CN120737263B - A thickener for high-temperature acidification and its preparation method - Google Patents
A thickener for high-temperature acidification and its preparation methodInfo
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Abstract
本发明涉及一种高温酸化用稠化剂及其制备方法，属于石油助剂技术领域。该稠化剂的重量百分比组分为：改性CMC增稠剂37‑45wt%、助溶剂5.2‑7.0wt%、助分散剂1.2‑1.6wt%和稳定剂2.4‑3.1wt%，余量为水；改性CMC增稠剂以羧甲基纤维素为基体，引入含磺基甜菜碱和环硅氧烷的侧链改性，在酸液注井过程中，其环硅氧烷结构水解缩合，大幅增加酸化液在井内粘度，在井下形成缓速分流，持续高温酸性环境，羧甲基纤维素主链分解破胶，进而形成自适应稠化，适配井下酸化稠化需求；同时，避免了难降解的聚合物使用，在油气的环保开采技术中具有深远的研究意义。
This invention relates to a thickener for high-temperature acidizing and its preparation method, belonging to the field of petroleum additives technology. The thickener comprises the following components by weight percentage: 37-45 wt% modified CMC thickener, 5.2-7.0 wt% co-solvent, 1.2-1.6 wt% dispersant, and 2.4-3.1 wt% stabilizer, with the balance being water. The modified CMC thickener uses carboxymethyl cellulose as a matrix and incorporates side chains containing sulfobetaine and cyclosiloxanes for modification. During acid injection, the cyclosiloxane structure undergoes hydrolysis and condensation, significantly increasing the viscosity of the acidizing fluid in the well. This creates a slow-flow splitting effect downhole, maintaining a sustained high-temperature acidic environment. The carboxymethyl cellulose backbone decomposes and breaks down, resulting in adaptive thickening that meets the thickening requirements of downhole acidizing. Simultaneously, it avoids the use of recalcitrant polymers, possessing profound research significance in environmentally friendly oil and gas extraction technologies.
Description
Technical Field
The invention belongs to the technical field of petroleum additives, and particularly relates to a thickener for high-temperature acidification and a preparation method thereof.
Background
In the oil-gas well production increasing process, the acidizing treatment is a key technology for increasing the permeability by injecting acid liquid (such as hydrochloric acid and earth acid) into the stratum to dissolve rock stratum minerals and enlarge pore channels. However, the conventional acid liquor has low viscosity and high acid rock reaction rate, so that the acid liquor is excessively consumed in near-wellbore zones, and effective transformation of deep stratum is difficult to realize. The thickener is used as an acid liquid additive, and delays the reaction rate of acid rocks by increasing the viscosity, so that deep migration and uniform corrosion of the acid liquid are realized.
At present, an acrylamide multipolymer is generally adopted for deep well high-temperature acidification as a main body of a thickener, the molecular chain of the thickener contains Wen Jituan (such as sulfonic acid groups and tertiary butyl acrylamide), good stability is kept at high temperature, the viscosity of acid liquor is further kept, the molecular chain of the thickener is strong in designability, the heat stability is improved by introducing a temperature-resistant monomer, and a basic thickening effect is provided at low concentration, but the polymer thickener has the unavoidable defects that the viscosity is continuously attenuated due to high-temperature depolymerization of a linear polymer chain, the corrosion cannot be carried out due to dynamic adaptation to well temperature change, the yield increasing effect is difficult to break through, the polymer is difficult to degrade naturally, the waste material after-treatment difficulty of flowback is high, and the environment-friendly development requirement is not met.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a thickener for high-temperature acidification and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
The thickener for high temperature acidification consists of modified CMC thickener 37-45wt%, cosolvent 5.2-7.0wt%, dispersant aid 1.2-1.6wt% and stabilizer 2.4-3.1wt% except water.
Wherein, the modified CMC thickener is prepared by the following method:
And A1, mixing and swelling carboxymethyl cellulose and anhydrous acetone under the protection of dry nitrogen, adding triethylamine, mixing, controlling the temperature to 25-40 ℃ in a water bath, slowly adding acryloyl chloride, stirring and reacting for 4.5-6.5h, heating and refluxing for 1.2-1.8h, removing the acetone by rotary evaporation after the reaction is finished, and drying in vacuum to obtain an intermediate.
