CN115197365A - Preparation method of polyacrylamide emulsion - Google Patents
Preparation method of polyacrylamide emulsion Download PDFInfo
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- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The application discloses a preparation method of polyacrylamide emulsion, which comprises the following steps: mixing acrylamide, an anionic monomer, a nano material, a functional monomer, a chelating agent, a molecular weight regulator, a thermal initiator and a low-temperature initiator, and then regulating the pH value to obtain a water phase; adding an emulsifier into the oil to obtain an oil phase; mixing the water phase and the oil phase to obtain an emulsion; adding a reducing agent into the emulsion for reaction, and then adding a phase inversion agent for reaction to obtain a polyacrylamide emulsion; the preparation method can prepare the polyacrylamide emulsion product which has good stability, can be quickly dissolved in water, has the functions of drag reduction and sand carrying, has excellent performance, effectively reduces the cost and saves resources.
Description
Technical Field
The application relates to the field of organic high molecular compounds, in particular to a preparation method of polyacrylamide emulsion.
Background
Polyacrylamide is a general name of water-soluble polymers prepared by homopolymerization or copolymerization of acrylamide monomers under the action of an initiator, and can be used as a high-efficiency flocculant, a thickening agent, a reinforcing agent and a drag reducer in liquid. The additive is mainly applied to the industries of water treatment, oil exploitation, mineral separation, agriculture and the like and is called as an all-industry additive.
The production mode of polyacrylamide mainly comprises an aqueous solution polymerization method and an inverse emulsion polymerization method. The aqueous solution polymerization method is to directly polymerize acrylamide with certain concentration in aqueous solution, and the product has two forms of aqueous solution and dry powder. The viscosity of the polyacrylamide aqueous solution is high, the content of polymers containing active ingredients is very low, and the polyacrylamide aqueous solution is not suitable for transportation; the polyacrylamide dry powder is prepared by the procedures of granulating, kneading, drying, crushing and the like of colloid obtained by aqueous solution polymerization, the process is complex, the product quality is obviously reduced in the post-treatment process, and the dry powder is generally dissolved in the aqueous solution for about 2 hours and cannot well meet the special requirements of petroleum production. The polyacrylamide inverse emulsion polymerization method is characterized in that polymerization is carried out under the action of a surfactant, and finally a stable polyacrylamide emulsion product is formed. The polyacrylamide emulsion product has the characteristics of direct use, high dissolution speed and controllable molecular weight.
When used as a thickening agent and a fracturing fluid, the emulsion polyacrylamide has the characteristics of convenience in construction, high application efficiency and the like, and is widely applied to fracturing construction of conventional oil-gas storage and unconventional oil-gas storage. In recent years, the product gradually shows unique product advantages in unconventional oil and gas storage multistage staged large-scale fracturing construction, and is popular and favored on site.
At the present stage, when the polyacrylamide emulsion is used as an additive of a thickening agent and a fracturing fluid in the field of oil fields, different types of polyacrylamide are required to be added as a drag reducer and a sand carrying agent, so that the thickening agent and the fracturing fluid have excellent resistance reduction and stable sand carrying capacity, the process is complicated, the cost is high, and the polyacrylamide emulsion has the following problems along with the gradual increase of the application range: high molecular weight, poor mechanical property, poor temperature resistance, high viscosity and poor stability, and can not simultaneously have the functions of carrying sand, reducing drag and the like.
Therefore, the existing market places higher technical demands on the production of polyacrylamide emulsions.
Disclosure of Invention
The preparation method of the polyacrylamide emulsion is used for solving the problem that the existing polyacrylamide emulsion is applied to the field of oil fields, and the polyacrylamide emulsion which is low in molecular weight, excellent in mechanical property, good in temperature resistance, low in viscosity, good in stability, sand-carrying performance and drag reduction performance is obtained through the preparation method.
In order to achieve the above object, the present invention provides the following technical solutions.
