CN115215978A - Modified acid thickener and preparation method thereof - Google Patents
Modified acid thickener and preparation method thereof Download PDFInfo
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- CN115215978A CN115215978A CN202211118409.4A CN202211118409A CN115215978A CN 115215978 A CN115215978 A CN 115215978A CN 202211118409 A CN202211118409 A CN 202211118409A CN 115215978 A CN115215978 A CN 115215978A
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Abstract
The invention provides a modified acid thickener and a preparation method thereof, which relate to the technical field of polymerization and oil field fracturing, and comprise the following steps: performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer; carrying out polycondensation reaction on the lactose aldehyde acid and allylamine to obtain a lactose aldehyde acid prepolymer; uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; mixing white oil, a main emulsifier and an auxiliary emulsifier uniformly to obtain an oil phase solution; and adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent. The modified acid thickener prepared by the invention has strong tackifying capability in acid liquor and excellent temperature resistance and shear resistance.
Description
Technical Field
The invention relates to the technical field of polymerization and oilfield fracturing, in particular to a modified acid thickener and a preparation method thereof.
Background
With the rapid development of economy and industry, the demand for oil and natural gas energy is increasing day by day, and it is important to reasonably develop oil and gas resources and improve the oil and gas recovery ratio to the maximum extent. The acidification reconstruction technology is one of the important technical means for realizing reservoir reconstruction, yield increase and water well injection enhancement of oil and gas wells in various oil fields at present so as to mainly remove the pollution of the reservoir of the oil and gas wells to recover the permeability of the underground reservoir. The acid fracturing is mainly characterized in that the stratum is reformed by utilizing the corrosion action of acid liquor to form a relatively long acid fracturing crack, so that the backflow capacity of an oil-gas layer is improved, and the yield of an oil-gas well is increased. The acid liquid thickener is used as a main component of thickening acid, reduces the diffusion rate of hydrogen ions to the surface of rock and the fluid loss by improving the viscosity of the acid liquid, and plays a role in delaying acid rock reaction and reducing friction resistance in the acid fracturing process.
The deep acidification is mainly used for preventing the acid liquor from being filtered on the fracture surface, and meanwhile, the acid liquor is filtered on the fracture surface to form acid etching holes. If serious acid liquor filtration occurs, the effective action distance of the acid liquor on the crack surface is greatly shortened. Research shows that the acid liquor with considerable viscosity can effectively slow down the filtration loss speed, thereby increasing the effective acid etching action distance. Although the polyacrylamide which is commonly used as the acid liquid thickener at present can meet the requirements of general operation, the polyacrylamide has the defects of tackifying performance, acid resistance stability, shearing resistance, temperature resistance and the like.
Disclosure of Invention
The embodiment of the invention provides a modified acid thickener and a preparation method thereof.
In a first aspect, the present invention provides a preparation method of a modified acid viscosifier, wherein the preparation method comprises:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; mixing white oil, a main emulsifier and an auxiliary emulsifier uniformly to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent;
the modified acid solution thickener is prepared from the following raw materials in parts by weight: 150-200 parts of acrylamide, 180-210 parts of (3-acrylamidopropyl) trimethyl ammonium chloride, 5-10 parts of triallyl cyanurate, 20-30 parts of a lignin prepolymer, 20-30 parts of a lactobionic acid prepolymer, 230-325 parts of water, 0.005-0.01 part of a first initiator, 230-270 parts of white oil, 15-30 parts of a main emulsifier, 3-7 parts of an auxiliary emulsifier and 22-24 parts of a phase transfer agent.
Preferably, in the step (1), the mass ratio of the sodium lignin sulfonate to the allyl halogenated hydrocarbon is (3.5 to 4.4): 1.
Preferably, in step (1), the temperature of the polycondensation reaction is 80 ℃ and the reaction time is not less than 24 hours.
Preferably, in step (1), the allylic halohydrocarbon is allyl chloride, allyl bromide, or allyl iodide.
Preferably, in the step (2), the mass ratio of the lactobionic acid to the allylamine is (2.5 to 3.2): 1.
Preferably, in the step (2), the temperature of the polycondensation reaction is 50 to 55 ℃, and the reaction time is not less than 12h.
Preferably, the step (3) further comprises: and adjusting the pH value of the aqueous phase solution to 3.8-5.
