CN1884324A - Cation acrylamide copolymer water-in-water emulsion and its preparation method - Google Patents
Cation acrylamide copolymer water-in-water emulsion and its preparation method Download PDFInfo
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- CN1884324A CN1884324A CN200610044560.2A CN200610044560A CN1884324A CN 1884324 A CN1884324 A CN 1884324A CN 200610044560 A CN200610044560 A CN 200610044560A CN 1884324 A CN1884324 A CN 1884324A
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- Prior art keywords
- water
- monomer
- acrylamide copolymer
- cationic
- water emulsion
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229920006322 acrylamide copolymer Polymers 0.000 title claims abstract description 26
- 239000000839 emulsion Substances 0.000 title claims description 41
- 150000001768 cations Chemical class 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 91
- 125000002091 cationic group Chemical group 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 13
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 22
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 230000003196 chaotropic effect Effects 0.000 claims description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012267 brine Substances 0.000 claims description 12
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims description 12
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 10
- 229920001519 homopolymer Polymers 0.000 claims description 10
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical group [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 240000003183 Manihot esculenta Species 0.000 claims description 8
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 238000010552 living cationic polymerization reaction Methods 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 229940038773 trisodium citrate Drugs 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 4
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229920000945 Amylopectin Polymers 0.000 claims description 3
- 229920002307 Dextran Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- 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 claims description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 3
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000015076 Shorea robusta Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000015870 tripotassium citrate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 125000005907 alkyl ester group Chemical group 0.000 abstract 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011149 active material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000003926 acrylamides Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229940065472 octyl acrylate Drugs 0.000 description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920006029 tetra-polymer Polymers 0.000 description 3
- 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 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- BMYQANDFJBPKIF-UHFFFAOYSA-M [Cl-].CC(C1=CC=CC=C1)([N+](C)(C)CC)OC(C=C)=O Chemical compound [Cl-].CC(C1=CC=CC=C1)([N+](C)(C)CC)OC(C=C)=O BMYQANDFJBPKIF-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 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
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention relates to a cationic acrylamide copolymer aqueous emulsion-water and the method for preparing the same. The compound comprises 5-25 wt% of cationic polymer, 1.0-15 wt% of polymer stabilizer and 15-32 wt% inorganic salt. Said active cationic polymer comprises 72.8-90 mol% of at least one water-soluble monomer (A), 10-26 mol% of at least one cationic monomer (B), and 0.2-1.0 mol% of at least one hydrophobic monomer (C), and said polymer is prepared through free radical polymerization with pH being 3-8. The monomer (A) (B) possesses general formula respectively, monomer (c) is C1-C8 dialkyl ester of itaconic acid or C1-C32 alkyl ester of acroleic acid or C1-C32 alkyl ester or diene monomer of methacrylic acid. The method is multi-stage, and it can reduce polymerization system viscosity, increase active material content and stability of aqueous emulsion-in-water, which is characterized by high concentration, low cost, good fluidity and easiness for treatment.
Description
Technical field
The invention belongs to the aqueous polymer dispersion technical field, more particularly relate to the proposition and the improvement of cation acrylamide copolymer water-in-water emulsion and preparation method thereof.
Background technology
The high-molecular weight water-soluble cationic polymer has purposes widely, can be used as retention filtration adjuvant in flocculation agent in the wastewater treatment and dewatering agent, the paper industry, soil improvement agent, oil-water separating agent, mineral flotation agent etc.But high solids content or high molecular weight polymers water-based system generally are gel state, and apparent viscosity is very high, bring difficulty for aftertreatment and storage.Therefore, how to prepare the aqueous polymer system that has high solids content and low viscosity, has good shelf-stability simultaneously again and become the thorny problem that those skilled in the art face.
The traditional method of synthesizing water-solubility cationic polymers comprises solution polymerization, inverse suspension polymerization and inverse emulsion polymerization.What solution polymerization and inverse suspension polymerization finally obtained is powdery product, therefore, easily produces problems such as dust, dissolving difficulty in use; Production cycle is long simultaneously, energy consumption is big, is unfavorable for the raising of production efficiency.For anti-phase suspension liquid and two kinds of liquid-type products of reversed-phase emulsion,, in use inevitably environment is caused secondary pollution, thereby limited their range of application owing to contain hydro carbons, mineral oil or tensio-active agent.