In a first aspect, the present application provides a method for preparing a polyacrylamide emulsion, which adopts the following technical scheme:
a preparation method of polyacrylamide emulsion comprises the following steps:
mixing acrylamide, an anionic monomer, a nano material, a functional monomer, a chelating agent, a molecular weight regulator, a thermal initiator and a low-temperature initiator, and then regulating the pH to be alkaline to obtain a water phase;
adding an emulsifier into the oil to obtain an oil phase;
mixing the water phase and the oil phase to obtain an emulsion;
adding a reducing agent into the emulsion for reaction, and then adding a phase inversion agent for reaction to obtain a polyacrylamide emulsion;
wherein the anionic monomer is at least one of acrylic acid, methacrylic acid, maleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid;
the functional monomer is at least one of 3-allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt, 2-acrylamide-tetradecyl sulfonic acid and dodecyl acrylamide;
the nano material is nano silicon dioxide.
Preferably, the low-temperature initiator is at least one of potassium persulfate, ammonium persulfate, sodium persulfate and benzoyl peroxide.
Preferably, the thermal initiator is at least one of azobisisobutyronitrile, azobisisopropylimidazoline hydrochloride, azobisisobutylamidine hydrochloride, and dimethyl azobisisobutyrate.
Preferably, the chelating agent is at least one of ethylenediamine tetraacetic acid sodium salt, diethylenetriamine pentaacetic acid pentasodium salt and ethylenediamine tetrapropionic acid.
Preferably, the molecular weight regulator is at least one of urea, formate and isopropanol.
Preferably, the emulsifier is at least one of sorbitan monolaurate, polyoxyethylene octylphenol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan glycerate and polyoxyethylene sorbitan monostearate;
preferably, the oil is at least one of gasoline, diesel oil, kerosene and white oil.
Preferably, the reducing agent is one or two of sodium metabisulfite and sodium bisulfite; the phase transfer agent is octyl phenol polyethenoxy ether or alkylphenol polyethenoxy ether.
Preferably, the liquid alkali is sodium hydroxide solution;
the present application improves polyacrylamide emulsions from 3 aspects: 1. functional monomers containing sulfonic acid groups or side groups are introduced, so that the rigidity of molecular chains and the insensitivity to external cations are increased, and the temperature resistance and salt resistance of the polymer are improved; 2. by introducing an anionic monomer and adopting a design concept of long side chains, on one hand, the rheological property of the product is improved through the steric hindrance effect of the long side chains, and on the other hand, a spatial network structure with certain strength is formed through the hydrophobic association effect among polymer molecules, so that the temperature resistance and salt resistance of the polymer and the suspension bearing capacity of sand particles are improved; 3. the nanometer material is introduced, the material has obvious flocculent or netted quasi-particle structure, small particle size, large specific surface area, three-dimensional chain structure in the branched state of the nanometer material, unsaturated bond and hydroxyl in different bonding states on the surfaceDue to nano SiO 2 The volume effect and the quantum tunnel effect of the nano silicon dioxide lead the nano silicon dioxide to generate the osmosis effect, lead the nano silicon dioxide to be overlapped with the electron cloud of the pi bond of the macromolecular compound to form a space network structure, and further greatly improve the mechanical strength, the temperature resistance, the rheological property and the thixotropy of the macromolecular material.
The low-temperature initiator and the reducing agent release free radicals under the reaction, the reaction is mild, and the smooth reaction is facilitated and the emulsion with higher molecular weight is obtained.
Preferably, the mass ratio of acrylamide, anionic monomer, nano material, functional monomer, chelating agent, molecular weight regulator, thermal initiator and low-temperature initiator is 5-10:6-12:1-5:3-8:0.01-0.05:0.001-0.006:0.01-0.05:0.01-0.04; the mass ratio of acrylamide, oil, emulsifier, reducing agent and phase transfer agent is 5-10:44-60:5-8:0.001-0.005:3-8; the mass ratio of the water phase to the oil phase is 9-1.
Preferably, the reducing agent is added into the emulsion for reaction, then the temperature is raised to 70-90 ℃, the stirring is carried out for 1-3 hours, then the temperature is lowered to 15-20 ℃, and then the phase inversion agent is added for reaction.
By adopting the technical scheme, the added raw material amount is limited, and the polyacrylamide emulsion with good stability and good solubility is obtained by the method.
Preferably, the nano-silica is pretreated nano-silica, and the pretreatment steps of the nano-silica are as follows: mixing nano silicon dioxide and deionized water, carrying out ultrasonic treatment for 1-2 hours at 25-35 ℃, adding a silane coupling agent for reaction, then filtering, adding a pretreatment emulsion, carrying out reaction for 1-3 hours under a vacuum condition, and then filtering to obtain the pretreated nano silicon dioxide.
