerization of response
Thing meeting Precipitation, is recovered by filtration, just permeates for next time；Described it is passed through N2Rate controlled 20～500ml/min, the time
Control at 30min～6h.
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| CN108047455A (en) * | 2018-02-09 | 2018-05-18 | 中国人民解放军陆军军医大学 | Amphipathy hyperbranched polymer for antigen vectors and its preparation method and application |
| CN108329483A (en) * | 2018-02-09 | 2018-07-27 | 中国人民解放军陆军军医大学 | Amphipathy hyperbranched polymer and its preparation method and application |
| CN108395498A (en) * | 2018-04-13 | 2018-08-14 | 沈阳工业大学 | A kind of PDMAEMA and its preparation method and application of hyperbranched macromolecular structure |
| CN109161045A (en) * | 2018-08-30 | 2019-01-08 | 江南大学 | A kind of temperature, pH double-response type intelligent macromolecular membrane and preparation method thereof |
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| CN106938194A (en) * | 2017-03-16 | 2017-07-11 | 天津大学 | A kind of synthetic method of single dispersing high catalytic performance solution state silver nano-grain and application |
| CN106938194B (en) * | 2017-03-16 | 2020-03-27 | 天津大学 | Synthesis method and application of monodisperse high-catalytic-performance solution-state silver nanoparticles |
| CN108047455A (en) * | 2018-02-09 | 2018-05-18 | 中国人民解放军陆军军医大学 | Amphipathy hyperbranched polymer for antigen vectors and its preparation method and application |
| CN108329483A (en) * | 2018-02-09 | 2018-07-27 | 中国人民解放军陆军军医大学 | Amphipathy hyperbranched polymer and its preparation method and application |
| CN108047455B (en) * | 2018-02-09 | 2020-12-25 | 中国人民解放军陆军军医大学 | Amphiphilic hyperbranched polymer for antigen carrier and preparation method and application thereof |
| CN108395498A (en) * | 2018-04-13 | 2018-08-14 | 沈阳工业大学 | A kind of PDMAEMA and its preparation method and application of hyperbranched macromolecular structure |
| CN109161045A (en) * | 2018-08-30 | 2019-01-08 | 江南大学 | A kind of temperature, pH double-response type intelligent macromolecular membrane and preparation method thereof |
| CN109161045B (en) * | 2018-08-30 | 2020-12-15 | 江南大学 | Temperature and pH dual-response type intelligent polymer film and preparation method thereof |
| CN114011241A (en) * | 2021-11-29 | 2022-02-08 | 中新国际联合研究院 | Responsive mixed draw solution containing organic molecules or polymers and inorganic salts and application |
| CN114011241B (en) * | 2021-11-29 | 2024-03-26 | 中新国际联合研究院 | Responsive mixed drawing liquid containing organic molecules or polymers and inorganic salts and application thereof |
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