For overcoming above-mentioned shortcoming, satisfy that production process cleans, the requirement of product environmental friendlinessization [0], the exploitation of new polymerization technique is very urgent.European patent EP-A-183,466, EP-A-657,478, U.S. Pat-A-4,929,655 and US-A-5,006,590 has described in the aqueous solution that contains multivalent anions salt and polymer stabilizer, and the method for carrying out precipitation polymerization by the mix monomer that (methyl) acrylamide, (methyl) acrylyl oxy-ethyl-trimethyl salmiac and (methyl) acrylyl oxy-ethyl dimethyl benzyl ammonium chloride are formed has obtained the water-in-water emulsion system of polymkeric substance.Sedimentary polymkeric substance is particle shape, and stablizes its granular system with polymer stabilizer.Although final polymeric system viscosity is 1,000mPa.s or lower, system viscosity is very high in the preparation process, needs a kind of special high viscosity polymerization reactor.Japanese Patent 96-180153 has proposed a kind of method for preparing water-soluble good cation type polymer product, this method is to be raw material monomer with N-vinyl formamide and acrylic acid derivative, with ammonium chloride is phase separation agent, adopts a feeding mode to prepare the stronger polymkeric substance water-in-water emulsion system of hydrophobicity; In the presence of nitrate ion, adopt hydrochloric acid that multipolymer is carried out modification in water medium then, the copolymer pellet diameter that obtains is several millimeters.
Above-mentioned patent has all been emphasized not break through the restriction of disposable feed way by using hydrophobic monomer to avoid the full-bodied importance of polymerization process, is difficult to obtain the water-in-water emulsion type product of high reactivity thing content.Though contain the good C1-C10 alkyl unit polymkeric substance easier precipitation in salt brine solution of benzyl structure unit or hydrophobic performance, but from economy and environment viewpoint, it is disadvantageous having benzyl in the polymkeric substance, and uses hydrophobic monomer also can have a negative impact to polymericular weight and application performance.In the polymerization process, monomer concentration is higher may to be to cause the unmanageable major cause of polymerization process medium viscosity.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned shortcoming and defect, and a kind of cation acrylamide copolymer water-in-water emulsion and preparation method thereof is provided.It is a kind of multistage water-in-water emulsion polymerization technique, can reduce the stability of viscosity, raising active matter content and the water-in-water emulsion of polymerization system.But utilize present method production high density, low cost, good fluidity is arranged, easy-to-handle acrylamide copolymer water-in-water emulsion system.
In order to achieve the above object, the present invention is made the water-in-water emulsion system of water solubility copolymer by monomer composition.Comprise the living cationic polymerization thing of 5-25wt%, the polymer stabilizer of 1.0-15.0wt% and the inorganic salt of 15-32wt%.This living cationic polymerization thing contains at least a water-soluble monomer (A) of 72.8-90mol%, at least a cationic monomer (B) of 10-26mol% and at least a hydrophobic monomer (C) of 0.2-1.0mol%.This polymkeric substance is to obtain by radical polymerization under the 3-8 condition at pH.
Monomer (A) is the molecule corresponding to following general formula (I):
R wherein
1Expression H or CH
3, R
2And R
3Represent H, C independently of one another
1-C
6Alkyl or cycloalkyl; Monomer (B) is the molecule corresponding to following general formula:
Monomers B with following general formula (II)
1
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
4Expression H or CH
3, R
5And R
6Represent CH independently of one another
3Or CH
2CH
3, R
7Expression H, CH
3, CH
2CH
3Or
X
-Expression counter anion Cl
-Or SCN
-
Or has the monomers B of following general formula (III)
2
R wherein
8Expression H or CH
3, R
9Expression C
12-C
16Alkyl, cycloalkyl or CH
3, R
10And R
11Represent CH independently of one another
3Or CH
2CH
3, X
-Expression counter anion Cl
-Or SCN
-
Monomer (C) is the C of methylene-succinic acid
1-C
8Dialkyl monomer or (methyl) acrylic acid C
1-C
32Alkyl ester monomer or diene monomers comprise dimethyl itaconate, dibutyl itaconate, dioctyl itaconate, ethyl propenoate, butyl acrylate, divinyl or chloroprene.
