High-temperature-resistant sulfonated phenolic resin for drilling fluid and preparation method thereof

Abstract

The invention relates to the technical field of drilling fluids, and discloses a high-temperature-resistant sulfonated phenolic resin for a drilling fluid and a preparation method thereof.The preparation method of the high-temperature-resistant sulfonated phenolic resin for the drilling fluid comprises the steps that 50-65 mL of N, N-dimethylformamide solvent, 2-4 parts by weight of benzenesulfonic acid modified phenolic resin and 0.01-0.02 part by weight of pyridine are added into a reactor; after stirring and dissolving, continuing to add 5-10 parts by weight of modified cardanol, reacting at 60-68 DEG C, and after the reaction is finished, performing reduced pressure distillation and filtering to obtain the high-temperature-resistant sulfonated phenolic resin for the drilling fluid. The high-temperature-resistant sulfonated phenolic resin for the drilling fluid has relatively good temperature-resistant and salt-resistant effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of drilling fluid, in particular to a high-temperature-resistant sulfonated phenolic resin for drilling fluid and a preparation method thereof. BACKGROUND

[0002] In the process of oil drilling, drilling fluid plays a crucial role, it not only needs to carry rock debris, cool the drill bit, but also stabilize the well wall, prevent blowout, etc. With the increase of drilling depth, the formation temperature and pressure also increase, which puts higher requirements on the performance of drilling fluid. Although the existing phenolic resin for drilling fluid can meet the use requirements in high temperature environment to a certain extent, there are still deficiencies in salt resistance and temperature resistance. Especially in high salt formation, the traditional phenolic resin is prone to degradation, resulting in a sharp decline in the performance of drilling fluid. Therefore, how to avoid this phenomenon is the key to solving the problem. SUMMARY

[0003] (I) Technical problems solved

[0004] In view of the deficiencies of the prior art, the present application provides a high-temperature-resistant sulfonated phenolic resin for drilling fluid and a preparation method thereof, which has good temperature resistance and salt resistance.

[0005] (II) Technical solutions

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solutions: a high-temperature-resistant sulfonated phenolic resin for drilling fluid, comprising the following components by weight: 2-4 parts by weight of benzene sulfonic acid modified phenolic resin, 5-10 parts by weight of modified cardanol.

[0007] The preparation method of the benzene sulfonic acid modified phenolic resin is as follows: 3.7-4.1g of o-aminobenzenesulfonic acid, 6.3-6.7g of glyoxal and 3.1-3.4g of p-hydroxybenzenesulfonic acid are dissolved in 40-50mL of dimethyl sulfoxide solution containing sulfuric acid (mass fraction is 96%, the amount of sulfuric acid is 0.2mL), mixed uniformly, then the mixed solution is transferred to a 200mL polytetrafluoroethylene reactor, reacted at 115-120℃ for 42-48h, after the end of the reaction, the product is washed with anhydrous ethanol and deionized water to obtain intermediate 1; intermediate 1 is added to a reactor containing toluene, then 1,3-propanesultone is added dropwise, and reacted at 105-110℃ for 45-48h, after the end of the reaction, it is filtered to obtain benzene sulfonic acid modified phenolic resin.

[0008] Further, the amount ratio of intermediate 1, toluene and 1,3-propanesultone is 1-2g:25-30mL:3.1-3.6g.

[0009] Further, the preparation method of the modified cardanol is as follows:

[0010] S1. Add 4-vinylbenzoyl chloride to N,N-dimethylformamide solvent, stir and disperse, then add 3-(dimethylamino)-1-propanethiol and benzoin dimethyl ether photoinitiator, irradiate under 365nm ultraviolet light at 25-40℃ for 2-3h, then centrifugal separation, washing and drying to obtain tertiary amine modified benzoyl chloride;

[0011] S2. Add 2-2.3g of 3-pentadecylphenol to 5-6mL of 1,2-bromoethane, then add 0.51-0.53g of potassium hydroxide, and react for 3-4h, then column chromatography separation to obtain 3-pentadecylphenoxyethyl bromide;

[0012] S3. Add 1.1-1.3mmol of tertiary amine modified benzoyl chloride and 1.26-1.41mmol of 3-pentadecylphenoxyethyl bromide to 40-50mL of N,N-dimethylformamide solvent, stir and mix, and react at 80-90℃, then distillation under reduced pressure, filtration and drying to obtain modified cardanol.

[0013] Further, the amount ratio of N,N-dimethylformamide solvent, 4-vinylbenzoyl chloride, 3-(dimethylamino)-1-propanethiol and benzoin dimethyl ether photoinitiator in S1 is 45-55mL:1.6-1.8g:0.9-1.2g:0.02-0.03g.