Preferably, the mass ratio of the nano silicon dioxide to the silane coupling agent to the pretreatment emulsion is 15:2-4:6-10.
Preferably, the pretreatment emulsion comprises the following raw material components in parts by mass: 10-15 parts of epoxy resin, 10-15 parts of sodium alginate, 6-17 parts of hexadecyl dimethyl betaine, 2-6 parts of sodium polymethacrylate, 1-2 parts of white carbon black and 1-2 parts of glycerol.
By adopting the technical scheme, the nano silicon dioxide is pretreated, the silane coupling agent with the bidirectional reaction function is added in advance, and the silane coupling agent can be hydrolyzed with the nano SiO 2 The silicon hydroxyl on the surface acts, and the modified nano SiO 2 The original hydrophilic surface rich in hydroxyl groups of the particles is changed into a lipophilic surface containing organic functional groups; and adding a pretreatment emulsion for reaction, mixing the pretreatment emulsion with the nano-silica, and forming a micelle with a network structure and a surface layer with resistance reduction and thickening functions on the surface of the nano-silica, so that the obtained polyacrylamide emulsion has the functions of resistance reduction and sand carrying.
In summary, the present application includes at least one of the following beneficial technical effects:
by adopting a compounding process, the invention prepares the polyacrylamide emulsion product which has good stability, can be quickly dissolved in water and has the functions of drag reduction and sand carrying, and the obtained product has excellent performance.
Detailed Description
The raw material sources are as follows:
preparation of 2-acrylamido-tetradecylsulfonic acid:
39.2g of 1-tetradecene, 5.3g of dehydrating agent and excessive acrylonitrile are mixed, cooled to below 0 ℃, 21.4g of fuming sulfuric acid is dropwise added under stirring (the reaction temperature is controlled not to exceed 5 ℃ in the dropwise adding process), the fuming sulfuric acid reacts for 30min after the fuming sulfuric acid is added, and then the temperature is increased to 25 ℃ for reaction for 24h. The mixture was cooled, excess acrylonitrile was filtered off, and the product was washed successively with acrylonitrile and acetone and dried under vacuum to give 40.9g of a white powder.
The raw materials involved in the application are all commercially available products, wherein the CAS number of the sodium polymethacrylate is as follows: 54193-36-1, CAS number for epoxy resin: 61788-97-4, and the CAS number of the silane coupling agent is 211519-85-6.
The present application will be described in further detail with reference to examples and comparative examples.
Preparation example 1: pretreatment of nanosilicon dioxide
The preparation of the pre-treatment emulsion comprises the following steps:
after 15g of sodium alginate, 11g of hexadecyl dimethyl betaine, 2g of sodium polymethacrylate, 1g of white carbon black and 200g of deionized water are uniformly mixed, 1g of glycerol and 13g of epoxy resin are added and uniformly mixed, and the pretreated emulsion is obtained.
The pretreatment of the nano silicon dioxide comprises the following steps:
mixing 90g of nano silicon dioxide and 100g of deionized water, and carrying out ultrasonic treatment at 30 ℃ for 1.5 hours; adding 20g of silane coupling agent, stirring, filtering, adding 60g of the prepared pretreatment emulsion, reacting for 1 hour under a vacuum condition, and filtering to obtain the pretreated nano silicon dioxide.
Preparation example 2: pretreatment of nanosilicon dioxide
The preparation of the pre-treatment emulsion comprises the following steps:
after 10g of sodium alginate, 17g of hexadecyl dimethyl betaine, 4g of sodium polymethacrylate, 2g of white carbon black and 200g of deionized water are uniformly mixed, 2g of glycerol and 15g of epoxy resin are added and uniformly mixed, and the pretreatment emulsion can be obtained.
The pretreatment of the nano silicon dioxide comprises the following steps:
mixing 90g of nano silicon dioxide and 100g of deionized water, and carrying out ultrasonic treatment for 1 hour at 25 ℃; adding 12g of silane coupling agent, stirring and filtering; and adding 36g of the prepared pretreatment emulsion, reacting for 1.5 hours under a vacuum condition, and filtering to obtain the pretreated nano silicon dioxide.