Preferably, the pH of the aqueous phase solution is adjusted with a pH adjuster; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
Preferably, the main emulsifier is at least one of span-20, span-60, span-80 and span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
Preferably, the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide and benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite.
Preferably, the phase inversion agent is OP-10 or NP-10.
Preferably, in step (4), the temperature of the polymerization reaction is controlled not to exceed 75 ℃ by controlling the amount of the second initiator.
Preferably, in the step (4), the emulsifying time is 20 to 30min;
the temperature for initiating the polymerization reaction is 15 to 20 ℃; the polymerization reaction time is 5 to 7h.
In a second aspect, the invention provides a modified acid thickener, which is prepared by using any one of the preparation methods in the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
the method comprises the steps of introducing a carbon-carbon double bond into sodium lignosulfonate through a polycondensation reaction of sodium lignosulfonate and allyl halohydrocarbon to obtain a lignin prepolymer; simultaneously, carbon-carbon double bonds are introduced into lactobionic acid molecules through the polycondensation reaction of allylamine and lactobionic acid to obtain a lactobionic acid prepolymer; then, the modified acid liquid thickener is obtained after the reversed phase emulsion polymerization reaction with acrylamide, (3-acrylamide propyl) trimethyl ammonium chloride and triallyl cyanurate. The modified acid solution densifier has strong tackifying capability in acid solution and excellent temperature resistance and shear resistance.
The amido and cationic groups in the modified acid thickener prepared by the invention have good hydrophilicity, so that the modified acid thickener has excellent water solubility; wherein, the cationic group has positive charge and has good acid resistance; the benzene ring structure in the lignin prepolymer improves the rigidity of a molecular chain, enhances the anti-shearing capacity, and in addition, the benzene ring has hydrophobic property, so that a polymer molecular chain can generate hydrophobic association micro-regions, intermolecular association is generated, a space network structure is formed, the tackifying effect is achieved, and the rigidity and the hydrophobic association of the molecular chain jointly improve the thermal stability of the polymer. Meanwhile, the salt resistance and hydrolysis resistance of the sulfonic acid group enable the prepared modified acid thickener to have salt resistance.
In the invention, the hydroxyl in the lactobionic acid prepolymer further enhances the solubility of the polymer and improves the dissolution speed, and the hydroxyl belongs to an insensitive group of hydrogen ions, thereby further improving the acid resistance of the polymer; the triallyl cyanurate is crosslinked in a molecular chain to form a net structure, and the net structure is mutually interlaced and interpenetrated with a six-membered ring in the lactobionic acid prepolymer, so that on one hand, the thermal stability and the shear resistance of the polymer molecular chain are further improved; on the other hand, the interpenetrating network structure can effectively prevent the activity of hydrogen ions in acid, thereby reducing the consumption rate of the acid liquor, increasing the effective action distance and achieving the purpose of slowing down.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions of the present invention will be described below in conjunction with the embodiments of the present invention, obviously, the described embodiments are a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a preparation method of a modified acid thickener, which comprises the following steps:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on lactobionic acid and allylamine to obtain a lactobionic acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, a lignin prepolymer, a lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; uniformly mixing white oil, a main emulsifier and an auxiliary emulsifier to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase transfer agent after the reaction is finished to obtain a modified acid solution densifier;
the modified acid solution thickener is prepared from the following raw materials in parts by weight: acrylamide 150 to 200 parts (for example, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts, 195 parts, or 200 parts) or (3-acrylamidopropyl) trimethylammonium chloride 180 to 210 parts (for example, 180 parts, 185 parts, 190 parts, 195 parts, 200 parts, 205 parts, or 210 parts) or (5 to 10 parts (for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts) of triallyl cyanurate), a lignin prepolymer 20 to 30 parts (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or a lactobionic acid prepolymer 20 to 30 parts (for example, 21 parts, 22 parts, 25 parts, 26 parts, 28 parts, 29 parts, or 30 parts) or (for example, 230 to 325 parts) or (for example, may be 235 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, 300 parts, 310 parts, 320 parts or 325 parts), 0.005 to 0.01 part (for example, may be 0.005 parts, 0.006 parts, 0.007 parts, 0.008 parts, 0.009 parts or 0.01 parts), white oil to 230 parts (for example, may be 230 parts, 235 parts, 240 parts, 245 parts, 250 parts, 255 parts, 260 parts, 265 parts or 270 parts), 15 to 30 parts (for example, may be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 25 parts, 26 parts, 28 parts or 30 parts), 3 to 7 parts (for example, may be 3 parts, 4 parts, 5 parts, 6 parts or 7 parts), 22 to 24 parts (for example, may be 22 parts, 22.5 parts, 23 parts, 23.5 parts or 24 parts) of a phase inversion agent.
