CN104250341A - Sulfonic acid type polyacrylamide emulsion preparation method - Google Patents
Sulfonic acid type polyacrylamide emulsion preparation method Download PDFInfo
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- CN104250341A CN104250341A CN201310267921.XA CN201310267921A CN104250341A CN 104250341 A CN104250341 A CN 104250341A CN 201310267921 A CN201310267921 A CN 201310267921A CN 104250341 A CN104250341 A CN 104250341A
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Abstract
The present invention discloses a sulfonic acid type polyacrylamide emulsion preparation method, which comprises: (1) mixing an acrylamide monomer, a sulfonic acid type monomer, a chelating agent, an azo initiator, a chain extender, an oxidizing agent and water to form an aqueous solution, and adjusting the pH value of the aqueous solution to 6-10; (2) making an emulsifier and an organic solvent form an oil solution; (3) mixing the aqueous solution and the oil solution to form a water-in-oil emulsion; and (4) deoxidizing the water-in-oil emulsion, and adding a reducing agent so as to sequentially carry out a polymerization reaction on the water-in-oil emulsion at a first temperature and a second temperature, wherein the second temperature is higher than the first temperature, and the chain extender is the compound represented by a formula (I). With the method of the invention, the sulfonic acid type polyacrylamide emulsion with characteristics of high viscosity-average molecular weight of sulfonic acid type polyacrylamide, good long-time storage stability, low residual monomer content, and rapid solubility in water can be prepared. The formula (I) is defined in the instruction.
Description
Technical field
The present invention relates to a kind of preparation method of sulfonic acid type acrylamide emulsion.
Background technology
Polyacrylamide is the general designation of acrylamide monomer water-soluble polymers that homopolymerization or copolymerization prepare under the effect of initiator, can be used as the flow improver in efficient flocculant, thickening material, toughener and liquid.Be mainly used in the industries such as water treatment, paper making additive, oil production, weaving, ore dressing, medicine, agricultural, have the title of " all trades auxiliary agent ".
The mode of production of polyacrylamide mainly contains water solution polymerization process and reversed emulsion polymerization.Water solution polymerization process be certain density acrylamide in aqueous direct polymerization form, its product has the aqueous solution and dry powder two kinds of forms.Polyacrylamide solution viscosity is comparatively large, and the polymer content including effective constituent is few, is not suitable for transport; Polyacrylamide dry powder is that the colloid obtained by aqueous solution polymerization is prepared through operations such as granulation, kneading, drying, pulverizing, complex process, quality product also obviously reduces in last handling process, and dry powder dissolves general needs 2 hours in aqueous, can not meet the special requirement of oil production well.Reversed phase latex of polyacrylamide polymerization process refers to the effect by tensio-active agent, and water miscible acrylamide monomer is dispersed in oil phase and forms emulsification system, is polymerized under the effect of initiator, finally forms stable polyacrylamide emulsion product.Polyacrylamide emulsion product has the advantages that possibility directly uses, dissolution rate fast, molecular weight is easy to control.
At present, high temperature resistance, the 2-of resistance to salt monomer acrylamide-2-methylpro panesulfonic acid (AMPS) and salt modified polyacrylamide thereof are widely used for the industries such as water treatment field, christmas industry, mineral industry, coal washing.The polyacrylamide of AMPS modification is mainly by the particulate species solid that water dissolution polymerization technique obtains, and not only molecular weight is low, and the dissolution rate in water is mostly at 2 hours.
CN102453192A discloses a kind of preparation method of ultra-high molecular weight sulfonic acid type acrylamide, the method is water solution polymerization process, comprise the following steps: the 1st step, a certain amount of 2-acrylamide-2-methylpro panesulfonic acid and acrylamide are added in reaction vessel, add deionized water, be stirred to and dissolve completely; Add alkali, be mixed with solution; In molar ratio, 2-acrylamide-2-methylpro panesulfonic acid: acrylamide=1:0.4-9,2-acrylamide-2-methylpro panesulfonic acid: alkali=1:0.9-1.1; 2nd step, upwards walks in gained solution and adds intercalating agent, azo-initiator and difunctionality superoxide; In mass ratio, 2-acrylamide-2-methylpro panesulfonic acid: intercalating agent=1:0.000001-0.0l, 2-acrylamide-2-methylpro panesulfonic acid: azo-initiator=1:0.000001-0.05,2-acrylamide-2-methylpro panesulfonic acid: difunctionality superoxide=1:0.000001-0.01; 3rd step is 4-13 by acid or above-mentioned alkali adjustment pH value of reaction system; 4th step, adds a certain amount of deionized water, makes in reaction system total mass, and the quality of 2-acrylamide-2-methylpro panesulfonic acid and acrylamide two kinds of monomers is 15%-40%; Control temperature of reaction system at 0 DEG C-20 DEG C, logical nitrogen deoxygenation added reductive agent after at least 10 minutes; In mass ratio, 2-acrylamide-2-methylpro panesulfonic acid: reductive agent=1:0.0000001-0.05,5th step, by airtight for above-mentioned reaction vessel, react after at least 2 hours, the gum-like product of gained is taken out, through cutting, drying, granulation, screening, obtains ultra-high molecular weight sulfonic acid type acrylamide product.Though the sulfonic acid type acrylamide of the method synthesis has higher molecular weight, in water, dissolution rate is comparatively slow, uses inconvenience.
