CN103012668B - Preparation method of cationic polyacrylamide water-in-water emulsion - Google Patents
Preparation method of cationic polyacrylamide water-in-water emulsion Download PDFInfo
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- CN103012668B CN103012668B CN201210536403.9A CN201210536403A CN103012668B CN 103012668 B CN103012668 B CN 103012668B CN 201210536403 A CN201210536403 A CN 201210536403A CN 103012668 B CN103012668 B CN 103012668B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 60
- 239000000839 emulsion Substances 0.000 title claims abstract description 57
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 11
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 78
- 239000003795 chemical substances by application Substances 0.000 claims description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000004159 Potassium persulphate Substances 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 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 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- MAZPIOPHRNWBNG-UHFFFAOYSA-N [Cl-].Cl[NH3+].[Na] Chemical compound [Cl-].Cl[NH3+].[Na] MAZPIOPHRNWBNG-UHFFFAOYSA-N 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 238000007342 radical addition reaction Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- 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 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 235000019263 trisodium citrate Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000002270 dispersing agent Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 6
- 238000012644 addition polymerization Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- RZSIBGYUCGYDKG-VIFPVBQESA-N (3s)-3-methyl-1-[4-(trifluoromethyl)-1-benzofuran-7-yl]piperazine Chemical compound C1CN[C@@H](C)CN1C1=CC=C(C(F)(F)F)C2=C1OC=C2 RZSIBGYUCGYDKG-VIFPVBQESA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- -1 anions salt Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229920006317 cationic polymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 C[N+](N(*)[Mn]C)[O-] Chemical compound C[N+](N(*)[Mn]C)[O-] 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- CPYRNEFBPGOZKT-UHFFFAOYSA-N 1-(2-methylpropyl)-4,5-dihydroimidazole Chemical class CC(C)CN1CCN=C1 CPYRNEFBPGOZKT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101000868791 Lophonetta specularioides Carboxypeptidase D Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VGHRSPNHHSLNCP-UHFFFAOYSA-M ethyl-dimethyl-[phenyl(prop-2-enoyloxy)methyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)OC([N+](C)(C)CC)C1=CC=CC=C1 VGHRSPNHHSLNCP-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a cationic polyacrylamide water-in-water emulsion. According to the preparation method, a monomer, an inorganic salt C and a dispersing agent D are subjected to addition polymerization reaction under the effect of an initiator I and then prepared into the target product, wherein the dispersing agent is the comb-like graft copolymer which is relatively small in molecular weight, low in positive charge density and high in side chain steric hindrance; the dispersing agent has the advantages of being low in viscosity, fast in dispersing and absorbing speed, stable in dispersing, and good in effect; furthermore, the dispersing agent is given an adjustable molecular structure, so that different structures can be designed for different polymerization systems, the pertinence is high, the viscosity of the polymerization systems can be effectively reduced, the solid content of the product is increased, and the stability of the water-in-water emulsion is improved; and furthermore, the cationic polyacrylamide water-in-water emulsion prepared by the preparation method disclosed by the invention has the advantages of being fast in dissolving speed, high in molecular weight, excellent in liquidity and convenient to use.
Description
Technical field
The invention belongs to water-soluble polymer synthesis technical field, relate in particular to a kind of preparation method of cationic polyacrylamide water-in-water emulsion.
Background technology
The constructional feature of polyacrylamide and complete kind make it to be widely applied in the every field of national economy, enjoy the title of " all trades auxiliary agent ".In China, because petroleum resources shortage, water resources shortage, the forest reserves lack, the application of polyacrylamide in oil, water treatment and the large field of papermaking three is even more important, and has strategic importance.
