CN116715807A - Anionic aquatic product in water and preparation method thereof - Google Patents
Anionic aquatic product in water and preparation method thereof Download PDFInfo
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- CN116715807A CN116715807A CN202311009774.6A CN202311009774A CN116715807A CN 116715807 A CN116715807 A CN 116715807A CN 202311009774 A CN202311009774 A CN 202311009774A CN 116715807 A CN116715807 A CN 116715807A
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- 125000000129 anionic group Chemical group 0.000 title claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000007664 blowing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002738 chelating agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- 229920002401 polyacrylamide Polymers 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001741 Ammonium adipate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- -1 adipic acid amine Chemical class 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000019293 ammonium adipate Nutrition 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000012674 dispersion polymerization Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides an anionic water-in-water aquatic product and a preparation method thereof, wherein the preparation method comprises the following steps: adding deionized water, an anionic dispersing agent, a metal ion chelating agent, acrylamide, inorganic salt, an anionic monomer and a stabilizer into a reaction kettle, stirring and dissolving, adjusting the pH value of a system to 6-9, blowing nitrogen for 20-50 minutes, and controlling the initial temperature of the system to 40-45 ℃; step two: after the initial temperature is reached, adding an initiator into a reaction kettle, adding an ageing agent for ageing for 1 hour after the reaction is raised to the highest temperature, adding an alkali substance into the reaction kettle to adjust the pH value of the system to 9-12, and keeping the pH value at the temperature of 60-70 ℃ for 1-3 hours; step three: cooling, adding the post-treatment agent, stirring uniformly, and filtering to obtain the anionic water-in-water aquatic product. The effective content of the anionic water-in-water aquatic product prepared by the method is 10% -30%, and the ionization degree is 20% -70%.
Description
Technical Field
The invention relates to the technical field of polyacrylamide preparation, in particular to an anionic water-in-water aquatic product and a preparation method thereof.
Background
Polyacrylamide (PAM) is known as a 'department assistant' because of its complete variety and wide application in various fields of national economy. The polyacrylamide is mainly polymerized by acrylamide and a comonomer, and the synthesis method mainly comprises the following steps: aqueous solution process, reverse phase suspension process, reverse phase emulsion process and dispersion polymerization process.
The aqueous solution polymerization method is easy to cause oxidative degradation of the polymer in the drying and crushing processes, so that the performance of PAM products is reduced. Dust generated in the crushing process is harmful to the environment and staff. In addition, powdery polyacrylamide has the defects of poor solubility and slow dissolution rate in the using process. These disadvantages limit the range of applications for polyacrylamide and its derivative products. The polyacrylamide prepared by the inverse emulsion method uses a large amount of organic solvent and a certain amount of emulsifier in polymerization, which makes the production cost of the product higher. The emulsifier and the organic solvent have the effect of chain transfer in the polymerization process, so that the high molecular weight polyacrylamide microsphere is difficult to prepare by adopting an emulsion polymerization method. Wherein a large amount of organic solvent can cause secondary pollution in the direct use process. In addition, the residual, difficult-to-remove emulsifiers in the invert emulsion products also affect the properties of the products, which limits their range of applications.
The polyacrylamide prepared by the dispersion polymerization method has the advantages of high molecular weight, high reaction speed, simple polymerization process, convenient operation, environment-friendly synthesis process, low energy consumption and low production cost. In addition, the dispersion polymerization system has the characteristics of low apparent viscosity, convenient heat transfer, quick dissolution of a polymerization product, convenient use and the like. Therefore, the polyacrylamide product prepared by the dispersion polymerization method has wide application prospect. However, due to the characteristics of the dispersion polymerization system, the limitation on the ionic degree of the system is very large, the product with high ionic degree is difficult to achieve, or the stability of the formed product with high ionic degree is relatively poor, the formation of the water-in-water system is not supported, and the requirements of the market on the product with high ionic degree and high stability are not met, so that the water-in-water product with high ionic degree and good stability needs to be developed in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an anionic water-in-water aquatic product and a preparation method thereof, which can prepare the anionic water-in-water aquatic product with high ionization degree and good stability.