CN1908026A discloses a kind of preparation method of acrylamide crosslinking copolymer emulsion, it is characterized in that content is the W/W accounting for emulsion gross weight and represents: A, under normal temperature and pressure whipped state, by 5-15% acrylamide and 19-34%2-acrylamide-2-methylpro panesulfonic acid water-soluble after add 0.05-0.5 ‰ cross-linking monomer, and 0.04-0.3 ‰ intercalating agent, then with adding alkaline assistant adjust ph to 5.0-9.0; B, under normal temperature and pressure whipped state, to the oil-phase solution of external phase add 1.6-3.5% water-in-oil type emulsifier dissolve; C, by solution A and B solution mixing after, use clarifixator homogeneous; D, C products therefrom is added 0.02-0.2 ‰ oxygenant, then pass into rare gas element and get rid of oxygen wherein; E, at low temperatures, 0.04-0.4 ‰ reductive agent is slowly added to D product, control whole dropping process reaction temperature and maintain normal temperature; F, in E product, add 0.04-0.4% oxygenant; G, F product added to the reaction of 0.2-2.0 ‰ reductive agent; H, at low temperatures, 2.5-5.0% oil-water emulsifiers is slowly added to G product, filters after reaction, namely obtain product emulsion.The method adopts inverse emulsion polymerization method by adding linking agent synthesis of acrylamide crosslinking copolymer emulsion, but polymkeric substance causes insolubles content in the aqueous solution higher due to the reason of linking agent, affects quality product.
Summary of the invention
The object of the invention is the preparation method in order to provide a kind of new sulfonic acid type acrylamide emulsion.The sulfonic acid type acrylamide emulsion obtained by the method not only in emulsion sulfonic acid type acrylamide there is higher viscosity-average molecular weight, and the extended storage stability of emulsion is good, the lower and emulsion of the content of residual monomer has the rapidly-soluble ability with water in emulsion.
To achieve these goals, the invention provides a kind of preparation method of sulfonic acid type acrylamide emulsion, wherein, the method comprises: acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, chainextender, oxygenant and water are mixed to form the aqueous solution by (1), and regulates the pH value of the aqueous solution to be 7-9; (2) emulsifying agent and organic solvent are formed oil solution; (3) the described aqueous solution is mixed to form water-in-oil emulsion with described oil solution; (4) by after described water-in-oil emulsion deoxygenation, add reductive agent, make water-in-oil emulsion at the first temperature and the second temperature, carry out polyreaction successively, described second temperature is higher than described first temperature; Wherein, described chainextender is the compound shown in formula (1):
Formula (1)
Wherein, the alkylidene group of R to be carbonatoms be 1-6 or carbonatoms are the alkylidene group of the hydroxyl of 1-6.
Pass through technique scheme, the present invention mainly utilizes above-mentioned chainextender to coordinate in water-in-oil emulsion polymerization system with redox initiation system (initiator system be made up of Oxidizing and Reducing Agents), and the viscosity-average molecular weight preparing sulfonic acid type acrylamide is higher, extended storage stability good, the content of residual monomer is lower and have the sulfonic acid type acrylamide emulsion with water rapid solution ability.The sulfonic acid type acrylamide emulsion prepared by method provided by the invention, the viscosity-average molecular weight of the sulfonic acid type acrylamide in product emulsion can reach 2,800 ten thousand; Product emulsion is not stratified through centrifugal 10 minutes of 5000rpm, normal temperature place 12 months not stratified; In product emulsion, the content of residual monomer is lower than 0.05 % by weight; In addition, product emulsion is dissolved with the concentration of 0.5 % by weight in deionized water, can dissolve completely in 3 minutes.