The method of synthetic polyacrylamide comprises solution polymerization, inverse suspension polymerization and inverse emulsion polymerization.Solution polymerization later stage viscosity is very high, stir and dispel the heat very difficult, need to use the dry powder of making of special equipment, complicated technical process tends to cause polyacrylamide chain that the side reactions such as crosslinked and degraded occur, simultaneously dry powder type polyacrylamide dissolves difficulty before use, needs for a long time and special dissolution equipment.The polyacrylamide of emulsion-type has good solvability, but this kind of method need to be used a large amount of hydrocarbon organic solvents and tensio-active agent, easily environment caused to secondary pollution.
Aqueous dispersion polymerization (aqueous dispersion polymerization is also referred to as the water polymerization of water bag or double-aqueous phase polymerization) is because production efficiency is high, technique environmental protection, and product dissolves and flocculating property excellence becomes various countries' research emphasis.European patent EP 0183466 and EP0657478, US Patent No. A4929655 and USA5006590 have all described in the aqueous solution that contains multivalent anions salt and polymer stabilizer, pass through acrylamide, acrylyl oxy-ethyl-trimethyl salmiac, the copolymerization of acrylyl oxy-ethyl dimethyl benzyl ammonium chloride obtains water-in-water emulsion, but its system viscosity in the process of preparation is very high, to stirring and conducting heat, high requirement is all proposed.
Water bag water polymerization key is the polymer chain Precipitation from system in time forming by radical polymerization, forms primary particle, adsorbs rapidly dispersion agent simultaneously, forms stable emulsion particle, avoids causing gel because system viscosity explodes.CN1884324A reduces acrylamide solubleness by introducing hydrophobic monomer copolymerization, makes it to separate out in time, adopts cationic polymers and polymerized polyalcohol one package stabilizer to improve stabilising effect simultaneously.CN101016352A adopts the cationic monomer that contains benzyl to reduce acrylamide solubleness; CN1709945A adopts the one package stabilizer of addition polymerization cationic polymers and condensation polymerization cationic polymers, because condensation polymer molecular weight is low, therefore has better stabilising effect.
The selection of dispersion agent is to reaction important as can be seen here, above-mentioned patent all adopts the multipolymer (as acrylyl oxy-ethyl-trimethyl salmiac and acrylamide copolymer) of linear cation high molecular (being mainly polyacrylamide oxy-ethyl-trimethyl salmiac) or cationic monomer and non-ionic monomer as dispersion agent, emulsion particle is stablized in the sterically hindered effect that utilizes polymer adsorption to produce at particle surface, this requires dispersion agent to have higher molecular weight (conventionally 50～1,000,000), so that enough steric hindrances to be provided, this brings series of problems: first, reaction is carried out in high salt medium, the too high dispersion agent of molecular weight is difficult to dissolve fast, its molecular chain is in the state of rolling up, greatly reduce its adsorption rate and stabilization, secondly, the too high initial reaction stage system viscosity that causes of dispersant molecule amount is larger, adds that macromolecular chain is difficult to diffusion motion, and the adsorption rate of initial reaction stage dispersion agent is very slow, often makes polymerization failure because not stablizing in time the emulsion particle of separating out, again, cation dispersing agent is with a large amount of positive charges, there is electrostatic repulsion with the emulsion particle of separating out in it, adsorb slower, particularly initial reaction stage, emulsion particle positively charged higher (because the reactivity ratio difference of cationic monomer and non-ionic monomer causes) repel very strongly, dispersion agent is difficult to play stabilization, initial reaction stage very easily produces particle coalescence and makes polymerization failure.