To achieve the above and other objects, the present invention is achieved by comprising the following technical solutions: the invention provides a preparation method of an anionic aquatic product in water, which is characterized by comprising the following steps of
Step one: sequentially adding deionized water, an anionic dispersing agent, a metal ion chelating agent, acrylamide, inorganic salt, an anionic monomer and a stabilizer into a reaction kettle, stirring and dissolving, adjusting the pH value of a system to 6-9 by using alkali substances, blowing nitrogen for 20-50 minutes, and controlling the initial temperature of the system at 40-45 ℃;
step two: after the initial temperature is reached, adding an initiator into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding an ageing agent, ageing for 1 hour, adding an alkali substance into the reaction kettle, adjusting the pH value of the system to 9-12, and keeping the system at the temperature of 60-70 ℃ for 1-3 hours;
step three: cooling, adding the post-treatment agent, stirring uniformly, and filtering to obtain the anionic water-in-water aquatic product.
Further, the anionic dispersing agent is one or more of polymerized acrylic acid, polymerized maleic acid, polymerized itaconic acid, polymerized 2-acrylamide-2-methylpropanesulfonic acid, polymerized acrylic acid-maleic acid copolymer, polymerized acrylic acid-itaconic acid copolymer, polymerized acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and polymerized acrylic acid-methacrylic acid copolymer; the viscosity average molecular weight of the anionic dispersing agent is 10-50 ten thousand; the dosage of the anionic dispersing agent accounts for 1.5% -5.0% of the total mass of the anionic aquatic product in water.
Further, the metal ion chelating agent is one or more of sodium citrate, disodium edetate, tetrasodium edetate, sodium gluconate and sodium tripolyphosphate; the dosage of the metal ion chelating agent accounts for 0.01% -0.04% of the total mass of the anionic aquatic product in water.
Further, the inorganic salt is one or more of sodium sulfate, ammonium sulfate, aluminum sulfate, ammonium adipate, sodium chloride and ammonium citrate; the dosage of the inorganic salt accounts for 20% -30% of the total mass of the anionic water-in-water aquatic product.
Further, the anionic monomer is one or more of acrylic acid, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid and maleic acid; the dosage of the anionic monomer accounts for 1% -5% of the total mass of the anionic aquatic product in water.
Further, the stabilizer is one or more of polyethylene glycol, polyvinyl alcohol, starch and methyl cellulose; the dosage of the stabilizer accounts for 0.5% -2.5% of the total mass of the anionic water-in-water aquatic product.
Further, the alkali substance is one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Further, the initiator is one or more of azodiiso Ding Mi hydrochloride, 2' -azo (2-methylpropionamidine) dihydrochloride and azodiisobutyronitrile; the usage amount of the initiator accounts for 0.01% -0.05% of the total mass of the anionic water-in-water aquatic product.
Further, the aging agent is one or more of sodium metabisulfite, sodium bisulphite, azo diiso Ding Mi hydrochloride and 2,2' -azo (2-methylpropionamidine) dihydrochloride, and the usage amount of the aging agent accounts for 0.02% -0.06% of the total mass of the anionic water-in-water aquatic product.
Further, the post-treatment agent is one or more of citric acid, ammonium sulfate, adipic acid amine, acetic acid and glycerin; the dosage of the post-treatment agent accounts for 2.5% -8.0% of the total mass of the anionic water-in-water aquatic product.
The invention also provides an anionic water-in-water product which is characterized by being prepared by adopting the preparation method of the anionic water-in-water product; the mass content of the polyacrylamide in the anionic water-in-water product is 10% -30%, and the ionic degree is 20% -70%, so that the anionic water-in-water product is used in the industries of oil fields, papermaking and water treatment.