Further, the dosage ratio of carboxymethyl cellulose, acryloyl chloride, triethylamine and anhydrous acetone is 50g:15-22mmol:10-15mL:350-400mL, and the high-activity acryloyl chloride is esterified with carboxymethyl cellulose to introduce an acrylic ester structure into a molecular side chain.
Preferably, the carboxymethyl cellulose has a substitution degree of 0.8 to 1.2, and has good swelling property and reactivity at the substitution degree.
And step A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and the ethanol solution, heating to 55-65 ℃, adding the azodiisobutyronitrile solution, stirring and reacting for 2.2-3.5h, and removing ethanol and water under reduced pressure after the reaction is finished to obtain the modified matrix.
Further, the dosage ratio of the intermediate to the methacryloyl ethyl sulfobetaine to the solution of the azodiisobutyronitrile to the ethanol is 50g:25-30mmol:0.1-0.13g:280-330mL, the methacryloyl ethyl sulfobetaine is added with the grafted acrylic ester structure in the intermediate molecule under the initiation of the azodiisobutyronitrile, and the side chain is introduced into the sulfobetaine for structural modification.
A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 70-80 ℃ under the protection of dry nitrogen, adding a platinum catalyst, stirring for reaction for 3-4 hours, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain a modifier;
further, the dosage ratio of the tetramethyl cyclotetrasiloxane to the allyl glycidyl ether to the platinum catalyst to the anhydrous toluene is 0.1mol:0.15-0.18mol:0.15-0.2g:170-220mL, and the allyl glycidyl ether and the tetramethyl cyclotetrasiloxane are subjected to hydrosilylation and an epoxy structure is introduced.
And step A4, mixing the modified matrix, the modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature in a water bath to be 45-60 ℃, stirring for 8-11h, then adding 4-dimethylaminopyridine, heating and refluxing for reaction for 0.4-0.6h, and removing the tetrahydrofuran by rotary evaporation after the reaction is finished to obtain the modified CMC thickener.
Further, the dosage ratio of the modified matrix, the modifier, the 4-dimethylaminopyridine and the tetrahydrofuran is 50g:8.5-12g:0.2-0.3g:200-280mL, and the betaine structure introduced by the side chain of the modified matrix molecule automatically promotes the ring-opening reaction of the epoxy group of the modifier and the oxygen-containing group (carboxyl and residual hydroxyl) on the cellulose molecule, so that cyclosiloxane is introduced into the side chain of the cellulose.
Preferably, the dispersion aid agent is sodium dodecyl sulfate, and interacts with the side chain sulfobetaine structure of the modified CMC thickener to improve the dispersibility.
A preparation method of a thickener for high-temperature acidification comprises the steps of grinding and dispersing a modified CMC thickener, a cosolvent, a dispersion aid agent and water, and then adding a stabilizer for mixing to obtain the thickener.
The invention has the beneficial effects that:
The invention is based on bio-based raw material carboxymethyl cellulose, which is used as a main thickening component through modification treatment, wherein partial hydroxyl groups in acrylic chloride and carboxymethyl cellulose molecules are esterified, an acrylic ester structure is introduced, then methacryloyl ethyl sulfobetaine is added with the introduced acrylic ester, a sulfobetaine branched chain is introduced to obtain a modified matrix, allyl glycidyl ether and tetramethyl cyclotetrasiloxane are subjected to hydrosilylation, epoxy groups are grafted on cyclosiloxane structural molecules to prepare a modifier, finally the epoxy groups in the modified matrix molecules are subjected to ring opening through the modifier and oxygen-containing groups in the modified matrix molecules, and the cyclosiloxane structure is introduced to the cellulose side chains of the modified matrix to modify, so that the modified CMC thickener is obtained; compared with the prior art, the molecular side chain of the modified CMC thickener contains hydrophilic structures such as sulfobetaine, hydroxyl and the like, is matched with an aqueous acidification system, provides moderate initial viscosity through water absorption swelling, greatly increases the viscosity of an acidizing fluid in a well along with the injection of the acidizing fluid and the rising of the temperature in the well under an acidic condition, forms retarded shunt in the well, is favorable for fully eroding underground gaps by an acid agent to improve oil gas exploitation efficiency, and is favorable for self-breaking gel and flowback along with the progress and continuous high-temperature acidic environment, the main chain of carboxymethyl cellulose is decomposed, the self-adaptive thickening mechanism is realized by the modified CMC thickener, and the self-adaptive thickening system is suitable for the underground acidification thickening requirement.