Summary of the invention
The technical problem to be solved in the present invention is, make the adsorption rate of dispersion agent very slow because molecular weight is too high for the dispersion agent adopting in polyacrylamide water-in-water emulsion preparation process in prior art, stabilization is poor, more may often separate out emulsion particle or emulsion particle and very easily produce particle coalescence and cause the polymerization above-mentioned defect such as unsuccessfully because not stablizing in time in initial reaction stage, a kind of preparation method of cationic polyacrylamide water-in-water emulsion is provided, in this preparation method, adopt a kind of molecular weight, positive charge density is low, the sterically hindered strong comb-grafted copolymer of side chain is as dispersion agent, it is little that this dispersion agent has viscosity, diffusion is rapid with absorption, the advantages such as stably dispersing is effective, and the molecular structure of this dispersion agent is adjustable, to hetero-polymer, system can design different structure, with strong points, effectively reduce polymerization system viscosity, improve the stability of product solid content and water-in-water emulsion, and it is fast that the cationic polyacrylamide water-in-water emulsion that utilizes preparation method of the present invention to obtain also has dissolution rate, the advantages such as molecular weight height and good fluidity.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of cationic polyacrylamide water-in-water emulsion, and preparation process is as follows:
(1) non-ionic monomer A, cationic monomer B, inorganic salt C and dispersion agent D are joined in reactor in proportion, be dissolved in water and obtain reaction solution, regulating pH is 4.0 ~ 5.5; Wherein, inorganic salt C accounts for 25-40wt%, and non-ionic monomer A and cationic monomer B account for 15-30wt% altogether, and dispersion agent D accounts for 1-3wt%, and surplus is water;
(2) reaction solution step (1) being obtained is warming up to 30-50 ° of C, and logical nitrogen deoxygenation, adds initiator I, carries out polyaddition reaction; The add-on of initiator I accounts for the 0.01-0.05wt% of the middle non-ionic monomer A of step (1) and cationic monomer B gross weight;
(3) insulation reaction is after 10 hours, cool to room temperature, and discharging, makes cationic polyacrylamide water-in-water emulsion;
Non-ionic monomer A is selected from acrylamide or Methacrylamide, and accounts for the 70-95mol% of non-ionic monomer A and cationic monomer B total amount;
Cationic monomer B adopts by the represented material of general formula (1):
Wherein A represents O or NH, and B represents CH
2cH
2, CH
2cH
2cH
2or CH
2cHOHCH
2, R
1represent H or CH
3, R
2and R
3represent independently of one another CH
3or CH
2cH
3, R
4represent H, CH
3, CH
2cH
3or CH
2c
6h
5;
Dispersion agent D is comb-shaped graft copolymer, and it adopts by the represented material of general formula (2):
Wherein, A represents O or NH, and B represents CH
2cH
2, CH
2cH
2cH
2or CH
2cHOHCH
2, X represents O, CH
2o, CH
2cH
2o or COO, R
1, R
5, R
7represent independently of one another H or CH
3, R
2and R
3represent independently of one another CH
3or CH
2cH
3, R
4represent H, CH
3, CH
2cH
3or CH
2c
6h
5, R
6represent OH, NH
2or N (CH
3)
2cH
2sO
3-, R
8represent OH or CH
3;
The span of dispersion agent D molecular weight is 10000～100000; A:b:c=(1～2): (0～2): 1; N value is 5～25.
In technical scheme of the present invention, in step (1), be dissolved in water again and obtain reaction solution adding in reactor after non-ionic monomer A, cationic monomer B, inorganic salt C and dispersion agent D, regulating pH is 4.0 ~ 5.5; If pH is greater than 5.5, the molecular weight of the product obtaining after reacting by step (2) and step (3) can be on the low side, do not reach the requirement of target product to molecular weight, and speed of response is also slow, if pH is less than 4.0, the speed that can accelerate polyaddition reaction, easily causes the generation of gel.
In technical scheme of the present invention, the reaction solution in step (2), step (1) being obtained is warming up to 30-50 ° of C, and logical nitrogen deoxygenation, adds initiator I, carries out polyaddition reaction; The temperature of reaction of addition polymerization is relevant with the kind of initiator I, but in the art, reaction solution is generally warming up to 30-50 ° of C.In addition, in step (2), the add-on of initiator I accounts for the 0.01-0.05wt% of non-ionic monomer A and cationic monomer gross weight; If the consumption of initiator I lower than 0.01wt%, can cause polyreaction unstable, repeatability is lower; If the consumption of initiator I exceedes 0.05wt%, can cause reaction gel or molecular weight on the low side, can not obtain stable cationic polyacrylamide water-in-water emulsion.