The mixture that uses acrylamide or Methacrylamide and cationic monomer is during as the water-soluble monomer composition, the content of cationic monomer had better not surpass the 30mol% of monomer component total amount, surpassing 30mol% can cause system viscosity sharply to increase because of the polymer particle dissolving that generates, and finally can't obtain the stable polymer water-in-water emulsion.
Said one or more stablizers are cationic polymers ionogen, for dissolving or the molecular weight that is partially dissolved in brine media between 1,000-800, cationic homopolymer between 000, wherein this polymkeric substance is to obtain by the cationic monomer radical polymerization that is selected from following material: hexadecyldimethyl benzyl ammonium allyl ammonium chloride, dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride or dimethyl aminoethyl acrylate or its methacrylate, and the mixture of above-mentioned substance.
Be meant at least a from the low mixture that salt and at least a chaotropic salt constituted of liquid sequence as the inorganic salt in the salt brine solution of polymerisation medium.From the low salt of liquid sequence is ammonium sulfate, sodium sulfate, sal epsom, sodium-chlor or SODIUM PHOSPHATE, MONOBASIC, and described chaotropic salt is Sodium Thiocyanate 99, potassium sulfocyanate, ammonium thiocyanate, Tripotassium Citrate or Trisodium Citrate.
The salt brine solution that the present invention uses can dissolve the lower polymer stabilizer of molecular weight, and does not dissolve the higher reactive polymer of molecular weight.These salt comprise at least a from liquid sequence low salt and at least a chaotropic salt.What the present invention chose comprises vitriol, phosphoric acid salt, muriate, Citrate trianion, acetate, tartrate or hydrophosphate from the low salt of liquid sequence, wherein preferably sulfuric acid ammonium, sodium sulfate, Tai-Ace S 150, SODIUM PHOSPHATE, MONOBASIC or sodium-chlor; 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.
Can use certain from the low inorganic salt of liquid sequence separately, or be used in combination from liquid sequence low inorganic salt and chaotropic salt; The composition of preferably sulfuric acid ammonium, sodium sulfate and ammonium thiocyanate, Sodium Thiocyanate 99.Other salt can not the lytic activity polymkeric substance as its aqueous solution, also belongs to the scope of the invention.
The present invention adds polyvalent alcohol as auxiliary stabilizer, and this polyvalent alcohol comprises multifunctional ethanol: glycerine or polyoxyethylene glycol, or polysaccharide: modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose.
Polymer stabilizer has two kinds of stabilizations: a kind of is the association of stablizer, can make the external phase thicknessization, thereby avoid particles settling; Another kind is the adsorption of stablizer on particle surface, can more effectively avoid particle aggregation as colloid protective agent.Therefore must contain at least one hydrophobic chain link and at least one hydrophilic chain link in the stablizer unit.
Good polymer stabilizer should all or part of dissolving in polymerisation medium, so stablizer should have less molecular weight.The weight-average molecular weight of this polymer stabilizer is 1,000-800, and 000, and preferred 5,000-400,000.Among the present invention, this stablizer obtains by the cationic monomer radical polymerization that is selected from following material: hexadecyldimethyl benzyl ammonium allyl ammonium chloride, dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride or dimethyl aminoethyl acrylate or its methacrylate, and the mixture of above-mentioned substance.
The add-on of stablizer used herein depends on its type, molecular weight and other factors, and its suitable consumption is the 1.0-15.0wt% of system, preferred 1.0-12.5wt%, and optimized scope is 3.4-12.5wt%.Should be pointed out that the increase with stabilizing agent dosage, the particle diameter of precipitation polymers reduces, and this nucleus quantity that shows formation increases.
According to embodiment of the present invention, in reaction system, add polyol as auxiliary stabilizer, the precipitation process of polymer beads is steadily carried out.The polyol that the present invention chooses comprises polyalcohols such as glycerine or polyoxyethylene glycol, and polysaccharide such as modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose.
The preparation method of cation acrylamide copolymer water-in-water emulsion of the present invention is to be under the 3-8 condition at pH, and the composite initiation system that adopts persulphate, hydrosulphite and azo-compound to form obtains by radical polymerization.Monomer adding mode is for adding monomer stage by stage or continuously adding in polymerization process.