[0014] Further, the reaction temperature in S2 is 62-68℃.

[0015] Further, the reaction time in S3 is 6-9h.

[0016] Further, the preparation method of the high-temperature-resistant sulfonated phenolic resin for drilling fluid is as follows: add 50-65mL of N,N-dimethylformamide solvent, 2-4 parts by weight of benzene sulfonic acid modified phenolic resin and 0.01-0.02 parts by weight of pyridine to a reactor, stir and dissolve, then continue to add 5-10 parts by weight of modified cardanol, react at 60-68℃, then distillation under reduced pressure, filtration to obtain the high-temperature-resistant sulfonated phenolic resin for drilling fluid.

[0017] Further, the reaction time is 2-4h.

[0018] (III) Beneficial technical effects

[0019] In the above reaction process, the alkenyl group in 4-vinylbenzoyl chloride and the mercapto group in 3-(dimethylamino)-1-propanethiol are subjected to a click reaction, and a tertiary amine group and a benzoyl chloride group are introduced, so as to obtain a tertiary amine group modified benzoyl chloride; the tertiary amine group in the tertiary amine group modified benzoyl chloride and the bromine group in 3-pentadecylphenoxyethyl bromide are subjected to a reaction, and a quaternary ammonium salt group is generated, so as to obtain a modified cardanol; the benzoyl chloride group in the modified cardanol and the phenolic hydroxyl group in the benzene sulfonic acid modified phenolic resin are subjected to a reaction, so as to obtain a high-temperature-resistant sulfonated phenolic resin for drilling fluid.

[0020] The quaternary ammonium salt group and the cardanol in the high-temperature-resistant sulfonated phenolic resin can reduce the filtration loss and salt resistance, the quaternary ammonium salt can be adsorbed with clay particles or formation minerals to form a dense filter cake, reducing the penetration of the drilling fluid into the formation; the hydrophobic long chain of the cardanol can enhance the high-temperature resistance and salt resistance of the filter cake, reduce the filtration loss under high temperature and high pressure, and the modified cardanol combined with the benzene sulfonic acid modified phenolic resin can form a more stable network structure, further reducing the filtration loss. The large number of sulfonic acid groups and benzene ring structures in the high-temperature-resistant sulfonated phenolic resin can improve the high-temperature resistance, salt resistance and reduce the filtration loss of the drilling fluid. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is the reaction formula of the modified cardanol. DETAILED DESCRIPTION

[0022] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] In order to better understand the above technical solutions, the above technical solutions will be described in detail below in combination with the drawings in the specification and specific embodiments.

[0024] 3-(dimethylamino)-1-propanethiol CAS: 42302-17-0.

[0025] The structure of 3-pentadecylphenoxyethyl bromide is as follows:

[0026]

[0027] Embodiment 1

[0028] The preparation method of the high-temperature-resistant sulfonated phenolic resin for drilling fluid is as follows:

[0029] S1. Add 1.6 g of 4-vinylbenzoyl chloride to 45 mL of N,N-dimethylformamide solvent and stir to disperse. Then, add 0.9 g of 3-(dimethylamino)-1-propanethiol and 0.02 g of benzoin dimethyl ether as a photoinitiator. Irradiate with 365 nm ultraviolet light at 25°C for 2 h. After completion, centrifuge, wash, and dry to obtain tertiary amino-modified benzoyl chloride.

[0030] S2. Add 2 g of 3-pentadecylphenol to 5 mL of 1,2-bromoethane, then add 0.51 g of potassium hydroxide, raise the temperature to 62°C, and react for 3 h. After reaction, column chromatography is performed to obtain 3-pentadecylphenoxyethyl bromide.

[0031] S3. To 40 mL of N, N-dimethylformamide solvent was added 1.1 mmol of tertiary amino-modified benzoyl chloride and 1.26 mmol of 3-pentadecylphenoxyethyl bromide, stirred and mixed, and reacted at 80 ° C for 6 h. After completion, the mixture was distilled under reduced pressure, filtered, and dried to obtain modified cardanol;

[0032] S4. 3.7 g of o-aminobenzenesulfonic acid, 6.3 g of glyoxal, and 3.1 g of p-hydroxybenzenesulfonic acid were dissolved in 40 mL of dimethyl sulfoxide solution containing sulfuric acid and mixed evenly. The mixture was then transferred to a 200 mL polytetrafluoroethylene reactor and reacted at 115° C. for 42 h. After reaction, the product was washed with anhydrous ethanol and deionized water to obtain intermediate 1. 1 g of intermediate 1 was added to a reactor containing 25 mL of toluene, and then 3.1 g of 1,3-propanesulfonic acid lactone was added dropwise and reacted at 105° C. for 45 h. After reaction, the mixture was filtered to obtain a benzenesulfonic acid-modified phenolic resin.