Under preferable case of the present invention, when the hydrophile-lipophile balance value of described emulsifying agent is 5-8, more preferably described hydrophile-lipophile balance value is that the emulsifying agent of 5-8 is mixed to get by water-in-oil type emulsifier and oil-in-water emulsifiers two kinds, particularly preferably hydrophile-lipophile balance value is the emulsifying agent of 5-8 when being the mixture of sorbitan oleate and sorbitan monooleate Soxylat A 25-7, is conducive to obtaining the better sulfonic acid type acrylamide emulsion of extended storage stability by method provided by the invention.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of sulfonic acid type acrylamide emulsion, wherein, the method comprises: acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, chainextender, oxygenant and water are mixed to form the aqueous solution by (1), and regulates the pH value of the aqueous solution to be 7-9; (2) emulsifying agent and organic solvent are formed oil solution; (3) the described aqueous solution is mixed to form water-in-oil emulsion with described oil solution; (4) by after described water-in-oil emulsion deoxygenation, add reductive agent, make water-in-oil emulsion at the first temperature and the second temperature, carry out polyreaction successively, described second temperature is higher than described first temperature; Wherein, described chainextender is the compound shown in formula (1):
Formula (1)
Wherein, the alkylidene group of R to be carbonatoms be 1-6 or carbonatoms are the alkylidene group of the hydroxyl of 1-6.
Under preferable case, R can be methylene radical, ethylidene, propylidene or 2-hydroxypropyl.Under most preferred case, R is ethylidene, propylidene or 2-hydroxypropyl.Described chainextender can be preferably in 2-cyclohexylamino ethyl sulfonic acid, 3-(Cyclohexylamino)-2-hydroxyl-1-propanesulfonic acid and 3-cyclohexylamino propanesulfonic acid one or more, be more preferably 2-cyclohexylamino ethyl sulfonic acid.
The present inventor finds under study for action, adopt above-mentioned chainextender and redox initiation system with the use of, the viscosity-average molecular weight that can be conducive to obtaining sulfonic acid type acrylamide is higher, extended storage stability good, the content of residual monomer is lower and have the sulfonic acid type acrylamide emulsion with water rapid solution ability.
In step of the present invention (1), as long as mixed with acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, oxygenant and water by chainextender, the viscosity-average molecular weight that the consumption of acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, chainextender, oxygenant and water can carry out selecting can be conducive to obtaining sulfonic acid type acrylamide according to consumption well known by persons skilled in the art is higher, extended storage stability good, the content of residual monomer is lower and have the sulfonic acid type acrylamide emulsion with water rapid solution ability.But in order to better realize object of the present invention, under preferable case, relative to the acrylamide monomer of 100 weight parts, the consumption of sulfonic acid type monomer is 20-200 weight part; The consumption of sequestrant is 0.001-5 weight part; The consumption of azo-initiator is 0.01-1 weight part; The consumption of chainextender is 0.001-1 weight part; The consumption of oxygenant is 0.001-0.5 weight part; The consumption of water is 50-300 weight part.More preferably in situation, relative to the acrylamide monomer of 100 weight parts, the consumption of sulfonic acid type monomer is 50-150 weight part; The consumption of sequestrant is 0.02-0.2 weight part; The consumption of azo-initiator is 0.05-0.5 weight part; The consumption of chainextender is 0.01-0.4 weight part; The consumption of oxygenant is 0.01-0.2 weight part; The consumption of water is 80-200 weight part.
In the present invention, described acrylamide monomer can be any one acrylamide monomer well known in the art, and the present invention does not specially require.Under preferable case, described acrylamide monomer can be selected from acrylamide, Methacrylamide, N, N-DMAA, N, one or more in N-acrylamide, NIPA, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, are more preferably acrylamide.
In the present invention, described sulfonic acid type monomer can be any one sulfonic acid type monomer well known in the art, and the present invention does not specially require.Under preferable case, described sulfonic acid type monomer can be selected from 2-acrylamide-2-methylpro panesulfonic acid, allyl sulphonic acid and styrene sulfonic acid one or more, be more preferably 2-acrylamide-2-methylpro panesulfonic acid.
In the present invention, described sequestrant can be any one sequestrant well known in the art.Under preferable case, described sequestrant be selected from disodium ethylene diamine tetraacetate (EDTA), Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic one or more, be more preferably disodium ethylene diamine tetraacetate and/or Citrate trianion.The one that described Citrate trianion can be selected from Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate is the more planted.