Compared with the prior art, the invention has the following beneficial effects:
the invention can overcome the limitation problem of the independent use of the anionic dispersing agent on the ionic degree of the system by using the stabilizing agent and the anionic dispersing agent together, and meanwhile, the stabilizing agent and the anionic dispersing agent also play a synergistic effect, so that a stable anionic water-in-water system can be formed; specifically, the anionic polymer is used as the dispersing agent, so that the whole system can be dispersed in the whole system through the charge repulsion effect, the precipitated high polymer is not easy to aggregate and precipitate through the charge repulsion effect, and certain steric hindrance is formed through the length of a molecular chain of the anionic dispersing agent, and the precipitation aggregation of the high polymer is hindered; simultaneously, glycol, polyvinyl alcohol, starch, methyl cellulose and the like are adopted as stabilizers, and can react with the oligomer through active hydrogen sites to form a graft copolymer, and the graft copolymer is separated out from the system when reaching a certain molecular weight, so that the high molecular polymer can be well dispersed;
2. the invention adopts the post-hydrolysis technology to carry out the post-hydrolysis on the formed anionic water-in-water, the technology can lead the ionic degree of the product to reach 20% -70%, breaks through the limitation of the water-in-water dispersion polymerization on the ionic degree, simultaneously adds the post-treatment agent in the post-hydrolysis process, prevents the product from demulsification or gel phenomenon in the post-hydrolysis process, obtains the product with high ionic degree and good stability, and meets the requirement of the market on the ionic degree in application.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further explain the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified. Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1 ]
Adding deionized water, 2.0% of polymerized acrylic acid with the viscosity average molecular weight of 10 ten thousand, 0.01% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 20% of ammonium sulfate, 1% of acrylic acid, 1% of polymerized ethylene glycol and the like with the total mass into a reaction kettle in sequence, stirring and dissolving, adjusting the pH value of the whole system to 7.1 by using sodium hydroxide, blowing nitrogen for 30 minutes, and controlling the initial temperature of the system to 40-45 ℃;
after the initial temperature reaches 42 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.01 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulphite accounting for 0.06 percent of the total mass, aging for 1 hour, starting adding ammonia water into the reaction kettle, adjusting the pH value of the system to 10, and keeping the pH value at the temperature of 65 ℃ for 1.5 hours;
cooling, adding citric acid accounting for 2.5% of the total mass, uniformly stirring, filtering, discharging to obtain the anionic water-in-water aquatic product A1.
Example 2 ]
Deionized water, 3.0% of polymerized acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer with the viscosity average molecular weight of 25 ten thousand, 0.03% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 25% of ammonium sulfate, 3% of acrylic acid, 1.5% of polymerized ethylene glycol and the like are sequentially added into a reaction kettle for stirring and dissolution, the pH value of the whole system is regulated to about 6.5 by ammonia water, nitrogen blowing is carried out for 30 minutes, and the initial temperature of the system is controlled at 40-45 ℃;
after the initial temperature reaches 45 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.03 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulphite accounting for 0.03 percent of the total mass, aging for 1 hour, starting adding ammonia water into the reaction kettle, adjusting the pH value of the system to 11, and keeping the temperature at 70 ℃ for 2 hours;
cooling, adding acetic acid accounting for 3% of the total mass, stirring uniformly, filtering, discharging to obtain the anionic water-in-water aquatic product A2.
Example 3 ]
Adding deionized water, 4.0% of polymerized acrylic acid-methacrylic acid copolymer with the viscosity average molecular weight of 50 ten thousand, 0.04% of ethylene diamine tetraacetic acid disodium, acrylamide, 20% of ammonium sulfate and 5% of sodium sulfate, 5% of acrylic acid and 2.5% of polyvinyl alcohol into a reaction kettle in sequence, stirring and dissolving, regulating the pH value of the whole system to about 6.8 by ammonia water, blowing nitrogen for 30 minutes, and controlling the initial temperature of the system at 40-45 ℃;
after the initial temperature reaches 43 ℃, adding 2,2' -azo (2-methylpropionamidine) dihydrochloride accounting for 0.05 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium metabisulfite accounting for 0.06 percent of the total mass, aging for 1 hour, starting adding ammonia water into the reaction kettle, adjusting the pH value of the system to 12, and keeping the temperature at 70 ℃ for 3 hours;
cooling, adding acetic acid accounting for 3 percent of the total mass and glycerin accounting for 2 percent of the total mass, uniformly stirring, filtering, and discharging to obtain the anionic water-in-water aquatic product A3.
