CN101649024B - Preparation method of water-in-water cationic polyacylamide emulsion - Google Patents

Preparation method of water-in-water cationic polyacylamide emulsion Download PDF

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CN101649024B
CN101649024B CN2009100909691A CN200910090969A CN101649024B CN 101649024 B CN101649024 B CN 101649024B CN 2009100909691 A CN2009100909691 A CN 2009100909691A CN 200910090969 A CN200910090969 A CN 200910090969A CN 101649024 B CN101649024 B CN 101649024B
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monomer
acrylamide
anionic
water
initiator
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CN101649024A (en
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郑书忠
滕厚开
陈军
王素芳
邢凡彬
林蓓
宋承鹏
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

The invention relates to a synthetic method of water-in-water cationic polyacylamide emulsion. The synthetic method is characterized by mixing inorganic salt, non-ionic hydrophilic monomers, anionic monomers, hydrophobic monomers, functional monomers having surface activity, a stabilizing agent, a chelating agent and deionized water, adjusting the pH value to be between 6.5 and 7.5, uniformly emulsifying the mixture by an emulsifying machine, introducing nitrogen for protection, adding an evocating agent at twice at the temperature of 18 to 50 DEG C, carrying out second polymerization reaction for 1 to 3 hours after 4 to 7 hours of the time of first polymerization reaction and making the emulsion product.

Description

A kind of preparation method of water-in-water cationic polyacylamide emulsion
Technical field
The invention belongs to the water-soluble polymer synthesis technical field, relate to the preparation method of a kind of " water Bao Shui " type anionic polyacrylamide emulsion.
Background technology
The polyacrylamide water-soluble high-molecular material has the tackifying of good water-solubility, excellence because of it, so it is widely used in fields such as thickening, drag reduction, bonding.Wherein, the polyacrylamide water-soluble high-molecular material of anionic necessarily makes it be widely used in the tertiary oil recovery because of molecular weight can reach several.
All there is shortcoming in traditional polyacrylamide synthetic method, is subjected to bigger restriction in industrial application.There is reaction later stage system viscosity height in water solution polymerization process, stirs difficult and the slow shortcoming of dispelling the heat, and need expend a large amount of heats, uses special equipment, carry out drying, make powder, and powder bad dispersibility in use, be difficult for dissolving, need high-speed stirring and heating, take time and effort.Inverse emulsion polymerization and inverse suspension polymerization are solvent with oil (hydro carbons) all, in use, these oil enter water system easily, not only wasted valuable hydrocarbon resource, caused the pollution of water system and environment, and the emulsion that makes needs breakdown of emulsion, more increased the complicacy of producing and the difficulty of processing.Seek more economically the polyacrylamide synthetic method with environmental protection, become the focus of various countries' research.
As a kind of novel polymer method, the water-in-water type letex polymerization is that water-soluble monomer is dissolved in the polymer or the micromolecular aqueous solution, form homogeneous system, polymerization under certain condition again forms the polymerization process of immiscible water-soluble polymer dispersion.Polyacrylamide water-in-water emulsion have viscosity low, the dissolving fast, free of contamination advantage, remedy homogeneous phase aqueous solution and be aggregated in polymerization process medium viscosity height, there are the shortcoming of Organic pollutants in inverse emulsion polymerization and inverse suspension polymerization, and it is the direction of polyacrylamide industrial development.
CN101016352A reported a kind of in brine media acrylamide and a kind of dispersion system of cationic monomer copolymerization, this dispersion system not only has high molecular weight, has quick-dissolving effect in water simultaneously.This patent report is synthesizing about cationic-type polyacrylamide, realize separating out the purpose of phase-splitting by adding some cationic monomers with hydrophobic grouping, but anionic polyacrylamide synthetic is difficult for choosing the anionic monomer that has hydrophobic grouping, can only add some hydrophobic monomers and realize separating out phase-splitting.The patent report of publication number CN1709945A solve the problem of the one-tenth breast of steadily separating out by the form of one package stabilizer.In order to relax the contradiction between polymerization velocity and the speed of separating out, CN1884324A and US006025426A patent are cost with the sacrificial molecule amount, add polyvalent alcohol.The CN1479762A patent is low because of no polyvalent alcohol and saltiness, and the polymer emulsion of preparation is mobile poor.