In the invention, the water-in-oil modified acid thickener is prepared by introducing the synergistic effect of lignin prepolymer, lactose aldehyde acid prepolymer, acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride and triallyl cyanurate. The modified acid solution densifier has excellent water solubility, strong tackifying capability in acid solution and excellent temperature resistance and shear resistance.
According to some preferred embodiments, in step (1), the mass ratio of sodium lignosulfonate to allylic halohydrocarbon is (3.5 to 4.4): 1 (for example, 1, 3.6.
In the present invention, the allyl halohydrocarbon is slightly in excess to ensure that the sodium lignosulfonate can be completely reacted, so that the mass ratio of the sodium lignosulfonate to the allyl halohydrocarbon is limited to the above range, thereby ensuring the yield of the lignin prepolymer.
According to some preferred embodiments, in step (1), the temperature of the polycondensation reaction is 80 ℃ and the reaction time is not less than 24 hours (for example, it may be 24 hours, 28 hours, 32 hours, 36 hours, etc.).
According to some preferred embodiments, in step (1), the allylic halohydrocarbon is allyl chloride, allyl bromide, or allyl iodide.
Specifically, when the allyl halogenated hydrocarbon is allyl bromide, the solvent medium is acetone, and the reaction formula of the polycondensation reaction in step (1) is as follows:
in this reaction scheme, potassium carbonate is used to provide an alkaline environment and to handle the byproduct hydrogen bromide. It should be noted that the solvent medium includes, but is not limited to, acetone, and may be any solvent that can ensure that the reactants are completely dissolved and do not participate in the reaction.
In the invention, carbon-carbon double bonds are introduced into sodium lignosulfonate through the polycondensation reaction of sodium lignosulfonate and allyl halohydrocarbon to obtain a lignin prepolymer, the benzene ring structure in the lignin prepolymer improves the rigidity of the molecular chain of the prepared modified acid thickener, the anti-shearing capability is enhanced, in addition, the benzene ring has hydrophobic property, a polymer molecular chain can generate hydrophobic association micro-areas, intermolecular association is generated, a space network structure is formed to achieve the adhesion increasing effect, and the rigidity and the hydrophobic association of the molecular chain jointly improve the thermal stability of the polymer.
According to some preferred embodiments, in step (2), the mass ratio of lactobionic acid to allylamine is (2.5 to 3.2): 1 (for example, 2.5.
In the present invention, the yield of the galacturonic acid prepolymer is ensured by limiting the mass ratio of galacturonic acid to allylamine to the above range by slightly adding an excess of allylamine to ensure complete reaction of galacturonic acid.
According to some preferred embodiments, in the step (2), the temperature of the polycondensation reaction is 50 to 55 ℃ (for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ or 55 ℃), and the reaction time is not less than 12h (for example, 12h, 14h, 16h, 18h, 24h, etc.).
Specifically, the reaction formula of the condensation reaction of step (2) is as follows:
it should be noted that the solvent medium in step (2) includes, but is not limited to, absolute ethanol, and may be any solvent that can ensure that the reactants can be completely dissolved and do not participate in the reaction.
In the invention, carbon-carbon double bonds are introduced into lactobionic acid molecules through the polycondensation reaction of allylamine and lactobionic acid to obtain a lactobionic acid prepolymer, the solubility of the polymer is further enhanced and the dissolution speed is improved due to the hydroxyl in the lactobionic acid prepolymer, and the hydroxyl belongs to an insensitive group of hydrogen ions, so that the acid resistance of the polymer is further improved; the triallyl cyanurate is crosslinked in a molecular chain to form a net structure, and the net structure is mutually interlaced and interpenetrated with a six-membered ring in the lactobionic acid prepolymer, so that on one hand, the thermal stability and the shear resistance of the polymer molecular chain are further improved; on the other hand, the interpenetrating network structure can effectively prevent the activity of hydrogen ions in acid, thereby reducing the consumption rate of the acid liquor, increasing the effective action distance and achieving the purpose of slowing down.
