CN104250346B - Preparation method of sulfonic acid type polyacrylamide emulsion - Google Patents
Preparation method of sulfonic acid type polyacrylamide emulsion Download PDFInfo
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- CN104250346B CN104250346B CN201310269130.0A CN201310269130A CN104250346B CN 104250346 B CN104250346 B CN 104250346B CN 201310269130 A CN201310269130 A CN 201310269130A CN 104250346 B CN104250346 B CN 104250346B
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Abstract
The invention discloses a preparation method of a sulfonic acid type polyacrylamide emulsion, and the method is as follows: (1) mixing an acrylamide series monomer, a sulfonic acid monomer, a chelating agent, an azo initiator, a chain extension agent, an oxidizing agent with water to form an aqueous solution, and adjusting the aqueous solution pH value to 7-9; (2) mixing an emulsifier and an organic solvent to 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, adding a reducing agent for polymerization of the water in oil emulsion orderly at a first temperature and a second temperature, wherein the second temperature is higher than the first temperature. By using the method provided by the invention; the sulfonic acid type polyacrylamide emulsion with higher viscosity average molecular weight of sulfonic acid type polyacrylamide, better long-term storage stability, lower residual monomer content and rapid dissolution ability in water can be prepared.
Description
Technical field
The present invention relates to a kind of preparation method of sulfonic acid type acrylamide emulsion.
Background technology
Polyacrylamide is the water-soluble poly that acrylamide monomer homopolymerization or copolymerization in the presence of initiator prepare
The general designation of compound, can be used as the drag reducer in efficient flocculant, thickener, reinforcing agent and liquid.Be mainly used in water process,
In the industries such as paper making additive, oil exploitation, weaving, ore dressing, medicine, agricultural, there is the title of " all trades auxiliary agent ".
The mode of production of polyacrylamide mainly has water solution polymerization process and reversed emulsion polymerization.Water solution polymerization process is
Direct polymerization forms certain density acrylamide in aqueous, and its product has the aqueous solution and two kinds of forms of dry powder.Polypropylene
Amide aqueous solution viscosity is larger, and the polymer content including active ingredient is few, is not suitable for transporting；Polyacrylamide dry powder is logical
Cross the colloid that aqueous solution polymerization obtains through granulation, operation preparation, the complex process such as mediate, be dried, pulverizing, product quality is rear
It is significantly reduced in processing procedure, and dry powder dissolves in aqueous and generally requires 2 hours about it is impossible to meet stone well
The special requirement that oil produces.Reversed phase latex of polyacrylamide polymerization refers to the effect by surfactant, water miscible
Acrylamide monomer is dispersed in formation emulsification system in oil phase, is polymerized, eventually forms stable in the presence of initiator
Polyacrylamide emulsion product.Polyacrylamide emulsion product has possibility directly using, dissolution velocity is fast, molecular weight is easy to control
The feature of system.
At present, high temperature resistance, the 2- of resistance to salt monomer acrylamide-2-methylpro panesulfonic acid（AMPS）And its salt modified polypropene acyl
Amine is widely used for the industries such as water treatment field, christmas industry, mineral industry, coal washing.The modified polyacrylamide master of AMPS
If the particulate species solid being obtained by water dissolves polymerization technique, not only molecular weight is low, and the dissolution velocity in water is mostly little 2
When about.
CN102453192A discloses a kind of preparation method of ultra-high molecular weight sulfonic acid type acrylamide, and the method is water
Solution polymerization process, comprises the following steps：1st step, a certain amount of 2- acrylamide-2-methylpro panesulfonic acid and acrylamide are added
Enter in reaction vessel, add deionized water, stir to being completely dissolved；Add alkali, be configured to solution；In molar ratio, 2- acryloyl
Amido -2- methyl propane sulfonic acid：Acrylamide=1：0.4-9,2- acrylamide-2-methylpro panesulfonic acid：Alkali=1：0.9-1.1；2nd
Step, adds intercalating agent, azo-initiator and bifunctionality peroxide in step resulting solution upwards；In mass ratio, 2- propylene
Amide groups -2- methyl propane sulfonic acid：Intercalating agent=1：0.000001-0.0l, 2- acrylamide-2-methylpro panesulfonic acid：Azo draws
Send out agent=1：0.000001-0.05,2- acrylamide-2-methylpro panesulfonic acid：Bifunctionality peroxide=1：0.000001-
0.01；3rd step, is 4-13 with sour or above-mentioned alkali adjustment pH value of reaction system；4th step, adds a certain amount of deionized water, makes
Obtain in reaction system gross mass, the quality of 2- acrylamide-2-methylpro panesulfonic acid and two kinds of monomers of acrylamide is 15%-
40%；Control temperature of reaction system at 0 DEG C -20 DEG C, logical nitrogen deoxygenation adds reducing agent after at least 10 minutes；In mass ratio, 2- third
Acrylamide base -2- methyl propane sulfonic acid：Reducing agent=1：0.0000001-0.05, the 5th step, will be airtight for above-mentioned reaction vessel, react to