Preparation example 3: pretreatment of nanosilicon dioxide
The preparation of the pre-treatment emulsion comprises the following steps:
after 13g of sodium alginate, 6g of hexadecyl dimethyl betaine, 6g of sodium polymethacrylate, 2g of white carbon black and 200g of deionized water are uniformly mixed, 1.5g of glycerol and 10g of epoxy resin are added and uniformly mixed, and the pretreated emulsion is obtained.
The pretreatment of the nano silicon dioxide comprises the following steps:
mixing 90g of nano silicon dioxide and 100g of deionized water, and carrying out ultrasonic treatment for 2 hours at 35 ℃; adding 24g of silane coupling agent, stirring and filtering; and adding 50g of the prepared pretreatment emulsion, reacting for 3 hours under a vacuum condition, and filtering to obtain the pretreated nano silicon dioxide.
Example 1:
a preparation method of polyacrylamide emulsion comprises the following steps:
putting 80g of acrylamide, 60g of acrylic acid, 30g of nano silicon dioxide, 40g of 3-allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt, 0.3g of sodium ethylene diamine tetracetate, 0.03g of sodium formate, 0.3g of azodiisobutyronitrile, 0.2g of potassium persulfate and 220g of deionized water into a beaker, stirring to completely dissolve all materials, slowly adding 69g of a 48% sodium hydroxide solution by volume, and continuously and gradually dropwise adding the sodium hydroxide solution until the pH =7.5 of the system to prepare a water phase for later use;
adding 42g of sorbitan glycerate and 18g of sorbitan monostearate polyoxyethylene ether into 440g of white oil, and stirring to completely dissolve the sorbitan glycerate and the sorbitan monostearate polyoxyethylene ether to obtain an oil phase;
gradually dropwise adding 900g of water phase into 100g of oil phase under stirring, continuing stirring and emulsifying for 30min after dropwise adding, and emulsifying for 5min by using a homogenizing emulsifying machine to obtain an emulsion;
pouring the homogenized emulsion into a four-neck flask (the four-neck flask is respectively provided with a stirring paddle, a thermometer and a nitrogen inlet and outlet), using nitrogen to bubble and remove oxygen for 60min, using a water bath to control the temperature of the emulsion to reach 20 ℃, adding 0.01g of sodium bisulfite and 5g of deionized water into the emulsion to carry out polymerization reaction, heating to 80 ℃, stirring for 2 hours, cooling to 15 ℃, adding 40g of alkylphenol polyoxyethylene ether to carry out reaction, and obtaining the polyacrylamide emulsion.
Example 2:
a preparation method of polyacrylamide emulsion comprises the following steps:
putting 50g of acrylamide, 100g of methacrylic acid, 10g of nano silicon dioxide, 30g of 2-acrylamido-tetradecyl sulfonic acid, 0.1g of diethylenetriaminepentaacetic acid pentasodium, 0.01g of urea, 0.1g of azodiisopropyl imidazoline hydrochloride, 0.1g of ammonium persulfate and 220g of deionized water into a beaker, stirring to completely dissolve all materials, slowly adding 75g of a 48% sodium hydroxide solution by volume concentration, and continuously and gradually dropwise adding the sodium hydroxide solution until the pH =7.5 of the system to prepare a water phase for later use.
Adding 30g of octyl phenol polyoxyethylene ether and 40g of polyethylene glycol octyl phenyl ether into 500g of gasoline, and stirring to completely dissolve the components to obtain an oil phase;
gradually dripping 500g of water phase into 100g of oil phase under stirring, continuing stirring and emulsifying for 30min after dripping is finished, and emulsifying for 5min by using a homogenizing emulsifying machine to obtain an emulsion;
pouring the homogenized emulsion into a four-neck flask (the four-neck flask is respectively provided with a stirring paddle, a thermometer and a nitrogen inlet and outlet), carrying out bubbling deoxygenation for 60min by using nitrogen, controlling the temperature of the emulsion to 20 ℃ by using a water bath, adding 0.03g of sodium metabisulfite and 5g of deionized water into the emulsion for polymerization reaction, heating to 70 ℃, stirring for 1 hour, cooling to 20 ℃, adding 30g of alkylphenol polyoxyethylene ether, and reacting to obtain the polyacrylamide emulsion.
