CN103242613A - Preparation method of anionic polyacrylamide emulsion and emulsion prepared by same - Google Patents
Preparation method of anionic polyacrylamide emulsion and emulsion prepared by same Download PDFInfo
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- CN103242613A CN103242613A CN2013101299266A CN201310129926A CN103242613A CN 103242613 A CN103242613 A CN 103242613A CN 2013101299266 A CN2013101299266 A CN 2013101299266A CN 201310129926 A CN201310129926 A CN 201310129926A CN 103242613 A CN103242613 A CN 103242613A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 51
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- -1 acrylic amine Chemical class 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 8
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003352 sequestering agent Substances 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920004890 Triton X-100 Polymers 0.000 claims description 2
- 239000013504 Triton X-100 Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical class C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 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
- 229940035044 sorbitan monolaurate Drugs 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 229920006318 anionic polymer Polymers 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002738 chelating agent Substances 0.000 abstract 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 241000237502 Ostreidae Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 235000020636 oyster Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000012688 inverse emulsion polymerization Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 238000005065 mining Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a preparation method of an anionic polyacrylamide emulsion, which comprises the following steps: 1) mixing 10-30 parts by weight of high-polymer stabilizer, 10-20 parts of emulsifier and 300-400 parts of organic hydrocarbon solvent; 2) adding 0.01-0.1 part of thermal initiator, and stirring uniformly; 3) mixing 200-400 parts of deionized water, 100-400 parts of monomer and 0.1-1 part of chelator; 4) emulsifying and homogenizing; 5) deoxidizing the emulsified and homogenized emulsion by nitrogen charging for 2-3 hours; and 6) adding 0.01-0.05 part of initiator until the temperature of the reaction mixture increases to a constant value, and keeping the temperature for 15-30 minutes. The reversed phase emulsion polymerization technique of combining the stabilizer and emulsifier can be used for preparing a high-concentration high-stability instant polyacrylamide emulsion product; and in addition, the synthesis technique can be adjusted to obtain the high-concentration anionic polymer emulsion with different molecular weights and different ion degrees.
Description
Technical field
The invention belongs to the field of organic high molecular compound preparation, be specifically related to a kind of preparation method and preparation-obtained product of acrylamide polymer.
Background technology
At present, studying both at home and abroad the molecular weight that how further improves anionic polyacrylamide, to satisfy consumers in general to the demand of high molecular weight products more.Although the development direction of this base polymer has had some reports both at home and abroad, because product stability is not good, also be in the laboratory study stage, do not carry out suitability for industrialized production or application.Because the anionic polyacrylamide emulsion concentration that marketing is sold is generally lower, molecular weight is lower, and storage stability is poor, uses for transportation and client and brings very big inconvenience.
Among the patent CN101029107A, by compound initiation reaction, prepare the anionic polyacrylamide powder, do not have the open stable polyacrylamide emulsion that how to reach; Among the patent CN101514240A, under laboratory scale, prepare the anionic polyacrylamide emulsion, do not had to obtain high molecular bigger (1,800 ten thousands') polyacrylamide emulsion.
Polyacrylamide powdery product of the prior art, exist dissolving to waste time and energy in the use, operating environment is abominable, dissolution rate is slow, defectives such as dissolution equipment is huge, make the foreign market be shifted to product emulsion by powder-product gradually, but traditional inverse emulsion polymerization gained PAM product emulsion stability extreme difference can not satisfy user's needs.The polyacrylamide emulsion concentration of existing market merchandise sales is lower (30～40%) generally, and storage stability poor (general 3 months～6 months, layering just occurs) uses for transportation and client and brings very big inconvenience.
Summary of the invention
At the problem that exists in the existing polyacrylamide emulsion field, the purpose of this invention is to provide a kind of preparation method of high dense anionic polyacrylamide emulsion.
Another object of the present invention is to propose the anionic polyacrylamide emulsion that described preparation method obtains.
For achieving the above object, concrete technical scheme is:
A kind of preparation method of anionic polyacrylamide emulsion comprises step:
1) with stablizer 10-30 part, emulsifying agent 10-20 part, organic hydrocarbon solvent 300-400 part, thermal initiator 0.01-0.1 part of weight part, mixing and stirring;
2) deionized water 200-400 part, monomer 100-400 part, sequestrant 0.1-1 part are mixed, and described monomer is sodium acrylate, 2-acrylamido-2-methyl propane sulfonic acid and acrylic amine;
3) step 2) the gained mixture joins in the step 1) gained mixture, the emulsification homogeneous; Then system is cooled to 10 ℃～20 ℃;
4) add 0.01～0.05 part of initiator in the step 3) gained mixture, be increased to constantly to reaction mixture temperature, be incubated 15-30 minute again, stop to fill nitrogen;
5) the step 4) products therefrom slowly is warmed up to 80 ℃～95 ℃ distillations 2-3 hour under vacuum;
6) add 10 parts～20 parts active activator in the emulsion that step 5) is obtained, obtain high concentrated emulsion product.