In technical scheme of the present invention, in step (3) time of insulation reaction generally all in 10 hours, after insulation reaction, cool to room temperature, discharging, can make target product cationic polyacrylamide water-in-water emulsion.
In addition, the transformation efficiency of polyaddition reaction of the present invention exceedes 99.5%, and product solid content is substantially equal to feed ratio, is approximately 15-30%.In addition, the enhanced dissolution rate of the cationic polyacrylamide water-in-water emulsion preparing by technical scheme of the present invention, and there is the advantages such as molecular weight height and good fluidity.
In technical scheme of the present invention, dispersion agent D is comb-shaped graft copolymer, its structure is as shown in general formula (2), the span of its molecular weight is 10000 ~ 100000, a:b:c=(1～2): (0～2): 1, n value is 5～25, molecular weight, the viscosity of dispersant solution is little, and in high salt, rate of diffusion and adsorption rate obviously improve, and the particle that initial reaction stage is separated out can play rapidly stabilization; Meanwhile, because graft side chain has larger steric hindrance, the relatively conventional linear polymeric of its stably dispersing effect is further promoted, and is conducive to polymerization reaction late stage maintenance system and stabilizes and increases the extended storage stability of emulsion; In addition, carboxylic acid on dispersion agent chain link or sulfonic acid group can strengthen dispersion agent with the adsorption between positively charged emulsion particle, the positive charge density on dispersion agent surface is reduced, the positive charge density that is dispersion agent surface is low, also reduce the desorption of stablizer, there is obvious effect for improving reaction later stage transformation efficiency, product solid content and electric charge degree.In addition,, from general formula (2), described dispersion agent D is comb-shaped graft copolymer, its molecular structure is adjustable, so just can design different structure for hetero-polymer system, with strong points, and the viscosity of this dispersion agent D is little, can effectively reduce like this polymerization system viscosity.
Improve as the one to technical scheme of the present invention, dispersion agent D is dissolved in water and is obtained reaction solution by monomer shown in cationic monomer B shown in general formula (1), general formula (3) and general formula (4), then issue raw free radical polyaddition reaction in initiator I effect and make, its formula of (3) and general formula (4) are respectively:
Wherein, R
5and R
7represent independently of one another H or CH
3, R
6represent OH, NH
2or N (CH
3)
2cH
2sO
3 -, R
8represent OH or CH
3, X represents O, CH
2o, CH
2cH
2o or COO, n value scope is 5～25;
Shown in general formula (1), general formula (3) and general formula (4), the molar ratio of monomer is a:b:c, and a, b and c are a, b and the c in general formula (2).
In technical scheme of the present invention, by monomer shown in cationic monomer B shown in general formula (1), general formula (3) and general formula (4), the dispersion agent D that polyaddition reaction prepares occurring under initiator I effect is comb-grafted copolymer, the molecular structure of this dispersion agent D is adjustable, to hetero-polymer, system can design different structure, with strong points, and can effectively reduce the viscosity of polymerization system.
Improve as the one to technical scheme of the present invention, n value scope is preferably 10 ~ 20.In the time that n value is 5 ~ 10, the adsorption rate of dispersion agent D is larger, makes the stability of emulsion particle of early origin stronger, and early stage viscosity is also lower, but because side chain is shorter, the dispersion liquid viscosity finally obtaining can become large; If n value is 20 ~ 25, the side chain of the dispersion agent D obtaining is longer, and early stage dispersion effect is slightly poor, and the latex particle size of formation is slightly large, can affect to a certain extent like this its solvability.
Improve as the one to technical scheme of the present invention, in dispersion agent D preparation process, shown in general formula (1), general formula (3) and general formula (4), the quality summation of monomer accounts for the 15-40% of reaction system total mass.If the total concn of monomer mixed solution is greater than 40%, easily produce gel, if the total concn of monomer mixed solution lower than 15%, is difficult to obtain target molecular weight product, and solid content also can be lower.