In the present invention, described azo-initiator can be any one azo-initiator well known in the art.Under preferable case, described azo-initiator can be selected from Diisopropyl azodicarboxylate, 2,2 '-azo diisobutyl amidine hydrochloride and 2, one or more in 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride], be more preferably 2,2 '-azo diisobutyl amidine hydrochloride and/or 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride.。
Described oxygenant is can be any one oxygenant well known in the art.Under preferable case, described oxygenant be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide one or more, more preferably ammonium persulphate.
In the present invention, the order of acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, chainextender, oxygenant and water mixing does not specially require.Under preferable case, first acrylamide monomer, sulfonic acid type monomer and water are mixed, then its pH is regulated to be 7-9 with alkali, add sequestrant, azo-initiator, chainextender and oxygenant again and form the aqueous solution, be conducive to obtaining more stable emulsion, and be conducive to obtaining the higher sulfonic acid type acrylamide of viscosity-average molecular weight.Described alkali can be mineral alkali or organic amine compound, as being selected from least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, thanomin and trolamine, is preferably sodium hydroxide.Described alkali can add with its solid form and also can add with its aqueous solution form.The present invention preferably adds with the aqueous solution form of alkali.Because the pH value of the aqueous solution of sequestrant, azo-initiator, chainextender and oxygenant is close to 7, and the amount of the sequestrant added, azo-initiator, chainextender and oxygenant is fewer, less on the impact of the pH value of the solution that acrylamide monomer, sulfonic acid type monomer and water are mixed to get, thus think add sequestrant, azo-initiator, chainextender and oxygenant again after the pH value of solution that is mixed to get of the pH value of the aqueous solution that formed and acrylamide monomer, sulfonic acid type monomer and water close.
In step of the present invention (2), the consumption of emulsifying agent and organic solvent does not specially require, as long as can form oil solution.Under preferable case, relative to the acrylamide monomer of 100 weight parts, the consumption of organic solvent is 50-200 weight part; The consumption of emulsifying agent is 5-20 weight part.More preferably in situation, relative to the acrylamide monomer of 100 weight parts, the consumption of organic solvent is 90-150 weight part; The consumption of emulsifying agent is 8-15 weight part.
In the present invention, described emulsifying agent can be any one nonionic emulsifying agent well known by persons skilled in the art.Can be such as one or more in sorbitan oleate (Span-80), sorbitan monooleate Soxylat A 25-7 (Tween-80), alkylphenol polyoxyethylene, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether.Under preferable case, the emulsifying agent of described emulsifying agent to be hydrophile-lipophile balance value be 5-8.
But, the present inventor is surprised to find that through a large amount of experiments, when the emulsifying agent that hydrophile-lipophile balance value is 5-8 is the mixture of water-in-oil type emulsifier and oil-in-water emulsifiers, compared with the emulsifying agent as hydrophile-lipophile balance value being 5-8 with independent a kind of water-in-oil type emulsifier, the permanent stability of the sulfonic acid type acrylamide emulsion obtained are better.More preferably, in situation, when described emulsifying agent is the mixture of sorbitan oleate and sorbitan monooleate Soxylat A 25-7, be more conducive to obtaining the good sulfonic acid type acrylamide emulsion of permanent stability.
When the hydrophile-lipophile balance value meeting emulsifying agent is 5-8, the weight ratio of described water-in-oil type emulsifier and oil-in-water emulsifiers is preferably 10-1:1, when being more preferably 3-5:1, being particularly conducive to and obtaining the better sulfonic acid type acrylamide emulsion of permanent stability.
Under most preferred case, the mixture of described hydrophile-lipophile balance value to be the emulsifying agent of 5-8 be sorbitan oleate and sorbitan monooleate Soxylat A 25-7, and the weight ratio of the two is preferably 10-1:1, when being more preferably 3-5:1, the permanent stability of sulfonic acid type acrylamide emulsion can be improved further.
When the emulsifying agent that described hydrophile-lipophile balance value is 5-8 is the mixture of water-in-oil type emulsifier and oil-in-water emulsifiers, emulsifying agent and the order by merging of organic solvent are not necessarily defined as first water-in-oil type emulsifier and oil-in-water emulsifiers to be mixed and mix with organic solvent.Water-in-oil type emulsifier, oil-in-water emulsifiers and organic solvent can mix with random order, as long as can ensure that water-in-oil type emulsifier and the mixed hydrophile-lipophile balance value of oil-in-water emulsifiers are 5-8.
