CN107325299B - Method for preparing water-in-water type nonionic polyacrylamide - Google Patents
Method for preparing water-in-water type nonionic polyacrylamide Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000000693 micelle Substances 0.000 claims abstract description 15
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000012966 redox initiator Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 235000015110 jellies Nutrition 0.000 claims abstract description 6
- 239000008274 jelly Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000499 gel Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 amidine hydrochloride Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Abstract
The invention relates to a method for preparing water-in-water type nonionic polyacrylamide, which comprises the following steps: (1) preparing acrylamide, low-molecular-weight polyacrylamide, n-butyl alcohol, ammonium sulfate and micelle dispersing agent into solution by using water; (2) adding a chain transfer agent, a water-soluble azo initiator and a redox initiator into the solution prepared in the step (1) in the absence of oxygen to carry out polymerization reaction on acrylamide; (3) adding anhydrous sodium sulphate into the reactant obtained in the step (2), converting the reaction system from jelly into liquid by stirring, and then filtering and removing solid impurities to obtain the water-in-water type nonionic polyacrylamide. The product prepared by the method has the advantages of high content of effective components, low price, high dissolution speed, low insoluble substance, good dispersion effect, storage resistance and the like, and fills the blank of the water-in-water type nonionic polyacrylamide product.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of water-in-water type nonionic polyacrylic ester.
Background
Polyacrylamide is called as an industrial auxiliary agent and is more and more widely applied in various industries. Polyacrylamide is generally classified into 4 types, i.e., a dry powder type, a water-in-oil emulsion type, a water-in-water emulsion type, and an aqueous solution type, depending on the state. In addition, polyacrylamide can be classified into 4 types, i.e., anionic, cationic, nonionic, and zwitterionic, according to its ionic characteristics. Wherein the nonionic type plays an important role in gold ore, nickel ore and sand washing treatment; the speed of dry powder type nonionic dissolution is very slow, and the dissolution time is generally more than 2 hours; the water-in-oil type nonionic has higher cost, and the water solution type is easy to degrade and is not durable to store, so that the application of the water-in-oil type nonionic in certain fields is limited; water-in-water type products have the characteristics of good dispersion, rapid dissolution and low cost, and are increasingly widely used. The technology of cationic water-in-water emulsion is mature, but the price of cationic polymer is high, so that the cost of emulsion is high; chinese patent CN105418839A discloses a preparation method of anionic water-in-water type polyacrylamide, but the method adopts acrylic acid and sodium hydroxide to adjust the pH, and the pH is higher, so that the method is not suitable for the preparation of water-in-water type nonionic polyacrylamide. In addition, in the prior art, acrylamide is proposed as a monomer, ammonium sulfate aqueous solution is proposed as a dispersion medium, azodiisobutyl amidine hydrochloride is proposed as an initiator, polymethacryloxyethyl trimethyl ammonium chloride is proposed as a dispersing agent, and a dispersion polymerization method is adopted to prepare non-ionic polyacrylamide water-in-water emulsion, but the viscosity of polyacrylamide prepared by the method is relatively low, the ammonium sulfate aqueous solution is adopted as the dispersing medium, the dispersion effect is not ideal, the system is easy to form gel, and in addition, the method adopts the polymethacryloxyethyl trimethyl ammonium chloride as the dispersing agent, the reaction cost is high (see: Liu Xiao Bao, Wangwei, Lizhongxian, and the like.
Disclosure of Invention
The invention mainly aims to obtain a water-in-water type nonionic polyacrylamide emulsion product which has high effective component content, low price, high dissolution speed, low insoluble substance, good dispersion effect and storage resistance, and solves one or more problems in the prior art.
The invention provides a method for preparing water-in-water type nonionic polyacrylamide, which comprises the following steps:
(1) solution preparation: preparing acrylamide, low-molecular-weight polyacrylamide, n-butyl alcohol, ammonium sulfate and micelle dispersing agent into solution by using water;
(2) a polymerization reaction step: adding a chain transfer agent, a water-soluble azo initiator and a redox initiator into the solution prepared in the step (1) in the absence of oxygen to carry out polymerization reaction on acrylamide; and
(3) post-treatment: adding anhydrous sodium sulphate into the reactant obtained in the step (2), converting the reaction system from jelly into liquid by stirring, and then filtering and removing solid impurities to obtain the water-in-water type nonionic polyacrylamide.