According to some preferred embodiments, step (3) further comprises: the pH of the aqueous solution is adjusted to 3.8 to 5 (e.g., 3.9, 4, 4.2, 4.5, 4.6, 4.8, or 5).
According to some preferred embodiments, the pH of the aqueous phase solution is adjusted with a pH adjuster; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
At least one of them is a mixture of any one or any several of them mixed in any ratio.
Experiments prove that the pH value of the aqueous phase solution is adjusted to 3.8 to 5, so that the influence of the acidity and alkalinity of a reaction medium on the decomposition rate of an initiator can be avoided, and the polymerization degree of the modified acid thickener is ensured.
According to some preferred embodiments, the primary emulsifier is at least one of span-20, span-60, span-80, span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
Experiments prove that the water-in-oil system of the prepared modified acid thickener is unstable due to the fact that the HLB value of the single emulsifier is fixed. Therefore, by using the two emulsifiers in a composite way, the HLB value of a water-in-oil system can be adjusted to reach a certain range, so that the modified acid thickener is more stable.
According to some preferred embodiments, the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide, benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium pyrosulfite.
The first initiator is an oxidative initiator and the second initiator is a corresponding reductive initiator.
According to some preferred embodiments, the phase transfer agent is OP-10 or NP-10.
According to some preferred embodiments, in step (4), the emulsification time is 20 to 30min (e.g., can be 20min, 25min, or 30 min);
the temperature at which the polymerization reaction is initiated is 15 to 20 ℃ (for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃ or 20 ℃); the polymerization time is 5 to 7h (for example, 5h, 5.5h, 6h, 6.5h or 7 h).
According to some preferred embodiments, in step (4), the temperature of the polymerization reaction is controlled not to exceed 75 ℃ by controlling the amount of the second initiator.
In the invention, because the reaction is exothermic and the temperature is too high, the polymerization degree of the prepared modified acid thickener can be caused by too high reaction rate, and the thickening effect of the modified acid thickener is further influenced. The maximum temperature at the end of the polymerization reaction is thus limited to a range of 70 to 75 ℃ by controlling the amount of the second initiator added.
In the invention, water is used as a reaction medium of the polymerization reaction, so that the cost is low, the influence of an organic solvent on environmental pollution can be eliminated, the preparation process is simple, and heating is not required. And the environment of the reaction medium is neutral, the preparation process is environment-friendly, pollution-free, low in energy consumption, nontoxic and noncorrosive in the product, and free of secondary pollution, and the method conforms to the development direction of green and environment-friendly chemical additives.
Specifically, in step (4): and adding the water phase solution with the pH of 3.8 to 5 into the oil phase solution, emulsifying for 20 to 30min, introducing nitrogen for deoxygenation, adding a second initiator to initiate polymerization reaction, and adding a phase transfer agent after the reaction is completed for 5 to 7h to obtain the modified acid liquid thickener.
According to the invention, by limiting the parts of the raw materials used by the modified acid solution thickener, the prepared modified acid solution thickener has strong tackifying capability in acid solution, good structural stability and excellent temperature resistance and shear resistance.
In the invention, when the usage amount of other components is unchanged, the usage amount of the lignin prepolymer used for preparing the modified acid thickener is limited to 20 to 30 parts. Therefore, the problems that when the dosage of the lignin prepolymer is excessive, the water-in-oil system is unstable due to excessively strong hydrophobicity, and slag or agglomeration is easy to occur in the reaction process can be avoided; meanwhile, the problems that the prepared polymer has poor shear resistance and poor tackifying effect when the dosage of the polymer is too low can be avoided. Similarly, when the dosage of other components is not changed, the dosage of the galacturonic acid prepolymer used for preparing the modified acid thickener is limited to 20 to 30 parts. Therefore, as the lactobionic acid prepolymer has a six-membered ring structure, if the dosage of the lactobionic acid prepolymer is too much, the hydrophobicity is too strong, and the other two double bonds are easy to crosslink, so that the reaction of a water-in-oil system is unstable; if the consumption of the lactobionic acid prepolymer is too low, the solubility and the acid resistance of the prepared polymer are poor.