In the present invention, described organic solvent can be any one organic solvent well known by persons skilled in the art, and the present invention does not specially require.Under preferable case, described organic solvent can be selected from toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane and isoparaffin one or more, also can be selected from gasoline, kerosene and white oil one or more; One or more more preferably in toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline, kerosene and white oil; Be particularly preferably isoparaffin and/or white oil; Particularly be preferably boiling point higher than 150 DEG C, the flash-point isoparaffin and/or the white oil that are greater than 60 DEG C.
The described aqueous solution does not limit with the order of addition that mixes of described oil solution, and can add in the described aqueous solution by described oil solution, also the described aqueous solution can be added in described oil solution, the present invention does not specially require.Under preferable case, the described aqueous solution is added in described oil solution and mixes.Hybrid mode the present invention of the described aqueous solution and described oil solution does not also specially require, as long as the two mixing can form stable water-in-oil emulsion (the stable water-in-oil emulsion described in the present invention refers to monomer solution under the effect of emulsifying agent to be disperseed in organic solvent with short grained form equably).Under preferable case, described oil solution and the described aqueous solution be blended in high speed shear emulsifying effect under carry out, to form stable water-in-oil emulsion.
In the present invention, in step (4), the first temperature and the second temperature can be polymeric reaction temperatures well known by persons skilled in the art.Under preferable case, described first temperature can be 10-35 DEG C, and described second temperature can be 40-60 DEG C.
According to the present invention, water-in-oil emulsion is made at the first temperature and the second temperature, to carry out polyreaction successively, as long as the second temperature can be conducive to realizing object of the present invention than the first temperature height.Under preferable case, described second temperature can high 5-40 DEG C than described first temperature, is conducive to obtaining the less sulfonic acid type acrylamide emulsion of residual monomer.
The time of described polyreaction also can be selected according to the scope of well known to a person skilled in the art, the present invention does not specially require.Under preferable case, carrying out polymerization reaction time is at a first temperature 4-8 hour; The time of carrying out polyreaction is at the second temperature 1-4 hour.
In step of the present invention (4), the consumption of described reductive agent can according to well known to a person skilled in the art that consumption is selected, and the present invention does not specially require.Under preferable case, relative to the acrylamide monomer of 100 weight parts, the consumption of described reductive agent is 0.001-2 weight part, is preferably 0.01-0.2 weight part.Described reductive agent can be any one reductive agent well known in the art.Under preferable case, described reductive agent can be selected from sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate and vat powder one or more, be preferably sodium bisulfite.
In the present invention, Oxidizing and Reducing Agents forms redox initiation system.Wherein, the usage ratio of Oxidizing and Reducing Agents can be selected according to scope well known in the art, and preferably, the weight ratio of described reductive agent and oxygenant is 1:1-3; Be preferably 1:1-2.
In the present invention, in step (4), the mode of described water-in-oil emulsion deoxygenation can be adopted any one mode well known by persons skilled in the art, such as, pass into rare gas element deoxygenation.Described rare gas element can be any one rare gas element well known in the art, is preferably nitrogen.
In the present invention, after the polyreaction that the method is also included in step (4) terminates, add the phase inversion agent accounting for sulfonic acid type acrylamide emulsion 2-3.5 % by weight, to make gained sulfonic acid type acrylamide emulsion rapid solution in water.Described phase inversion agent can be any one phase inversion agent well known in the art.Under preferable case, described phase inversion agent can be selected from polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether one or more.More preferably in situation, described phase inversion agent can be selected from polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7 and isomerous tridecanol polyoxyethylene ether one or more.
The sulfonic acid type acrylamide emulsion prepared by method provided by the invention, the viscosity-average molecular weight of the sulfonic acid type acrylamide in product emulsion can reach 2,800 ten thousand; Product emulsion is not stratified through centrifugal 10 minutes of 5000rpm, normal temperature place 12 months not stratified; In product emulsion, the content of residual monomer is lower than 0.05 % by weight; In addition, product emulsion is dissolved with the concentration of 0.5 % by weight in deionized water, can dissolve completely in 3 minutes.
Adopt sulfonic acid type acrylamide emulsion prepared by method of the present invention, can use as flocculation agent or discoloring agent at water treatment field; Use as tackifier, flow improver, adjuvant, fluid loss agent, viscosity-depression agent or coating agent in christmas industry; Use as flocculation agent in mineral industry; As uses such as flocculation agents in coal washing industry.During application, the aqueous solution that obtained sulfonic acid type acrylamide emulsion can be diluted with water to as required lower concentration uses.
By the following examples the specific embodiment of the present invention is described in detail.