After few 2 hours, the gum-like product of gained is taken out, cleaved, drys, granulation, screening, obtain super high molecular weight sulfonic acid type poly-
Acrylamide product.Though the sulfonic acid type acrylamide of the method synthesis has higher molecular weight, dissolution velocity in water
Relatively slow, using 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 represents：A, under normal temperature and pressure stirring, by 5-15% acrylamide and 19-34%2- acrylamide
Being dissolved in of base -2- methyl propane sulfonic acid adds 0.05-0.5 ‰ cross-linking monomer after water, and 0.04-0.3 ‰ intercalating agent, then with adding
Alkaline assistant adjusts pH value to 5.0-9.0；B, the oil-phase solution addition 1.6- under normal temperature and pressure stirring, to continuous phase
3.5% water-in-oil emulsifier dissolving；C, solution A and B solution are mixed after, use homogenizer homogeneous；D, by C products therefrom add
0.02-0.2 ‰ oxidant, then passes to inert gas and excludes oxygen therein；E, at low temperature, is slowly added to D product
0.04-0.4 ‰ reducing agent, controls the whole process reaction temperature that drips to maintain normal temperature；F, in E product add 0.04-0.4% oxygen
Agent；G, to F product add 0.2-2.0 ‰ reducing agent reaction；H, at low temperature, is slowly added to 2.5-5.0% water bag to G product
Emulsifier, is filtered after reaction, that is, obtain product emulsion.The method adopts inverse emulsion polymerization method to pass through to add crosslinking
Agent synthesis of acrylamide crosslinking copolymer emulsion, but polymer is due to leading to insolubles content in the aqueous solution due to crosslinking agent
Higher, affect product quality.
Content of the invention
The invention aims to providing a kind of preparation method of new sulfonic acid type acrylamide emulsion.By the party
The sulfonic acid type acrylamide emulsion that method obtains not only in emulsion sulfonic acid type acrylamide there is higher viscosity average molecular weigh, and
And the extended storage stability of emulsion is good, the content of residual monomer is relatively low and emulsion has the rapidly-soluble energy with water in emulsion
Power.
To achieve these goals, the invention provides a kind of preparation method of sulfonic acid type acrylamide emulsion, wherein,
The method includes：（1）By acrylamide monomer, sulfonic acid type monomer, chelating agent, azo-initiator, chain extender, oxidant and
Water is mixed to form the aqueous solution, and to adjust the pH value of the aqueous solution be 7-9；（2）Emulsifying agent is formed oil solution with organic solvent；（3）
The described aqueous solution is mixed with described oil solution to form water-in-oil emulsion；（4）After described water-in-oil emulsion deoxygenation, add also
Former dose, water-in-oil emulsion is made to carry out polymerisation successively at the first temperature and second temperature, described second temperature is higher than described
First temperature.
By technique scheme, the present invention mainly utilizes chain extender and redox initiation system（By oxidant with also
The initiator system of former dose of composition）Water-in-oil emulsion polymerization system coordinates, to prepare the viscous equal of sulfonic acid type acrylamide
Molecular weight is higher, extended storage stability is good, residual monomer content is relatively low and has the sulfonic acid type with the quick solvability of water
Polyacrylamide emulsion.The sulfonic acid type acrylamide emulsion of the method preparation being provided by the present invention, the sulphur in product emulsion
The viscosity average molecular weigh of acid type polyacrylamide can reach 30,000,000；By product emulsion through 5000rpm be centrifuged 10 minutes regardless of
Layer, normal temperature place 12 months not stratified；In product emulsion, the content of residual monomer is less than 0.05 weight %；In addition, by product emulsion
Dissolved with the concentration of 0.5 weight % in deionized water, can be completely dissolved in 3 minutes.
Under preferable case of the present invention, when the hydrophilic lipophilic balance of described emulsifying agent is 5-8, more preferably described hydrophilic and oleophilic
Equilibrium valve is that the emulsifying agent of 5-8 is mixed to get for two kinds by water-in-oil emulsifier and oil-in-water emulsifiers, particularly preferably hydrophilic
Lipophilic balance value is the mixture for sorbitan oleate and sorbitan monooleate APEO for the emulsifying agent of 5-8
When, be conducive to obtaining extended storage stability more preferable sulfonic acid type acrylamide emulsion by the method that the present invention provides.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains 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 includes：（1）Will
Acrylamide monomer, sulfonic acid type monomer, chelating agent, azo-initiator, chain extender, oxidant and water are mixed to form water-soluble
Liquid, and adjust the aqueous solution pH value be 7-9；（2）Emulsifying agent is formed oil solution with organic solvent；（3）By the described aqueous solution with
Described oil solution mixes to form water-in-oil emulsion；（4）After described water-in-oil emulsion deoxygenation, add reducing agent, make Water-In-Oil
Emulsion carries out polymerisation successively at the first temperature and second temperature, and described second temperature is higher than described first temperature.