Improve as the one to technical scheme of the present invention, in dispersion agent D preparation process, radical addition polymerization reaction is carried out under 30 ~ 50 ° of C, and the reaction times is controlled at 4-5 hour.Temperature of reaction depends on the decomposition temperature with initiator I; In addition, if the reaction times is less than 4 hours, monomer can not be converted into target product completely, has reduced transformation efficiency; If the reaction times is greater than 5 hours, completely need not, in a word, the reaction times is controlled at 4-5 hour, so just can control better the transformation efficiency of monomer.
Improve as the one to technical scheme of the present invention, in dispersion agent D preparation process, take separately dropping mode to drip mixed solution and the initiator by monomer shown in described general formula (1), general formula (3) and general formula (4), and the time for adding of the two is all controlled at 1.5-2 hour.Take separately to drip the mode of monomer mixture and initiator, so more easily control the homogeneity of multipolymer chain link distribution and the stability of polyreaction, can also avoid to a certain extent producing gel.
Improve as the one to technical scheme of the present invention, in dispersion agent D preparation process, initiator I is selected from a group in hydrogen peroxide and xitix, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium bisulfite, ammonium persulphate and S-WAT, Sodium Persulfate and sodium bisulfite or ammonium persulphate and trolamine, and initiator I accounts for the 0.2-1wt% of monomer total amount.The consumption of initiator I is controlled at the 0.2-1wt% of monomer total amount, so more easily control the molecular weight of dispersion agent D, if the consumption of initiator I is too low, polyreaction is unstable, if consumption is too high, can cause the consequence that reaction gel or target molecular weight are too low.
Improve as the one to technical scheme of the present invention, non-ionic monomer A is acrylamide.
Improve as the one to technical scheme of the present invention, inorganic salt C is sodium, ammonium, lithium ion salt, is selected from one or more arbitrary combination in ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate, sodium tartrate.In technical scheme of the present invention, cationic polyacrylamide water-in-water emulsion synthetic taking inorganic salt solution as medium, inorganic salt used are necessary for the good solvent of monomer, the poor solvent of final polymkeric substance.
Improve as the one to technical scheme of the present invention, inorganic salt C is one or more arbitrary combination in ammonium sulfate, Lithium Sulphate or sodium-chlor.While adopting above-mentioned several inorganic salt, the viscosity of the cationic polyacrylamide water-in-water emulsion of prepared acquisition is lower, also makes the dissolution rate of cationic polyacrylamide water-in-water emulsion faster simultaneously.
In technical scheme of the present invention, initiator I can adopt one or both compound uses in water-soluble azo class initiator, redox initiator.Water-soluble azo class initiator is selected from azo diisobutyl amidine hydrochloride or azo two isobutyl imidazoline salt hydrochlorates; Redox initiator is selected from a group in hydrogen peroxide and xitix, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium bisulfite, ammonium persulphate and S-WAT, ammonium persulphate and sodium bisulfite or ammonium persulphate and trolamine.In addition, in the time adopting water-soluble azo class initiator and redox initiator, both amounts are not had to special requirement, as long as total amount meets the demands.
Therefore, the invention has the beneficial effects as follows the preparation method that a kind of cationic polyacrylamide water-in-water emulsion is provided, in this preparation method, adopt a kind of molecular weight, positive charge density is low, the sterically hindered strong comb-grafted copolymer of side chain is as dispersion agent, it is little that this dispersion agent has viscosity, diffusion is rapid with absorption, the advantages such as stably dispersing is effective, and the molecular structure of this dispersion agent is adjustable, to hetero-polymer, system can design different structure, with strong points, effectively reduce polymerization system viscosity, improve the stability of product solid content and water-in-water emulsion, and it is fast that the cationic polyacrylamide water-in-water emulsion that utilizes preparation method of the present invention to obtain also has dissolution rate, molecular weight is high, good fluidity and the advantage such as easy to use.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Raw material used and to be called for short cationic polyacrylamide water-in-water emulsion brief note as shown in table 1, synthetic be CPD in cationic polyacrylamide water-in-water emulsion Preparation Example of the present invention and dispersion agent D synthetic example.
