CN1884321A - AMPS analog anion copolymer water dispersoid preparation method - Google Patents
AMPS analog anion copolymer water dispersoid preparation method Download PDFInfo
- Publication number
- CN1884321A CN1884321A CN200610044559.XA CN200610044559A CN1884321A CN 1884321 A CN1884321 A CN 1884321A CN 200610044559 A CN200610044559 A CN 200610044559A CN 1884321 A CN1884321 A CN 1884321A
- Authority
- CN
- China
- Prior art keywords
- monomer
- dispersion
- salt
- water
- preparation
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229920001577 copolymer Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 41
- 239000000178 monomer Substances 0.000 claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000977 initiatory effect Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- -1 alcohol compound Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims description 92
- 239000007788 liquid Substances 0.000 claims description 28
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 23
- 238000005516 engineering process Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 19
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005191 phase separation Methods 0.000 claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 15
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 230000003196 chaotropic effect Effects 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000012674 dispersion polymerization Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920001519 homopolymer Polymers 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 229920006318 anionic polymer Polymers 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 240000003183 Manihot esculenta Species 0.000 claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 208000031639 Chromosome Deletion Diseases 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 5
- 210000003608 fece Anatomy 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000003851 azoles Chemical class 0.000 claims description 4
- 239000004815 dispersion polymer Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- NJVCTPGWQVBVIO-UHFFFAOYSA-N N-(4-hydroxy-2-methylbutan-2-yl)prop-2-enamide Chemical compound C(C=C)(=O)NC(CCO)(C)C NJVCTPGWQVBVIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 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
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical group SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 3
- NSSIZMPQSZKECB-UHFFFAOYSA-N (diethoxyamino)oxyethane Chemical compound CCON(OCC)OCC NSSIZMPQSZKECB-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920000945 Amylopectin Polymers 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 230000000670 limiting effect Effects 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 239000002671 adjuvant Substances 0.000 abstract 3
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 14
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical class C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 229920001897 terpolymer Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KIIJKMXOKZEZEH-UHFFFAOYSA-M CC[N+](CC1=CC=CC=C1)(N)OC(C=C)=O.[Cl-] Chemical compound CC[N+](CC1=CC=CC=C1)(N)OC(C=C)=O.[Cl-] KIIJKMXOKZEZEH-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CGNRQCGWXXLTIA-UHFFFAOYSA-N bis(2-ethylhexyl) 2-methylidenebutanedioate Chemical compound CCCCC(CC)COC(=O)CC(=C)C(=O)OCC(CC)CCCC CGNRQCGWXXLTIA-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a method for preparing AMPS anionic copolymer water-dispersible system, which is a multi-stage water-dispersible polymerization with pH between 1 to 4. The method takes 1-50 mol% of at least one water soluble anionic vinyl monomer and at least one 50-99 mol% non-ionic vinyl monomer as raw material; taking hydrophobic monomer as adjuvant co-polymerization monomer, with its consumption being 0.1-5% of total weight of monomer; taking water soluble anionic monomer as dispersing agent, taking salt of high and low discrete series as phase separating agent, polyatomic alcohol compound as organic adjuvant dispersing agent, gas silica dioxide as inorganic adjuvant dispersing agent, oxidant- reducer- organic azo salt as composite initiating system (dropped for 2-5 times), and the consumption are 0.1- 5%, 5-40%, 0.05-5%, 0.05-10% and 0.001-5% of the total weight of dispersing system respectively. The proportion by weight of water soluble polymer in dispersing system is 5-40%, the relative molecular quality is high and stability is sound.
Description
Technical field
The invention belongs to high-molecular copolymer, colloid and interface and chemical technology interleaving techniques field, more particularly relate to the preparation method of AMPS analog anion copolymer water dispersoid.This multipolymer is evenly dispersed in and forms micron-sized nonhomogeneous system in the salt brine solution by means of the specific chemical technology and the stabilization of dispersion agent.It is the thick colloidal dispersion system of a class, belongs to thermodynamic unstable system.
Background technology
Water-soluble anionic copolymers has extremely widely at numerous areas such as oil production, water treatment, papermaking, weaving, printing and dyeing, coal washing, medicine, sugaring, building materials, agriculturals to be used.
Traditional water-soluble polymers is exactly the aqueous solutions of polymers of dilution, or polyalcohol hydrogel.Along with the development of technology, the solid powdery product has appearred.Publication number be the Chinese patent of CN85102644A, CN1057057A and CN1168894A disclosed all be the aqueous solution polymerization in homogeneous phase of pressed powder product.The productive unit operation of powdery product is many, the production cycle is long, technical equipment is complicated, and has the relative molecular mass poor more contradiction that this is difficult to be in harmonious proportion of solvability of high polymers more, and easily forms the big micelle of indissoluble in dissolution process.These defectives have limited the use of polymer powder product and the development of polymerization technique technology thereof to a certain extent.
Inverse emulsion polymerization product solubility property is good, relative molecular mass and degree of hydrolysis can free adjustment, but preparation process need consume a large amount of organic solvents, and products obtained therefrom also needs breakdown of emulsion and decon to handle, and technology is more numerous and diverse.And in emulsion polymerization process, unavoidably to use organic substances such as mineral oil, tensio-active agent, the two addition accounts for about 30% of product weight.It is unnecessary that these organic substances are said so to the user, finally also will therefore also cause secondary pollution to environment when cost improves to environmental emission.
The aqueous dispersion polymerization technology is one of the research focus in international water-soluble polymer field.Its reaction principle is: monomer is dissolving fully in salt brine solution, and polymer particle does not dissolve in salt brine solution; Along with the carrying out of polyreaction, polymer particle increases gradually, will precipitate because of the salting-out effect of inorganic salt when its relative molecular mass increases to a certain threshold value, causes product and solution to be separated; By the stably dispersing effect of all kinds of organic or inorganic dispersion agents, the polymer particle that is settled out is evenly dispersed in forms micron-sized nonhomogeneous system in the salt brine solution simultaneously.This method has kept the advantage of solution polymerization, and heat of polymerization is easy to distribute, and system viscosity is little, and product rheology can be excellent; Polymerization process is easy to operate, polymkeric substance relative molecular mass narrowly distributing, and residual monomer is retained in the solvent substantially, helps obtaining the high-purity polymer product.With respect to other three kinds of polymerization techniques of water-soluble polymer, the aqueous dispersion polymerization technology belongs to eco-friendly macromolecule chemical industry technology, has huge development potentiality.