In the invention, when the using amounts of other components are unchanged, the using amount of the triallyl cyanurate used for preparing the modified acid thickener is limited to 5 to 10 parts. Therefore, the phenomenon that the water-in-oil system is unstable due to excessive crosslinking reaction in the polymerization reaction process when the dosage of the water-in-oil system is excessive can be avoided.
The invention also provides a modified acid thickener prepared by the preparation method.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a modified acid thickener and a preparation method thereof are described in detail by using several examples.
Preparing a lignin prepolymer:
17.8g of sodium lignosulfonate, 4.5g of allyl bromide and 4.33g of potassium carbonate are weighed and placed in a three-neck flask, 350mL of acetone solvent is added into the three-neck flask, nitrogen protection is started after uniform mixing, the three-neck flask is placed in a hot water bath, the temperature is controlled to be 80 ℃, and the reaction is stopped after heating reflux is carried out for 24 hours. And after the reaction is finished, filtering, recrystallizing the product for 3 times by using absolute ethyl alcohol, and drying to obtain the target product lignin prepolymer.
Preparation of galacturonic acid prepolymer:
12.34g of lactobionic acid was weighed into a three-necked flask with a stirrer containing 200mL of absolute ethanol, and 4.1g of allylamine was weighed and dissolved in 50mL of absolute ethanol. And (3) putting the three-neck flask into a water bath kettle, setting the temperature at 50 ℃, starting nitrogen protection, stirring, dropwise adding an ethanol solution of allylamine into the three-neck flask, and continuing to react for 12 hours after dropwise adding is finished within 30 min. And after the reaction is finished, filtering, washing the product for 3 times by using ether, and performing suction filtration and drying to obtain the target product, namely the lactobionic acid prepolymer.
Example 1
Preparing a modified acid thickener:
adding 305g of deionized water, 150g of acrylamide, 210g of (3-acrylamidopropyl) trimethyl ammonium chloride, 5g of triallyl cyanurate, 20g of lignin prepolymer, 20g of lactose aldehyde acid prepolymer and 0.008g of first initiator (ammonium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 3.8 by adopting adipic acid;
adding 15g of main emulsifier (span-20) and 4g of auxiliary emulsifier (Tween-65) into 230g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the uniform water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium sulfite aqueous solution, the mass fraction of sodium sulfite is 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization, simultaneously using an ice water bath to cooperatively control the temperature of the reactor, enabling the temperature rise rate of the reaction system to be 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 6h, adding 22g of phase inversion agent (OP-10), and stirring and uniformly mixing to obtain the modified acid thickener.
Example 2
Preparing a modified acid thickener:
adding 300g of deionized water, 160g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, 6g of triallyl cyanurate, 21g of lignin prepolymer, 23g of galacturonic acid prepolymer and 0.007g of first initiator (potassium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.1 by adopting acetic acid;
adding 17g of main emulsifier (span-60) and 3g of auxiliary emulsifier (Tween-81) into 260g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (a sodium bisulfite aqueous solution, the mass fraction of sodium bisulfite is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 7h, adding 22g of a phase transfer agent (NP-10), and stirring and uniformly mixing to obtain the modified acid solution thickening agent.
Example 3
Preparing a modified acid thickener:
adding 273g of deionized water, 180g of acrylamide, 200g of (3-acrylamidopropyl) trimethyl ammonium chloride, 7g of triallyl cyanurate, 25g of lignin prepolymer, 25g of lactose aldehyde acid prepolymer and 0.01g of first initiator (tert-butyl hydroperoxide) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.2 by adopting hydrochloric acid;
adding 19g of main emulsifier (span-80) and 7g of auxiliary emulsifier (Tween-85) into 240g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the uniform water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium metabisulfite aqueous solution with the mass fraction of 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization, cooperatively controlling the temperature of the reactor by using an ice-water bath to enable the temperature rising rate of the reaction system to be 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 5h, adding 24g of phase transfer agent (OP-10), and stirring and uniformly mixing to obtain the modified acid thickener.