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the dynamic viscosity of an acid solution prepared from the thickener of example 4 and comparative example according to the present invention according to the change of temperature.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1, a thickener for high temperature acidification was prepared as follows:
(1) Preparation of modified CMC thickener
Step A1, mixing carboxymethyl cellulose (CMC) and anhydrous acetone under the protection of dry nitrogen, heating to 50 ℃ to swell for 2 hours, cooling, controlling the temperature to 25 ℃ in a water bath, adding triethylamine to mix, slowly adding acryloyl chloride to stir and react for 6.5 hours, heating and refluxing for 1.8 hours, wherein the substitution degree of the carboxymethyl cellulose is about 0.85, the dosage ratio of the carboxymethyl cellulose to the acryloyl chloride to the triethylamine to the anhydrous acetone is 50g:15mmol:10mL:350mL, and after the reaction, removing the acetone by rotary evaporation and vacuum drying, thereby obtaining an intermediate.
And A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and an ethanol solution, heating to 55 ℃, adding an azodiisobutyronitrile solution, stirring and reacting for 3.5h, wherein the volume fraction of the ethanol solution is 65%, the azodiisobutyronitrile solution is an ethanol saturated solution at room temperature, the dosage ratio of the intermediate, the methacryloyl ethyl sulfobetaine, the azodiisobutyronitrile and the ethanol solution is 50g:25mmol:0.1g:280mL, and removing ethanol and water after the reaction is finished under reduced pressure to obtain the modified matrix.
And A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 70 ℃ under the protection of dry nitrogen, adding a platinum catalyst, stirring and reacting for 4 hours, wherein the platinum catalyst adopts a Carbster catalyst with an active platinum component of 5000ppm, the dosage ratio of the tetramethyl cyclotetrasiloxane, the allyl glycidyl ether, the platinum catalyst and the anhydrous toluene is 0.1mol:0.15 g:170mL, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain the modifier.
And A4, mixing a modified matrix, a modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature at 45 ℃ in a water bath, stirring for 11 hours, and then adding 4-dimethylaminopyridine for heating reflux reaction for 0.6 hour, wherein the dosage ratio of the modified matrix to the modifier to the 4-dimethylaminopyridine to the tetrahydrofuran is 50g:8.5g:0.2g:200mL, and removing the tetrahydrofuran after the reaction is finished by rotary evaporation to obtain the modified CMC thickener.
(2) Preparation of thickener
The modified CMC thickener consists of modified CMC thickener 37wt%, cosolvent 5.2wt%, glycol mono tertiary butyl ether, dispersant 1.2wt%, sodium dodecyl sulfate, stabilizer 3.1wt%, polyglycol 400 and water for the rest.
Mixing and feeding the modified CMC thickener, the cosolvent, the dispersing aid and water, grinding and dispersing, and then adding the stabilizer for mixing to obtain the thickener.
Example 2a thickener for high temperature acidification was prepared as follows:
(1) Preparation of modified CMC thickener
Step A1, mixing carboxymethyl cellulose and anhydrous acetone under the protection of dry nitrogen, heating to 50 ℃ to swell for 1.5 hours, cooling, controlling the temperature to 40 ℃ in a water bath, adding triethylamine to mix, slowly adding acryloyl chloride to stir and react for 4.5 hours, heating and refluxing for 1.2 hours, wherein the substitution degree of the carboxymethyl cellulose is about 1.2, the dosage ratio of the carboxymethyl cellulose, the acryloyl chloride, the triethylamine and the anhydrous acetone is 50g:22mmol:15mL:400mL, and after the reaction, removing the acetone by rotary evaporation and vacuum drying, thereby obtaining an intermediate.