In recent years, Hesperian researchist has studied the preparation technology of aqueous polymer dispersion successively, dabbles fields such as negatively charged ion, positively charged ion and amphoteric ion type aqueous dispersed polymer.Calendar year 2001, people such as the loose island Shang Si of Japan are raw material monomer with N-vinyl formamide and acrylic acid derivative, are phase separation agent with ammonium chloride, are initiator with the water-soluble azo compounds, adopt the mode that once feeds intake to prepare negatively charged ion hydrophobic type aqueous dispersion, the several microns of multipolymer diameter.And people such as American scholar John Connors are starting monomer with acrylamide, acrylyl oxy-ethyl-trimethyl salmiac and acrylyl oxy-ethyl aminobenzyl ammonium chloride, with ammonium sulfate is phase separation agent, with modified starch and melon glue is dispersion agent, adopts disposable reinforced mode to prepare cationic polymeric dispersion system under high-speed stirring.In above two examples, because the restriction of disposable feed way, the preparation stability and the stability in storage of products obtained therefrom are relatively poor, the polymer particle size skewness, and the shelf lives is shorter.
U.S. Pat 3,658,772 disclose, and are phase separation agent with salts solutions such as sodium sulfate, sodium-chlor, adopt redox initiation system to cause terpolymers such as sodium acrylate, acrylamide and dimethylaminoethyl methacrylate down at 25 ℃, obtained mobile better polymerization thing dispersion liquid.It should be noted that the pH value should be adjusted to 1～3.2 when reporting polymerization in this patent,, can produce not flowable gel product if the pH value is increased to 4 or higher.And, in 500, be higher than in the pH value under 4 the situation and fail to obtain stable dispersion liquid too in U.S. Pat 3,493.
Above-mentioned several example has been represented the research level of current aqueous dispersed polymer substantially.The disposable reinforced restriction and the selection problem of dispersion agent make these products all have stability problem to some extent.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned shortcoming and defect, and a kind of preparation method of AMPS analog anion copolymer water dispersoid is provided.It adopts AMPS class monomer and acrylamide monomers is raw material, add water-soluble anionic polymer and make dispersion agent, add all kinds of organic auxiliary dispersants and inorganic auxiliary dispersants simultaneously, with oxygenant-reductive agent-organic diazo salt is composite initiation system, adopts multistage aqueous dispersion polymerization technology can prepare the aqueous polymer dispersion of relative molecular mass height, good stability in salt brine solution.
Present method is a composite dispersing agent with water-soluble anionic polymer, polyol compound and aerosil, is composite initiation system with oxidation-reduction-organic diazo salt, adopts the multistage polymerization technology, has made the stable polymer aqueous dispersion.It has overcome because disposable feeding in raw material reaches the product stability problems of using single dispersion agent to cause, and adopts composite initiation system, is easy to obtain the copolymer product of high molecular weight.
In order to achieve the above object, the present invention is in the pH value is 1～4 scope, by following material proportion, adopts multistage aqueous dispersion polymerization method polymerization:
A. be raw material with at least a water soluble anion vinyl monomer of 1～50mol% and the nonionic ethylene base monomer of at least a 50～99mol%;
B. make auxiliary comonomer with hydrophobic monomer, consumption is 0.1～5% of an above-mentioned total monomer weight;
C. make dispersion agent with water-soluble anionic polymer, consumption is 0.1～5% of a dispersion system gross weight;
D. with at least a chaotropic salt with at least aly make phase separation agent from the low salt of liquid sequence, consumption is 5～40% of a dispersion system gross weight;
E. make organic class auxiliary dispersants with multicomponent alcoholics compound, consumption is 0.05～5% of a dispersion system gross weight;
F. make the mineral-type auxiliary dispersants with aerosil, consumption is 0.05～10% of a dispersion system gross weight;
G. be composite initiation system with oxygenant-reductive agent-organic diazo salt, consumption is 0.001～5% of a total monomer weight, divides 2～5 droppings;
H. surplus is a water;
The weight percent of water-soluble polymers is 5～40% in the dispersion system of preparation.
Its preparation technology is as follows: partial monosomy, salt, dispersion agent and other auxiliary agent are dropped in the reactor, and the pH value of regulation system stirs and intensification, in nitrogen atmosphere, drips the part initiator.After reaction for some time, adopt the mode of multistage polymerization, add the monomer and the initiator of remainder in batches, isothermal reaction 6～8h reduces to the room temperature discharging at last.The finished product are the level and smooth liquid of oyster white, and are mobile, have good stability.Dispersed polymeres relative molecular mass of the present invention is usually 2,000, and in 000～20,000,000 scope, 20 ℃ of following brookfield viscosity are less than 2,000mPas.
Anionic vinyl monomer used in the present invention can be chosen in very wide scope.Used monomer should have vinyl or propenyl functional group, and comprises carboxyl, sulfonic group, phosphate or other anionic group, and the water-soluble alkali metal salts of above-mentioned substance, alkaline earth salt or ammonium salt.
Suitable water soluble anion vinyl monomer is selected from vinylformic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, 3-acrylamido-3-methyl butanol acid, maleic acid or styrene sulfonic acid, and the water-soluble alkali metal salts of above-mentioned substance, alkaline earth salt or ammonium salt.
Non-ionic monomer used in the present invention can be any uncharged vinyl monomer.Suitable monomers comprises acrylamide, Methacrylamide, N-N-isopropylacrylamide, N-t-butyl acrylamide or N methacrylamide.
The monomer consumption accounts for 5～40% of dispersion weight in the copolymer water dispersoid, generally selects 10～40%, and preferred 15～30%.