Preferably, the amounts of the materials are: 400 parts of acrylamide 350-one material, 3-10 parts of low-molecular polyacrylamide, 5-10 parts of n-butanol, 20-40 parts of ammonium sulfate, 2-6 parts of micelle dispersant, 600 parts of water 500-one material, 0.03-0.06 part of chain transfer agent, 0.1-0.5 part of water-soluble azo initiator, 0.08-0.18 part of redox initiator and 5-10 parts of anhydrous sodium sulphate.
Preferably, the method further comprises controlling the reaction temperature to be between 50 and 55 ℃ during the polymerization reaction of step (2).
In particular, the method further comprises a preparation step of low-molecular polyacrylamide carried out before the step (1), the preparation step comprising the following sub-steps:
(a) preparing 100-200 parts by weight of 15 wt% acrylamide solution;
(b) adding 0.1-0.3 part by weight of ammonium persulfate and 3-6 parts by weight of isopropanol into the step (a), heating to 55-60 ℃ after the ammonium persulfate and the isopropanol are completely dissolved, stirring for 4-5 hours, cooling to normal temperature, and discharging to obtain low-molecular polyacrylamide; the viscosity average relative molecular weight of the prepared low molecular polyacrylamide is 100-200 kg/mol.
Preferably, the pH value of the solution in the step (1) is adjusted to 3.5-4; and/or adjusting the temperature of the solution in the step (1) to 15-18 ℃.
Preferably, the micelle dispersing agent is a mixture of 5-8 parts by weight of polyethylene glycol having a number average molecular weight of 6kg/mol, 3-5 parts by weight of xanthan gum and 15-20 parts by weight of water.
Preferably, the chain transfer agent is a mixture of 2: (0.8-1): (7-10) a mixture of sodium benzenesulfonate, n-butanol and water.
Preferably, in the redox initiator, the oxidant is ammonium persulfate, and the reducing agent is sodium bisulfite; and/or the water-soluble azo initiator is azodiisobutyramidine hydrochloride.
Compared with the prior art, the invention at least has the following beneficial effects:
1. the product prepared by the method has the characteristics of low price, good solubility, good dispersion effect, storage resistance, high dissolution speed and the like, can be completely dissolved within 6min, obviously shortens the dissolution time, reduces the energy consumption caused by dissolving the product, improves the production efficiency and reduces the waste.
2. The method of the invention improves the content of the effective components of the product to 35-40%, and greatly reduces the transportation cost.
3. The low molecular polyacrylamide involved in the method plays a role of a stabilizer in the process of forming the water-in-water emulsion, and simultaneously has a certain dispersion effect in the reaction process of the water-in-water emulsion, and the low molecular polyacrylamide and the micelle dispersant can play a synergistic role.
4. The micelle dispersing agent adopted in the method has good dispersing effect, and can overcome the defects of difficult control of polymerization reaction, easy occurrence of sudden aggregation, easy delamination of products, difficult flowing, easy formation of gel and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Specifically, the invention provides a method for preparing water-in-water type nonionic polyacrylamide, which comprises the following steps:
(1) solution preparation: preparing 350-400 parts by weight (for example 350, 360, 370, 380, 390 or 400 parts by weight) of acrylamide, 3-10 parts by weight (for example 3, 4, 5, 6, 7, 8, 9 or 10 parts by weight) of low molecular polyacrylamide, 5-10 parts by weight (for example 5, 6, 7, 8, 9 or 10 parts by weight) of n-butanol, 20-40 parts by weight (for example 20, 25, 30, 35 or 40 parts by weight) of ammonium sulfate, 2-6 parts by weight (for example 2, 3, 4, 5 or 6 parts by weight) of micelle dispersant into a solution by using 500-600 parts by weight (for example 500, 510, 520, 530, 540, 550, 560, 570, 580, 590 or 600 parts by weight) of water, and adjusting the temperature and the pH value of the prepared solution; the water is preferably deionized water, the temperature of the solution is preferably 15-18 ℃ (e.g., 15 ℃, 16 ℃, 17 ℃ or 18 ℃), the pH of the solution is preferably 3.5-4 (e.g., 3.5, 3.6, 3.7, 3.8, 3.9 or 4), and the pH of the solution is adjusted with a weak acid, preferably acetic acid, oxalic acid or phosphoric acid.