The water-in-water emulsion polymerization initiation that can in all sorts of ways as causing with initiators such as superoxide, azo-compound and persulphates, also can cause by plasma body or radiation.Be applicable to that azo-compound of the present invention comprises 2,2 '-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (VA-044), 2,2 '-azo two (2-amidine propane) dihydrochloride (ABAH) or 2,2 '-Diisopropyl azodicarboxylate (AIBN), preferable methods of the present invention is the composite initiation system that adopts persulphate, hydrosulphite and azo-compound VA-044 to form.
The add-on of described initiator depends on initiator type and temperature of reaction, and the composite initiation system consumption is the 0.001-5% of various total monomer weights.
This polymeric reaction temperature is between 40-90 ℃, and polymerization time is 3-8h, and the final transformation efficiency of monomer is greater than 96%.In the polymerization process, can add chain-transfer agent in case of necessity, preferably be selected from benzyl alcohol, Virahol, tertiary amine or sodium formiate, anion surfactant such as dodecylbenzene sulfonate or lauryl mercaptan, nonionic surface active agent such as polyoxyethylene sorbitan mono-laurate; Its consumption is generally the 0.01-0.02% of total monomer weight.
Task of the present invention comes to this and finishes.
The present invention is a kind of multistage water-in-water emulsion polymerization technique, can reduce the stability of viscosity, raising active matter content and the water-in-water emulsion of polymerization system.But utilize present method production high density, low cost, good fluidity is arranged, easy-to-handle acrylamide copolymer water-in-water emulsion system.
Embodiment
Embodiment 1.A kind of cation acrylamide copolymer water-in-water emulsion.It comprises the living cationic polymerization thing of 25wt%, the polymer stabilizer of 15wt% and the inorganic salt of 15wt%.This living cationic polymerization thing contains at least a water-soluble monomer (A) of 72.8-90mol%, at least a cationic monomer (B) of 10-26mol% and at least a hydrophobic monomer (C) of 0.2-1.0mol%.This polymkeric substance is to obtain by radical polymerization under the 3-8 condition at pH.
Monomer (A) is the molecule corresponding to following general formula (I):
R wherein
1Expression H or CH
3, R
2And R
3Represent H, C independently of one another
1-C
6Alkyl or cycloalkyl; Monomer (B) is the molecule corresponding to following general formula:
Monomers B with following general formula (II)
1
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
4Expression H or CH
3, R
5And R
6Represent CH independently of one another
3Or CH
2CH
3, R
7Expression H, CH
3, CH
2CH
3Or
X
-Expression counter anion Cl
-Or SCN
-
Or has the monomers B of following general formula (III)
2
R wherein
8Expression H or CH
3, R
9Expression C
12-C
16Alkyl, cycloalkyl or CH
3, R
10And R
11Represent CH independently of one another
3Or CH
2CH
3, X
-Expression counter anion Cl
-Or SCN
-
Monomer (C) is the C of methylene-succinic acid
1-C
8The C of dialkyl monomer, acrylic or methacrylic acid
1-C
32Alkyl ester monomer or diene monomers, present embodiment are dimethyl itaconate.
Said stablizer is the cationic polymers ionogen, for dissolving or the molecular weight that is partially dissolved in brine media between 1,000-800, the cationic homopolymer between 000.Wherein this polymkeric substance is that radical polymerization by cationic monomer obtains, and described cationic monomer is the hexadecyldimethyl benzyl ammonium allyl ammonium chloride.
Be meant at least a from the low mixture that salt and at least a chaotropic salt constituted of liquid sequence as the inorganic salt in the salt brine solution of polymerisation medium.From the low salt of liquid sequence is ammonium sulfate, and described chaotropic salt is a Sodium Thiocyanate 99.
The present invention also adds polyvalent alcohol as auxiliary stabilizer.This polyvalent alcohol is multifunctional ethanol: glycerine.
Embodiment 2.A kind of cation acrylamide copolymer water-in-water emulsion.It comprises the living cationic polymerization thing of 15wt%, the polymer stabilizer of 1.0wt% and the inorganic salt of 22wt%.This living cationic polymerization thing contains at least a water-soluble monomer (A) of 72.8-90mol%, at least a cationic monomer (B) of 10-26mol% and at least a hydrophobic monomer (C) of 0.2-1.0mol%.This polymkeric substance is to obtain by radical polymerization under the 3-8 condition at pH.