The present inventor finds under study for action, is used cooperatively with redox initiation system using chain extender, can
Be conducive to obtain sulfonic acid type acrylamide viscosity average molecular weigh higher, extended storage stability is good, residual monomer content relatively
Low and there is sulfonic acid type acrylamide emulsion with the quick solvability of water.
Step in the present invention（1）In, as long as by chain extender and acrylamide monomer, sulfonic acid type monomer, chelating agent, idol
Nitrogen class initiator, oxidant and water mixing, acrylamide monomer, sulfonic acid type monomer, chelating agent, azo-initiator, chain extension
The consumption of agent, oxidant and water can carry out selection according to consumption well known by persons skilled in the art and can be conducive to obtaining sulfonic acid
The viscosity average molecular weigh of type polyacrylamide is higher, extended storage stability is good, residual monomer content is relatively low and has fast with water
The sulfonic acid type acrylamide emulsion of fast solvability.But in order to preferably realize the purpose of the present invention, under preferable case, relatively
In the acrylamide monomer of 100 weight portions, the consumption of sulfonic acid type monomer is 20-200 weight portion；The consumption of chelating agent is
0.001-5 weight portion；The consumption of azo-initiator is 0.01-1 weight portion；The consumption of chain extender is 0.001-1 weight portion；Oxygen
The consumption of agent is 0.001-0.5 weight portion；The consumption of water is 50-300 weight portion.In the case of more preferably, with respect to 100 weight
The acrylamide monomer of part, the consumption of sulfonic acid type monomer is 50-150 weight portion；The consumption of chelating agent is 0.02-0.2 weight
Part；The consumption of azo-initiator is 0.05-0.5 weight portion；The consumption of chain extender is 0.01-0.4 weight portion；The use of oxidant
Measure as 0.01-0.2 weight portion；The consumption of water is 80-200 weight portion.
In the present invention, any one acrylamide monomer that described acrylamide monomer can be known in the art,
The present invention does not specially require.Under preferable case, described acrylamide monomer can be selected from acrylamide, methacryl
Amine, N, N- DMAA, N, N- acrylamide, NIPA, N hydroxymethyl acrylamide, N-
One or more of hydroxyethyl acrylamide, more preferably acrylamide.
In the present invention, any one sulfonic acid type monomer that described sulfonic acid type monomer can be known in the art, the present invention does not have
There are special requirement.Under preferable case, described sulfonic acid type monomer can be selected from 2- acrylamide-2-methylpro panesulfonic acid, pi-allyl
One or more of sulfonic acid and styrene sulfonic acid, more preferably 2- acrylamide-2-methylpro panesulfonic acid.
In the present invention, any one chelating agent that described chelating agent can be known in the art.Under preferable case, described chela
Mixture can be selected from disodium ethylene diamine tetraacetate（EDTA）, triethylenediamine pentaacetic acid, citric acid, citrate and poly- hydroxy
One or more of acid, more preferably disodium ethylene diamine tetraacetate and/or citrate.Described citrate can be selected from lemon
One or more of lemon acid potassium, sodium citrate, calcium citrate and ammonium citrate.
In the present invention, any one azo-initiator that described azo-initiator can be known in the art.Preferably
In the case of, described azo-initiator can selected from azodiisobutyronitrile, 2,2 '-azo diisobutyl amidine hydrochloride and 2,2 '-
One or more of azo [2- (2- imidazoline -2- propane)-dihydrochloride], more preferably 2,2 '-azo diisobutyl amidine
Hydrochloride and/or 2,2'- azo [2- (2- imidazoline -2- base) propane] dihydrochloride.
In the present invention, described chain extender can be formula（1）Shown compound：
Wherein, R1And R2Can be each H, NH2, carbon number is the straight or branched alkyl of 1-5 or carbon number is 1-
5 aminoalkyl, R1And R2Can be identical or different.Wherein, carbon number be 1-5 straight or branched alkyl can for methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, n-pentyl, isopentyl, tertiary pentyl or neopentyl.Carbon number
Can be for primary amino radical, secondary amino group or tertiary amino it is preferable that described aminoalkyl can be for the amino in the aminoalkyl of 1-5
By NH2R3The primary amino radical of-expression, wherein, R3For the straight or branched alkyl for 1-5 for the carbon number, for example can for methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, n-pentyl, isopentyl, tertiary pentyl or neopentyl.Excellent further
In the case of choosing, R1And R2Each can be for H, amino, carbon number is the straight or branched alkyl of 1-3 or carbon number is 1-3's
Aminoalkyl.It is further preferred that R1And R2Can be each H, methyl, aminomethyl, ethyl or aminoethyl.It is particularly preferred that
R1And R2It can be each aminoethyl.Described chain extender can be preferably 1,4- piperazine diethylamine, 1- methyl piperazine, N- ethyl piperazine
One or more of piperazine and N- aminoethyl piperazine, more preferably Isosorbide-5-Nitrae-piperazine diethylamine.