Example 3:
a preparation method of polyacrylamide emulsion comprises the following steps:
100g of acrylamide, 90g of maleic anhydride, 30g of 2-acrylamido-2-methylpropanesulfonic acid, 50g of nano-silica, 80g of dodecyl acrylamide, 0.5g of ethylenediamine tetrapropionic acid, 0.06g of isopropanol, 0.3g of azodiisobutyl amidine hydrochloride, 0.2g of dimethyl azodiisobutyrate, 0.2g of sodium persulfate, 0.2g of benzoyl peroxide and 220g of deionized water are placed in a beaker, stirred to completely dissolve all the materials, 69g of a 48% sodium hydroxide solution in volume concentration is slowly added, and the sodium hydroxide solution is continuously and gradually added until the pH =7.5 of the system to prepare an aqueous phase for later use.
Adding 30g of sorbitan monolaurate and 50g of polyoxyethylene sorbitan fatty acid ester into 100g of diesel oil and 500g of kerosene, and stirring to completely dissolve the sorbitan monolaurate and the polyoxyethylene sorbitan fatty acid ester to obtain an oil phase;
gradually adding 100g of water phase into 100g of oil phase under stirring, continuing stirring and emulsifying for 30min after adding dropwise, and emulsifying for 5min with a homogenizing emulsifying machine to obtain an emulsion;
pouring the homogenized emulsion into a four-neck flask (the four-neck flask is respectively provided with a stirring paddle, a thermometer and a nitrogen inlet and outlet), bubbling helium to remove oxygen for 60min, controlling the temperature of the emulsion to 20 ℃ by using a water bath, adding 0.01g of sodium metabisulfite, 0.04g of sodium bisulfite and 5g of deionized water into the emulsion to perform polymerization reaction, heating to 90 ℃, stirring for 3 hours, cooling to 18 ℃, adding 30g of octylphenol polyoxyethylene ether and 50g of alkylphenol polyoxyethylene ether to perform reaction, and obtaining the polyacrylamide emulsion.
Example 4:
a polyacrylamide emulsion was prepared as in example 1, except that: the nano-material used was the pretreated nano-silica obtained in preparation example 1.
Example 5:
a polyacrylamide emulsion was prepared as in example 2, except that: the nano material used was the pretreated nano silica obtained in preparation example 2.
Example 6:
a polyacrylamide emulsion was prepared as in example 3, except that: the nano material used was the pretreated nano silica obtained in preparation example 3.
Comparative example 1:
a polyacrylamide emulsion was prepared as in example 1, except that: after the temperature is increased to 69 ℃, stirring is carried out for 2 hours, and then the temperature is reduced to 15 ℃.
Comparative example 2:
a polyacrylamide emulsion was prepared as in example 1, except that: the temperature is raised to 91 ℃, the mixture is stirred for 2 hours, and then the temperature is reduced to 15 ℃.
Comparative example 3:
a polyacrylamide emulsion was prepared as in example 1, except that: no pretreatment emulsion was added.
Comparative example 4:
a polyacrylamide emulsion was prepared as in example 1, except that: no anionic monomer was added.
Comparative example 5:
a polyacrylamide emulsion was prepared as in example 2, except that: no nanomaterial was added.
Comparative example 6:
a polyacrylamide emulsion was prepared as in example 3, except that: no functional monomer was added.
And (3) performance detection:
1. the polyacrylamide emulsions prepared in examples 1 to 6 and the polyacrylamide emulsions prepared in comparative examples 1 to 6 were subjected to performance tests, and the test results are shown in table 1, and the molecular weights of the polyacrylamide emulsions prepared in examples 1 to 6 were 100 ten thousand or less.
TABLE 1 detection of the Properties of Polyacrylamide emulsions
1. It can be known from the combination of examples 1-6 and comparative examples 1-6 that the polyacrylamide emulsions prepared in examples 1-6 have lower surface tension and interfacial tension, and the surface tension and interfacial tension of the polyacrylamide emulsions prepared in examples 1-6 are lower than those of the polyacrylamide emulsions prepared in comparative examples 1-6, which indicates that the preparation method of the present application greatly improves the mechanical properties of the polyacrylamide emulsions.