In this patent, adopted the interpolation hydrophobic monomer to solve the too fast problem of polymerization system tackify, and adopted in salt brine solution, to add the good oligopolymer stablizer of solubility property and have surface-active function monomer and realize stablizing of emulsion.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of " water Bao Shui " type anionic polyacrylamide emulsion, this synthetic method can remedy high and this high shortcoming of reversed-phase emulsion product product of aqueous solution polymerization process medium viscosity.Should " water Bao Shui " type anionic polyacrylamide emulsion be oyster white, particle diameter be less than 5 μ m; Should " water Bao Shui " type anionic polyacrylamide emulsion have the advantages that dissolution rate was fast, molecular weight is high, cost is low and easy to use, be a kind of water-soluble polymer product of more environmental protection.
For reaching above technical purpose, the invention provides following technical scheme.
The synthetic method of a kind of " water Bao Shui " type anionic polyacrylamide emulsion, it is characterized in that, synthesis technique for earlier with inorganic salt, nonionic hydrophilic monomer, anionic monomer, hydrophobic monomer, have surface-active function monomer, stablizer, sequestrant, deionized water and mix, regulate pH to 6.5~7.5, even with mulser emulsification; Logical again nitrogen protection is added initiator at twice at 18-50 ℃, behind the polymerization reaction time 4~7h, carries out the after polymerization reaction, and the reaction times is 1~3h, makes this product emulsion;
As medium, the aqueous solution of this inorganic salt must be monomeric good solvent, and does not dissolve the high-molecular weight anionic polyacrylamide with inorganic salt solution in the present invention.Above-mentioned inorganic salt mainly contain the salt of sodium, ammonium ion, are selected from sodium sulfate, ammonium sulfate, ammonium chloride.The content of inorganic salt should account for the 20-30wt% of whole dispersion system.The preferably sulfuric acid ammonium.
The monomer that " water Bao Shui " type non-ionic polyacrylamide emulsion is somebody's turn to do in preparation comprises nonionic hydrophilic monomer, anionic monomer, hydrophobic monomer and has surface-active function monomer.
Above-mentioned nonionic hydrophilic monomer is the water-soluble cpds that contains the radical polymerization carried out of two keys, is selected from wherein one or more of acrylamide, hydroxypropyl acrylamide or hydroxyethyl acrylamide; Participate in the 75-85mol% that polymeric nonionic hydrophilic monomer accounts for whole monomer system; Preferred acrylamide.
Above-mentioned anionic monomer is selected from wherein one or more of sodium acrylate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, and anionic monomer accounts for the 4-8mol% of whole monomer system; Preferred 2-acrylamide-2-methyl propane sulfonic acid.
Above-mentioned hydrophobic monomer is selected from wherein one or more of methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate or butyl methacrylate, and hydrophobic monomer accounts for the 5-9mol% of whole monomer system; The preferable methyl ethyl propenoate.
Above-mentioned have surface-active function monomer and be selected from wherein one or more of Macrogol 200 mono acrylic ester, Macrogol 200 monomethacrylates, poly(oxyethylene glycol) 400 mono acrylic ester, poly(oxyethylene glycol) 400 monomethacrylates, has the 6-8mol% that surface-active function monomer accounts for whole monomer system; Preferred Macrogol 200 mono acrylic ester.