Example 4
Preparing a modified acid thickener:
277g of deionized water, 180g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, 190g of triallyl cyanurate, 30g of lignin prepolymer, 25g of galacturonic acid prepolymer and 0.01g of first initiator (ammonium persulfate) are sequentially added into a reactor and uniformly mixed to obtain an aqueous phase solution, and the pH value of the aqueous phase solution is adjusted to 5.0 by adopting adipic acid;
adding 25g of main emulsifier (span-83) and 5g of auxiliary emulsifier (Tween-81) into 250g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the uniform water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (sodium metabisulfite aqueous solution with the mass fraction of 1 wt%) by using a micro-injection pump under the nitrogen atmosphere to initiate polymerization, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 6.5h, adding 24g of phase transfer agent (NP-10), and stirring and uniformly mixing to obtain the modified acid solution densifier.
Example 5
Preparing a modified acid thickener:
adding 260g of deionized water, 200g of acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride 180g, 10g of triallyl cyanurate, 30g of lignin prepolymer, 30g of galacturonic acid prepolymer and 0.009g of first initiator (potassium persulfate) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 4.0 by adopting acetic acid;
adding 30g of main emulsifier (span-80) and 6g of auxiliary emulsifier (Tween-81) into 270g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (a sodium bisulfite aqueous solution, the mass fraction of sodium bisulfite is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 5.5h, adding 23g of a phase transfer agent (NP-10), and stirring and uniformly mixing to obtain the modified acid solution densifier.
Comparative example 1
Preparing an acid thickener:
adding 350g of deionized water, 170g of acrylamide, 190g of (3-acrylamidopropyl) trimethyl ammonium chloride and 0.01g of first initiator (tert-butyl hydroperoxide) into a reactor in sequence, uniformly mixing to obtain an aqueous phase solution, and adjusting the pH of the aqueous phase solution to 5.0 by adopting adipic acid;
adding 20g of main emulsifier (span-80) and 5g of auxiliary emulsifier (Tween-85) into 250g of white oil, and mixing uniformly to obtain an oil phase solution;
adding the water phase solution into the oil phase solution, emulsifying for 20min by using a homogenizer to obtain a uniform water-in-oil emulsion, transferring the water-in-oil emulsion into a reactor, introducing nitrogen for 30min, controlling the temperature of the system to be 15-20 ℃, adding a second initiator (a sodium bisulfite aqueous solution, the mass fraction of sodium bisulfite is 1 wt%) by using a micro injection pump under the nitrogen atmosphere to initiate polymerization reaction, simultaneously cooperatively controlling the temperature of the reactor by using an ice water bath to ensure that the temperature rising rate of the reaction system is 30 s/0.1-40 s/0.1 ℃, finishing the reaction for 6h, adding 23g of a phase transfer agent (OP-10), and stirring and uniformly mixing to obtain an acid thickener.
Comparative example 2
Comparative example 2 is substantially the same as example 4 except that: no lignin prepolymer was added instead of 30g of deionized water, i.e., 307g of deionized water.
Comparative example 3
Comparative example 3 is substantially the same as example 4 except that: lactose aldehyde acid prepolymer is not added, and 25g of deionized water is added instead, namely 302g of deionized water is added.
Comparative example 4
Comparative example 4 is substantially the same as example 4 except that: triallyl cyanurate was not added instead of 8g of deionized water, i.e. 285g of deionized water.
The modified acid viscosifiers obtained in examples 1 to 5 and the acid viscosifiers obtained in comparative examples 1 to 4 are used as samples, 4g of the samples are weighed respectively, slowly added into 396g of hydrochloric acid solution (wherein the mass fraction of hydrochloric acid is 20%) under magnetic stirring, and dispersed and mixed uniformly to obtain sample solutions. Wherein the adding time of the sample is less than 10s, stirring is stopped and covered after the sample is stirred until no insoluble substances exist and the sample is homogeneous, and the mixture is kept stand in a constant-temperature water bath kettle at the temperature of 20 ℃ for 0.5h to fully swell the mixture to prepare the thickening acid. The thickening acids obtained above were then tested for apparent viscosity, viscosity retention, and high temperature stability, respectively, and the test results are shown in table 1.