It can be seen from the combination of examples 1-3 and examples 4-6 that the surface tension and interfacial tension of the polyacrylamide emulsion prepared in examples 4-6 are better than those of the polyacrylamide emulsion prepared in examples 1-3, which illustrates the improvement of the mechanical properties of the polyacrylamide emulsion after the pretreated nano-silica participates in the reaction.
Combining examples 1-3 and comparative examples 4-6, it can be seen that the surface tension and interfacial tension of the polyacrylamide emulsion prepared in examples 1-3 are better than those of the polyacrylamide emulsion prepared in comparative examples 4-6, which indicates that the mechanical properties of the product are enhanced by the synergistic effect among the anionic monomer, the nanomaterial and the functional monomer.
2. As can be seen by combining examples 1-6 and comparative examples 1-6, the drag reduction rates of the polyacrylamide emulsions prepared in examples 1-6 are higher than those of the polyacrylamide emulsions prepared in comparative examples 1-6, which indicates that the polyacrylamide emulsions prepared in the present application have higher drag reduction capability.
As can be seen from the combination of examples 1-3 and examples 4-6, the drag reduction rate of the polyacrylamide emulsion prepared in examples 4-6 is better than that of the polyacrylamide emulsion prepared in examples 1-3, which indicates that the drag reduction rate of the product is improved after the pretreated nano-silica participates in the reaction.
As can be seen by combining examples 1-3 and comparative examples 4-6, the drag reduction rate of the polyacrylamide emulsion prepared in comparative examples 4-6 is lower than that of the polyacrylamide emulsion prepared in examples 1-3, which shows that the drag reduction performance of the product is improved by the synergistic effect among the anionic monomer, the nano material and the functional monomer.
It can be seen from the combination of example 1 and comparative example 3 that, when the pretreatment is performed, the reaction is performed without adding the pretreatment emulsion, and the drag reduction rate of the polyacrylamide emulsion prepared in comparative example 3 is lower than that of example 1, which indicates that the drag reduction rate of the polyacrylamide emulsion prepared in the pretreatment reaction with adding the pretreatment emulsion is improved.
3. As can be seen from the combination of examples 1-6 and comparative examples 1-6, the viscosity of the polyacrylamide emulsions prepared in examples 1-6 is higher than that of the polyacrylamide emulsions prepared in comparative examples 1-6, which indicates that the polyacrylamide emulsions prepared in the present application have higher viscosity.
As can be seen from the combination of examples 1-3 and examples 4-6, the viscosity of the polyacrylamide emulsion prepared in examples 4-6 is better than that of the polyacrylamide emulsion prepared in examples 1-3, which indicates that the viscosity of the product is improved after the pretreated nano-silica participates in the reaction.
Combining examples 1-3 and comparative examples 4-6, it can be seen that the viscosity of the polyacrylamide emulsion prepared in comparative examples 4-6 is lower than that of the polyacrylamide emulsion prepared in examples 1-3, which indicates that the product viscosity is increased by the synergistic effect among the anionic monomer, the nanomaterial and the functional monomer.
Combining example 1 and comparative example 3, it can be seen that, when the pretreatment is performed, the reaction is performed without adding the pretreatment emulsion, and the viscosity of the polyacrylamide emulsion prepared in comparative example 3 is lower than that of example 1, which indicates that the viscosity of the polyacrylamide emulsion prepared by adding the pretreatment emulsion to perform the pretreatment reaction is improved.
4. As can be seen by combining examples 1-6 and comparative examples 1-6, the oil displacement efficiency of the polyacrylamide emulsions prepared in examples 1-6 is higher than that of the polyacrylamide emulsions prepared in comparative examples 1-6, which indicates that the polyacrylamide emulsions prepared in the present application have higher oil displacement efficiency.
As can be seen from the combination of examples 1 to 3 and examples 4 to 6, the oil displacement efficiency of the polyacrylamide emulsion prepared in examples 4 to 6 is better than that of the polyacrylamide emulsion prepared in examples 1 to 3, which indicates that the oil displacement efficiency of the product is improved after the pretreated nano-silica participates in the reaction.