Described oxidant is any one oxidant that can be known in the art.Under preferable case, described oxidant can
With selected from one or more of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide, more preferably persulfuric acid
Ammonium.
In the present invention, acrylamide monomer, sulfonic acid type monomer, chelating agent, azo-initiator, chain extender, oxidant
Do not specially require with the order of water mixing.Under preferable case, first acrylamide monomer, sulfonic acid type monomer and water are mixed,
Then adjusting its pH with alkali is 7-9, then adds chelating agent, azo-initiator, chain extender and the oxidant formation aqueous solution, favorably
In the emulsion that acquisition is more stable, and be conducive to obtaining the higher sulfonic acid type acrylamide of viscosity average molecular weigh.Described alkali is permissible
Inorganic base or organic amine compound, such as can selected from NaOH, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, monoethanolamine and
At least one in triethanolamine, preferably NaOH.Described alkali can be added with its solid form can also be water-soluble with it
Liquid form is added.The present invention is preferably added with the aqueous solution form of alkali.Due to chelating agent, azo-initiator, chain extender and oxygen
The pH value of the aqueous solution of agent is close to 7, and the chelating agent adding, the amount of azo-initiator, chain extender and oxidant compare
Few, the pH value of the solution that acrylamide monomer, sulfonic acid type monomer and water are mixed to get is affected less, it is believed that adding
The pH value of the aqueous solution being formed after chelating agent, azo-initiator, chain extender and oxidant and acrylamide monomer, sulfonic acid type
The pH value of the solution that monomer and water are mixed to get is close.
Step in the present invention（2）In, emulsifying agent is not specially required with the consumption of organic solvent, as long as oil can be formed
Solution.Under preferable case, with respect to the acrylamide monomer of 100 weight portions, the consumption of organic solvent is 50-200 weight
Amount part；The consumption of emulsifying agent is 5-20 weight portion.In the case of more preferably, with respect to the acrylamide monomer of 100 weight portions, have
The consumption of machine solvent is 90-150 weight portion；The consumption of emulsifying agent is 8-15 weight portion.
In the present invention, described emulsifying agent can be any one nonionic emulsifier well known by persons skilled in the art.Example
As being sorbitan oleate（Span-80）, sorbitan monooleate APEO（Tween-80）, alkyl phenol
One of APEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether or many
Kind.Under preferable case, described emulsifying agent can be any one emulsifying agent of 5-8 for hydrophilic lipophilic balance.
However, the present inventor tests it was unexpectedly observed that working as the breast that hydrophilic lipophilic balance is 5-8 through substantial amounts of
When agent is the mixture of water-in-oil emulsifier and oil-in-water emulsifiers, with a kind of individually water-in-oil emulsifier as parent
Hydrophile-lipophile balance value is that the emulsifying agent of 5-8 is compared, and the long-time stability of the sulfonic acid type acrylamide emulsion obtaining are more preferable.More excellent
In the case of choosing, when described emulsifying agent is the mixture of sorbitan oleate and sorbitan monooleate APEO,
It is more beneficial for obtaining the good sulfonic acid type acrylamide emulsion of long-time stability.
In the case that the hydrophilic lipophilic balance meeting emulsifying agent is 5-8, described water-in-oil emulsifier and oil-in-water
The weight of type emulsifying agent is than preferably 10-1：1, more preferably 3-5:When 1, it is particularly conducive to obtain the more preferable sulphur of long-time stability
Acid type polyacrylamide emulsion.
Under most preferred case, described hydrophilic lipophilic balance is the emulsifying agent of 5-8 is sorbitan oleate and dehydration mountain
The mixture of pears alcohol monoleate APEO, and the weight of the two is than preferably 10-1：1, more preferably 3-5：When 1,
The long-time stability of sulfonic acid type acrylamide emulsion can be improved further.
When the emulsifying agent that described hydrophilic lipophilic balance is 5-8 is the mixed of water-in-oil emulsifier and oil-in-water emulsifiers
During compound, emulsifying agent is not necessarily defined to first by water-in-oil emulsifier and oil-in-water type emulsion with the order by merging of organic solvent
Agent mixing is mixed with organic solvent again.Water-in-oil emulsifier, oil-in-water emulsifiers and organic solvent can be with random orders
Mixing, as long as ensure that water-in-oil emulsifier and the mixed hydrophilic lipophilic balance of oil-in-water emulsifiers for 5-8 are
Can.
In the present invention, described organic solvent can be any one organic solvent well known by persons skilled in the art, this
Bright not special requirement.Under preferable case, described organic solvent can be selected from toluene, dimethylbenzene, hexane, hexamethylene, normal heptane
With one or more of isoparaffin it is also possible to selected from one or more of gasoline, kerosene and white oil；More preferably
One or more of toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline, kerosene and white oil；Particularly preferably isoparaffin
And/or white oil；Particularly be preferably boiling point be higher than 150 DEG C, flash-point be more than 60 DEG C of isoparaffin and/or white oil.