Specifically, the method comprises the following steps: transferring the thickening acid into a sample cup of a six-speed rotary viscometer, standing for 0.5h in an environment at 20 ℃, and then standing for 170s -1 Measurement of viscosity at 20 ℃ at shear Rate η 0 . Standing the thickening acid in an environment of 120 ℃ for 6 hours, cooling to 20 ℃, and visually testing the stability (whether the thickening acid is precipitated or layered) under natural light; and using six-speed rotary viscometer at 170s -1 Measuring viscosity eta at shear rate 1 . Viscosity retention = η 1 /η 0 ×100%。
TABLE 1
As can be seen from the data in Table 1, the modified acid viscosifier prepared according to the present invention has an acid resistance increase in a 20wt% hydrochloric acid solutionStrong adhesive power, 170s -1 The viscosity reaches more than 60 mPas at the shearing rate, and the high-viscosity polyurethane elastomer has good shearing resistance. The viscosity retention rate after standing for 6 hours at 120 ℃ is kept above 90%, no delamination and no precipitate appear, and the high-temperature stability is good, which indicates that the modified acid thickener has excellent temperature resistance and shear resistance stability.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention. The invention has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. The preparation method of the modified acid thickener is characterized by comprising the following steps:
(1) Performing polycondensation reaction on sodium lignosulfonate and allyl halohydrocarbon to obtain lignin prepolymer;
(2) Carrying out polycondensation reaction on the lactose aldehyde acid and allylamine to obtain a lactose aldehyde acid prepolymer;
(3) Uniformly mixing acrylamide, (3-acrylamidopropyl) trimethyl ammonium chloride, triallyl cyanurate, the lignin prepolymer, the lactobionic acid prepolymer, water and a first initiator to obtain an aqueous phase solution; mixing white oil, a main emulsifier and an auxiliary emulsifier uniformly to obtain an oil phase solution;
(4) Adding the water phase solution into the oil phase solution for emulsification, then adding a second initiator to initiate polymerization reaction, and adding a phase inversion agent after the reaction is finished to obtain the modified acid solution thickening agent;
the modified acid thickener is prepared from the following raw materials in parts by weight: 150-200 parts of acrylamide, 180-210 parts of (3-acrylamidopropyl) trimethyl ammonium chloride, 5-10 parts of triallyl cyanurate, 20-30 parts of a lignin prepolymer, 20-30 parts of a lactobionic acid prepolymer, 230-325 parts of water, 0.005-0.01 part of a first initiator, 230-270 parts of white oil, 15-30 parts of a main emulsifier, 3-7 parts of an auxiliary emulsifier and 22-24 parts of a phase transfer agent.
2. The production method according to claim 1, wherein in step (1):
the mass ratio of the sodium lignin sulfonate to the allyl halogenated hydrocarbon is (3.5-4.4) to 1; and/or
The temperature of the polycondensation reaction is 80 ℃, and the reaction time is not less than 24h; and/or
The allylic halohydrocarbon is allyl chloride, allyl bromide, or allyl iodide.
3. The production method according to claim 1, wherein in step (2):
the mass ratio of the lactobionic acid to the allylamine is (2.5 to 3.2) to 1; and/or
The temperature of the polycondensation reaction is 50 to 55 ℃, and the reaction time is not less than 12h.
4. The method of claim 1, wherein:
the step (3) further comprises: and adjusting the pH value of the aqueous phase solution to 3.8-5.
5. The method of claim 4, wherein:
adjusting the pH of the aqueous phase solution with a pH adjusting agent; wherein the pH regulator is at least one of adipic acid, acetic acid and hydrochloric acid.
6. The method of claim 1, wherein:
the main emulsifier is at least one of span-20, span-60, span-80 and span-83;
the auxiliary emulsifier is at least one of tween-65, tween-81 and tween-85.
7. The method of claim 1, wherein:
the first initiator is at least one of ammonium persulfate, potassium persulfate, tert-butyl hydroperoxide and benzoyl peroxide;
the second initiator is at least one of sodium sulfite, sodium bisulfite and sodium metabisulfite; and/or
The phase transfer agent is OP-10 or NP-10.
8. The production method according to claim 1, wherein in step (4):
controlling the temperature of the polymerization reaction to not exceed 75 ℃ by controlling the amount of the second initiator.
9. The production method according to any one of claims 1 to 8, characterized in that, in step (4):
the emulsifying time is 20 to 30min;
the temperature for initiating the polymerization reaction is 15 to 20 ℃; the polymerization reaction time is 5 to 7h.
10. A modified acid viscosifier which is prepared by the preparation method of any one of claims 1 to 9.
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