Nonionic ethylene base monomer can mix by arbitrary proportion with the anionic vinyl monomer, and according to the difference of various monomer ratios, the performance of the aqueous dispersed polymer that makes also is different.
The present invention selects for use hydrophobic monomer as auxiliary comonomer.Hydrophobic monomer is selected from C
2～C
32Alkyl ester, or have the compound of stiffening ring.Suitable hydrophobic monomer comprises the C of methylene-succinic acid
1～C
8Dialkyl monomer: dimethyl itaconate, dibutyl itaconate or dioctyl itaconate; Or the C of acrylic or methacrylic acid
1～C
32Alkyl ester monomer: ethyl propenoate, butyl acrylate, vinylformic acid stearyl or methacrylic acid stearyl; Or diene monomers: divinyl, chloroprene; Or sodium p styrene sulfonate, N-V-Pyrol RC.The hydrophobic monomer consumption accounts for 0.1～5% of total monomer weight among the present invention, generally selects 0.1～4%, and preferred 0.1～3%.
Hydrophobic monomer mostly has long hydrophobic chain link or stiffening ring unit.This can improve the rigidity and the regularity of polymer molecular chain from the microcosmic; And, the polymkeric substance that contains hydrophobic grouping in salt brine solution than the easier precipitation of polymkeric substance that does not contain hydrophobic grouping.From the macroscopic perspective analysis, a spot of hydrophobic monomer participates in polymerization, helps to improve the preparation and the package stability of aqueous dispersion.Aqueous dispersed polymer type and aqueous dispersion polymerization processing condition are depended in the selection of polymeric dispersant.Good dispersant should have stronger adsorption and be dissolvable in water in the dispersion medium on the polymer beads surface.
Under the condition without any dispersion agent, polymer beads may dissolve in the short period of time after formation, and the polymer dispersed system of preparation can produce the paste thing as the thin pulp shape, and retrogradation forms blob of viscose in the quite short time.Yet,, just produce stable dispersion particle as long as a small amount of suitable dispersion agent is joined in the polymkeric substance.Particle stabilizedization phenomenon in the dispersion polymerization has the feature of " spatial stability ".
Dispersion agent is selected from the homopolymer or the multipolymer of 2-acrylamido-2-methyl propane sulfonic acid, contains volumetric molar concentration in this dispersion agent at least and be 2-acrylamido-2-methyl propane sulfonic acid of 10%, and this polymkeric substance can make by traditional aqueous solution polymerization technology.
This polymeric dispersant intrinsic viscosity in 1M NaCl is 0.1～12dL/g, is generally 0.3～10.0dL/g, preferred 0.5～7.0dL/g.
The consumption of dispersion agent accounts for 0.1～5% of whole dispersion weight among the present invention, is preferably 0.25～1.5%, and more preferably 0.4～1.25%.Dispersant dosage is too small, and polymkeric substance is not had due stabilization, and the polymer beads that is generated is with soluble in water, and solution viscosity increases, and what finally obtain is the polymkeric substance blob of viscose, rather than aqueous dispersion; And excessive when its consumption, the stabilization of dispersion agent can obviously not strengthen, and can cause the polymkeric substance relative molecular mass to reduce on the contrary.
The present invention adds polyol as organic class auxiliary dispersants in reaction system, the precipitation process of polymer beads is steadily carried out.
Organic class auxiliary dispersants that the present invention chooses is a polyvalent alcohol, comprises multifunctional ethanol: glycerine or polyoxyethylene glycol, or polysaccharide: modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose.
The effect of organic class auxiliary dispersants is to be used as colloid protective agent at the polyreaction initial stage.In use, the consumption of organic class auxiliary dispersants accounts for 0.05～5% of dispersion system gross weight, selects 0.05～4%, preferred 0.05～2%.
The present invention uses aerosil as the mineral-type auxiliary dispersants.In aqueous dispersion, because the aerosil particle diameter is little, surface energy is high, they can be adsorbed on the surface of polymer beads, and form a top layer at particle surface, improve the hydrophobic dispersing property of polymkeric substance, use so can be used as inorganic dispersant.The aerosil addition is too much unsuitable, causes the system thixotropic property too strong because addition is crossed conference, and edge scissor shear force is not enough when causing disperseing, and is gelatin, influences dispersion effect.The consumption of aerosil is chosen to be 0.01～10% among the present invention, is preferably 0.05～7%, and optimized scope is 0.05～5%.
It is at least a from liquid sequence low salt and at least a chaotropic salt to be applicable to that phase separation agent of the present invention comprises.What the present invention chose comprises inorganic salt from the low salt of liquid sequence: vitriol, phosphoric acid salt, hydrophosphate or fluorochemical, or organic salt: Citrate trianion, acetate, tartrate.Positively charged ion also can produce certain influence to the solubleness of polymkeric substance, and it can be ammonium ion or alkalimetal ion and alkaline-earth metal ions, as lithium, sodium, potassium, magnesium, calcium ion etc.But anionic copolymer and divalent-metal ion are (as Ca
2+) tendency that forms complex compound is arranged, so use salts of monovalent usually.The chaotropic salt that the present invention chooses comprises thiocyanate-, perchlorate, oxymuriate, bromate or nitrate, wherein preferred Sodium Thiocyanate 99, ammonium thiocyanate, potassium sulfocyanate, sodium perchlorate or sodium chlorate.The low excessively sedimentation that is unfavorable for polymer beads of phase separation agent concentration, and the too high dissolving difficulty that causes, and do not meet economic requirement.The phase separation agent consumption is 5～40% of a total dispersion weight, and is preferred 5～30%, more preferably 8～25%.
The present invention adopts the composite initiation system that oxidation-reduction-organic diazo salt is formed.Wherein oxygenant is ammonium persulphate, Potassium Persulphate or hydrogen peroxide, reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, triethoxy amine or Tetramethyl Ethylene Diamine, organic diazo salt is 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (V-044), 2,2-azo two (2-amidine propane) dihydrochloride (ABAH) or 2,2-Diisopropyl azodicarboxylate (AIBN).The present invention preferably adopts Potassium Persulphate, sodium bisulfite and 2, the composite initiation system that 2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (V-044) are formed.The add-on of described composite initiator can change according to temperature of reaction, but consumption is generally 0.001～5% of total monomer weight.