(2) A polymerization reaction step: adding 0.03-0.06 part by weight (for example, 0.03, 0.04, 0.05 or 0.06 part by weight) of a chain transfer agent, 0.1-0.5 part by weight (for example, 0.1, 0.2, 0.3, 0.4 or 0.5 part by weight) of a water-soluble azo initiator, and 0.08-0.18 part by weight (for example, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17 or 0.18 part by weight) of a redox initiator to the solution prepared in the step (1) in the absence of oxygen to initiate acrylamide polymerization; during the polymerization, the reaction temperature rises and, according to a preferred embodiment, is controlled between 50 and 55 ℃ by lowering the temperature and continuously stirring during the polymerization. Specifically, when the reaction temperature rises to 55 ℃, the temperature is reduced, the temperature is continuously stirred for heat dissipation, the temperature fluctuation range is controlled to be 50-55 ℃, and the reaction is considered to be finished when the temperature is not increased after the temperature reduction is closed. The oxygen-free condition can be achieved by introducing a rare gas (such as nitrogen, helium or argon) into a reaction device (such as a reaction kettle), and specifically, nitrogen can be introduced into the reaction kettle for 40min to remove oxygen.
(3) Post-treatment: and (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 5-10 parts by weight (such as 5, 6, 7, 8, 9 or 10 parts by weight) of anhydrous sodium sulphate in the step (2), continuously stirring to convert the reaction system from a jelly state to a liquid state, cooling to the normal temperature (such as 25 ℃), and filtering solid residues to obtain the water-in-water type nonionic polyacrylamide.
According to a preferred embodiment, the method further comprises the preparation of low molecular weight polyacrylamide before step (1), comprising the steps of:
(a) preparing 100-200 parts by weight (e.g., 100, 150 or 200 parts by weight) of an acrylamide solution having a concentration of 15 wt%;
(b) adding 0.1-0.3 part by weight (such as 0.1, 0.2 or 0.3 part by weight) of ammonium persulfate and 3-6 parts by weight (3, 4, 5 or 6 parts by weight) of isopropanol into the step (a), heating to 55-60 ℃ after the ammonium persulfate and the isopropanol are completely dissolved, mechanically stirring for 4-5 hours (such as 4 hours, 4.5 hours or 5 hours), cooling to normal temperature, and discharging to prepare the low-molecular polyacrylamide with the viscosity-average relative molecular weight of 100-200 kg/mol.
According to a preferred embodiment, the micelle dispersing agent is a mixture of 5-8 parts by weight (e.g. 5, 6, 7 or 8 parts by weight) of polyethylene glycol having a number average molecular weight of 6kg/mol, 3-5 parts by weight (e.g. 3, 4 or 5 parts by weight) of xanthan gum and 15-20 parts by weight (e.g. 15, 16, 17, 18, 19 or 20 parts by weight) of water.
According to a preferred embodiment, the chain transfer agent is present in a mass ratio of 2: (0.8-1): (7-10) (e.g., 2:0.8:7, 2:0.8:8, 2:0.8:9, 2:0.8:10, 2:0.9:7, 2:0.9:8, 2:0.9:9, 2:0.9:10, 2:1:7, 2:1:8, 2:1:9, or 2:1:10), a mixture of sodium benzenesulfonate, n-butanol, and water.
According to a preferred embodiment, the redox initiator comprises ammonium persulfate, sodium bisulfite and/or azodiisobutymidine hydrochloride.
Example 1
Preparing a solution from 380 parts by weight of acrylamide, 7 parts by weight of low-molecular-weight polyacrylamide, 8 parts by weight of n-butanol, 30 parts by weight of ammonium sulfate and 4 parts by weight of micelle dispersing agent by 590 parts by weight of deionized water, transferring the solution into a reaction kettle, uniformly stirring, adjusting the temperature of the solution to 16 ℃, adjusting the pH value of the solution to 3.5, introducing nitrogen for 40min to remove oxygen, adding 0.03 part by weight of chain transfer agent (a mixture of sodium benzenesulfonate, n-butanol and water in a mass ratio of 2:1: 7), 0.4 part by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of ammonium persulfate and 0.08 part by weight of sodium bisulfite to initiate polymerization, raising the temperature to 55 ℃, starting to cool, and continuously stirring to control the temperature fluctuation range to be 50-55 ℃. And (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 6 parts by weight of anhydrous sodium sulphate, continuously stirring until the viscosity of the system is not reduced any more, converting the reaction system from a jelly state into a liquid state, cooling to normal temperature, and filtering residues to obtain the product, namely the water-in-water type nonionic polyacrylamide.
The product obtained by the process has effective component content of 37.7%, viscosity average relative molecular weight of 14000kg/mol, normal temperature dissolution time of 5min, and insoluble matter content of 0.01%.