Monomer (A) is the molecule corresponding to following general formula (I):
R wherein
1Expression H or CH
3, R
2And R
3Represent H, C independently of one another
1-C
6Alkyl or cycloalkyl; Monomer (B) is the molecule corresponding to following general formula:
Monomers B with following general formula (II)
1
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
4Expression H or CH
3, R
5And R
6Represent CH independently of one another
3Or CH
2CH
3, R
7Expression H, CH
3, CH
2CH
3Or
X
-Expression counter anion Cl
-Or SCN
-
Or has the monomers B of following general formula (III)
2
R wherein
8Expression H or CH
3, R
9Expression C
12-C
16Alkyl, cycloalkyl or CH
3, R
10And R
11Represent CH independently of one another
3Or CH
2CH
3, X
-Expression counter anion Cl
-Or SCN
-
Monomer (C) is the C of methylene-succinic acid
1-C
8The C of dialkyl monomer, acrylic or methacrylic acid
1-C
32Alkyl ester monomer or diene monomers, present embodiment are dioctyl itaconate.
Said stablizer is the cationic polymers ionogen, for dissolving or the molecular weight that is partially dissolved in brine media between 1,000-800, the cationic homopolymer between 000.Wherein this polymkeric substance is that radical polymerization by cationic monomer obtains, and described cationic monomer is a dimethyl diallyl ammonium chloride.
Be meant at least a from the low mixture that salt and at least a chaotropic salt constituted of liquid sequence as the inorganic salt in the salt brine solution of polymerisation medium.From the low salt of liquid sequence is sodium sulfate, and described chaotropic salt is a potassium sulfocyanate.
The present invention also adds polyvalent alcohol as auxiliary stabilizer.This polyvalent alcohol is a polysaccharide: modified tapioca starch.
Embodiment 3.A kind of cation acrylamide copolymer water-in-water emulsion.It comprises the cationic polymers of 5wt%, the polymer stabilizer of 30wt% and the inorganic salt of 32wt%.This living cationic polymerization thing contains at least a water-soluble monomer (A) of 72.8-90mol%, at least a cationic monomer (B) of 10-26mol% and at least a hydrophobic monomer (C) of 0.2-1.0mol%.This polymkeric substance is to obtain by radical polymerization under the 3-8 condition at pH.
Monomer (A) is the molecule corresponding to following general formula (I):
R wherein
1Expression H or CH
3, R
2And R
3Represent H, C independently of one another
1-C
6Alkyl or cycloalkyl; Monomer (B) is the molecule corresponding to following general formula:
Monomers B with following general formula (II)
1
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
4Expression H or CH
3, R
5And R
6Represent CH independently of one another
3Or CH
2CH
3, R
7Expression H, CH
3, CH
2CH
3Or
X
-Expression counter anion Cl
-Or SCN
-
Or has the monomers B of following general formula (III)
2
R wherein
8Expression H or CH
3, R
9Expression C
12-C
16Alkyl, cycloalkyl or CH
3, R
10And R
11Represent CH independently of one another
3Or CH
2CH
3, X
-Expression counter anion Cl
-Or SCN
-
Monomer (C) is the C of methylene-succinic acid
1-C
8The C of dialkyl monomer, acrylic or methacrylic acid
1-C
32Alkyl ester monomer or diene monomers, present embodiment are chloroprene.
Said stablizer is the cationic polymers ionogen, for dissolving or the molecular weight that is partially dissolved in brine media between 1,000-800, the cationic homopolymer between 000.Wherein this polymkeric substance is that radical polymerization by cationic monomer obtains, and described cationic monomer is group material down: the dimethyl aminoethyl acrylate.
Be meant at least a from the low mixture that salt and at least a chaotropic salt constituted of liquid sequence as the inorganic salt in the salt brine solution of polymerisation medium.From the low salt of liquid sequence is SODIUM PHOSPHATE, MONOBASIC, and described chaotropic salt is a Trisodium Citrate.