Except above-mentioned substance, in preparation process of the present invention, also can use other additive, sequestrant is used for removing the foreign metal ion, in order to avoid disturb the activity of employed free radical catalyst, and be used to chain-transfer agent of regulating relative molecular mass etc.
Task of the present invention comes to this and finishes.
It is raw material that the present invention adopts AMPS class monomer and acrylamide monomers, add water-soluble polymers and make dispersion agent, add organic class auxiliary dispersants and mineral-type auxiliary dispersants simultaneously, with oxygenant-reductive agent-organic diazo salt is composite initiation system, adopts multistage aqueous dispersion polymerization technology to prepare the copolymer water dispersoid of relative molecular mass height, good stability in salt brine solution.But wide popularization and application.
Embodiment
Following embodiment further describes the present invention, but these embodiment do not limit the scope of the invention.
Embodiment 1.A kind of preparation method of AMPS analog anion copolymer water dispersoid.It is in the pH value is 1～4 scope, by following material proportion, adopts multistage aqueous dispersion polymerization method polymerization:
A. be raw material with at least a water soluble anion vinyl monomer of 1～50mol% and the nonionic ethylene base monomer of at least a 50～99mol%;
B. make auxiliary comonomer with hydrophobic monomer, consumption is 5% of an above-mentioned total monomer weight;
C. make dispersion agent with water-soluble anionic polymer, consumption is 3% of a dispersion system gross weight;
D. with at least a chaotropic salt with at least aly make phase separation agent from the low salt of liquid sequence, consumption is 5% of a dispersion system gross weight;
E. make organic class auxiliary dispersants with multicomponent alcoholics compound, consumption is 0.2% of a dispersion system gross weight;
F. make the mineral-type auxiliary dispersants with aerosil, consumption is 5% of a dispersion system gross weight;
G. be composite initiation system with oxygenant-reductive agent-organic diazo salt, the composite initiator consumption is 5% of a total monomer weight, divides 3 droppings;
H. surplus is a water;
The weight percent of water-soluble polymers is 5～40% in the dispersion system of preparation.
Its preparation technology is: earlier partial monosomy, salt, dispersion agent and other auxiliary agent are dropped in the reactor, the pH value of regulation system stirs and intensification, in nitrogen atmosphere, drips the part initiator; After reaction for some time, adopt the mode of multistage polymerization, add the monomer and the initiator of remainder in batches, isothermal reaction is 7 hours then, reduces to the room temperature discharging at last.
Said water soluble anion vinyl monomer is a vinylformic acid.
Nonionic ethylene base monomer is a N methacrylamide.
Hydrophobic monomer is C
2～C
32Alkyl ester or have the compound of stiffening ring, be the C of methylene-succinic acid
1～C
8The dialkyl monomer.
Dispersion agent is selected from the homopolymer or the multipolymer of 2-acrylamido-2-methyl propane sulfonic acid, contains volumetric molar concentration in this dispersion agent at least and be 2-acrylamido-2-methyl propane sulfonic acid of 10%.
Organic class auxiliary dispersants is a polyvalent alcohol, comprises multifunctional ethanol: glycerine or polyoxyethylene glycol, mineral-type auxiliary dispersants are aerosil.
Phase separation agent comprises at least a from liquid sequence low salt and at least a chaotropic salt, and said is vitriol from the low salt of liquid sequence, and chaotropic salt is a thiocyanate-.
Oxygenant is an ammonium persulphate in oxygenant-reductive agent-organic diazo salt composite initiation system, and reductive agent is a S-WAT, and organic diazo salt is 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (V-044).
Embodiment 2.A kind of preparation method of AMPS analog anion copolymer water dispersoid.It is in the pH value is 1～4 scope, by following material proportion, adopts multistage aqueous dispersion polymerization method polymerization:
A. be raw material with at least a water soluble anion vinyl monomer of 1～50mol% and the nonionic ethylene base monomer of at least a 50～99mol%;
B. make auxiliary comonomer with hydrophobic monomer, consumption is 0.1% of an above-mentioned total monomer weight;
C. make dispersion agent with water-soluble anionic polymer, consumption is 5% of a dispersion system gross weight;
D. with at least a chaotropic salt with at least aly make phase separation agent from the low salt of liquid sequence, consumption is 30% of a dispersion system gross weight;
E. make organic class auxiliary dispersants with multicomponent alcoholics compound, consumption is 2% of a dispersion system gross weight;
F. make the mineral-type auxiliary dispersants with aerosil, consumption is 4% of a dispersion system gross weight;
G. be composite initiation system with oxygenant-reductive agent-organic diazo salt, the composite initiator consumption is 0.001% of a total monomer weight, divides 2 droppings;
H. surplus is a water;
The weight percent of water-soluble polymers is 5～40% in the dispersion system of preparation.
Its preparation technology is: earlier partial monosomy, salt, dispersion agent and other auxiliary agent are dropped in the reactor, the pH value of regulation system stirs and intensification, in nitrogen atmosphere, drips the part initiator; After reaction for some time, adopt the mode of multistage polymerization, add the monomer and the initiator of remainder in batches, isothermal reaction 8h reduces to the room temperature discharging at last then.
The water soluble anion vinyl monomer is 2-acrylamido-2-methyl propane sulfonic acid.
Nonionic ethylene base monomer is a Methacrylamide.
Said hydrophobic monomer is selected from C
2～C
32Alkyl ester or have the compound of stiffening ring, be the C of methylene-succinic acid
1-C
8The dialkyl monomer.
Dispersion agent is selected from the homopolymer or the multipolymer of 2-acrylamido-2-methyl propane sulfonic acid, and the limiting viscosity of this dispersion agent in 1M NaCl is 0.5～7.0dL/g, and its consumption accounts for 0.1～5% of dispersion weight per-cent.