Above nonionic hydrophilic monomer, anionic monomer, hydrophobic monomer, have the monomer system that surface-active function monomer mutual group becomes dispersion system, monomer system accounts for the 15-30wt% of whole dispersion system;
Above-mentioned stablizer is an anionic oligomer, this aqueous solution anionic oligomer is formed by anionic monomer and non-ionic monomer copolymerization, anionic monomer is chosen one or more of sodium acrylate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid etc., and non-ionic monomer is chosen one or more of acrylamide, hydroxypropyl acrylamide, hydroxyethyl acrylamide or N-vinyl pyrrolidone.Stablizer measured limiting viscosity in the NaCl of the 1mol/L aqueous solution is 100-300mL/g, and stabilizing agent dosage accounts for the 15-20wt% of monomer system; Preferred sodium acrylate-acrylamide polymer stablizer.
Above-mentioned sequestrant is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate, and the consumption of sequestrant accounts for the 0.012-0.02wt% of whole dispersion system; Preferred disodium ethylene diamine tetraacetate.
Above-mentioned initiator is an oxidation-reduction initiator, or water miscible azo class thermal decomposition initiating; Or the composite initiation system of oxidation-reduction initiator and water miscible azo class thermal decomposition initiating formation; Wherein oxidation-reduction initiator is selected from wherein one or more of ammonium persulphate/sodium bisulfite, Potassium Persulphate/sodium bisulfite or ammonium persulphate/trolamine, water miscible azo class thermal decomposition initiating is selected from wherein one or more of azo-bis-isobutyrate hydrochloride, azo diisopropylamidinateand azoles quinoline hydrochloride or azo two isocyano-valeric acids, and the consumption of initiator is the 0.010-0.024% of monomer mass; The use temperature of oxidation-reduction initiator is 18-35 ℃, and the use temperature of water-soluble azo class thermal decomposition initiating is 35-50 ℃, and the use temperature of the composite initiation system that oxidation-reduction initiator and thermal decomposition initiating constitute is 30-45 ℃.Preferred oxidation-reduction system ammonium persulphate/trolamine initiator.
Synthetic method according to a kind of " water Bao Shui " of the present invention type anionic polyacrylamide emulsion, it is characterized in that: synthesis technique for earlier with inorganic salt ammonium sulfate, nonionic hydrophilic monomer acrylamide, anionic monomer 2-acrylamide-2-methyl propane sulfonic acid, hydrophobic monomer Jia Jibingxisuanyizhi, have surface-active function monomer Macrogol 200 mono acrylic ester, stablizer sodium acrylate-acrylamide, sequestrant disodium ethylene diamine tetraacetate, deionized water and mix, regulate pH to 6.5~7.0, even with mulser emulsification; Logical again nitrogen protection is added initiator oxidation-reduction system ammonium persulphate/trolamine at twice at 18-35 ℃, behind the polymerization reaction time 5~6h, carries out the after polymerization reaction, and the reaction times is 1.5~2h, makes this product emulsion.
Embodiment
Embodiment 1
In beaker, add 82.1240g deionized water, 55.4108g ammonium sulfate, 25.6506g acrylamide, 3.6362g 2-acrylamide-2-methyl propane sulfonic acid, 2.4783g Jia Jibingxisuanyizhi, 8.8696g Macrogol 200 mono acrylic ester, stablizer 6.5015g, 0.0296g EDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 30 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add 1.2mL0.3wt% ammonium persulphate/trolamine respectively, polyreaction 7h is carried out in 30 ℃ of insulations.Polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 6h, add 0.4mL 0.3wt% ammonium persulphate/trolamine more respectively in polymerization system, 30 ℃ of insulations continue reaction 1h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 440mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 63750mPas.
Embodiment 2
In beaker, add 96.8902g deionized water, 36.1652g ammonium sulfate, 25.0325g acrylamide, 3.6362g 2-acrylamide-2-methyl propane sulfonic acid, 4.4609g Jia Jibingxisuanyizhi, 6.6522g Macrogol 200 mono acrylic ester, 7.9563g stablizer, 0.0289gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 18 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add 1.8mL 0.3wt% ammonium persulphate/trolamine respectively, polyreaction is carried out in 18 ℃ of insulations, and polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 6h, add 0.6mL 0.3wt% ammonium persulphate/trolamine more respectively in polymerization system, 35 ℃ of insulations continue reaction 2h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 630mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 49600mPas.