As can be seen by combining examples 1-3 and comparative examples 4-6, the oil displacement efficiency of the polyacrylamide emulsion prepared in comparative examples 4-6 is lower than that of the polyacrylamide emulsion prepared in examples 1-3, which indicates that the oil displacement performance of the product is improved by the synergistic effect among the anionic monomer, the nano material and the functional monomer.
5. Combining examples 1-6 and comparative examples 1-6, it can be seen that the gelling time of the polyacrylamide emulsions prepared in examples 1-6 at 180 ℃ is much shorter than that of the polyacrylamide emulsions prepared in comparative examples 1-6, indicating that the polyacrylamide emulsions prepared in the present application have temperature resistance.
Combining examples 1-3 and examples 4-6, it can be seen that the gelling time of the polyacrylamide emulsions prepared in examples 4-6 is shorter than that of examples 1-3, which illustrates the improvement of the temperature resistance of the product after the pretreated nano-silica participates in the reaction.
Combining examples 1-3 and comparative examples 4-6, it can be seen that the gelling time of the polyacrylamide emulsion prepared in comparative examples 4-6 is longer than that of examples 1-3, which indicates that the temperature resistance of the product is improved by the synergistic effect among the anionic monomer, the nano material and the functional monomer.
6. Combining examples 1-6 and comparative examples 1-6, it can be seen that the dissolution time of the polyacrylamide emulsions prepared in examples 1-6 is much shorter than that of the polyacrylamide emulsions prepared in comparative examples 1-6, which indicates that the polyacrylamide emulsions prepared in the present application have a fast dissolution rate and a short dissolution time.
As can be seen from the combination of examples 1-3 and examples 4-6, the dissolution time of the polyacrylamide emulsion prepared in examples 4-6 is shorter than that of examples 1-3, which shows that the solubility of the pretreated nanosilicon dioxide is improved after the reaction.
Combining examples 1-3 and comparative examples 4-6, it can be seen that the dissolution time of the polyacrylamide emulsion prepared in comparative examples 4-6 is longer than that of the polyacrylamide emulsion prepared in examples 1-3, which indicates that the solubility of the product is improved by the synergistic effect among the anionic monomer, the nanomaterial, and the functional monomer.
It can be seen from the combination of example 1 and comparative example 3 that the reaction was carried out without adding the pre-treatment emulsion during the pre-treatment, and the dissolution time of the polyacrylamide emulsion prepared in comparative example 3 was longer than that of example 1, which indicates that the solubility of the polyacrylamide emulsion prepared by adding the pre-treatment emulsion during the pre-treatment reaction was improved.
2. The stability of the polyacrylamide emulsions prepared in examples 1 to 6 and the stability of the polyacrylamide emulsions prepared in comparative examples 1 to 6 were measured in accordance with GB/T12005.2 to 89, and the results are shown in Table 2.
TABLE 2 detection of delamination of Polyacrylamide emulsions
As can be seen from Table 2, the polyacrylamide emulsions prepared in examples 1-6 of the present application did not delaminate when centrifuged at 8500rpm for 10 minutes, and the polyacrylamide emulsions did not delaminate after standing at room temperature for 18 months, indicating that the polyacrylamide emulsions prepared in examples 1-6 of the present application were stable.
3. Sand carrying performance:
the sand-carrying properties of the polyacrylamide emulsions prepared in examples 1 to 6 and those of the polyacrylamide emulsions prepared in comparative examples 1 to 6 were measured, and the results are shown in table 3.
TABLE 3 Sand carrying Performance test of Polyacrylamide emulsions
The sand-carrying performance of the polyacrylamide emulsions prepared in examples 1 to 6 is higher than that of the polyacrylamide emulsions prepared in comparative examples 1 to 6, which shows that the polyacrylamide emulsions prepared in the application have higher sand-carrying performance.
It can be known from examples 1 to 3 and examples 4 to 6 that, when the nano-silica is not pretreated, the sand-carrying performance of the polyacrylamide emulsion prepared in examples 1 to 3 is lower than that of examples 4 to 6, which indicates that the sand-carrying performance of the polyacrylamide emulsion prepared by the pretreatment step in the application is improved.