Said organic class auxiliary dispersants polyvalent alcohol is a polyoxyethylene glycol, and the mineral-type auxiliary dispersants is an aerosil.
Phase separation agent comprises at least a from liquid sequence low salt and at least a chaotropic salt, and said is phosphoric acid salt from the low salt of liquid sequence, and chaotropic salt is a nitrate.
Oxygenant in oxygenant-reductive agent-organic diazo salt composite initiation system is a Potassium Persulphate, and reductive agent is a sodium bisulfite, and organic diazo salt is 2,2-azo two (2-amidine propane) dihydrochloride (ABAH).
Embodiment 3.A kind of preparation method of AMPS analog anion copolymer water dispersoid.It is in the pH value is 1～4 scope, by following material proportion, adopts multistage aqueous dispersion polymerization method polymerization:
A. be raw material with at least a water soluble anion vinyl monomer of 1～50mol% and the nonionic ethylene base monomer of at least a 50～99mol%;
B. make auxiliary comonomer with hydrophobic monomer, consumption is 3% of an above-mentioned total monomer weight;
C. make dispersion agent with water-soluble anionic polymer, consumption is 0.1% of a dispersion system gross weight;
D. with at least a chaotropic salt with at least aly make phase separation agent from the low salt of liquid sequence, consumption is 40% of a dispersion system gross weight;
E. make organic class auxiliary dispersants with multicomponent alcoholics compound, consumption is 0.05% of a dispersion system gross weight;
F. make the mineral-type auxiliary dispersants with aerosil, consumption is 0.05% of a dispersion system gross weight;
G. be composite initiation system with oxygenant-reductive agent-organic diazo salt, the composite initiator consumption is 4% of a total monomer weight, divides 5 droppings;
H. surplus is a water;
The weight percent of water-soluble polymers is 5～40% in the dispersion system of preparation.Its preparation technology is: earlier partial monosomy, salt, dispersion agent and other auxiliary agent are dropped in the reactor, the pH value of regulation system stirs and intensification, in nitrogen atmosphere, drips the part initiator; After reaction for some time, adopt the mode of multistage polymerization, add the monomer and the initiator of remainder in batches, isothermal reaction is 6 hours then, reduces to the room temperature discharging at last.
Soluble anionic monomers is 3-acrylamido-3-methyl butanol acid.
The non-ionic water-soluble monomer is N-N-isopropylacrylamide, N methacrylamide etc.
Said hydrophobic monomer is selected from C
2～C
32Alkyl ester or have the compound of stiffening ring, be sodium p styrene sulfonate, N-V-Pyrol RC.
Dispersion agent is selected from the homopolymer or the multipolymer of 2-acrylamido-2-methyl propane sulfonic acid, contains volumetric molar concentration in this dispersion agent at least and be 2-acrylamido-2-methyl propane sulfonic acid of 10%.
Said organic class auxiliary dispersants polyvalent alcohol is a polysaccharide: modified tapioca starch, mineral-type auxiliary dispersants are aerosil.
Phase separation agent comprises at least a from liquid sequence low salt and at least a chaotropic salt, and said is hydrophosphate from the low salt of liquid sequence, and chaotropic salt is a bromate.
Oxygenant in oxygenant-reductive agent-organic diazo salt composite initiation system is a hydrogen peroxide, and reductive agent is a ferrous sulfate, and organic diazo salt is 2,2-azo two (2-amidine propane) dihydrochloride (ABAH).
Embodiment 4.Present embodiment is set forth the preparation method of employed polymeric dispersant in the present invention.
In the 2L reactor, drop into 200g2-acrylamido-2-methyl propane sulfonic acid, 1466g deionized water and 0.2g EDTA2Na successively.Stir and with mixture heating up to 45 ℃, the nitrogen that feeds 1000cc/min is with abundant expeling oxygen.Add 0.1gV-044, the 15min post-polymerization begins, and soltion viscosity increases.After stirring 4～5h, promptly get the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid.The intrinsic viscosity that records this polymkeric substance in 1MNaCl is 1～4dL/g.
Embodiment 5.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
It is to have agitator, temperature is taken into account in the reactor of condenser, add the 419.08g deionized water successively, 105.00g sodium sulfate, 135.00g ammonium sulfate, 5.00g potassium sulfocyanate, 60g2-acrylamido-2-methyl propane sulfonic acid homopolymer (12%, intrinsic viscosity is 3.76dL/g among the 1M NaCl), 62.7g acrylamide (AM), 27.2g2-acrylamido-2-methyl propane sulfonic acid (AMPS), 6.00g butyl acrylate (BA), 2.70g50%NaOH solution, 0.15g EDTA2Na and 5.00g aerosil, 8.00g modified tapioca starch stirs and feeds simultaneously nitrogen.Solution is heated to 45 ℃, adds 1.92gK
2S
2O
8, 4.8gNaHSO
3, 1.00g4% V-044 solution.The 15min afterreaction begins, and forms the emulsus dispersion liquid.Behind 45 ℃ of following constant temperature 2h, progressively drip NaOH solution and the 0.05gEDTA2Na of 125.00g deionized water, 20.91g acrylamide, 9.09g2-acrylamido-2-methyl propane sulfonic acid, 0.9g50% afterwards in the 1.5h.Continue reaction 1h down at 50 ℃, add the V-044 solution of 0.25g4% then.Be warming up to 60 ℃, add the V-044 solution of 0.25g4%, continue to reduce to the room temperature discharging behind the reaction 4h.
The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 430mPas, and pH is 3.40, and relative molecular mass is 562.6 * 10
4, active matter content is 12%, the negatively charged ion degree is 30%.