Example 2
Preparing a solution from 400 parts by weight of acrylamide, 10 parts by weight of low-molecular-weight polyacrylamide, 7 parts by weight of n-butanol, 40 parts by weight of ammonium sulfate and 5 parts by weight of micelle dispersing agent by 600 parts by weight of deionized water, transferring the solution into a reaction kettle, uniformly stirring, adjusting the temperature of the solution to 16 ℃, adjusting the pH value of the solution to 4, introducing nitrogen for 40min to remove oxygen, adding 0.05 part by weight of chain transfer agent (a mixture of sodium benzenesulfonate, n-butanol and water in a mass ratio of 2:1: 7), 0.35 part by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of ammonium persulfate and 0.08 part by weight of sodium bisulfite to initiate polymerization, raising the temperature to 55 ℃, starting to reduce the temperature, and continuously stirring to control the temperature fluctuation range to be 50-55. And (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 8 parts by weight of anhydrous sodium sulphate, continuously stirring until the viscosity of the system is not reduced, converting the gel state of the reaction system into a liquid state, cooling to normal temperature, and filtering residues to obtain the product, namely the water-in-water type nonionic polyacrylamide.
The product obtained by the process has an effective component content of 38.3%, a viscosity average relative molecular weight of 9500kg/mol, a dissolving time of 5min at normal temperature, and an insoluble content of 0.01%.
Example 3
Preparing a solution from 350 parts by weight of acrylamide, 3 parts by weight of low-molecular-weight polyacrylamide, 5 parts by weight of n-butyl alcohol, 20 parts by weight of ammonium sulfate and 2 parts by weight of micelle dispersing agent by using 500 parts by weight of deionized water, transferring the solution into a reaction kettle, uniformly stirring, adjusting the temperature of the solution to 16 ℃, adjusting the pH value of the solution to 4, introducing nitrogen for 40min to remove oxygen, adding 0.04 part by weight of chain transfer agent (a mixture of sodium benzenesulfonate, n-butyl alcohol and water in a mass ratio of 2:1: 7), 0.45 part by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of ammonium persulfate and 0.08 part by weight of sodium bisulfite to initiate polymerization, raising the temperature to 55 ℃, starting to cool, and continuously stirring to control the temperature fluctuation range to be 50-55. And (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 10 parts by weight of anhydrous sodium sulphate, continuously stirring until the viscosity of the system is not reduced, converting the gel state of the reaction system into a liquid state, cooling to normal temperature, and filtering residues to obtain the product, namely the water-in-water type nonionic polyacrylamide.
The product obtained by the process has an effective component content of 39.7%, a viscosity average relative molecular weight of 11000kg/mol, a dissolving time of 6min at normal temperature, and an insoluble content of 0.01%.
Examples 4-9 were conducted in substantially the same manner as example 1 except as set forth in table 1 below.
Table 1: the raw material formulations and product effects of examples 4-9.
Comparative example 1
Comparative example 1 was prepared substantially the same as example 1, except that:
the pH is different from that of the example 1, the pH value of the comparative example 1 is 6.5, and the specific scheme is as follows:
preparing a solution from 380 parts by weight of acrylamide, 7 parts by weight of low-molecular-weight polyacrylamide, 8 parts by weight of n-butanol, 30 parts by weight of ammonium sulfate and 4 parts by weight of micelle dispersing agent by 590 parts by weight of deionized water, transferring the solution into a reaction kettle, uniformly stirring, adjusting the temperature of the solution to 16 ℃, adjusting the pH value of the solution to 6.5, introducing nitrogen for 40min to remove oxygen, adding 0.03 part by weight of chain transfer agent (a mixture of sodium benzenesulfonate, n-butanol and water in a mass ratio of 2:1: 7), 0.4 part by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of ammonium persulfate and 0.08 part by weight of sodium bisulfite to initiate polymerization, raising the temperature to 55 ℃, starting to cool, and continuously stirring to control the temperature fluctuation range to be 50-55 ℃. And (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 6 parts by weight of anhydrous sodium sulphate, and continuously stirring until the viscosity of the system is not reduced any more, so that the reaction system is converted into a liquid state.
Comparative example 1 has too high viscosity to be in a gel state during the reaction, the dispersibility between polyacrylamide particles is poor during the reaction, and the gel state cannot be transformed into a uniform liquid phase but into a small colloidal particle liquid state after anhydrous sodium sulphate is added.