Embodiment 3
In beaker, add 89.6753g deionized water, 46.1460g ammonium sulfate, 25.0325g acrylamide, 5.4543g 2-acrylamide-2-methyl propane sulfonic acid, 3.4696g methyl methacrylate, 6.6522g Macrogol 200 mono acrylic ester, 8.1217g stablizer, 0.0295gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 35 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add 1.8mL 0.3wt% ammonium persulphate/trolamine respectively, polyreaction is carried out in 35 ℃ of insulations, and polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 5h, add 0.6mL 0.3wt% ammonium persulphate/trolamine more respectively in polymerization system, 25 ℃ of insulations continue reaction 2h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 510mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 38500mPas.
Embodiment 4
In beaker, add 105.4103g deionized water, 38.7100g ammonium sulfate, 23.7963g acrylamide, 5.4543g2-acrylamide-2-methyl propane sulfonic acid, 4.4609g Jia Jibingxisuanyizhi, 8.8696g Macrogol 200 mono acrylic ester, 6.8130g stablizer, 0.0310gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 18 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 2.4mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, polyreaction is carried out in 18 ℃ of insulations, and polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 4h, add the oxygenant and the reductive agent of 0.8mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 25 ℃ of insulations continue reaction 3h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 720mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 39250mPas.
Embodiment 5
In beaker, add 92.3244g deionized water, 47.5097g ammonium sulfate, 24.4144g acrylamide, 7.2723g 2-acrylamide-2-methyl propane sulfonic acid, 3.4696g Jia Jibingxisuanyizhi, 6.6522g Macrogol 200 mono acrylic ester, 8.3617g stablizer, 0.0304gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 18 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.8mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 18 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 5h, add the oxygenant and the reductive agent of 0.6mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 35 ℃ of insulations continue reaction 3h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 810mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 41500mPas.
Embodiment 6
In beaker, add 105.5444g deionized water, 39.0740g ammonium sulfate, 23.4873g acrylamide, 7.2723g2-acrylamide-2-methyl propane sulfonic acid, 4.4609g Jia Jibingxisuanyizhi, 7.7609g Macrogol 200 mono acrylic ester, 7.7367g stablizer, 0.0313gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 30 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.2mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 30 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 6h, add the oxygenant and the reductive agent of 0.4mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 25 ℃ of insulations continue reaction 2h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 910mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 62500mPas.
Embodiment 7
In beaker, add 89.5955g deionized water, 45.6911g ammonium sulfate, 25.3416g acrylamide, 3.6362g 2-acrylamide-2-methyl propane sulfonic acid, 3.4696g Jia Jibingxisuanyizhi, 7.7609g Macrogol 200 mono acrylic ester, 7.2375g stablizer, 0.0292gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 30 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.8mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 30 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases step-down more earlier, finally tends towards stability.After polyreaction is carried out 6h, add the oxygenant and the reductive agent of 0.6mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 35 ℃ of insulations continue reaction 1h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 495mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 47100mPas.
Embodiment 8
In beaker, add 79.7053g deionized water, 54.8663g ammonium sulfate, 25.6506g acrylamide, 5.4543g2-acrylamide-2-methyl propane sulfonic acid, 2.4783g Jia Jibingxisuanyizhi, 6.6522g Macrogol 200 mono acrylic ester, 8.0471g stablizer, 0.0293gEDTA, regulate pH to 7.0 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 35 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 2.4mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 35 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 7h, add the oxygenant and the reductive agent of 0.8mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 25 ℃ of insulations continue reaction 2h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 710mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 34200mPas.