Raw materials used in table 1 water-in-water emulsion Preparation Example and dispersion agent synthetic example
In dispersion agent synthetic example of the present invention, dispersion agent D molecular weight uses aqueous gel permeation chromatography (GPC) to measure.Experiment condition is as follows:
Gel column: Shodex SB806+803 two root chromatogram column series connection
Eluant: 0.1M NaNO
3solution
Moving phase speed: 1.0ml/min
Injection: 20 μ l 0.5% aqueous solution
Detector: Shodex RI-71 type differential refraction detector
Standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
Dispersion agent synthetic example 1(dispersion agent D-1's is synthetic)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 18.2 grams (F-1), 0.15 gram of hydrogen peroxide, 100 ml deionized water, use while stirring nitrogen purging reaction vessel, be warming up to 45 DEG C, then by 80 milliliters, 9.68 grams (B-1) and 7.2 grams (E-1) and water, make the mix monomer aqueous solution, splashed into reactor, time for adding is 2 hours, and drip 20 grams of 1% ascorbic acid solutions simultaneously, time for adding is 2 hours, dropwise rear insulation reaction and within 3 hours, be cooled to room temperature, obtain dispersion agent D-1, then adopt above-mentioned aqueous gel permeation chromatography (GPC) to measure, measurement result shows that its molecular weight is 17000.
Dispersion agent synthetic example 2-4(dispersion agent D-2 ~ D-4's is synthetic)
Prepare dispersion agent D-2 ~ D-4 according to the step and method of dispersion agent synthetic example 1, feed intake according to the described ratio of table 2, obtaining after dispersion agent D-2 ~ D-4, continuing to adopt above-mentioned aqueous gel permeation chromatography (GPC) to measure, thereby obtaining the molecular weight of dispersion agent D-2 ~ D-4.
Ingredient proportion prepared by table 2 dispersion agent and molecular weight
The common dispersion agent D-5's of dispersion agent contrast synthetic example 1(is synthetic)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 100g acrylyl oxy-ethyl-trimethyl salmiac and 398g water, be warming up to 50 DEG C, purge nitrogen after 30 minutes, adding 2g concentration is the aqueous solution of 5% initiator V-50, react stopped reaction after 20 hours, obtain polyacrylamide oxy-ethyl-trimethyl salmiac (dispersion agent D-5), in 25 DEG C of waters bath with thermostatic control taking 1.00mol/L sodium chloride aqueous solution as solvent, adopt Ubbelohde viscometer to measure the limiting viscosity number of PDAC according to GB17514-2008, according to document (Polymer 1984, 25, (9), 1317-1322.) report relational expression calculating molecular weight is about 7.5 × 10
5da.
The molecular weight of conventional dispersion agent is generally between 50-150 ten thousand, and the molecular weight of known common dispersion agent D-5 is 7.5 × 10 from dispersion agent contrast synthetic example 1
5da, and show in table 2, utilize the molecular weight of the dispersion agent that technical scheme of the present invention prepares between 10000-100000, can utilize thus the molecular weight of the dispersion agent of dispersant preparation method acquisition of the present invention, its soltion viscosity is little, molecule more easily moves, therefore there is diffusion and adsorption rate faster, avoid initial reaction stage generation system gel, simultaneously, because graft side chain has larger tail resistance effect, the relatively conventional linear polymeric of its stably dispersing effect is further promoted.The dispersion agent that utilizes above-mentioned dispersion agent synthetic example to prepare carries out the preparation of cationic polyacrylamide water-in-water emulsion.