[0033] S5. Add 50 mL of N,N-dimethylformamide solvent, 2 parts by weight of benzenesulfonic acid-modified phenolic resin, and 0.01 parts by weight of pyridine to the reactor, stir and dissolve, then add 5 parts by weight of modified cardanol, and react at 60°C for 2 hours. After reaction, perform vacuum distillation and filter to obtain a high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0034] Example 2

[0035] The preparation method of high temperature resistant sulfonated phenolic resin for drilling fluid is as follows:

[0036] S1. Add 1.8 g of 4-vinylbenzoyl chloride to 55 mL of N,N-dimethylformamide solvent and stir to disperse. Then, add 1.2 g of 3-(dimethylamino)-1-propanethiol and 0.03 g of benzoin dimethyl ether as a photoinitiator. Irradiate with 365 nm ultraviolet light at 40°C for 3 h. After completion, centrifuge, wash, and dry to obtain tertiary amino-modified benzoyl chloride.

[0037] S2. 2.3 g of 3-pentadecylphenol was added to 6 mL of 1,2-bromoethane, then 0.53 g of potassium hydroxide was added, and the temperature was raised to 68°C for 4 h, and after the reaction was completed, column chromatography was used to separate 3-pentadecylphenoxyethyl bromide;

[0038] S3. 1.3 mmol of tertiary amine modified benzoyl chloride, 1.41 mmol of 3-pentadecylphenoxyethyl bromide were added to 50 mL of N,N-dimethylformamide solvent, the mixture was stirred and reacted at 90°C for 9 h, after the reaction was completed, vacuum distillation, filtration and drying were performed to obtain the modified cardanol;

[0039] S4. 4.1 g of o-aminobenzenesulfonic acid, 6.7 g of glyoxal and 3.4 g of p-hydroxybenzenesulfonic acid were dissolved in 50 mL of dimethyl sulfoxide solution containing sulfuric acid, and the mixture was uniformly mixed, and then the mixture was transferred to a 200 mL polytetrafluoroethylene reactor and reacted at 120°C for 48 h, and after the reaction was completed, the product was washed with anhydrous ethanol and deionized water to obtain intermediate 1; 2 g of intermediate 1 was added to a reactor containing 30 mL of toluene, and then 3.6 g of 1,3-propanesultone was added dropwise, and the reaction was carried out at 110°C for 48 h, and after the reaction was completed, filtration was performed to obtain a benzene sulfonic acid modified phenolic resin;

[0040] S5. 65 mL of N,N-dimethylformamide solvent, 4 parts by weight of benzene sulfonic acid modified phenolic resin, 0.02 parts by weight of pyridine were added to the reactor, after stirring and dissolving, 10 parts by weight of modified cardanol was continuously added, and the reaction was carried out at 68°C for 4 h, and after the reaction was completed, vacuum distillation and filtration were performed to obtain a high-temperature-resistant sulfonated phenolic resin for drilling fluid.

[0041] Example 3

[0042] The preparation method of the high-temperature-resistant sulfonated phenolic resin for drilling fluid is as follows:

[0043] S1. 1.7 g of 4-vinylbenzoyl chloride was added to 42 mL of N,N-dimethylformamide solvent, and the mixture was stirred and dispersed, and then 1.1 g of 3-(dimethylamino)-1-propanethiol and 0.025 g of benzoin dimethyl ether photoinitiator were added, and the mixture was irradiated with 365 nm ultraviolet light at 35°C for 2 h, and after the reaction was completed, centrifugal separation, washing and drying were performed to obtain a tertiary amine modified benzoyl chloride;

[0044] S2. 2.1 g of 3-pentadecylphenol was added to 6 mL of 1,2-bromoethane, then 0.52 g of potassium hydroxide was added, and the temperature was raised to 65°C for 4 h, and after the reaction was completed, column chromatography was used to separate 3-pentadecylphenoxyethyl bromide;

[0045] S3. 1.2 mmol of tertiary amine modified benzoyl chloride, 1.34 mmol of 3-pentadecylphenoxyethyl bromide were added to 45 mL of N,N-dimethylformamide solvent, the mixture was stirred and reacted at 85°C for 8 h, after the reaction was completed, it was distilled under reduced pressure, filtered, and dried to obtain modified cardanol;