And A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and an ethanol solution, heating to 65 ℃, adding an azodiisobutyronitrile solution, stirring and reacting for 2.2 hours, wherein the volume fraction of the ethanol solution is 65%, the azodiisobutyronitrile solution is an ethanol saturated solution at room temperature, the dosage ratio of the intermediate, the methacryloyl ethyl sulfobetaine, the azodiisobutyronitrile and the ethanol solution is 50g:30mmol:0.13g:330mL, and removing ethanol and water after the reaction is finished under reduced pressure to obtain the modified matrix.
And A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 80 ℃ under the protection of dry nitrogen, adding a platinum catalyst, stirring and reacting for 3 hours, wherein the platinum catalyst adopts a Carbster catalyst with an active platinum component of 5000ppm, the dosage ratio of the tetramethyl cyclotetrasiloxane, the allyl glycidyl ether, the platinum catalyst and the anhydrous toluene is 0.1mol:0.18mol:0.2g:220mL, and removing toluene by reduced pressure rotary evaporation after the reaction is finished to obtain the modifier.
And A4, mixing the modified matrix, the modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature at 60 ℃ in a water bath, stirring for 8 hours, and then adding 4-dimethylaminopyridine for heating reflux reaction for 0.4 hours, wherein the dosage ratio of the modified matrix to the modifier to the 4-dimethylaminopyridine to the tetrahydrofuran is 50g:12g:0.3g:280mL, and removing the tetrahydrofuran after the reaction is finished by rotary evaporation to obtain the modified CMC thickener.
(2) Preparation of thickener
The modified CMC thickener consists of modified CMC thickener 45wt%, cosolvent 7.0wt%, glycol mono tertiary butyl ether, dispersant 1.6wt%, sodium dodecyl sulfate, stabilizer 2.4wt%, polyglycol 400 and water for the rest.
Mixing and feeding the modified CMC thickener, the cosolvent, the dispersing aid and water, grinding and dispersing, and then adding the stabilizer for mixing to obtain the thickener.
Example 3a thickener for high temperature acidification was prepared as follows:
(1) Preparation of modified CMC thickener
And A1, mixing carboxymethyl cellulose and anhydrous acetone under the protection of dry nitrogen, heating to 50 ℃ to swell for 1.5 hours, cooling, controlling the temperature to 30 ℃ in a water bath, adding triethylamine to mix, slowly adding acryloyl chloride to stir and react for 5.5 hours, heating and refluxing for 1.6 hours, wherein the substitution degree of the carboxymethyl cellulose is about 1.1, the dosage ratio of the carboxymethyl cellulose, the acryloyl chloride, the triethylamine and the anhydrous acetone is 50g:20mmol:12mL:380mL, and after the reaction, removing the acetone by rotary evaporation and vacuum drying, thereby obtaining an intermediate.
And A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and an ethanol solution, heating to 60 ℃, adding an azodiisobutyronitrile solution, stirring and reacting for 2.8 hours, wherein the volume fraction of the ethanol solution is 65%, the azodiisobutyronitrile solution is an ethanol saturated solution at room temperature, the dosage ratio of the intermediate, the methacryloyl ethyl sulfobetaine, the azodiisobutyronitrile and the ethanol solution is 50g:27mmol:0.11g:300mL, and removing ethanol and water after the reaction is finished under reduced pressure, thereby obtaining the modified matrix.
And A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 75 ℃ under the protection of dry nitrogen, adding a platinum catalyst, stirring and reacting for 3.5h, wherein the platinum catalyst adopts a Carbster catalyst with an active platinum component of 5000ppm, the dosage ratio of the tetramethyl cyclotetrasiloxane, the allyl glycidyl ether, the platinum catalyst and the anhydrous toluene is 0.1mol:0.17mol:0.15g:200mL, and removing toluene by rotary evaporation under reduced pressure after the reaction is finished to obtain the modifier.
And A4, mixing a modified matrix, a modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature at 55 ℃ in a water bath, stirring for 10 hours, and then adding 4-dimethylaminopyridine for heating reflux reaction for 0.6 hour, wherein the dosage ratio of the modified matrix to the modifier to the 4-dimethylaminopyridine to the tetrahydrofuran is 50g:10g:0.25g:250mL, and removing the tetrahydrofuran after the reaction is finished by rotary evaporation to obtain the modified CMC thickener.