Wherein, described macromolecule stabilizer is one or more in multipolymer, vinyl pyrrolidone and the vinyl acetate copolymer of fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyglycerol ester, polyvinyl, vinylbenzene and maleic anhydride.
Wherein, the emulsifying agent in the described step 1) is nonionogenic tenside, is selected from sorbitan mono-laurate, polyoxyethylene octylphenol ether, Triton X-100 and the polyoxyethylene sorbitan fatty acid ester one or more; Described organic hydrocarbon solvent be selected from gasoline, kerosene, diesel oil or white oil one or more.
Wherein, the thermal initiator in the described step 1) is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, 2,2'-azo two (isopropyl cyanide), 2, one or more of 2'-azo two (2-methyl isopropyl cyanide) etc.;
Wherein, sequestrant is one or more in EDTA, Sodium Dimercapto Sulfonate, EGTA, ethylenediamine tetrapropionic acid(EDTP), the triethylenetetramine etc. in described step 2);
Wherein, the initiator in the described step 4) is selected from Potassium Persulphate, Sodium Persulfate, ammonium persulphate, benzoyl peroxide, lauroyl peroxide, crosses two carbonic acid dicyclohexyl esters, crosses the sad tert-butyl ester, crosses sad tert-pentyl ester, crosses one or more of nonane diacid di tert butyl carbonate, t-butyl peroxy-acetate etc.;
Wherein, 3-6 ℃ of the adding control temperature of reaction system per minute rising by initiator in the described step 4), the adding mode of initiator can divide 3-6 to criticize adding, also can adopt the mode of dropping, 3-6 ℃ of my concentration rising of control per minute.Initiator to reaction mixture temperature is increased to constant, is incubated 15-30 minute then;
Wherein, active activator is among the hydrophilic surfactant actives such as polyoxyethylenesorbitan sorbitan monooleate, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, Viscotrol C phosphate ester salt one or more in the described step 6).
The emulsion that preparation method of the present invention prepares.
Beneficial effect of the present invention is:
The present invention adopts macromolecule stabilizer and the composite inverse emulsion polymerization technology of emulsifying agent, can prepare high density (solid content 〉=55%), the instant polyacrylamide emulsion product of stability splendid (placing not stratified more than 2 years), and can obtain the high dense anionic polymer emulsion of different molecular weight and different ions degree by adjusting synthesis technique.The products obtained therefrom excellent performance, excellent stability can extensively substitute the form of powdery particles product and be used for each field such as oilfield exploitation, processing, mining, papermaking, dyeing, and prospect is very wide.Develop this series products, can further enlarge the foreign market recoverable amount, maintenance technology and product leading position promote competitive power, have important economic and social benefit.
Embodiment
Following examples are used for explanation the present invention, but do not limit the scope of the invention.
The testing method of molecular weight is: limiting viscosity is according to GB12005.1-89 polyacrylamide viscosity measurement, and molecular weight M is according to formula
M η-viscosity-average molecular weight wherein; IV-intrinsic viscosity.
The testing method of solid content: GB12005.2-89 polyacrylamide determination of solid content method.Embodiment 1
With vinyl pyrrolidone and vinyl acetate copolymer 20g(Shanghai Yu'ang Chemical Technology Development Co., Ltd.), polyoxyethylene sorbitan fatty acid ester 15g, organic hydrocarbon industrial naptha 350g add the oil phase container, thermal initiator Potassium Persulphate 0.05g is added in the oil phase container, start agitator, stirring velocity is 100rpm, open condenser system simultaneously, the temperature in the control oil phase container is 15 ℃.
Deionized water 344g part is added water in the phase container, start agitator (stirring velocity 200rpm) and condenser system (20 ℃ of control temperature), add monomer component acrylic amine 250g, EDTA0.5g, under this cold condition, stir.Carried out the emulsification homogeneous 15 minutes in the oil phase system with monomer solution adding oil phase container in the water container, emulsifying rate is 9000r/min; After emulsification is finished, emulsion is poured in the reactor.Open cooling system (20 ℃ of control temperature) and agitator (stirring velocity 200rpm), in reactor, charge into nitrogen.Fill nitrogen continuously and stopped to fill nitrogen in 2 hours.Slowly add initiator potassium persulfate then and divide 5 addings, control emulsion heat-up rate is 4 ℃/min, and the initiator quality that adds is 0.03g altogether.When emulsion be warming up to 68 ℃ of top temperatures and constant after, insulation reaction is 30 minutes again.Emulsion is cooled to 38 ℃, adjusts valve and open steam valve so that distillation.