Embodiment 9
In beaker, add 94.8961g deionized water, 47.9634g ammonium sulfate, 24.4144g acrylamide, 5.4543g2-acrylamide-2-methyl propane sulfonic acid, 3.4696g Jia Jibingxisuanyizhi, 8.8696g Macrogol 200 mono acrylic ester, 6.7533g stablizer, 0.0307gEDTA, regulate pH to 6.5 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 30 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.2mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 30 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 7h, add the oxygenant and the reductive agent of 0.4mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 30 ℃ of insulations continue reaction 3h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 640mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 59500mPas.
Embodiment 10
In beaker, add 84.5130g deionized water, 57.5931g ammonium sulfate, 24.7235g acrylamide, 7.2723g2-acrylamide-2-methyl propane sulfonic acid, 2.4783g Jia Jibingxisuanyizhi, 7.7609g Macrogol 200 mono acrylic ester, 7.6023g stablizer, 0.0307gEDTA, regulate pH to 7.5 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 30 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.8mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 30 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 4h, in polymerization system, add the oxygenant and the reductive agent of 0.6mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively, be incubated 35 ℃ and continue reaction 2h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 840mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 50900mPas.
Embodiment 11
In beaker, add 95.7936g deionized water, 48.4184g ammonium sulfate, 24.1054g acrylamide, 7.2723g2-acrylamide-2-methyl propane sulfonic acid, 3.4696g Jia Jibingxisuanyizhi, 7.7609g Macrogol 200 mono acrylic ester, 6.8173g stablizer, 0.0310gEDTA, regulate pH to 6.5 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 35 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 2.4mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 35 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 4h, add the oxygenant and the reductive agent of 0.8mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 35 ℃ of insulations continue reaction 1h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 715mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 22100mPas.
Embodiment 12
In beaker, add 77.3289g deionized water, 53.2300g ammonium sulfate, 26.2687g acrylamide, 3.6362g2-acrylamide-2-methyl propane sulfonic acid, 2.4783g Jia Jibingxisuanyizhi, 6.6522g Macrogol 200 mono acrylic ester, 7.8071g stablizer, 0.0284gEDTA, regulate pH to 6.5 with 40%NaOH, use mulser emulsification even again; Solution is slowly poured into the four-hole boiling flask that stirring rod, logical nitrogen pipe and microthrmometer are housed from beaker, and 18 ℃ of constant temperature are opened and are stirred, 450 rev/mins of stirring velocitys, and logical nitrogen drives oxygen; Behind the 15min, add the oxygenant and the reductive agent of 1.8mL 0.3wt% ammonium persulphate/trolamine initiator system respectively, be incubated 18 ℃ and carry out polyreaction, polymerization system becomes oyster white by translucent, and viscosity increases the back step-down earlier, finally tends towards stability.After polyreaction is carried out 6h, add the oxygenant and the reductive agent of 0.6mL 0.3wt% ammonium persulphate/trolamine initiator system more respectively in polymerization system, 25 ℃ of insulations continue reaction 1h.Finish reaction, obtaining apparent viscosity is the oyster white dispersion liquid of 570mPas.The polymerisate that takes a morsel, with the deionized water dilution, the viscosity of solution becomes earlier and diminishes after big, and the apparent viscosity of the solution of effective content 3wt% is 59500mPas.