Comparative example 2
Comparative example 2 was prepared substantially the same as example 1, except that:
in comparative example 2, a polyethylene glycol aqueous solution is directly used as a dispersant, and the specific scheme is as follows:
preparing a solution from 380 parts by weight of acrylamide, 7 parts by weight of low-molecular polyacrylamide, 8 parts by weight of n-butanol, 30 parts by weight of ammonium sulfate and 4 parts by weight of a dispersant (33 wt% of polyethylene glycol aqueous solution with the number average molecular weight of 6 kg/mol), transferring the solution into a reaction kettle, uniformly stirring, adjusting the temperature of the solution to 16 ℃, adjusting the pH value of the solution to 3.5, introducing nitrogen for 40min to remove oxygen, adding 0.03 part by weight of a chain transfer agent (a mixture of sodium benzenesulfonate, n-butanol and water in a mass ratio of 2:1: 7), 0.4 part by weight of azobisisobutyramidine hydrochloride, 0.1 part by weight of ammonium persulfate and 0.08 part by weight of sodium bisulfite to initiate polymerization, increasing the temperature to 55 ℃, starting to reduce the temperature, and continuously controlling the stirring temperature to be within the fluctuation range of 50-55 ℃. And (3) obtaining a colloidal polymer after the reaction temperature does not rise any more, adding 6 parts by weight of anhydrous sodium sulphate, continuously stirring until the viscosity of the system is not reduced any more, converting the reaction system from a jelly state into a liquid state, cooling to normal temperature, and filtering residues to obtain the product, namely the water-in-water type nonionic polyacrylamide.
The product obtained by the process has the effective component content of 37.7 percent, the viscosity-average relative molecular weight of 12000kg/mol, the dissolving time of 5min at normal temperature and the insoluble content of 0.01 percent, the stability of the product obtained by the process is poor, and the phenomenon of emulsion stratification appears after the product is placed for 20 days.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for preparing a water-in-water nonionic polyacrylamide, comprising the steps of:
(1) solution preparation: preparing acrylamide, low-molecular-weight polyacrylamide, n-butyl alcohol, ammonium sulfate and micelle dispersing agent into solution by using water; adjusting the temperature of the prepared solution to 15-18 ℃; adjusting the pH value of the prepared solution to 3.5-4; the micelle dispersing agent is a mixture of 5-8 parts by weight of polyethylene glycol with the number average molecular weight of 6kg/mol, 3-5 parts by weight of xanthan gum and 15-20 parts by weight of water; the viscosity average relative molecular weight of the low molecular polyacrylamide is 100-200 kg/mol;
(2) a polymerization reaction step: adding a chain transfer agent, a water-soluble azo initiator and a redox initiator into the solution prepared in the step (1) in the absence of oxygen to carry out polymerization reaction on acrylamide; the chain transfer agent is prepared from the following components in a mass ratio of 2: (0.8-1): (7-10) a mixture of sodium benzenesulfonate, n-butanol and water;
(3) post-treatment: adding anhydrous sodium sulphate into the reactant obtained in the step (2), converting a reaction system from a jelly state into a liquid state by stirring, and then filtering and removing solid impurities to obtain water-in-water type nonionic polyacrylamide;
wherein the dosage of each material is as follows: 400 parts of acrylamide 350-one material, 3-10 parts of low-molecular polyacrylamide, 5-10 parts of n-butanol, 20-40 parts of ammonium sulfate, 2-6 parts of micelle dispersant, 600 parts of water 500-one material, 0.03-0.06 part of chain transfer agent, 0.1-0.5 part of water-soluble azo initiator, 0.08-0.18 part of redox initiator and 5-10 parts of anhydrous sodium sulphate.
2. The method of claim 1, further comprising controlling the reaction temperature to be between 50-55 ℃ during the polymerization reaction of step (2).
3. The process according to claim 1 or 2, further comprising a step of preparing a low molecular polyacrylamide before step (1), the step of preparing comprising the substeps of:
(a) preparing 100-200 parts by weight of 15 wt% acrylamide solution;
(b) adding 0.1-0.3 part by weight of ammonium persulfate and 3-6 parts by weight of isopropanol into the step (a), heating to 55-60 ℃ after the ammonium persulfate and the isopropanol are completely dissolved, stirring for 4-5 hours, cooling to normal temperature, and discharging to obtain the low-molecular-weight polyacrylamide.
4. The method of claim 1, wherein: the oxidant in the redox initiator is ammonium persulfate, and the reducing agent is sodium bisulfite.
5. The method of claim 1, wherein: the water-soluble azo initiator is azobisisobutyramidine hydrochloride.
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