(2) Preparation of thickener
The modified CMC thickener consists of modified CMC thickener 40wt%, cosolvent 5.8wt%, glycol mono tertiary butyl ether, dispersant 1.3wt%, sodium dodecyl sulfate, stabilizer 2.7wt%, polyglycol 400 and water for the rest.
Mixing and feeding the modified CMC thickener, the cosolvent, the dispersing aid and water, grinding and dispersing, and then adding the stabilizer for mixing to obtain the thickener.
Example 4a thickener for high temperature acidification was prepared as follows:
(1) Preparation of modified CMC thickener
And A1, mixing carboxymethyl cellulose and anhydrous acetone under the protection of dry nitrogen, heating to 50 ℃ for swelling for 2 hours, cooling, controlling the temperature to 35 ℃ in a water bath, adding triethylamine for mixing, slowly adding acryloyl chloride for stirring reaction for 5.2 hours, heating for refluxing for 1.8 hours, wherein the substitution degree of the carboxymethyl cellulose is about 1.1, the dosage ratio of the carboxymethyl cellulose, the acryloyl chloride, the triethylamine and the anhydrous acetone is 50g:20mmol:13mL:350mL, and after the reaction, removing the acetone by rotary evaporation and vacuum drying, thereby obtaining an intermediate.
And A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and an ethanol solution, heating to 65 ℃, adding an azodiisobutyronitrile solution, stirring and reacting for 3.2 hours, wherein the volume fraction of the ethanol solution is 65%, the azodiisobutyronitrile solution is an ethanol saturated solution at room temperature, the dosage ratio of the intermediate, the methacryloyl ethyl sulfobetaine, the azodiisobutyronitrile and the ethanol solution is 50g:25-mmol:0.12g:300mL, and removing ethanol and water after the reaction is finished under reduced pressure to obtain the modified matrix.
And A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 80 ℃ under the protection of dry nitrogen, adding a platinum catalyst, stirring and reacting for 3.3 hours, wherein the platinum catalyst adopts a Carbster catalyst with an active platinum component of 5000ppm, the dosage ratio of the tetramethyl cyclotetrasiloxane, the allyl glycidyl ether, the platinum catalyst and the anhydrous toluene is 0.1mol:0.18mol:0.2g:190mL, and removing toluene by rotary evaporation under reduced pressure after the reaction is finished to obtain the modifier.
And A4, mixing a modified matrix, a modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature at 50 ℃ in a water bath, stirring for 11 hours, and then adding 4-dimethylaminopyridine for heating reflux reaction for 0.5 hour, wherein the dosage ratio of the modified matrix to the modifier to the 4-dimethylaminopyridine to the tetrahydrofuran is 50g:11g:0.3g:270mL, and removing the tetrahydrofuran after the reaction is finished by rotary evaporation, thus obtaining the modified CMC thickener.
(2) Preparation of thickener
The modified CMC thickener consists of modified CMC thickener 42wt%, cosolvent 6.5wt%, glycol mono tertiary butyl ether, dispersant 1.3wt%, sodium dodecyl sulfate, stabilizer 2.5wt%, polyglycol 400 and water for the rest.
Mixing and feeding the modified CMC thickener, the cosolvent, the dispersing aid and water, grinding and dispersing, and then adding the stabilizer for mixing to obtain the thickener.
In the comparative example, commercially available KHF071 type polyacrylamide high temperature resistant thickener was selected.
The acid liquor is prepared by taking 15% of hydrochloric acid as an acid agent, adding YTY-04 quinoline quaternary ammonium salt of which the weight percent is 0.12 as a corrosion inhibitor, taking 0.08% of ascorbic acid as an iron ion stabilizer and 1.5% of thickening agent as above, and uniformly mixing to obtain the acid liquor.
The dynamic viscosity test, namely shearing the acid liquor prepared by the thickener of the example 4 and the comparative example at 170s -1, heating from 30 ℃ to 180 ℃ and preserving heat, detecting the viscosity of the acid liquor, and drawing a dynamic viscosity change curve, wherein the dynamic viscosity change curve is shown in figure 1;
In the simulated acid injection well dynamic viscosity test, as can be seen from fig. 1, the initial viscosity of the thickened acid solution prepared in example 4 is slightly lower than that of the comparative example, the viscosity of example 4 is reduced first and then is increased with the increase of temperature, the peak viscosity is about 125 mpa.s, and the viscosity of the comparative example is reduced in a visible stage with the increase of temperature.