The present invention also adds polyvalent alcohol as auxiliary stabilizer.This polyvalent alcohol is the methoxycarbonyl Mierocrystalline cellulose.
Embodiment 4.A kind of preparation method of cation acrylamide copolymer water-in-water emulsion.It is under agitation to add in the 0.5L reaction vessel: 5.99 parts of acrylamides (AM), 7.18 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 3.09 hexadecyldimethyl benzyl ammonium allyl ammonium chloride (DMHAAC) solution of part 30%, 26.1 the hexadecyldimethyl benzyl ammonium allyl ammonium chloride homopolymer solution ([η]=2.0dL/g) of part 20%, 22.95 part water, 30 parts of ammonium sulfate, 0.5 part Sodium Thiocyanate 99 and 0.75 part of Trisodium Citrate, 0.5 part Octyl acrylate (CAA), 0.045 part modified tapioca starch, (100rpm, the anchor formula stirs) obtains homogeneous solution at nitrogen bubble with under stirring.In 30min, reactor is heated to 40 ℃, adds 0.0072 part of Potassium Persulphate that in 5 parts of water, dilutes and 0.00438 part of VA-044 that in 5 parts of water, dilutes, react 1.5h down at 40 ℃.The acrylamide (AM) that in 3h after this, adds 11.98 parts, 14.35 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 6.18 hexadecyldimethyl benzyl ammonium allyl ammonium chloride (DMHAAC) solution of part 30%, 0.00876 the VA-044 that part is diluted in 5 parts of water, temperature is risen to 50 ℃, add 0.00876 part of VA-044 solution that in 5 parts of water, dilutes again, continue reaction 2.0h down at 50 ℃, mixture is cooled to 30 ℃, empties reactor.So obtain cationic degree and be 26%, active matter content is 25% DMC/DMHAAC/CAA/AM tetrapolymer water-in-water emulsion, this emulsion has good mobile and stable, the weight-average molecular weight of polymkeric substance is 5,200,000.
Embodiment 5.A kind of preparation method of cation acrylamide copolymer water-in-water emulsion.It is under agitation to add in the 0.5L reaction vessel: 14.25 parts of acrylamides (AM), 5.28 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 2.27 hexadecyldimethyl benzyl ammonium allyl ammonium chloride (DMHAAC) solution of part 30%, 32.63 the hexadecyldimethyl benzyl ammonium allyl ammonium chloride homopolymer solution ([η]=2.0dL/g) of part 20%, 21.98 part water, 30 parts of ammonium sulfate, 0.5 part Sodium Thiocyanate 99 and 0.75 part of Trisodium Citrate, 0.5 part Octyl acrylate, 0.045 part of modified tapioca starch.(100rpm, the anchor formula stirs) obtains homogeneous solution at nitrogen bubble with under stirring.Simultaneously in 30min, reactor is heated to 40 ℃, adds 0.0072 part of Potassium Persulphate that in 5 parts of water, dilutes and 0.00516 part of VA-044 that in 5 parts of water, dilutes, react 1.5h down at 40 ℃.The acrylamide (AM) that in 3h after this, adds 14.25 parts, 5.28 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 2.27 hexadecyldimethyl benzyl ammonium allyl ammonium chloride (DMHAAC) solution of part 30%, 0.00876 the VA-044 that part is diluted in 5 parts of water, temperature is risen to 50 ℃, add 0.00876 part of VA-044 solution that in 5 parts of water, dilutes again, continue reaction 2.0h down at 50 ℃, mixture is cooled to 30 ℃, empties reactor.So obtain cationic degree and be 10%, active matter content is 25% DMC/DMHAAC/CAA/AM tetrapolymer water-in-water emulsion, this emulsion has good mobile and stable.The weight-average molecular weight of polymkeric substance is 9,510,000.