The described aqueous solution is not limited with the mixing order of addition of described oil solution, described oil solution can be added to institute
State in the aqueous solution it is also possible to the described aqueous solution be added in described oil solution, the present invention does not specially require.Preferable case
Under, the described aqueous solution is added in described oil solution and is mixed.The hybrid mode of the described aqueous solution and described oil solution is originally
Invention does not also specially require, as long as the two mixing can form stable water-in-oil emulsion（Heretofore described is stable
Water-in-oil emulsion refers to monomer solution in the presence of emulsifying agent（Drop）Equably it has been dispersed in short grained form
In machine solvent）?.Under preferable case, the described aqueous solution is blended under high speed shearing emulsification effect with described oil solution
OK, to form stable water-in-oil emulsion.
In the present invention, in step（4）In, the first temperature and second temperature can be polymerizations well known by persons skilled in the art
Reaction temperature.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 to carry out polymerisation at the first temperature and second temperature successively, as long as the
Two temperature are higher than the first temperature can be advantageously implemented the purpose of the present invention.Under preferable case, described second temperature is than described
One temperature can be high 5-40 DEG C, is conducive to obtaining the less sulfonic acid type acrylamide emulsion of residual monomer.
The time of described polymerisation can also be according to well known to a person skilled in the art scope be selected, and the present invention does not have
There are special requirement.Under preferable case, carrying out polymerization reaction time at the first temperature is 4-8 hour；Carry out at the second temperature
The time of polymerisation is 1-4 hour.
The step of the present invention（4）In, the consumption of described reducing agent can be according to well known to a person skilled in the art consumption enters
Row selects, and the present invention does not specially require.Under preferable case, with respect to the acrylamide monomer of 100 weight portions, described reduction
The consumption of agent is 0.001-2 weight portion, preferably 0.001-0.2 weight portion.What described reducing agent can be known in the art appoints
Anticipate a kind of reducing agent.Under preferable case, described reducing agent can be selected from sodium hydrogensulfite, sodium sulfite, rongalite, thiosulfuric acid
One or more of sodium, ferrous sulfate and sodium hydrosulfite, preferably sodium hydrogensulfite.
In the present invention, Oxidizing and Reducing Agents forms redox initiation system.Wherein, the consumption of Oxidizing and Reducing Agents
Ratio can be selected according to scope well known in the art it is preferable that the weight of described reducing agent and oxidant is than for 1：1-
3；It is preferably 1：1-2.
In the present invention, in step（4）The middle mode by described water-in-oil emulsion deoxygenation can adopt those skilled in the art
Any one mode known, for example, be passed through inert gas deoxygenation.It is any one that described inert gas can be known in the art
Plant inert gas, preferably nitrogen.
In the present invention, the method is additionally included in step（4）Polymerisation terminate after add account for sulfonic acid type acrylamide
The phase inversion agent of emulsion 2-3.5 weight %, so that gained sulfonic acid type acrylamide emulsion quickly dissolves in water.Described phase inversion agent
Any one the phase inversion agent that can be known in the art.Under preferable case, described phase inversion agent can be selected from polyoxyethylene sorbitan mountain
Pears alcohol fatty acid ester, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyoxy
Vinethene, heterogeneous ten alcohol polyoxyethylene ether, isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether and fatty amine gather
One or more of oxygen vinethene.In the case of more preferably, described phase inversion agent can be selected from polyoxyethylene sorbitan fat
Acid esters, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, different
One or more of structure ten alcohol APEO, isomery undecyl alcohol APEO and isomerous tridecanol polyoxyethylene ether.
The sulfonic acid type acrylamide emulsion of the method preparation being provided by the present invention, the sulfonic acid type in product emulsion poly- third
The viscosity average molecular weigh of acrylamide can reach 30,000,000；By product emulsion through 5000rpm be centrifuged 10 minutes not stratified, normal temperature is put
Put 12 months not stratified；In product emulsion, the content of residual monomer is less than 0.05 weight %；In addition, by product emulsion in deionization
Dissolved with the concentration of 0.5 weight % in water, can be completely dissolved in 3 minutes.
Using the sulfonic acid type acrylamide emulsion of method of the present invention preparation, can be in water treatment field as flocculant
Or decolorising agent uses；Christmas industry makes as tackifier, drag reducer, adjuvant, fluid loss additive, thinner or coating agent
With；Mineral industry uses as flocculant；Coal washing industry uses as flocculant etc..During application, can will be obtained
Sulfonic acid type acrylamide emulsion be diluted with water to as needed low concentration the aqueous solution use.
By the following examples the specific embodiment of the present invention is described in detail.
Intrinsic viscosity is measured according to GB12005.1-89 polyacrylamide Intrinsic Viscosity Measurements method；Glue and divide equally
Son amount is according to formula Mv=（[η]/K）1\α, wherein K=4.5 × 10-3, α=0.80 is calculated.