[0046] S4. 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal, and 3.2 g of p-hydroxybenzenesulfonic acid were dissolved in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mixed uniformly, and then the mixture was transferred to a 200 mL polytetrafluoroethylene reactor and reacted at 117°C for 45 h, after the reaction was completed, the product was washed with anhydrous ethanol and deionized water to obtain intermediate 1; 1.5 g of intermediate 1 was added to a reactor containing 28 mL of toluene, and then 3.3 g of 1,3-propanesultone was added dropwise and reacted at 107°C for 46 h, after the reaction was completed, it was filtered to obtain a phenyl sulfonic acid modified phenolic resin;

[0047] S5. 55 mL of N,N-dimethylformamide solvent, 3 parts by weight of the phenyl sulfonic acid modified phenolic resin, and 0.015 parts by weight of pyridine were added to the reactor, stirred and dissolved, then 6 parts by weight of modified cardanol was added, and reacted at 64°C for 3 h, after the reaction was completed, it was distilled under reduced pressure and filtered to obtain a high-temperature-resistant sulfonated phenolic resin for drilling fluid.

[0048] Comparative Example 1

[0049] The preparation method of the high-temperature-resistant sulfonated phenolic resin for drilling fluid is as follows:

[0050] S1. 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal, and 3.2 g of p-hydroxybenzenesulfonic acid were dissolved in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mixed uniformly, and then the mixture was transferred to a 200 mL polytetrafluoroethylene reactor and reacted at 117°C for 45 h, after the reaction was completed, the product was washed with anhydrous ethanol and deionized water to obtain intermediate 1; 1.5 g of intermediate 1 was added to a reactor containing 28 mL of toluene, and then 3.3 g of 1,3-propanesultone was added dropwise and reacted at 107°C for 46 h, after the reaction was completed, it was filtered to obtain a phenyl sulfonic acid modified phenolic resin;

[0051] S2. 3 parts by weight of the phenyl sulfonic acid modified phenolic resin were added to the reactor to obtain a high-temperature-resistant sulfonated phenolic resin for drilling fluid.

[0052] Comparative Example 2

[0053] S1. 1.7 g of 4-vinylbenzoyl chloride was added to 42 mL of N,N-dimethylformamide solvent, stirred and dispersed, and then 1.1 g of 3-(dimethylamino)-1-propanethiol and 0.025 g of benzoin dimethyl ether photoinitiator were added thereto, and irradiated with 365 nm ultraviolet light at 35°C for 2 h. After centrifugal separation, washing and drying, a tertiary amine group modified benzoyl chloride was obtained.

[0054] S2. 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal and 3.2 g of p-hydroxybenzenesulfonic acid were dissolved in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mixed uniformly, and then the mixture was transferred to a 200 mL polytetrafluoroethylene reactor and reacted at 117°C for 45 h. After the reaction was completed, the product was washed with anhydrous ethanol and deionized water to obtain an intermediate 1. 1.5 g of the intermediate 1 was added to a reactor containing 28 mL of toluene, and then 3.3 g of 1,3-propanesultone was added dropwise, and reacted at 107°C for 46 h. After the reaction was completed, filtration was performed to obtain a benzene sulfonic acid modified phenolic resin.

[0055] S3. 55 mL of N,N-dimethylformamide solvent, 3 parts by weight of the benzene sulfonic acid modified phenolic resin, and 0.015 parts by weight of pyridine were added to a reactor, stirred and dissolved, and then 6 parts by weight of the tertiary amine group modified benzoyl chloride was added, and reacted at 64°C for 3 h. After the reaction was completed, distillation was performed under reduced pressure, and filtration was performed to obtain a high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0056] Performance test

[0057] Saturated salt water base slurry preparation: 350 mL of water, 0.49 g of sodium carbonate, and 14 g of test sodium bentonite were added to a high-speed stirring cup under stirring, and stirred for 20 min. After sealing and standing for 24 h, 4% fresh water base slurry was obtained.

[0058] Experimental slurry preparation: 8% sulfonated lignite (SMC) + 10% high-temperature resistant sulfonated phenolic resin for drilling fluid prepared in Examples 1-3 and Comparative Examples 1-2 were added to 4% fresh water base slurry under high-speed stirring, and stirred for 25 min. Under stirring, 105 g of NaCl was added to obtain the experimental slurry.

[0059] After the experimental slurry was aged at 220°C / 16 h and cooled, the rheological properties, medium pressure filtration loss FL API and high temperature and high pressure filtration loss FL HTHP (test temperature 180°C, pressure 3.45 MPa) were determined according to GB / T16783.1-2014 "Petroleum and Natural Gas Industry Drilling Fluid Field Test Part 1: Water-based Drilling Fluid". The rheological property test included apparent viscosity AV and plastic viscosity PV, and the test results are shown in Table 1.