Comparative example 1 ]
Deionized water, 2.0% of polymerized acrylic acid with the total mass, wherein the viscosity average molecular weight is 10 ten thousand, the total mass is 0.01% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 20% of ammonium sulfate and 1% of acrylic acid, the pH value of the whole system is adjusted to 7.1 by sodium hydroxide, nitrogen is blown for 30 minutes, and the initial temperature of the system is controlled to be 40-45 ℃;
after the initial temperature reaches 42 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.01 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulphite accounting for 0.06 percent of the total mass, aging for 1 hour, starting adding ammonia water into the reaction kettle, adjusting the pH value of the system to 10, and keeping the pH value at the temperature of 65 ℃ for 1.5 hours;
cooling, adding citric acid accounting for 2.5% of the total mass, uniformly stirring, filtering, discharging to obtain the anionic water-in-water product B1.
Comparative example 2 ]
Adding deionized water, 2.0% of polymerized acrylic acid with the viscosity average molecular weight of 10 ten thousand, 0.01% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 20% of ammonium sulfate, 1% of acrylic acid, 1% of polymerized ethylene glycol and the like with the total mass into a reaction kettle in sequence, stirring and dissolving, adjusting the pH value of the whole system to 7.1 by using sodium hydroxide, blowing nitrogen for 30 minutes, and controlling the initial temperature of the system to 40-45 ℃;
after the initial temperature reaches 42 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.01 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulphite accounting for 0.06 percent of the total mass, aging for 1 hour, starting adding ammonia water into the reaction kettle, adjusting the pH value of the system to 10, and keeping the pH value at the temperature of 65 ℃ for 1.5 hours;
cooling, filtering, discharging to obtain the anionic water-in-water aquatic product B2.
Comparative example 3 ]
Adding deionized water, 2.0% of polymerized acrylic acid with the viscosity average molecular weight of 10 ten thousand, 0.01% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 20% of ammonium sulfate, 1% of acrylic acid, 1% of polymerized ethylene glycol and the like with the total mass into a reaction kettle in sequence, stirring and dissolving, adjusting the pH value of the whole system to 7.1 by using sodium hydroxide, blowing nitrogen for 30 minutes, and controlling the initial temperature of the system to 40-45 ℃;
after the initial temperature reaches 42 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.01 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulfite aging agent accounting for 0.06 percent of the total mass, and aging for 1 hour;
cooling, adding citric acid accounting for 2.5% of the total mass, uniformly stirring, filtering, discharging to obtain the anionic water-in-water product B3.
Comparative example 4 ]
Adding deionized water, 2.0% of polymerized acrylic acid with the viscosity average molecular weight of 10 ten thousand, 0.01% of ethylene diamine tetraacetic acid tetrasodium salt, acrylamide, 20% of ammonium sulfate, 7.5% of acrylic acid, 1% of polymerized ethylene glycol and the like with the total mass into a reaction kettle in sequence, stirring and dissolving, adjusting the pH value of the whole system to 7.1 by using sodium hydroxide, blowing nitrogen for 30 minutes, and controlling the initial temperature of the system to 40-45 ℃;
after the initial temperature reaches 42 ℃, adding azo diiso Ding Mi hydrochloride accounting for 0.01 percent of the total mass into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding sodium bisulphite accounting for 0.06 percent of the total mass, and aging for 1 hour;
cooling, adding citric acid accounting for 2.5% of the total mass, uniformly stirring, filtering, discharging, and obtaining the anionic water-in-water product.
< discussion >
1. Summary of reaction Process conditions
The reactions of examples 1 to 3 and comparative examples 1 to 3 were each easily dispersed, the viscosity was increased in the initial course of the reaction, and the final viscosity was decreased with gradual dispersion, so that a water-in-water system could be formed. In comparative example 4, the anionic monomer was relatively high in the reaction process, and the anionic monomer was beyond the scope of the present invention, and the anionic monomer could not be dispersed in the reaction process, the reaction process formed a gel state, and water in water could not be formed by dispersion, and the experiment failed. It has thus been shown that it is not feasible to form anionic water-in-water with high ionic strength simply by increasing the anionic monomer ratio in the system.