The dissolution time method of testing of sulfonic acid type acrylamide emulsion is：200mL deionized water is added to 250mL burn
In cup, the 3- blade screw paddle mechanical agitator that will be configured with 4.5cm diameter is placed on beaker center, and blade is away from beaker bottom
1cm, agitator is stirred with the speed of 500rpm to produce vortex.By the electrode of 307A type electric conductivity instrument be inserted into vortex liquid level with
Under.Rapidly join 1mL sulfonic acid type acrylamide product emulsion using syringe in vortex, measure electrical conductivity and change over
Curve, the flex point corresponding time of conductance-time graph is the dissolution time of emulsion.
In sulfonic acid type acrylamide emulsion, residual monomer content is residual according to GB/T22312-2008 plastics polyacrylamide
Acrylamide content assay method is stayed to be measured.
Unless specifically indicated, the reagent used in embodiment and comparative example is commercially available product, and identical rule of origin
Identical.
Embodiment 1
At 20 DEG C, by 80g deionized water, 100g acrylamide, 50g2- acrylamide-2-methylpro panesulfonic acid adds
To in 1000mL beaker, stir, be then slowly added into 50 weight % sodium hydrate aqueous solution adjust the aqueous solution pH value to
7.Then add 0.02g disodium ethylene diamine tetraacetate in beaker, add 0.01g chain extender Isosorbide-5-Nitrae-piperazine diethylamine, add
0.01g ammonium persulfate, adds 0.05g azo diisobutyl to narrow hydrochloride, forms the aqueous solution.
6gSpan-80 is mixed with 2gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is 6.98, then will
Blended emulsifier and 90g white oil（Boiling range is 200-250 DEG C, and flash-point is 80 DEG C）It is completely dissolved acquisition oil solution.
The above-mentioned aqueous solution is added in oil solution, emulsifies 1min with high speed shear dispersion and emulsion device, obtain stable breast
White reversed-phase emulsion.After the nitrogen deoxygenation being 400mL/min with flow 30 minutes, by the aqueous solution of sodium bisulfite of 1 weight %
1.0g is added gradually in emulsion, controls emulsion temperature to be less than 35 DEG C, and reaction is warming up to 40 DEG C of continuation reactions 1 after 4 hours little
When, it is cooled to room temperature and adds 7g APES op-10, obtain sulfonic acid type acrylamide with 80 mesh filter-cloth filterings
Emulsion.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.4 minutes；This emulsion by the centrifuge of 5000rpm from
The heart 10 minutes is not stratified, and standing 12 months is not stratified at room temperature；The viscosity average molecular weigh of sulfonic acid type acrylamide in this emulsion
For 26,500,000, the content of residual monomer is 0.04 weight %.
Comparative example 1
Method according to embodiment 1 prepares sulfonic acid type acrylamide emulsion, is except for the difference that added without chain extender Isosorbide-5-Nitrae-piperazine
Diethylamine.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 15 minutes；This emulsion by the centrifuge of 5000rpm from
The heart 10 minutes is not stratified, and standing 12 months is not stratified at room temperature；The viscosity average molecular weigh of sulfonic acid type acrylamide in this emulsion
For 8,200,000；In this emulsion, the content of residual monomer is 0.08 weight %.
Embodiment 2
At 25 DEG C, by 200g deionized water, 100g acrylamide, 150g2- acrylamide-2-methylpro panesulfonic acid adds
Enter in 1000mL beaker, stir, be then slowly added into 50 weight % sodium hydrate aqueous solutions adjust the aqueous solution pH value to
8.Then add 0.2g disodium ethylene diamine tetraacetate in beaker, add 0.2g chain extender 1- methyl piperazine, add 0.2g over cure
Sour ammonium, adds 0.5g azo diisobutyl to narrow hydrochloride.
12.5gSpan-80 is mixed with 2.5gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is
6.08, then by blended emulsifier and 150g white oil（Boiling range is 240-280 DEG C, and flash-point is 100 DEG C）It is completely dissolved and make oil solution.
The above-mentioned aqueous solution is added in oil solution, emulsifies 1min with high speed shear dispersion and emulsion device, obtain stable
Milky reversed-phase emulsion.After being 400mL/min nitrogen deoxygenation 30 minutes with flow, by 10 weight % aqueous solution of sodium bisulfite
1.0g being added gradually in emulsion, emulsion temperature is controlled to be less than 35 DEG C, reaction is warming up to 60 DEG C of continuation reactions 4 after 8 hours little
When, it is cooled to room temperature and adds 20g APES op-10, obtain sulfonic acid type polyacrylamide with 80 mesh filter-cloth filterings
Amine emulsion.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.2 minutes；This emulsion by the centrifuge of 5000rpm from
The heart 10 minutes is not stratified, and standing 12 months is not stratified at room temperature；The viscosity average molecular weigh of sulfonic acid type acrylamide in this emulsion
For 28,600,000, the content of residual monomer is 0.03 weight %.