Embodiment 6.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
It is to have agitator, temperature is taken into account in the reactor of condenser, add the 419.08g deionized water successively, 105.00g sodium sulfate, 135.00g ammonium sulfate, 5.00g potassium sulfocyanate, 60g2-acrylamido-2-methyl propane sulfonic acid homopolymer (12% concentration, intrinsic viscosity is 3.76dL/g among the 1M NaCl), 59.32g acrylamide (AM), 30.58g2-acrylamido-2-methyl propane sulfonic acid (AMPS), 6.00g butyl acrylate (BA), 2.70g50%NaOH solution, 0.15gEDTA2Na and 5.00g aerosil, 8.00g modified tapioca starch stirs and feeds simultaneously nitrogen.Solution is heated to 45 ℃, adds 1.92gNa
2S
2O
8, 4.8gNa
2SO
3, 1.00g4% V-044 solution.The 15min afterreaction begins, and forms the emulsus dispersion liquid.Behind 45 ℃ of following constant temperature 2h, progressively drip NaOH solution and the 0.05gEDTA2Na of 125.00g deionized water, 19.78g acrylamide, 10.22g2-acrylamido-2-methyl propane sulfonic acid, 0.9g50% afterwards in the 1.5h.Continue reaction 1h down at 50 ℃, add the V-044 solution of 0.25g4% then.Be warming up to 60 ℃, add the V-044 solution of 0.25g4%, reduce to the room temperature discharging after continuing to stir 4h.
The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 380mPas, and pH is 3.40, and relative molecular mass is 693.6 * 10
4, active matter content is 12%, the negatively charged ion degree is 15%.
Embodiment 7.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
Having agitator, temperature is taken into account in the reactor of condenser, add the 259.26g deionized water successively, 105.00g sodium sulfate, 135.00g ammonium sulfate, 5.00g potassium sulfocyanate, 120g2-acrylamido-2-methyl propane sulfonic acid homopolymer (12%, intrinsic viscosity is 3.76dL/g among the 1M NaCl), 125.4g acrylamide (AM), 54.4g2-acrylamido-2-methyl propane sulfonic acid (AMPS), 12.00g butyl acrylate (BA), 5.40g50%NaOH solution, 0.3gEDTA2Na and 5.00g aerosil, 8.00g modified tapioca starch stirs and feeds simultaneously nitrogen.Solution is heated to 45 ℃, adds 3.84gNa
2S
2O
8, 9.6gNa
2SO
3, 2.00g4% V-044 solution.The 15min afterreaction begins, and forms the emulsus dispersion liquid.Behind 45 ℃ of following constant temperature 2h, progressively drip NaOH solution and the 0.10gEDTA2Na of 90.00g deionized water, 40.82g acrylamide, 18.08g2-acrylamido-2-methyl propane sulfonic acid, 0.8g50% afterwards in the 1.5h.Continue reaction 1h down at 50 ℃, add the V-044 solution of 0.50g4% then.Be warming up to 60 ℃, add the V-044 solution of 0.50g4%, reduce to the room temperature discharging after continuing to stir 4h.
The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 540mPas, and pH is 3.40, and relative molecular mass is 623.6 * 10
4, active matter content is 24%, the negatively charged ion degree is 30%.
Comparative Examples 1: according to embodiment 5 same way as, do not use aerosil and modified tapioca starch.The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 390mPas, and relative molecular mass is 572.3 * 10
4, active matter content is 12%, the negatively charged ion degree is 30%.In the gained white dispersion liquid volume macrobead is arranged, place and layering occurs after 60 days.
Comparative Examples 2: replace K with V-044
2S
2O
8, NaHSO
3, V-044 composite initiation system, three times add-on is constant.The add-on of other component and operation, polymerizing condition are with embodiment 5.The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 501mPas, and relative molecular mass is 430.5 * 10
4, active matter content is 12%, the negatively charged ion degree is 30%.
Embodiment 8.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
Its sodium sulfate consumption is reduced to 78.75g, and the ammonium sulfate consumption is reduced to 101.25g, and simultaneously, amount of water increases to 560g for the first time.Like this, the phase separation agent consumption accounts for 18% of water dispersion gross weight.The add-on of monomer, dispersion agent and other component and operation, polymerizing condition are with embodiment 5.
The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 312mPas, and relative molecular mass is 534.6 * 10
4, active matter content is 18%, the negatively charged ion degree is 30%.
Embodiment 9.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
Present embodiment has been set forth the importance of inorganic salt in the aqueous dispersed polymer preparation process.
Sodium sulfate, ammonium sulfate consumption are reduced to 0g.Amount of water increases to 740g for the first time.The add-on of monomer, dispersion agent and other component and operation, polymerizing condition are with embodiment 5.
Product conglomerate in stirring polymerization process as a result.
Embodiment 10.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
Dispersion agent 2-acrylamido-2-methyl propane sulfonic acid homopolymer consumption is increased to 80g, and amount of water is reduced to 480g for the first time.The add-on of monomer, phase separation agent and other component and operation, polymerizing condition are with embodiment 5.
The AM/BA/AMPS terpolymer dispersion liquid brookfield viscosity that makes is 689mPas, and relative molecular mass is 596.3 * 10
4, active matter content is 12%, the negatively charged ion degree is 30%.
Embodiment 11.A kind of preparation method of AMPS analog anion copolymer water dispersoid.
The importance of dispersion agent in the aqueous dispersed polymer preparation process has been set forth in this enforcement.
Dispersion agent 2-acrylamido-2-methyl propane sulfonic acid homopolymer consumption is 0g, and amount of water increases to 560g for the first time.The add-on of monomer, phase separation agent and other component and operation, polymerizing condition are with embodiment 5.The result produces the paste thing of thin pulp shape under the condition that no dispersion agent exists, and retrogradation forms blob of viscose in the quite short time.
It is raw material that embodiment 1～11 adopts AMPS class monomer and acrylamide monomers, add water-soluble anionic polymer and make dispersion agent, add all kinds of organic and inorganic supplementary additives simultaneously, with oxygenant-reductive agent-organic diazo salt is composite initiation system, adopts multistage aqueous dispersion polymerization technology can prepare the aqueous polymer dispersion of relative molecular mass height, good stability in salt brine solution.But present method wide popularization and application.