Cationic polyacrylamide water-in-water emulsion synthetic example 1(CPD-1)
Being equipped with in the glass reactor of thermometer, agitator, nitrogen ingress pipe and reflux exchanger, add 65.09 grams (A-1), 9.91 grams (B-1), 100 grams (C-1) and 25 grams (C-4), 5 grams (D-2) and 295 grams of deionized waters, regulation system pH value is 4.0～5.5, use while stirring nitrogen purging reaction vessel, and be warming up to 35 DEG C, then add 0.015 gram (I-1), insulation reaction was cooled to room temperature after 10 hours, obtained cationic polyacrylamide water-in-water emulsion CPD-1.
Cationic polyacrylamide water-in-water emulsion synthetic example 2-12(CPD-2 ~ CPD-12)
Step according to cationic polyacrylamide water-in-water emulsion synthetic example 1 is prepared CPD-2-CPD-12 of the present invention, feeds intake according to the described ratio of table 3.
Utilize above-mentioned steps to prepare after cationic polyacrylamide water-in-water emulsion CPD1-12, adopt SNB AI intelligence Brookfield viscometer, No. 27 rotors are measured cloth network gram Field (Brookfield) viscosity of dispersion liquid under 10RPM, and dispersion liquid viscosity is lower, illustrate that its mobility is better.In the embodiment of the present invention, the intrinsic viscosity of all cationic polyacrylamides adopts viscosimetry to measure according to GB17514-2008, adopt document (Journal of Polymer Science Part C-Polymer Symposium, 1973,42:173-183.) MH Equation for Calculating molecular weight.Before measuring, must process sample, to remove inorganic salt and the complete monomer of unreacted in sample, concrete treating processes is as follows: by soluble in water cationic polyacrylamide water-in-water emulsion, be made into mass concentration and be 2% the aqueous solution, then be poured in aqueous ethanolic solution (volume ratio of dehydrated alcohol and the aqueous solution is 3:1) and be settled out polymkeric substance, then use washing with acetone.This process in triplicate, then by throw out vacuum-drying at 40 DEG C.Dissolution time is measured the sample of 0.1g is joined in 9.9 grams of water, adopts SNB AI intelligence Brookfield viscometer, and No. 21 rotor is measured soltion viscosity over time under 200RPM, writes down the time that viscosity reaches while stablizing to be dissolution time.
Cationic polyacrylamide water-in-water emulsion synthesizes comparative example 1
Use the synthetic cationic polyacrylamide water-in-water emulsion CPD-13 with the similar composition of CPD-1 of common dispersion agent D-5, according to above-mentioned detection method, gained cationic polyacrylamide water-in-water emulsion CPD-13 is tested, dispersion liquid viscosity, molecular weight and the dissolution time of CPD-1 and CPD-13 are as shown in table 4 again.
As known from Table 3, the dispersion liquid viscosity of CPD-1 ~ CPD-13 is at 89 ~ 371mPaS, and molecular weight is 6,400,000-1,280 ten thousand, and dissolution time is 3-8min; Contrast from table 3 and table 4, compared with CPD-13, utilize the dispersion liquid viscosity of the cationic polyacrylamide water-in-water emulsion CPD-1 that technical scheme of the present invention prepares little, good fluidity, molecular weight is high, and dissolution time is short, and dissolution rate is fast.