Embodiment 3
At 15 DEG C, by 120g deionized water, 100g acrylamide, 100g2- acrylamide-2-methylpro panesulfonic acid adds
Enter in 1000mL beaker, stir, the sodium hydrate aqueous solution being then slowly added into 50 weight % adjusts the pH value of the aqueous solution
To 7.Then add 0.1g disodium ethylene diamine tetraacetate in beaker, add 0.4g chain extender N- aminoethyl piperazine, add 0.1g
Ammonium persulfate, adds 0.2g azo diisobutyl to narrow hydrochloride.
9.6gSpan-80 is mixed with 2.4gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is 5.58,
Again by blended emulsifier and 120g white oil（Boiling range is 220-255 DEG C, and flash-point is 100 DEG C）It is completely dissolved and make oil solution.
The above-mentioned aqueous solution is added in oil solution, emulsifies 1min with high speed shear dispersion and emulsion device, obtain stable breast
White reversed-phase emulsion.After being 400mL/min nitrogen deoxygenation 30 minutes with flow, by 10 weight % aqueous solution of sodium bisulfite 1.0g
It is added gradually in emulsion, controls emulsion temperature to be less than 35 DEG C, reaction is warming up to 50 DEG C and continues reaction 2 hours after 6 hours, cold
But arrive room temperature and add 12.5g APES op-10, obtain sulfonic acid type acrylamide breast with 80 mesh filter-cloth filterings
Liquid.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 1.6 minutes；This emulsion by the centrifuge of 5000rpm from
The heart 10 minutes is not stratified, and standing 12 months is not stratified at room temperature；The viscosity average molecular weigh of sulfonic acid type acrylamide in this emulsion
For 30,800,000, the content of residual monomer is 0.01 weight %.
Embodiment 4
At 25 DEG C, by 50g deionized water, 100g acrylamide, 20g2- acrylamide-2-methylpro panesulfonic acid adds
To in 500mL beaker, stir, be then slowly added into the sodium hydrate aqueous solution of 50 weight % and adjust the pH value of the aqueous solution
To 9.Then add 0.5g disodium ethylene diamine tetraacetate in beaker, add 1g chain extender NEP, add 0.5g over cure
Sour ammonium, adds 0.8g azo diisobutyl to narrow hydrochloride.
13.3gSpan-80 is mixed with 6.7gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is
7.87, then by blended emulsifier and 200g white oil（Boiling range is 220-255 DEG C, and flash-point is 80 DEG C）It is completely dissolved and make oil solution.
The above-mentioned aqueous solution is added in oil solution, emulsifies 1min with high speed shear dispersion and emulsion device, obtain stable breast
White reversed-phase emulsion.After the nitrogen deoxygenation being 400mL/min with flow 30 minutes, by 25 weight % aqueous solution of sodium bisulfite
0.8g is added gradually in emulsion, controls emulsion temperature to be less than 35 DEG C, and reaction is warming up to 40 DEG C of continuation reactions 2 after 6 hours little
When.It is cooled to room temperature and adds 8g APES op-10, obtain sulfonic acid type acrylamide with 80 mesh filter-cloth filterings
Emulsion.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 3 minutes；This emulsion is by the centrifuge of 5000rpm
10 minutes are not stratified, at room temperature standing 12 months not stratified；In this emulsion, the viscosity average molecular weigh of sulfonic acid type acrylamide is
12500000, the content of residual monomer is 0.05 weight %.
Embodiment 5
Method according to embodiment 1 prepares sulfonic acid type acrylamide emulsion, except for the difference that chain extender Isosorbide-5-Nitrae-piperazine diethylamine
Consumption be 0.0005g.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2 minutes；This emulsion is by the centrifuge of 5000rpm
10 minutes are not stratified, at room temperature standing 12 months not stratified；In this emulsion, the viscosity average molecular weigh of sulfonic acid type acrylamide is
9650000, the content of residual monomer is 0.05 weight %.
Embodiment 6
Method according to embodiment 1 prepares sulfonic acid type acrylamide emulsion, is except for the difference that replaced with 2gTween-40
2gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is 7.12.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 2.8 minutes；This emulsion by the centrifuge of 5000rpm from
The heart 10 minutes is not stratified, and standing 12 months is not stratified at room temperature；The viscosity average molecular weigh of sulfonic acid type acrylamide in this emulsion
For 12,800,000, content position 0.05 weight % of residual monomer.
Embodiment 7
Method according to embodiment 1 prepares sulfonic acid type acrylamide emulsion, is except for the difference that replaced with 8gSpan-80
6gSpan-80 and 2gTween-80, the hydrophilic lipophilic balance of gained blended emulsifier is 6.7.
The dissolution time of gained sulfonic acid type acrylamide emulsion is 3 minutes；This emulsion is by the centrifuge of 5000rpm
10 minutes are not stratified, at room temperature standing 12 months not stratified；In this emulsion, the viscosity average molecular weigh of sulfonic acid type acrylamide is
10800000, the content of residual monomer is 0.05 weight %.