Reactor is vacuumized gradually, and vacuum tightness reaches 0.5MPa, and distillation slowly heats up, after 98 ℃ of temperature, continue distillation 30min, emulsion is transferred in the emulsion activation vessel, activated with polyoxyethylene octylphenol ether 10g phase inversion, obtain molecular weight and be 2,210 ten thousand anionic polyacrylamide latex.Emulsion concentration is 55%.This emulsion color is uniform oyster white, and normal temperature is placed the phenomenon of not observing layering in 2 years.
Embodiment 2
Vinyl pyrrolidone and vinyl acetate copolymer 28g, polyoxyethylene sorbitan fatty acid ester 15g, the organic hydrocarbon solvent kerosene 380g of weight part are added the oil phase container, thermal initiator 0.08g is added in the oil phase container, start agitator, stirring velocity is 100rpm, open condenser system simultaneously, 15 ℃ of the temperature in the control oil phase container.Deionized water 352g part is added water in the phase container, start agitator (stirring velocity 200rpm) and condenser system (20 ℃ of control temperature), add monomer component acrylic amine 250g, EDTA0.5g, under cold condition, stir.Carried out the emulsification homogeneous 15 minutes in the oil phase system with monomer solution adding oil phase container in the water container, emulsifying rate is 9000r/min; After emulsification is finished, emulsion is poured in the reactor.Open cooling system (20 ℃ of control temperature) and agitator (stirring velocity 200rpm), in reactor, charge into nitrogen.Fill nitrogen continuously and stop to fill nitrogen after 2 hours.Will be retained in the liquid level top in the gas inlet after filling nitrogen, make system obtain nitrogen protection.Slowly divide to add initiator potassium persulfate 5 times, 5 ℃/min of control heat-up rate, the initiator quality that adds is 0.05g altogether.When emulsion be warming up to 70 ℃ of top temperatures and constant after, insulation reaction is 30 minutes again.Emulsion is cooled to 38 ℃, adjusts valve and open steam valve so that distillation.
Reactor is vacuumized gradually, vacuum tightness reaches the distillation that slowly heats up of maximum back, continues distillation 30min after 98 ℃ of temperature, and emulsion is transferred in the emulsion activation vessel, activate with the polyoxyethylene octylphenol ether phase inversion, obtain molecular weight and be 1,810 ten thousand anionic polyacrylamide latex.Emulsion concentration is 55%.This emulsion color is uniform oyster white, and normal temperature is placed the phenomenon of not observing layering in 2 years.
Embodiment 3
Vinyl pyrrolidone and vinyl acetate copolymer 18g, polyoxyethylene sorbitan fatty acid ester 13g, organic hydrocarbon solvent 350g are added the oil phase container, thermal initiator 0.03g is added in the oil phase container, start agitator, stirring velocity is 100rpm, open condenser system simultaneously, 15 ℃ of the temperature in the control oil phase container.Deionized water 344g part is added water in the phase container, start agitator (stirring velocity 200rpm) and condenser system (20 ℃ of control temperature), add monomer component acrylic amine 250g, EDTA0.5g, under cold condition, stir.
Carried out the emulsification homogeneous 15 minutes in the oil phase system with monomer solution adding oil phase container in the water container, emulsifying rate is 9000r/min; After emulsification is good, emulsion is poured in the reactor.Open cooling system (20 ℃ of control temperature) and agitator (stirring velocity 200rpm), in reactor, charge into nitrogen.Fill nitrogen continuously and stopped to fill nitrogen in 2 hours.Slowly adding initiator potassium persulfate control emulsion heat-up rate is 4-6 ℃/min, divides 5 addings, and the initiator quality that adds is 0.04 altogether.When emulsion be warming up to 73 ℃ of top temperatures and constant after, insulation reaction is 30 minutes again.Emulsion is cooled to 38 ℃, adjusts valve and open steam valve so that distillation.