Embodiment 6.A kind of preparation method of cation acrylamide copolymer water-in-water emulsion.It is under agitation to add in the 0.5L reaction vessel: 7.8 parts of acrylamides (AM), 7.05 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 3.06 dimethyl diallyl ammonium chloride (DMDAAC) solution of part 60%, 26.1 the dimethyl diallyl ammonium chloride homopolymer solution ([η]=2.0dL/g) of part 20%, 43.2 part water, 23 parts of ammonium sulfate, 0.5 part Sodium Thiocyanate 99 and 0.75 part of Trisodium Citrate, 0.5 part Octyl acrylate, 0.045 part modified tapioca starch, (100rpm, the anchor formula stirs) obtains homogeneous solution at nitrogen bubble with under stirring.Simultaneously in 30min, reactor is heated to 40 ℃, adds 0.0063 part of Potassium Persulphate that in 5 parts of water, dilutes and 0.0045 part of VA-044 that in 5 parts of water, dilutes, react 1.5h down at 40 ℃.The acrylamide (AM) that in 3h after this, adds 7.8 parts, 7.05 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 3.06 dimethyl diallyl ammonium chloride (DMDAAC) solution of part 60%, 0.00876 the VA-044 that part is diluted in 5 parts of water, temperature is risen to 50 ℃, add 0.00876 part of VA-044 solution that in 5 parts of water, dilutes again, continue reaction 2.0h down at 50 ℃, mixture is cooled to 30 ℃ then, empties reactor.So obtain cationic degree and be 26%, the DMC/DMDAAC/CAA/AM tetrapolymer water-in-water emulsion of active matter content 20%, this emulsion has good mobile and stable.The weight-average molecular weight of polymkeric substance is 7,320,000.
Embodiment 7.A kind of preparation method of cation acrylamide copolymer water-in-water emulsion.It is to be to obtain by radical polymerization under the 3-8 condition at pH.Monomer adding mode is for adding monomer stage by stage or continuously adding in polymerization process.The composite initiation system that adopts persulphate, hydrosulphite and azo-compound to form.Described azo-compound comprises 2,2 '-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (VA-044), 2,2 '-azo two (2-amidine propane) dihydrochloride (ABAH) or 2,2 '-Diisopropyl azodicarboxylate (AIBN), the composite initiation system consumption is the 0.001-5% of various total monomer weights.
The foregoing description is a kind of multistage water-in-water emulsion polymerization technique, can reduce the stability of viscosity, raising active matter content and the water-in-water emulsion of polymerization system.But utilize present method production high density, low cost, good fluidity is arranged, easy-to-handle acrylamide copolymer water-in-water emulsion system.
Following embodiment explanation, traditional method do not reach the viscosity that reduces polymerization system, the purpose that improves active matter content and water-in-water emulsion stability.
Embodiment 8. under agitation adds in the 0.5L reaction vessel: 17.9 parts of acrylamides (AM), 21.54 methylacryoyloxyethyl trimethyl ammonium chloride (DMC) solution of part 78%, 9.27 hexadecyldimethyl benzyl ammonium allyl ammonium chloride (DMHAAC) solution of part 30%, 26.1 the hexadecyldimethyl benzyl ammonium allyl ammonium chloride homopolymer solution ([η]=2.0dL/g) of part 20%, 22.95 part water, 30 parts of ammonium sulfate, 0.5 part Sodium Thiocyanate 99 and 0.75 part of Trisodium Citrate, 0.5 part Octyl acrylate, 0.045 part modified tapioca starch, (100rpm, the anchor formula stirs) obtains homogeneous solution at nitrogen bubble with under stirring.In 30min, reactor is heated to 40 ℃, adds 0.0072 part of Potassium Persulphate that in 5 parts of water, dilutes and 0.00438 part of VA-044 that in 5 parts of water, dilutes.Along with the carrying out of polyreaction, system viscosity increases gradually, finally obtains the water white transparency jelly.
Embodiment 9.According to the mode identical with embodiment 4, difference is not use stablizer.Behind the initiated polymerization 20min, system viscosity increases, and finally obtains the bigger gelation caking of viscosity.
Embodiment 10.According to embodiment 4 same way as, difference is to add 7.6 part 20% methylacryoyloxyethyl trimethyl ammonium chloride homopolymer solution ([η]=2.0dL/g).Behind the initiated polymerization 30min, system viscosity increases, and finally obtains white thick liquid, and many macrobeads are arranged, and demixing phenomenon occurs behind the placement 24h.