Intrinsic viscosity measures according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M
v=([η]/K)
1 α, wherein K=4.5 × 10
-3, α=0.80 calculates;
The dissolution time testing method of sulfonic acid type acrylamide emulsion is: joined by 200mL deionized water in 250mL beaker, beaker center is placed on by being equipped with the 3-blade screw paddle mechanical stirrer of 4.5cm diameter, blade pitch beaker bottom 1cm, agitator stirs with the speed of 500rpm to produce eddy current.The electrode of 307A type electric conductivity instrument is inserted into below eddy current liquid level.Use syringe in eddy current, add 1mL sulfonic acid type acrylamide product emulsion fast, measure specific conductivity change curve in time, the time that the flex point of conductance-time curve is corresponding is the dissolution time of emulsion;
In sulfonic acid type acrylamide emulsion, residual monomer content measures according to GB/T22312-2008 plastics polyacrylamide Residual acrylamide content assaying method.
Unless specifically indicated, the reagent used in embodiment and comparative example is commercially available product, and identical rule of origin is identical.
Embodiment 1
At 20 DEG C, by 80g deionized water, 100g acrylamide, 50g2-acrylamide-2-methylpro panesulfonic acid joins in 1000mL beaker, stirs, and then slowly adds the pH value to 7 of the aqueous sodium hydroxide solution adjustment aqueous solution of 50 % by weight.Then in beaker, add 0.02g disodium ethylene diamine tetraacetate, add 0.01g chainextender 2-cyclohexylamino ethyl sulfonic acid, add 0.01g ammonium persulphate, add 0.05g azo diisobutyl and narrow hydrochloride.
Mixed with 2g Tween-80 by 6g Span-80, the hydrophile-lipophile balance value of gained blending emulsifiers is 6.98, then blending emulsifiers and 90g white oil (boiling range is 200-250 DEG C, and flash-point is 80 DEG C) is dissolved completely and make oil solution.
The above-mentioned aqueous solution is joined in oil solution, with high speed shear dispersion and emulsion device emulsification 1min, obtains stable oyster white reversed-phase emulsion.Be the nitrogen deoxygenation of 400mL/min after 30 minutes with flow, the aqueous solution of sodium bisulfite 1.0g of 1 % by weight joined in emulsion gradually, controls emulsion temperature and be no more than 35 DEG C, react after 4 hours and be warming up to 50 DEG C of continuation reactions 1 hour.Cool to room temperature adds 7g alkylphenol polyoxyethylene op-10, namely obtains sulfonic acid type acrylamide emulsion with 80 order filter-cloth filterings.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.5 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 2,450 ten thousand, and the content of residual monomer is 0.04 % by weight.
Comparative example 1
Sulfonic acid type acrylamide emulsion is prepared, unlike not adding chainextender 2-cyclohexylamino ethyl sulfonic acid according to the method for embodiment 1.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 15 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 8,200,000, and the content of residual monomer is 0.07 % by weight.
Embodiment 2
At 25 DEG C, by 200g deionized water, 100g acrylamide, 150g2-acrylamide-2-methylpro panesulfonic acid joins in 1000mL beaker, stirs, and then slowly adds the pH value to 8 that 50 % by weight aqueous sodium hydroxide solutions regulate the aqueous solution.。Then in beaker, add 0.2g disodium ethylene diamine tetraacetate, add 0.2g chainextender 3-(Cyclohexylamino)-2-hydroxyl-1-propanesulfonic acid, add 0.2g ammonium persulphate, add 0.5g azo diisobutyl and narrow hydrochloride.
Mixed with 2.5g Tween-80 by 12.5g Span-80, the hydrophile-lipophile balance value of gained blending emulsifiers is 6.08, then blending emulsifiers and 150g white oil (boiling point is boiling range is 240-280 DEG C, and flash-point is 100 DEG C) is dissolved completely and make oil solution.
The above-mentioned aqueous solution is joined in oil solution, with high speed shear dispersion and emulsion device emulsification 1min, obtains stable oyster white reversed-phase emulsion.Be 400mL/min nitrogen deoxygenation after 30 minutes with flow, 10 % by weight aqueous solution of sodium bisulfite 1.0g joined in emulsion gradually, controls emulsion temperature and be no more than 35 DEG C, react after 8 hours and be warming up to 60 DEG C of continuation reactions 4 hours.Cool to room temperature adds 20g alkylphenol polyoxyethylene op-10, namely obtains sulfonic acid type acrylamide emulsion with 80 order filter-cloth filterings.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.8 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 2,660 ten thousand, and the content of residual monomer is 0.02 % by weight.