Reactor is vacuumized gradually, vacuum tightness reaches the distillation that slowly heats up behind the 0.5MPa, continues distillation 30min after 98 ℃ of temperature, and emulsion is transferred in the emulsion activation vessel, activate with the polyoxyethylene octylphenol ether phase inversion, obtain molecular weight and be 2,110 ten thousand anionic polyacrylamide latex.Emulsion concentration is 55%.This emulsion color is uniform oyster white, and normal temperature is placed the phenomenon of not observing layering in 2 years.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of an anionic polyacrylamide emulsion is characterized in that, comprises step:
1) with stablizer 10-30 part, emulsifying agent 10-20 part, organic hydrocarbon solvent 300-400 part, thermal initiator 0.01-0.1 part of weight part, mixing and stirring;
2) deionized water 200-400 part, monomer 100-400 part, sequestrant 0.1-1 part are mixed, and described monomer is a kind of in sodium acrylate, 2-acrylamido-2-methyl propane sulfonic acid and the acrylic amine;
3) step 2) the gained mixture joins in the step 1) gained mixture, the emulsification homogeneous; Then system is cooled to 10 ℃-20 ℃, use the nitrogen protection reaction system;
4) add 0.01～0.05 part of initiator in the step 3) gained mixture, be increased to constantly to reaction mixture temperature, be incubated 15-30 minute again, stop to fill nitrogen;
5) product that step 4) is obtained slowly is warmed up to 80 ℃～95 ℃ under vacuum, distills 2-3 hour;
6) emulsion of step 5) gained is added 10 parts～20 parts active activator, obtain high concentrated emulsion product.
2. preparation method as claimed in claim 1, it is characterized in that macromolecule stabilizer described in the described step 1) is one or more in multipolymer, vinyl pyrrolidone and the vinyl acetate copolymer of fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyglycerol ester, polyvinyl, vinylbenzene and maleic anhydride.
3. preparation method as claimed in claim 1, it is characterized in that, emulsifying agent in the described step 1) is nonionogenic tenside, is selected from sorbitan mono-laurate, polyoxyethylene octylphenol ether, Triton X-100 and the polyoxyethylene sorbitan fatty acid ester one or more; Described organic hydrocarbon solvent be selected from gasoline, kerosene, diesel oil or white oil one or more.
4. preparation method as claimed in claim 1, it is characterized in that, thermal initiator in the described step 1) is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, 2,2'-azo two (isopropyl cyanide), 2, one or more in the 2'-azo two (2-methyl isopropyl cyanide).
5. preparation method as claimed in claim 1 is characterized in that, described step 2) in sequestrant be in EDTA, Sodium Dimercapto Sulfonate, EGTA, ethylenediamine tetrapropionic acid(EDTP), the triethylenetetramine one or more.
6. as the arbitrary described preparation method of claim 1-6, it is characterized in that the initiator in the described step 4) is selected from Potassium Persulphate, Sodium Persulfate, ammonium persulphate, benzoyl peroxide, lauroyl peroxide, cross two carbonic acid dicyclohexyl esters, cross the sad tert-butyl ester, cross sad tert-pentyl ester, cross in nonane diacid di tert butyl carbonate, the t-butyl peroxy-acetate one or more.
7. preparation method as claimed in claim 7 is characterized in that, 3-6 ℃ of the adding control temperature of reaction system per minute rising by initiator in the described step 4) is increased to constantly to reaction mixture temperature, be incubated 15-30 minute then.
8. preparation method as claimed in claim 1 is characterized in that, described step 5) distillation condition distilled 2～3 hours for slowly to be warmed up to 80 ℃～95 ℃ under maximum vacuum.
9. preparation method as claimed in claim 1, it is characterized in that active activator is one or more among the hydrophilic surfactant actives such as polyoxyethylenesorbitan sorbitan monooleate, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, Viscotrol C phosphate ester salt in the described step 6).
10. the high concentrated emulsion for preparing of the arbitrary described preparation method of claim 1-9.
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| CN104558401A (en) * | 2013-10-14 | 2015-04-29 | 郭保祥 | Multi-functional ion association type emulsion and preparation method thereof |
| CN105692851A (en) * | 2016-04-21 | 2016-06-22 | 苏州云舒新材料科技有限公司 | Method for treating wastewater on basis of magnetic polyacrylamide |
| CN106220764A (en) * | 2016-08-29 | 2016-12-14 | 浙江大川新材料股份有限公司 | A kind of preparation method of PAM nanometer micro-emulsion |
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| CN101845105A (en) * | 2010-05-18 | 2010-09-29 | 马云峰 | Synthetic method of inverse emulsion of polyacrylamide |
| CN102731699A (en) * | 2011-04-01 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of ultra high molecular weight anionic polyacrylamide |
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| CN104558401A (en) * | 2013-10-14 | 2015-04-29 | 郭保祥 | Multi-functional ion association type emulsion and preparation method thereof |
| CN103881006A (en) * | 2014-04-01 | 2014-06-25 | 山东宝莫生物化工股份有限公司 | Polymerization method of anion modified polyacrylamide inverse emulsion having high solid content and high molecular weight |
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