By embodiment 1-7 and comparative example 1 as can be seen that the method providing using the present invention, sulfonic acid type can be prepared
The viscosity average molecular weigh of polyacrylamide is higher, extended storage stability more preferable, the content of residual monomer is lower and has fast with water
The sulfonic acid type acrylamide emulsion of fast solvability.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (9)
1. a kind of preparation method of sulfonic acid type acrylamide emulsion is it is characterised in that the method includes：
(1) acrylamide monomer, sulfonic acid type monomer, chelating agent, azo-initiator, chain extender, oxidant and water are mixed
Formed the aqueous solution, and adjust the aqueous solution pH value be 7-9；
(2) emulsifying agent is formed oil solution with organic solvent；
(3) the described aqueous solution is mixed with described oil solution to form water-in-oil emulsion；
(4) by after described water-in-oil emulsion deoxygenation, add reducing agent, make water-in-oil emulsion successively in the first temperature and second temperature
Under carry out polymerisation, described second temperature be higher than described first temperature；
Described emulsifying agent is the weight ratio of sorbitan oleate and sorbitan monooleate APEO for 3-5：1
Mixture；
Methods described be additionally included in step (4) polymerisation terminate after add account for sulfonic acid type acrylamide emulsion 2-3.5 weight
The phase inversion agent of amount %, described phase inversion agent is selected from polyoxyethylene sorbitan fatty acid ester, NPE, octyl phenol
APEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, heterogeneous ten alcohol polyoxyethylene ether, isomery undecyl alcohol
One or more of APEO, isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether；
Described organic solvent for boiling point be higher than 150 DEG C, flash-point be more than 60 DEG C of isoparaffin and/or white oil.
2. method according to claim 1, wherein, in step (1), with respect to the acrylamide list of 100 weight portions
Body, the consumption of sulfonic acid type monomer is 20-200 weight portion；The consumption of chelating agent is 0.001-5 weight portion；Azo-initiator
Consumption is 0.01-1 weight portion；The consumption of chain extender is 0.001-1 weight portion；The consumption of oxidant is 0.001-0.5 weight portion；
The consumption of water is 50-300 weight portion.
3. method according to claim 2, wherein, with respect to the acrylamide monomer of 100 weight portions, sulfonic acid type monomer
Consumption be 50-150 weight portion；The consumption of chelating agent is 0.02-0.2 weight portion；The consumption of azo-initiator is 0.05-
0.5 weight portion；The consumption of chain extender is 0.01-0.4 weight portion；The consumption of oxidant is 0.01-0.2 weight portion；The consumption of water
For 80-200 weight portion.
4. the method according to any one in claim 1-3, wherein, described acrylamide monomer is selected from acryloyl
Amine, Methacrylamide, N, N- DMAA, N, N- acrylamide, NIPA, N- hydroxyl first
One or more of base acrylamide, N- hydroxyethyl acrylamide；Described sulfonic acid type monomer is selected from 2- acrylamido -2- first
One or more of base propane sulfonic acid, allyl sulphonic acid and styrene sulfonic acid；Described chelating agent is selected from ethylenediamine tetra-acetic acid two
One or more of sodium, triethylenediamine pentaacetic acid, citric acid, citrate and poly- hydroxy acrylic acid；Described azo causes
Agent is selected from azodiisobutyronitrile, 2,2 '-azo diisobutyl amidine hydrochloride and 2,2'- azo [2- (2- imidazoline -2- base) third
One or more of alkane] dihydrochloride.
5. the method according to any one in claim 1-3, wherein, described chain extender is the compound shown in formula (1)：
Wherein, R1And R2It is respectively H, NH2, carbon number is the straight or branched alkyl of 1-5 or carbon number is the amino of 1-5
Alkyl, R1And R2Identical or different.
6. method according to claim 1, wherein, in step (2), with respect to the acrylamide list of 100 weight portions
Body, the consumption of described organic solvent is 50-200 weight portion；The consumption of described emulsifying agent is 5-20 weight portion.
7. the method according to claim 1 or 6, wherein, described emulsifying agent is the emulsification of 5-8 for hydrophilic lipophilic balance
Agent.
8. method according to claim 1, wherein, in step (4), described first temperature is 10-35 DEG C, described second
Temperature is 40-60 DEG C, and described second temperature is higher 5-40 DEG C than described first temperature.
9. method according to claim 1, wherein, in step (4), with respect to the acrylamide list of 100 weight portions
Body, the consumption of described reducing agent is 0.001-2 weight portion；Described reducing agent be selected from sodium hydrogensulfite, sodium sulfite, rongalite,
One or more of sodium thiosulfate, ferrous sulfate and sodium hydrosulfite.
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| CN102453113A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Redox initiator system and acrylamide polymer and preparation method thereof and application thereof |
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| CN102453113A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Redox initiator system and acrylamide polymer and preparation method thereof and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| AM/NVP/DMMAC共聚物反相乳液聚合研究;刘勇等;《应用化工》;20060531;第35卷(第5期);第345-347页 * |
| 反相乳液聚合法制备驱油用高分子表面活性剂;王晓春等;《石油化工》;20100915;第39卷(第9期);第1023-1027页 * |
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