Embodiment 3
At 15 DEG C, by 120g deionized water, 100g acrylamide, 100g2-acrylamide-2-methylpro panesulfonic acid joins in 1000mL beaker, stirs, and then slowly adds the pH value to 7 of the aqueous sodium hydroxide solution adjustment aqueous solution of 50 % by weight.Then in beaker, add 0.1g disodium ethylene diamine tetraacetate, add 0.4g chainextender 3-cyclohexylamino propanesulfonic acid, add 0.1g ammonium persulphate, add 0.2g azo diisobutyl and narrow hydrochloride.
Mixed by 9.6gSpan-80 and 2.4gTween-80, the hydrophile-lipophile balance value of gained blending emulsifiers is 5.58, then blending emulsifiers and 120g white oil (boiling point is boiling range is 220-255 DEG C, and flash-point is 80 DEG C) is dissolved completely and make oil solution.
The above-mentioned aqueous solution is joined in oil solution, with high speed shear dispersion and emulsion device emulsification 1min, obtains stable oyster white reversed-phase emulsion.Be that the deoxygenation of 400mL/min nitrogen is after 30 minutes with flow, 10 % by weight aqueous solution of sodium bisulfite 1.0g are joined in emulsion gradually, control emulsion temperature and be no more than 35 DEG C, react after 6 hours and be warming up to 50 DEG C of continuation reactions 2 hours, cool to room temperature adds 12.5g alkylphenol polyoxyethylene op-10, namely obtains sulfonic acid type acrylamide emulsion with 80 order filter-cloth filterings.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 1.8 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 2,820 ten thousand, and the content of residual monomer is 0.01 % by weight.
Embodiment 4
At 25 DEG C, by 50g deionized water, 100g acrylamide, 20g2-acrylamide-2-methylpro panesulfonic acid joins in 500mL beaker, stirs, and then slowly adds the pH value to 9 of the aqueous sodium hydroxide solution adjustment aqueous solution of 50 % by weight.Then in beaker, add 0.5g disodium ethylene diamine tetraacetate, add 1g chainextender 2-cyclohexylamino ethyl sulfonic acid, add 0.5g ammonium persulphate, add 0.8g azo diisobutyl and narrow hydrochloride.
Mixed by 17.5gSpan-80 and 2.5gTween-80, the hydrophile-lipophile balance value of gained blending emulsifiers is 7.87, then blending emulsifiers and 200g white oil (boiling point is boiling range is 220-255 DEG C, and flash-point is 80 DEG C) is dissolved completely and make oil solution.
The above-mentioned aqueous solution is joined in oil solution, with high speed shear dispersion and emulsion device emulsification 1min, obtains stable oyster white reversed-phase emulsion.Be the nitrogen deoxygenation of 400mL/min after 30 minutes with flow, 10 % by weight aqueous solution of sodium bisulfite 2g joined in emulsion gradually, controls emulsion temperature and be no more than 35 DEG C, react after 6 hours and be warming up to 40 DEG C of continuation reactions 2 hours.Cool to room temperature adds 8g alkylphenol polyoxyethylene op-10, namely obtains sulfonic acid type acrylamide emulsion with 80 order filter-cloth filterings.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 3 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 1,450 ten thousand, and the content of residual monomer is 0.05 % by weight.
Embodiment 5
Prepare sulfonic acid type acrylamide emulsion according to the method for embodiment 1, the consumption unlike chainextender 2-cyclohexylamino ethyl sulfonic acid is 0.0005g.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.1 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 9,350,000, and the content of residual monomer is 0.05 % by weight.
Embodiment 6
Prepare sulfonic acid type acrylamide emulsion according to the method for embodiment 1, replace 2g Tween-80 unlike with 2g Tween-40, the hydrophile-lipophile balance value of gained blending emulsifiers is 7.12.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.8 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 1,150 ten thousand, and the content of residual monomer is 0.05 % by weight.
Embodiment 7
Prepare sulfonic acid type acrylamide emulsion according to the method for embodiment 1, replace 6gSpan-80 and 2gTween-80 unlike with 8g Span-80, the hydrophile-lipophile balance value of gained blending emulsifiers is 6.7.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 3 minutes; This emulsion is not stratified by the centrifuge of 5000rpm 10 minutes, at room temperature leave standstill 12 months not stratified; In this emulsion, the viscosity-average molecular weight of sulfonic acid type acrylamide is 1,060 ten thousand, and the content of residual monomer is 0.05 % by weight.