Claims (11)
1. the preparation method of an AMPS analog anion copolymer water dispersoid is characterized in that it is in the pH value is 1～4 scope, by following material proportion, adopts multistage aqueous dispersion polymerization method polymerization:
A. be raw material with at least a water soluble anion vinyl monomer of 1～50mol% and the nonionic ethylene base monomer of at least a 50～99mol%;
B. make auxiliary comonomer with hydrophobic monomer, consumption is 0.1～5% of an above-mentioned total monomer weight;
C. make dispersion agent with water-soluble anionic polymer, consumption is 0.1～5% of a dispersion system gross weight;
D. with at least a chaotropic salt with at least aly make phase separation agent from the low salt of liquid sequence, consumption is 5～40% of a dispersion system gross weight;
E. make organic class auxiliary dispersants with multicomponent alcoholics compound, consumption is 0.05～5% of a dispersion system gross weight;
F. make the mineral-type auxiliary dispersants with aerosil, consumption is 0.05～10% of a dispersion system gross weight;
G. be composite initiation system with oxygenant-reductive agent-organic diazo salt, consumption is 0.001～5% of a total monomer weight, divides 2～5 droppings;
H. surplus is a water;
The weight percent of water-soluble polymers is 5～40% in the dispersion system of preparation.
2. according to the preparation method of the described AMPS analog anion copolymer water dispersoid of claim 1, it is characterized in that preparation technology is: earlier partial monosomy, salt, dispersion agent and other auxiliary agent are dropped in the reactor, the pH value of regulation system, stir and intensification, in nitrogen atmosphere, drip the part initiator; After reaction for some time, adopt the mode of multistage polymerization, add the monomer and the initiator of remainder in batches, isothermal reaction 6～8h reduces to the room temperature discharging at last then.
3. according to the preparation method of claim 1 or 2 described AMPS analog anion copolymer water dispersoids, it is characterized in that said water soluble anion vinyl monomer is selected from vinylformic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, 3-acrylamido-3-methyl butanol acid, maleic acid or styrene sulfonic acid, and the water-soluble alkali metal salts of above-mentioned substance, alkaline earth salt or ammonium salt.
4. according to the preparation method of the described AMPS analog anion copolymer water dispersoid of claim 1, it is characterized in that said nonionic ethylene base monomer is acrylamide, Methacrylamide, N-N-isopropylacrylamide or N methacrylamide.
5. according to the preparation method of the described AMPS analog anion copolymer water dispersoid of claim 4, it is characterized in that said hydrophobic monomer is selected from C
2～C
32Alkyl ester or have the compound of stiffening ring.
6. the C that comprises methylene-succinic acid according to the described hydrophobic monomer of claim 5
1～C
8The C of dialkyl monomer, acrylic or methacrylic acid
1～C
32Alkyl ester monomer, diene monomers and sodium p styrene sulfonate or N-V-Pyrol RC.
7. according to the preparation method of the described AMPS analog anion copolymer water dispersoid of claim 1, it is characterized in that said dispersion agent is selected from the homopolymer or the multipolymer of 2-acrylamido-2-methyl propane sulfonic acid, contain volumetric molar concentration in this dispersion agent at least and be 2-acrylamido-2-methyl propane sulfonic acid of 10%.
8. the method for preparing the described water-soluble anionic polymer dispersion agent of claim 7 is characterized in that the limiting viscosity of this dispersion agent in 1M NaCl is 0.5～7.0dL/g, and its consumption accounts for 0.1～5% of dispersion weight per-cent.
9. comprise multitube energy ethanol according to the described organic class auxiliary dispersants polyvalent alcohol of claim 1: glycerine or polyoxyethylene glycol, or polysaccharide such as modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose.
10. according to the preparation method of the described AMPS analog anion copolymer water dispersoid of claim 1, it is characterized in that said is vitriol, phosphoric acid salt, hydrophosphate, fluorochemical, Citrate trianion, acetate or tartrate from the low salt of liquid sequence, and chaotropic salt is thiocyanate-, perchlorate, oxymuriate, bromate or nitrate.
11. preparation method according to the described AMPS analog anion copolymer water dispersoid of claim 1, it is characterized in that oxygenant is ammonium persulphate, Potassium Persulphate or hydrogen peroxide in said oxygenant-reductive agent-organic diazo salt composite initiation system, reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, triethoxy amine or Tetramethyl Ethylene Diamine, organic diazo salt is 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid, 2,2-azo two (2-amidine propane) dihydrochloride or 2, the 2-Diisopropyl azodicarboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610044559XA CN100487006C (en) | 2006-05-23 | 2006-05-23 | AMPS analog anion copolymer water dispersoid preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610044559XA CN100487006C (en) | 2006-05-23 | 2006-05-23 | AMPS analog anion copolymer water dispersoid preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1884321A true CN1884321A (en) | 2006-12-27 |
| CN100487006C CN100487006C (en) | 2009-05-13 |
Family
ID=37582637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610044559XA Expired - Fee Related CN100487006C (en) | 2006-05-23 | 2006-05-23 | AMPS analog anion copolymer water dispersoid preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100487006C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712730B (en) * | 2009-05-13 | 2011-07-27 | 北京瑞仕邦精细化工技术有限公司 | Preparation method of water-soluble polymer dispersion |
| CN102746456A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Terpolymer and polymer and preparation method and application thereof |
| CN102746455A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Acrylamide terpolymer and polymer and preparation method and application thereof |
| CN102875724A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Copolymer, and preparation method and application thereof |
| CN102875726A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Copolymer and preparation method and application thereof |
| CN103571256A (en) * | 2012-07-31 | 2014-02-12 | 罗门哈斯公司 | Sulfonic acid monomer based compositions |