Claims (10)
1. cation acrylamide copolymer water-in-water emulsion, it is characterized in that it comprises the cationic polymers of 5-25wt%, the polymer stabilizer of 1.0-15.0wt% and the inorganic salt of 15-32wt%, this living cationic polymerization thing contains at least a water-soluble monomer (A) of 72.8-90mol%, at least a cationic monomer (B) of 10-26mol% and at least a hydrophobic monomer (C) of 0.2-1.0mol%, and this polymkeric substance obtains by radical polymerization.
2. according to the described cation acrylamide copolymer water-in-water emulsion of claim 1, it is characterized in that said monomer (A) is the molecule corresponding to following general formula (I):
R wherein
1Expression H or CH
3, R
2And R
3Represent H, C independently of one another
1-C
6Alkyl or cycloalkyl; Monomer (B) is the molecule corresponding to following general formula:
Monomers B with following general formula (II)
1
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
4Expression H or CH
3, R
5And R
6Represent CH independently of one another
3Or CH
2CH
3, R
7Expression H, CH
3, CH
2CH
3Or
X
-Expression counter anion Cl
-Or SCN
-
Or has the monomers B of following general formula (III)
2
R wherein
8Expression H or CH
3, R
9Expression C
12-C
16Alkyl, cycloalkyl or CH
3, R
10And R
11Represent CH independently of one another
3Or CH
2CH
3, X
-Expression counter anion Cl
-Or SCN
-
Monomer (C) is the C of methylene-succinic acid
1-C
8The C of dialkyl monomer, acrylic or methacrylic acid
1-C
32Alkyl ester monomer or diene monomers.
3. according to the described cation acrylamide copolymer water-in-water emulsion of claim 2, it is characterized in that said monomer (C) is dimethyl itaconate, dibutyl itaconate, dioctyl itaconate, ethyl propenoate, butyl acrylate, divinyl or chloroprene.
4. according to the described cation acrylamide copolymer water-in-water emulsion of claim 1, it is characterized in that said stablizer is the cationic polymers ionogen, for dissolving or the molecular weight that is partially dissolved in brine media between 1,000-800, cationic homopolymer between 000, wherein this polymkeric substance is to obtain by the cationic monomer radical polymerization that is selected from following material: the hexadecyldimethyl benzyl ammonium allyl ammonium chloride, dimethyl diallyl ammonium chloride, methylacryoyloxyethyl trimethyl ammonium chloride or dimethyl aminoethyl acrylate or its methacrylate, and the mixture of above-mentioned substance.
5. according to the described cation acrylamide copolymer water-in-water emulsion of claim 1, it is characterized in that being meant at least a from the low mixture that salt and at least a chaotropic salt constituted of liquid sequence as the inorganic salt in the salt brine solution of polymerisation medium, from the low salt of liquid sequence is ammonium sulfate, sodium sulfate, sal epsom, sodium-chlor or SODIUM PHOSPHATE, MONOBASIC, and described chaotropic salt is Sodium Thiocyanate 99, potassium sulfocyanate, ammonium thiocyanate, Tripotassium Citrate or Trisodium Citrate.
6. according to the described cation acrylamide copolymer water-in-water emulsion of claim 1, it is characterized in that in aforementioned polymerisation medium, adding polyvalent alcohol as auxiliary stabilizer.
7. according to the described cation acrylamide copolymer water-in-water emulsion of claim 6, it is characterized in that the auxiliary stabilizer polyvalent alcohol comprises multifunctional ethanol: glycerine or polyoxyethylene glycol, or polysaccharide: modified tapioca starch, amylopectin, dextran or methoxycarbonyl Mierocrystalline cellulose.
8. the preparation method of preparation claim 1 described cation acrylamide copolymer water-in-water emulsion is characterized in that it is is to obtain by radical polymerization under the 3-8 condition at pH; Monomer adding mode is for adding stage by stage or continuously adding in polymerization process; The composite initiation system that initiator system adopts persulphate, hydrosulphite and azo-compound to form.
9. the preparation method of cation acrylamide copolymer water-in-water emulsion according to claim 8 is characterized in that the 0.001-5% that this composite initiation system consumption is a total monomer weight.
10. according to the preparation method of claim 8 or 9 described cation acrylamide copolymer water-in-water emulsions, it is characterized in that said azo-compound comprises 2,2 '-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid, 2,2 '-azo two (2-amidine propane) dihydrochloride or 2,2 '-Diisopropyl azodicarboxylate.
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