2. Discussion of conventional test results for products
The anionic water-in-water products prepared in examples 1-3 and comparative examples 1-3 were respectively tested for ionic strength and molecular weight, and the ionic strength and molecular weight were tested by the national standard method GB17514-08, and the results of the tested products are shown in Table 1:
table 1 results of routine testing of various anionic water-in-water products
，
As can be seen from Table 1, the product A1 prepared in example 1 had a better ionic strength than the product B2 prepared in comparative example 2, which did not employ the post-hydrolysis process; meanwhile, since comparative example 3 was not subjected to pH adjustment and incubation reaction after aging, post-hydrolysis was not finally achieved, resulting in a product B3 having an ionic degree of 13.5, which is far lower than that of product A1 prepared in example 1. Therefore, the ionic degree of the product can be improved by adopting the post-hydrolysis process. In addition, as shown by the measurement results of the ion degrees of the products A1, A2 and A3, the ion degree range can be regulated and controlled according to the alkali addition amount and the reaction time in the reaction process, the ion degree is required to be detected in the middle of the process, and the post-treatment agent is added at any time to stop the hydrolysis so as to control the ion degree in a desired range.
3. Discussion of product stability test results
The anionic water-in-water product emulsions prepared in examples 1-3 and comparative examples 1-3 are equally divided into three parts and are respectively placed at 0 ℃,25 ℃ and 50 ℃ for 8 months of viscosity tracking test, the test method adopts a Brinell digital display viscometer, 10rpm and 25 ℃ for test, and specific test results are shown in table 2 (viscosity units in table are mPa.s):
TABLE 2 stability test results for various anionic aquatic products in water
，
As can be seen from Table 2, the anionic water-in-water emulsion products A1, A2 and A3 prepared according to the process of the present invention have smaller initial viscosity, less change in storage viscosity at different temperatures and good stability. In contrast, the product B1 prepared in comparative example 1 was free from the addition of a stabilizer during the polymerization stage, resulting in the appearance of a paste and delamination during storage of the product; the product B2 prepared in comparative example 2 was post-hydrolyzed without adding a post-treating agent after the hydrolysis was completed, resulting in a very high initial viscosity and a creamy appearance of delamination and gelation in a very short storage time.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of an anionic aquatic product in water is characterized by comprising the following steps of
Step one: sequentially adding deionized water, an anionic dispersing agent, a metal ion chelating agent, acrylamide, inorganic salt, an anionic monomer and a stabilizer into a reaction kettle, stirring and dissolving, adjusting the pH value of a system to 6-9 by using alkali substances, blowing nitrogen for 20-50 minutes, and controlling the initial temperature of the system at 40-45 ℃;
step two: after the initial temperature is reached, adding an initiator into a reaction kettle, waiting for the reaction to rise to the highest temperature, adding an ageing agent, ageing for 1 hour, adding an alkali substance into the reaction kettle, adjusting the pH value of the system to 9-12, and keeping the system at the temperature of 60-70 ℃ for 1-3 hours;
step three: cooling, adding the post-treatment agent, stirring uniformly, and filtering to obtain the anionic water-in-water aquatic product.
2. The method for preparing an anionic aquatic product in water according to claim 1, wherein the anionic dispersant is one or more of polymerized acrylic acid, polymerized maleic acid, polymerized itaconic acid, polymerized 2-acrylamide-2-methylpropanesulfonic acid, polymerized acrylic acid-maleic acid copolymer, polymerized acrylic acid-itaconic acid copolymer, polymerized acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, and polymerized acrylic acid-methacrylic acid copolymer; the viscosity average molecular weight of the anionic dispersing agent is 10-50 ten thousand; the dosage of the anionic dispersing agent accounts for 1.5% -5.0% of the total mass of the anionic aquatic product in water.
3. The method for preparing an anionic aquatic product in water according to claim 1, wherein the metal ion chelating agent is one or more of sodium citrate, disodium edetate, tetrasodium edetate, sodium gluconate, and sodium tripolyphosphate; the dosage of the metal ion chelating agent accounts for 0.01% -0.04% of the total mass of the anionic aquatic product in water.