It can be known from the combination of example 1 and comparative example 3 that, when the pretreatment is performed, no pretreatment emulsion is added for reaction, and the sand carrying performance of the polyacrylamide emulsion prepared in comparative example 3 is lower than that of example 1, which indicates that the sand carrying performance of the polyacrylamide emulsion prepared in the pretreatment reaction with the pretreatment emulsion is improved.
By combining examples 1-3 and comparative examples 4-6, it can be known that the sand carrying performance of comparative examples 1-3 is lower than that of comparative examples 4-6, which shows that the sand carrying performance of the product is improved through the synergistic effect among the anionic monomer, the nano material and the functional monomer.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The preparation method of the polyacrylamide emulsion is characterized by comprising the following steps:
mixing acrylamide, an anionic monomer, a nano material, a functional monomer, a chelating agent, a molecular weight regulator, a thermal initiator and a low-temperature initiator, and then regulating the pH to 7-9 to obtain a water phase;
adding an emulsifier into the oil to obtain an oil phase;
mixing the water phase and the oil phase to obtain an emulsion;
adding a reducing agent into the emulsion for reaction, and then adding a phase inversion agent for reaction to obtain a polyacrylamide emulsion;
wherein the anionic monomer is at least one of acrylic acid, methacrylic acid, maleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid;
the functional monomer is at least one of 3-allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt, 2-acrylamide-tetradecyl sulfonic acid and dodecyl acrylamide;
the nano material is nano silicon dioxide.
2. The preparation method of the polyacrylamide emulsion according to claim 1, wherein the nano-silica is pretreated nano-silica, and the pretreatment steps of the nano-silica are as follows: mixing nano silicon dioxide and deionized water, carrying out ultrasonic treatment for 1-2 hours at 25-35 ℃, adding a silane coupling agent for reaction, then filtering, adding a pretreatment emulsion, carrying out reaction for 1-3 hours under a vacuum condition, and then filtering to obtain the pretreated nano silicon dioxide.
3. The method for preparing a polyacrylamide emulsion according to claim 2, wherein: the mass ratio of the nano silicon dioxide to the silane coupling agent to the pretreated emulsion is 15:2-4:6-10.
4. The preparation method of the polyacrylamide emulsion according to claim 2, wherein the pre-treatment emulsion comprises the following raw material components in parts by mass: 10-15 parts of epoxy resin, 10-15 parts of sodium alginate, 6-17 parts of hexadecyl dimethyl betaine, 2-6 parts of sodium polymethacrylate, 1-2 parts of white carbon black and 1-2 parts of glycerol.
5. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: the low-temperature initiator is at least one of potassium persulfate, ammonium persulfate, sodium persulfate and benzoyl peroxide; the thermal initiator is at least one of azobisisobutyronitrile, azobisisopropylimidazoline hydrochloride, azobisisobutylamidine hydrochloride and dimethyl azobisisobutyrate.
6. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: the chelating agent is at least one of ethylenediamine tetraacetic acid sodium salt, diethylenetriamine pentaacetic acid pentasodium salt and ethylenediamine tetrapropionic acid; the molecular weight regulator is at least one of urea, formate and isopropanol.
7. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: the emulsifier is at least one of sorbitan monolaurate, polyoxyethylene octylphenol ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan glycerate and sorbitan monostearate polyoxyethylene ether;
the oil is at least one of gasoline, diesel oil, kerosene and white oil.
8. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: the reducing agent is one or two of sodium metabisulfite and sodium bisulfite; the phase transfer agent is one or two of octyl phenol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
9. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: adding a reducing agent into the emulsion for reaction, heating to 70-90 ℃, stirring for 1-3 hours, cooling to 15-20 ℃, and adding a phase inversion agent for reaction.
10. The method for preparing a polyacrylamide emulsion according to claim 1, wherein: the mass ratio of acrylamide, anionic monomer, nano material, functional monomer, chelating agent, molecular weight regulator, thermal initiator and low-temperature initiator is 5-10:6-12:1-5:3-8:0.01-0.05:0.001-0.006:0.01-0.05:0.01-0.04; the mass ratio of acrylamide, oil, emulsifier, reducing agent and phase transfer agent is 5-10:44-60:5-8:0.001-0.005:3-8;
the mass ratio of the water phase to the oil phase is 9-1.
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