Can be found out by embodiment 1-7 and comparative example 1, adopt method provided by the invention, the viscosity-average molecular weight can preparing sulfonic acid type acrylamide is higher, extended storage stability better, the content of residual monomer is lower and have the sulfonic acid type acrylamide emulsion with water rapid solution ability.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. a preparation method for sulfonic acid type acrylamide emulsion, is characterized in that, the method comprises:
(1) acrylamide monomer, sulfonic acid type monomer, sequestrant, azo-initiator, chainextender, oxygenant and water are mixed to form the aqueous solution, and regulate the pH value of the aqueous solution to be 7-9;
(2) emulsifying agent and organic solvent are formed oil solution;
(3) the described aqueous solution is mixed to form water-in-oil emulsion with described oil solution;
(4) by after described water-in-oil emulsion deoxygenation, add reductive agent, make water-in-oil emulsion at the first temperature and the second temperature, carry out polyreaction successively, described second temperature is higher than described first temperature;
Wherein, described chainextender is the compound shown in formula (1):
Formula (1)
Wherein, the alkylidene group of R to be carbonatoms be 1-6 or carbonatoms are the alkylidene group of the hydroxyl of 1-6.
2. method according to claim 1, wherein, in step (1), relative to the acrylamide monomer of 100 weight parts, the consumption of sulfonic acid type monomer is 20-200 weight part; The consumption of sequestrant is 0.001-5 weight part; The consumption of azo-initiator is 0.01-1 weight part; The consumption of chainextender is 0.001-1 weight part; The consumption of oxygenant is 0.001-0.5 weight part; The consumption of water is 50-300 weight part.
3. method according to claim 2, wherein, relative to the acrylamide monomer of 100 weight parts, the consumption of sulfonic acid type monomer is 50-150 weight part; The consumption of sequestrant is 0.02-0.2 weight part; The consumption of azo-initiator is 0.05-0.5 weight part; The consumption of chainextender is 0.01-0.4 weight part; The consumption of oxygenant is 0.01-0.2 weight part; The consumption of water is 80-200 weight part.
4. according to the method in claim 1-3 described in any one, wherein, described acrylamide monomer is selected from acrylamide, Methacrylamide, N, one or more in N-DMAA, N, N-acrylamide, NIPA, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide; Described sulfonic acid type monomer be selected from 2-acrylamide-2-methylpro panesulfonic acid, allyl sulphonic acid and styrene sulfonic acid one or more; Described sequestrant be selected from disodium ethylene diamine tetraacetate, Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic one or more; Described azo-initiator is selected from Diisopropyl azodicarboxylate, 2, one or more in 2 '-azo diisobutyl amidine hydrochloride and 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride.
5. method according to claim 1, wherein, in step (2), relative to the acrylamide monomer of 100 weight parts, the consumption of organic solvent is 50-200 weight part; The consumption of emulsifying agent is 5-20 weight part.
6. method according to claim 1 or 5, wherein, the emulsifying agent of described emulsifying agent to be hydrophile-lipophile balance value be 5-8.
7. method according to claim 6, wherein, described emulsifying agent is the mixture of water-in-oil type emulsifier and oil-in-water emulsifiers.
8. method according to claim 7, wherein, described emulsifying agent is the mixture of sorbitan oleate and sorbitan monooleate Soxylat A 25-7.
9. method according to claim 7, wherein, the weight ratio of described water-in-oil type emulsifier and described oil-in-water emulsifiers is 10-1:1.
10. method according to claim 1, wherein, described organic solvent be selected from toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline, kerosene and white oil one or more.
11. methods according to claim 1, wherein, in step (4), described first temperature is 10-35 DEG C, and described second temperature is 40-60 DEG C, and described second temperature is than described first temperature height 5-40 DEG C.
12. methods according to claim 1, wherein, in step (4), relative to the acrylamide monomer of 100 weight parts, the consumption of described reductive agent is 0.001-2 weight part; Described reductive agent be selected from sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate and vat powder one or more.
13. methods according to claim 1, wherein, add the phase inversion agent accounting for sulfonic acid type acrylamide emulsion 2-3.5 % by weight after the reaction that the method is also included in step (4) terminates, described phase inversion agent be selected from polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether one or more.
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| CN116854739A (en) * | 2023-07-06 | 2023-10-10 | 山东诺尔生物科技有限公司 | Emulsifying agent for preparing filtrate reducer, composition, filtrate reducer and preparation method of filtrate reducer |
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| CN116854739A (en) * | 2023-07-06 | 2023-10-10 | 山东诺尔生物科技有限公司 | Emulsifying agent for preparing filtrate reducer, composition, filtrate reducer and preparation method of filtrate reducer |
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