Claims (10)
1. a preparation method for cationic polyacrylamide water-in-water emulsion, is characterized in that, preparation process is as follows:
(1) non-ionic monomer A, cationic monomer B, inorganic salt C and dispersion agent D are joined in reactor in proportion, be dissolved in water and obtain reaction solution, regulating pH is 4.0 ~ 5.5; Wherein, inorganic salt C accounts for 25-40wt%, and non-ionic monomer A and cationic monomer B account for 15-30wt% altogether, and dispersion agent D accounts for 1-3wt%, and surplus is water;
(2) reaction solution step (1) being obtained is warming up to 30-50 ° of C, and logical nitrogen deoxygenation, adds initiator I, carries out polyaddition reaction; The add-on of described initiator I accounts for the 0.01-0.05wt% of non-ionic monomer A and cationic monomer B gross weight;
(3) insulation reaction is after 10 hours, cool to room temperature, and discharging, makes cationic polyacrylamide water-in-water emulsion;
Described non-ionic monomer A is selected from acrylamide or Methacrylamide, and accounts for the 70-95mol% of non-ionic monomer A and cationic monomer B total amount;
Described cationic monomer B adopts by the represented material of general formula (1):
Wherein A represents O or NH, and B represents CH
2cH
2, CH
2cH
2cH
2or CH
2cHOHCH
2, R
1represent H or CH
3, R
2and R
3represent independently of one another CH
3or CH
2cH
3, R
4represent H, CH
3, CH
2cH
3or CH
2c
6h
5;
Described dispersion agent D is comb-shaped graft copolymer, and it adopts by the represented material of general formula (2):
Wherein, A represents O or NH, and B represents CH
2cH
2, CH
2cH
2cH
2or CH
2cHOHCH
2, X represents O, CH
2o, CH
2cH
2o or COO, R
1, R
5, R
7represent independently of one another H or CH
3, R
2and R
3represent independently of one another CH
3or CH
2cH
3, R
4represent H, CH
3, CH
2cH
3or CH
2c
6h
5, R
6represent OH, NH
2or N (CH
3)
2cH
2sO
3 -, R
8represent OH or CH
3;
The span of described dispersion agent D molecular weight is 10000～100000; A:b:c=(1～2): (0～2): 1; N value is 5～25.
2. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 1, it is characterized in that, described dispersion agent D is dissolved in water and is obtained reaction solution by monomer shown in cationic monomer B shown in general formula (1), general formula (3) and general formula (4), then issue raw free radical polyaddition reaction in initiator I effect and make, its formula of (3) and general formula (4) are respectively:
Wherein, R
5and R
7represent independently of one another H or CH
3, R
6represent OH, NH
2or N (CH
3)
2cH
2sO
3 -, R
8represent OH or CH
3, X represents O, CH
2o, CH
2cH
2o or COO, n value is 5～25;
Shown in described general formula (1), general formula (3) and general formula (4), the molar ratio of monomer is a:b:c, and described a, b and c are a, b and the c in general formula (2).
3. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 1 and 2, is characterized in that, described n value is 10 ~ 20.
4. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 2, it is characterized in that, in dispersion agent D preparation process, shown in described general formula (1), general formula (3) and general formula (4), the quality summation of monomer accounts for the 15-40% of reaction system total mass.
5. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 2, is characterized in that, in dispersion agent D preparation process, described radical addition polymerization reaction is carried out under 30 ~ 50 ° of C, and the reaction times is controlled at 4-5 hour.
6. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 2, it is characterized in that, in dispersion agent D preparation process, take separately dropping mode to drip mixed solution and the initiator I by monomer shown in described general formula (1), general formula (3) and general formula (4), and the time for adding of the two is all controlled at 1.5-2 hour.
7. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 2, it is characterized in that, in dispersion agent D preparation process, described initiator I is selected from a group in hydrogen peroxide and xitix, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium bisulfite, ammonium persulphate and S-WAT, Sodium Persulfate and sodium bisulfite or ammonium persulphate and trolamine, and initiator I accounts for the 0.2-1wt% of monomer total amount.
8. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 1, is characterized in that, described non-ionic monomer A is acrylamide.
9. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 1, it is characterized in that, described inorganic salt C is sodium, ammonium, lithium ion salt, is selected from one or more arbitrary combination in ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate, sodium tartrate.
10. the preparation method of cationic polyacrylamide water-in-water emulsion according to claim 9, is characterized in that, described inorganic salt C is one or more arbitrary combination in ammonium sulfate, Lithium Sulphate or sodium-chlor.
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