Core erosion test, namely taking artificial marble Dan Yanxin (porosity 18%), with specification of phi 25 multiplied by 50mm, injecting the acid liquor prepared by the method, controlling the temperature to be 150 ℃, pressurizing compressed air to 2.0MPa, and respectively detecting the erosion rate and the erosion depth of the core in 120min and 240h, wherein the specific test results are shown in table 1:
as can be seen from the test results in Table 1, the acid solution prepared from the thickener prepared in the examples has good corrosion performance on the core, and the corrosion efficiency and depth are obviously better than those of the comparative examples particularly in the long-term corrosion process.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. The thickener for high temperature acidification is characterized by comprising, by weight, 37-45% of modified CMC thickener, 5.2-7.0% of cosolvent, 1.2-1.6% of dispersant, 2.4-3.1% of stabilizer and the balance of water;
The modified CMC thickener is prepared by the following method:
Step A1, mixing and swelling carboxymethyl cellulose and anhydrous acetone under the protection of dry nitrogen, adding triethylamine, mixing, controlling the temperature at 25-40 ℃ in a water bath, slowly adding acryloyl chloride, stirring and reacting for 4.5-6.5h, and then heating and refluxing for 1.2-1.8h to obtain an intermediate;
A2, mixing the intermediate, the methacryloyl ethyl sulfobetaine and the ethanol solution, heating to 55-65 ℃, adding the azodiisobutyronitrile solution, and stirring for reacting for 2.2-3.5 hours to obtain a modified matrix;
A3, premixing tetramethyl cyclotetrasiloxane, allyl glycidyl ether and anhydrous toluene, heating to 70-80 ℃ under the protection of dry nitrogen, adding a platinum catalyst, and stirring for reaction for 3-4 hours to prepare a modifier;
And step A4, mixing the modified matrix, the modifier and tetrahydrofuran, introducing dry nitrogen for protection, controlling the temperature in a water bath to be 45-60 ℃ and stirring for 8-11h, and then adding 4-dimethylaminopyridine for heating reflux reaction for 0.4-0.6h to prepare the modified CMC thickener.
2. The thickener for high temperature acidification according to claim 1, wherein the dosage ratio of carboxymethyl cellulose, acryloyl chloride, triethylamine and anhydrous acetone is 50g:15-22mmol:10-15ml:350-400mL.
3. The thickener for high temperature acidification as claimed in claim 2, wherein the degree of substitution of carboxymethyl cellulose is 0.8 to 1.2.
4. The thickener for high temperature acidification according to claim 2, wherein the amount ratio of the intermediate, methacryloyl ethyl sulfobetaine, azobisisobutyronitrile and ethanol solution is 50g:25-30mmol:0.1-0.13g:280-330mL.
5. A thickener for high temperature acidification as claimed in claim 4, wherein the amount ratio of the tetramethyl cyclotetrasiloxane, the allyl glycidyl ether, the platinum catalyst and the anhydrous toluene is 0.1mol:0.15-0.18mol:0.15-0.2g:170-220mL.
6. The thickener for high temperature acidification according to claim 5, wherein the dosage ratio of the modified substrate, the modifier, the 4-dimethylaminopyridine and the tetrahydrofuran is 50g:8.5-12g:0.2-0.3g:200-280mL.
7. A thickener for high temperature acidification as claimed in claim 1, wherein the dispersion aid agent is sodium dodecyl sulfate.
8. The method for preparing the thickener for high temperature acidification according to any one of claims 1 to 7, wherein the thickener is prepared by grinding and dispersing a modified CMC thickener, a cosolvent, a dispersion aid agent and water, and then adding a stabilizer for mixing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102574961A (en) * | 2009-07-31 | 2012-07-11 | 阿克佐诺贝尔股份有限公司 | Hybrid Copolymer Composition |
| CN119285832A (en) * | 2024-12-10 | 2025-01-10 | 东营众悦石油科技有限公司 | Acid liquid thickener and preparation method and application thereof |
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