| CN104761678A (en) * | 2015-04-11 | 2015-07-08 | 烟台润星环保科技发展有限公司 | Method for preparing flocculating agent for dry discharge of tailings |
| CN112300321A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Preparation method of polyacrylamide aqueous dispersion |
| CN112300023A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method and application thereof |
| CN116284622A (en) * | 2023-03-15 | 2023-06-23 | 上海宇昂水性新材料科技股份有限公司 | Phosphate type copolymer dispersing agent and preparation method thereof |
| CN116875291A (en) * | 2023-09-06 | 2023-10-13 | 胜利星科石油技术开发(山东)有限公司 | Composite flooding containing acrylic acid fatty ester-butene benzene-sulfonated acrylamide copolymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694831A (en) * | 2016-03-17 | 2016-06-22 | 中国石油集团渤海钻探工程有限公司 | High-temperature-resistant and salt-resistant viscosity reducer and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350006A (en) * | 2001-11-28 | 2002-05-22 | 王丕新 | Synthesis of water soluble anionic and non-ionic polymer dispersion |
-
2006
- 2006-05-23 CN CNB200610044559XA patent/CN100487006C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712730B (en) * | 2009-05-13 | 2011-07-27 | 北京瑞仕邦精细化工技术有限公司 | Preparation method of water-soluble polymer dispersion |
| CN102746456B (en) * | 2011-04-22 | 2014-08-06 | 中国石油化工股份有限公司 | Terpolymer and polymer and preparation method and application thereof |
| CN102746456A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Terpolymer and polymer and preparation method and application thereof |
| CN102746455A (en) * | 2011-04-22 | 2012-10-24 | 中国石油化工股份有限公司 | Acrylamide terpolymer and polymer and preparation method and application thereof |
| CN102746455B (en) * | 2011-04-22 | 2014-08-06 | 中国石油化工股份有限公司 | Acrylamide terpolymer and polymer and preparation method and application thereof |
| CN102875726A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Copolymer and preparation method and application thereof |
| CN102875726B (en) * | 2011-07-14 | 2014-04-02 | 中国石油化工股份有限公司 | Copolymer and preparation method and application thereof |
| CN102875724B (en) * | 2011-07-14 | 2014-04-02 | 中国石油化工股份有限公司 | Copolymer, and preparation method and application thereof |
| CN102875724A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Copolymer, and preparation method and application thereof |
| CN103571256A (en) * | 2012-07-31 | 2014-02-12 | 罗门哈斯公司 | Sulfonic acid monomer based compositions |
| CN104761678A (en) * | 2015-04-11 | 2015-07-08 | 烟台润星环保科技发展有限公司 | Method for preparing flocculating agent for dry discharge of tailings |
| CN112300321A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Preparation method of polyacrylamide aqueous dispersion |
| CN112300023A (en) * | 2019-07-31 | 2021-02-02 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method and application thereof |
| CN112300023B (en) * | 2019-07-31 | 2023-06-16 | 中国石油化工股份有限公司 | Acrylamide monomer, and preparation method and application thereof |
| CN116284622A (en) * | 2023-03-15 | 2023-06-23 | 上海宇昂水性新材料科技股份有限公司 | Phosphate type copolymer dispersing agent and preparation method thereof |
| CN116875291A (en) * | 2023-09-06 | 2023-10-13 | 胜利星科石油技术开发(山东)有限公司 | Composite flooding containing acrylic acid fatty ester-butene benzene-sulfonated acrylamide copolymer |
| CN116875291B (en) * | 2023-09-06 | 2023-11-07 | 胜利星科石油技术开发(山东)有限公司 | Composite flooding containing acrylic acid fatty ester-butene benzene-sulfonated acrylamide copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100487006C (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1884321A (en) | AMPS analog anion copolymer water dispersoid preparation method | |
| CN1131243C (en) | Process for producing water-soluble anionic dispersion polymers | |
| CN1051323C (en) | Hydrophobic dispersants used in forming polymer dispersions | |
| CN1152888C (en) | Method for making hydrophobically associative polymers, method of use and compositions | |
| CN1271090C (en) | Polymerizable compounds and use thereof | |
| CN1113069C (en) | Polymer dispersion | |
| CN104250334B (en) | Preparation method for vinyl chloride-acrylic ester copolymer | |
| CN1884324A (en) | Cation acrylamide copolymer water-in-water emulsion and its preparation method | |
| CN1847269A (en) | Process for preparing aqueous dispersions of multistage emulsion polymers | |
| CN1279109C (en) | Amphoteric water-soluble polymer dispersion and use thereof | |
| CN100347199C (en) | A water-soluble polymer dispersion and a method of producing a water-soluble polymer dispersion | |
| CN1165554C (en) | Prep. of polyvinyl ester resin emulsion | |
| CN102112501A (en) | Aqueous polymerization process for the manufacture of fluoropolymer comprising repeating units arising from a perfluoromonomer and a monomer having a functional group and a polymerizable carbon-carbon double bond | |
| CN101775105B (en) | Preparation method of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin | |
| CN1298745C (en) | Method for preparing hollow microspheres self film-formed in latex of low soap system | |
| CN1816568A (en) | Method for production of a waterborne copolymer dispersion | |
| CN1303116C (en) | Preparation of multimodal polymer dispersions using polymeric stabilizers, and use thereof | |
| CN1125838C (en) | Synthetic resin powder | |
| CN1560164A (en) | High molecule compound of aldehyde-free adhesives for producing artificial board | |
| CN108623735B (en) | Preparation method and application of soap-free coating emulsion | |
| CN107715112B (en) | Modified polyacrylate medicine coating material and preparation method thereof | |
| CN1807471A (en) | Vinyl acetate based high viscosity latex preparation method | |
| CN1784435A (en) | Polymer mixture and method for production thereof | |
| CN108084340A (en) | A kind of decentralized flocculant and preparation method and application | |
| CN109666366B (en) | Urea-formaldehyde resin waste material regenerated modified acrylate interpenetrating network structure polymer emulsion and preparation and curing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Qingdao Kehai Biological Co., Ltd. Assignor: Qingdao University of Science & Technology Contract record no.: 2010370000408 Denomination of invention: AMPS analog anion copolymer water dispersoid preparation method Granted publication date: 20090513 License type: Exclusive License Open date: 20061227 Record date: 20100730 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090513 Termination date: 20120523 |