[0060]

[0061] As shown in Table 1, the high-temperature-resistant sulfonated phenolic resin for drilling fluid embodiments 1-3 of the present application have better temperature resistance and salt resistance compared to the comparative examples 1-2, and the filtration loss is significantly reduced at high temperature and high pressure, and the rheological properties are also good.

[0062] It should be noted that in this document, the terms "comprising", "containing" or any other variant thereof are intended to cover non-exclusive inclusion, so that processes, methods, articles or devices that include a series of elements not only include those elements, but also include other elements not explicitly listed, or include elements inherent to such processes, methods, articles or devices. Without more limitations, the element defined by the statement "comprising a" does not exclude the presence of other identical elements in the process, method, article or device comprising the element.

[0063] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

[0064] Those skilled in the art should understand that the above only describes several specific embodiments of the present application, rather than all embodiments.

Claims

1. A high temperature resistant sulfonated phenolic resin for drilling fluid, characterized in that: The invention comprises the following components by weight: 2-4 parts by weight of benzenesulfonic acid modified phenolic resin and 5-10 parts by weight of modified cardanol; The preparation method of the benzenesulfonic acid modified phenolic resin comprises: dissolving 3.7-4.1 g of o-aminobenzenesulfonic acid, 6.3-6.7 g of glyoxal and 3.1-3.4 g of p-hydroxybenzenesulfonic acid in 40-50 mL of a dimethyl sulfoxide solution containing sulfuric acid, mixing the mixture evenly, transferring the mixture to a 200 mL polytetrafluoroethylene reactor, reacting at 115-120° C. for 42-48 hours, and washing the product with anhydrous ethanol and deionized water to obtain an intermediate 1; adding the intermediate 1 to a reactor filled with toluene, and then dropwise adding 1,3-propane sultone to react at 105-110° C. for 45-48 hours. After reaction, filtering the mixture to obtain the benzenesulfonic acid modified phenolic resin.

2. The high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 1, characterized in that The usage ratio of the intermediate 1, toluene, and 1,3-propane sultone is 1-2 g: 25-30 mL: 3.1-3.6 g.

3. The high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 1, wherein The preparation method of the modified cardanol is: S1. Add 4-vinylbenzoyl chloride to N,N-dimethylformamide solvent, stir and disperse, then add 3-(dimethylamino)-1-propanethiol and benzoin dimethyl ether as photoinitiators, irradiate with 365 nm ultraviolet light at 25-40°C for 2-3 hours, centrifuge, wash, and dry to obtain tertiary amino-modified benzoyl chloride; S2. 2-2.3 g of 3-pentadecylphenol was added to 5-6 mL of 1,2-bromoethane, followed by the addition of 0.51-0.53 g of potassium hydroxide. The reaction was heated for 3-4 h, and then column chromatography was performed to obtain 3-pentadecylphenoxyethyl bromide. S3. Add 1.1-1.3 mmol of tertiary amino-modified benzoyl chloride and 1.26-1.41 mmol of 3-pentadecylphenoxyethyl bromide to 40-50 mL of N,N-dimethylformamide solvent, stir and mix, react at 80-90°C, and then distill under reduced pressure, filter, and dry to obtain modified cardanol.

4. The high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 3, characterized in that The amount ratio of N,N-dimethylformamide solvent, 4-vinylbenzoyl chloride, 3-(dimethylamino)-1-propanethiol, and benzoin dimethyl ether photoinitiator in S1 is 45-55 mL: 1.6-1.8g: 0.9-1.2g: 0.02-0.03g.

5. The high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 3, characterized in that: The reaction temperature in S2 is 62-68°C.

6. The high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 3, characterized in that: The reaction time in S3 is 6-9h.

7. A method for preparing a high temperature resistant sulfonated phenolic resin for drilling fluid according to any one of claims 1 to 6, characterized in that: The preparation method of the high-temperature resistant sulfonated phenolic resin for drilling fluid comprises the following steps: adding 50-65 mL of N,N-dimethylformamide solvent, 2-4 parts by weight of benzenesulfonic acid-modified phenolic resin, and 0.01-0.02 parts by weight of pyridine into a reactor, stirring and dissolving the mixture, then adding 5-10 parts by weight of modified cardanol, reacting the mixture at 60-68° C., performing reduced pressure distillation after the reaction, and filtering the mixture to obtain the high-temperature resistant sulfonated phenolic resin for drilling fluid.

8. The method for preparing the high temperature resistant sulfonated phenolic resin for drilling fluid according to claim 7, wherein: The reaction time is 2-4 hours.

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