4. The method for preparing the anionic aquatic product in water according to claim 1, wherein the inorganic salt is one or more of sodium sulfate, ammonium sulfate, aluminum sulfate, ammonium adipate, sodium chloride and ammonium citrate; the dosage of the inorganic salt accounts for 20% -30% of the total mass of the anionic water-in-water aquatic product.
5. The method for preparing the anionic aquatic product in water according to claim 1, wherein the anionic monomer is one or more of acrylic acid, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid and maleic acid; the dosage of the anionic monomer accounts for 1% -5% of the total mass of the anionic aquatic product in water.
6. The method for preparing the anionic aquatic product in water according to claim 1, wherein the stabilizer is one or more of polyethylene glycol, polyvinyl alcohol, starch and methyl cellulose; the dosage of the stabilizer accounts for 0.5% -2.5% of the total mass of the anionic water-in-water aquatic product.
7. The method for preparing the anionic aquatic product in water according to claim 1, wherein the initiator is one or more of azo diiso Ding Mi hydrochloride, 2' -azo (2-methylpropionamidine) dihydrochloride and azo diisobutyronitrile; the usage amount of the initiator accounts for 0.01% -0.05% of the total mass of the anionic water-in-water aquatic product.
8. The method for preparing the anionic water-in-water product according to claim 1, wherein the aging agent is one or more of sodium metabisulfite, sodium bisulphite, azo diiso Ding Mi hydrochloride and 2,2' -azo (2-methylpropionamidine) dihydrochloride, and the usage amount of the aging agent accounts for 0.02% -0.06% of the total mass of the anionic water-in-water product.
9. The method for preparing the anionic aquatic product in water according to claim 1, wherein the post-treatment agent is one or more of citric acid, ammonium sulfate, adipic acid amine, acetic acid and glycerin; the dosage of the post-treatment agent accounts for 2.5% -8.0% of the total mass of the anionic water-in-water aquatic product.
10. An anionic water-in-water product characterized in that it is prepared by the method of any one of claims 1 to 9; the mass content of the polyacrylamide in the anionic water-in-water product is 10% -30%, and the ionic degree is 20% -70%, so that the anionic water-in-water product is used in the industries of oil fields, papermaking and water treatment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649024A (en) * | 2009-08-19 | 2010-02-17 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
| CN104403054A (en) * | 2014-11-27 | 2015-03-11 | 胜利油田胜利化工有限责任公司 | Hydrophobic associated anionic polyacrylamide water-in-water emulsion and preparation method thereof |
| CN104449617A (en) * | 2014-11-26 | 2015-03-25 | 胜利油田胜利化工有限责任公司 | Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof |
| CN105418839A (en) * | 2015-11-17 | 2016-03-23 | 山东诺尔生物科技有限公司 | Preparation method of anion water-in-water type polyacrylamide |
| CN115651120A (en) * | 2022-11-09 | 2023-01-31 | 东营宝莫环境工程有限公司 | Method for preparing efficient instant papermaking dispersant by hydrolysis after copolymerization |
-
2023
- 2023-08-11 CN CN202311009774.6A patent/CN116715807A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649024A (en) * | 2009-08-19 | 2010-02-17 | 中国海洋石油总公司 | Preparation method of water-in-water cationic polyacylamide emulsion |
| CN104449617A (en) * | 2014-11-26 | 2015-03-25 | 胜利油田胜利化工有限责任公司 | Anionic polyacrylamide water-in-water emulsion water shutoff profile control agent, and preparation method and using method thereof |
| CN104403054A (en) * | 2014-11-27 | 2015-03-11 | 胜利油田胜利化工有限责任公司 | Hydrophobic associated anionic polyacrylamide water-in-water emulsion and preparation method thereof |
| CN105418839A (en) * | 2015-11-17 | 2016-03-23 | 山东诺尔生物科技有限公司 | Preparation method of anion water-in-water type polyacrylamide |
| CN115651120A (en) * | 2022-11-09 | 2023-01-31 | 东营宝莫环境工程有限公司 | Method for preparing efficient instant papermaking dispersant by hydrolysis after copolymerization |
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