Claims (2)

1. the synthetic method of one kind " water Bao Shui " type anionic polyacrylamide emulsion, it is characterized in that, synthesis technique for earlier with inorganic salt, nonionic hydrophilic monomer, anionic monomer, hydrophobic monomer, have surface-active function monomer, stablizer, sequestrant, deionized water and mix, regulate pH to 6.5~7.5, even with mulser emulsification; Logical again nitrogen protection is added initiator at twice at 18-50 ℃, behind the polymerization reaction time 4~7h, carries out the after polymerization reaction, and the reaction times is 1~3h, makes this product emulsion;
Above-mentioned inorganic salt are selected from sodium sulfate, ammonium sulfate or sodium-chlor, and the content of inorganic salt accounts for the 20-30wt% of whole dispersion system;
Above-mentioned nonionic hydrophilic monomer is selected from wherein one or more of acrylamide, hydroxypropyl acrylamide or hydroxyethyl acrylamide; Participate in the 75-85mol% that polymeric nonionic hydrophilic monomer accounts for whole monomer system;
Above-mentioned anionic monomer is selected from wherein one or more of sodium acrylate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, and anionic monomer accounts for the 4-8mol% of whole monomer system;
Above-mentioned hydrophobic monomer is selected from wherein one or more of methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate or butyl methacrylate, and hydrophobic monomer accounts for the 5-9mol% of whole monomer system;
Above-mentioned have surface-active function monomer and be selected from wherein one or more of Macrogol 200 mono acrylic ester, Macrogol 200 monomethacrylates, poly(oxyethylene glycol) 400 mono acrylic ester, poly(oxyethylene glycol) 400 monomethacrylates, has the 6-8mol% that surface-active function monomer accounts for whole monomer system;
Above nonionic hydrophilic monomer, anionic monomer, hydrophobic monomer, have the monomer system that surface-active function monomer mutual group becomes dispersion system, monomer system accounts for the 15-30wt% of whole dispersion system;
Above-mentioned stablizer is an anionic oligomer, this aqueous solution anionic oligomer is formed by anionic monomer and non-ionic monomer copolymerization, anionic monomer is chosen one or more of sodium acrylate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid, and non-ionic monomer is chosen one or more of acrylamide, hydroxypropyl acrylamide, hydroxyethyl acrylamide or N-vinyl pyrrolidone; Stablizer measured limiting viscosity in the NaCl of the 1mol/L aqueous solution is 100-300mL/g, and stabilizing agent dosage accounts for the 15-20wt% of monomer system;
Above-mentioned sequestrant is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate, and the consumption of sequestrant accounts for the 0.012-0.02wt% of whole dispersion system;
Above-mentioned initiator is an oxidation-reduction initiator, or water miscible azo class thermal decomposition initiating; Or the composite initiation system of oxidation-reduction initiator and water miscible azo class thermal decomposition initiating formation; Wherein oxidation-reduction initiator is selected from wherein one or more of ammonium persulphate/sodium bisulfite, Potassium Persulphate/sodium bisulfite or ammonium persulphate/trolamine, water miscible azo class thermal decomposition initiating is selected from wherein one or more of azo-bis-isobutyrate hydrochloride, azo diisopropylamidinateand azoles quinoline hydrochloride or azo two isocyano-valeric acids, and the consumption of initiator is monomeric 0.010-0.024wt%; The use temperature of oxidation-reduction initiator is 18-35 ℃, and the use temperature of water-soluble azo class thermal decomposition initiating is 35-50 ℃, and the use temperature of the composite initiation system that oxidation-reduction initiator and thermal decomposition initiating constitute is 30-45 ℃.
2. according to the synthetic method of the described emulsion of claim 1, it is characterized in that: synthesis technique for earlier with inorganic salt ammonium sulfate, nonionic hydrophilic monomer acrylamide, anionic monomer 2-acrylamide-2-methyl propane sulfonic acid, hydrophobic monomer Jia Jibingxisuanyizhi, have surface-active function monomer Macrogol 200 mono acrylic ester, stablizer sodium acrylate-acrylamide polymer, sequestrant disodium ethylene diamine tetraacetate, deionized water and mix, regulate pH to 6.5~7.0, even with mulser emulsification; Logical again nitrogen protection is added initiator oxidation-reduction system ammonium persulphate/trolamine at twice at 18-35 ℃, behind the polymerization reaction time 5~6h, carries out the after polymerization reaction, and the reaction times is 1.5~2h, makes this product emulsion.
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