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

Abstract

The application relates to the technical field of drilling fluids, and discloses a high-temperature-resistant sulfonated phenolic aldehyde resin for drilling fluids and a preparation method thereof. The preparation method of the high-temperature-resistant sulfonated phenolic aldehyde resin for drilling fluids is as follows: 50-65 mL of N,N-dimethylformamide solvent, 2-4 parts by weight of benzene sulfonic acid modified phenolic aldehyde resin and 0.01-0.02 parts by weight of pyridine are added into a reactor, after stirring and dissolving, 5-10 parts by weight of modified cardanol is continuously added, reaction is carried out at 60-68 DEG C, after the reaction is finished, vacuum distillation is carried out, and filtration is carried out, so that the high-temperature-resistant sulfonated phenolic aldehyde resin for drilling fluids is obtained. The high-temperature-resistant sulfonated phenolic aldehyde resin for drilling fluids has good temperature resistance and salt resistance.

Description

Technical Field

[0001] This invention relates to the field of drilling fluid technology, specifically to a high-temperature resistant sulfonated phenolic resin for drilling fluid and its preparation method. Background Technology

[0002] In oil drilling, drilling fluid plays a crucial role, not only carrying rock cuttings and cooling the drill bit, but also stabilizing the wellbore and preventing blowouts. As drilling depth increases, formation temperature and pressure also rise, placing higher demands on drilling fluid performance. While existing phenolic resins for drilling fluids can meet the requirements of high-temperature environments to some extent, they still have shortcomings in salt resistance and temperature resistance. Especially in high-salt formations, traditional phenolic resins are prone to degradation, leading to a sharp decline in drilling fluid performance. Therefore, avoiding this phenomenon is key to solving the problem. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a high-temperature resistant sulfonated phenolic resin for drilling fluids and its preparation method, which exhibits good temperature and salt resistance.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a high-temperature resistant sulfonated phenolic resin for drilling fluid, comprising the following weight components: 2-4 parts by weight of benzenesulfonic acid modified phenolic resin and 5-10 parts by weight of modified cashew nut phenol.

[0007] The preparation method of the benzenesulfonic 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 of 96%, amount of sulfuric acid of 0.2mL), mixed evenly, and then the mixture is transferred to a 200mL polytetrafluoroethylene reactor and reacted at 115-120℃ for 42-48h. After 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, and then 1,3-propanesulfonic acid lactone is added dropwise and reacted at 105-110℃ for 45-48h. After the reaction, the mixture is filtered to obtain benzenesulfonic acid modified phenolic resin.

[0008] Furthermore, the ratio of intermediate 1, toluene, and 1,3-propanesulfonic acid lactone is 1-2g: 25-30mL: 3.1-3.6g.

[0009] Furthermore, the preparation method of the modified cashew phenol 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 with 365nm ultraviolet light at 25-40℃ for 2-3h, centrifuge, wash and dry to obtain tertiary amine-modified benzoyl chloride;

[0011] S2. Add 2-2.3 g of 3-pentadecanylphenol to 5-6 mL of 1,2-bromoethane, then add 0.51-0.53 g of potassium hydroxide, heat the mixture for 3-4 h, and then separate the reaction by column chromatography to obtain 3-pentadecanylphenoxyethyl bromide.

[0012] S3. Add 1.1-1.3 mmol of tertiary amine-modified benzoyl chloride and 1.26-1.41 mmol of 3-pentadecanylphenoxyethyl bromide to 40-50 mL of N,N-dimethylformamide solvent, stir and mix, react at 80-90 °C, distill under reduced pressure after reaction, filter, and dry to obtain modified cashew phenol.

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

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

[0015] Furthermore, the reaction time in S3 is 6-9 hours.

[0016] Further, the preparation method of the high-temperature resistant sulfonated phenolic resin for drilling fluid is as follows: 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 are added to a reactor. After stirring and dissolving, 5-10 parts by weight of modified cashew phenol are added. The reaction is carried out at 60-68°C. After the reaction is completed, the mixture is distilled under reduced pressure and filtered to obtain the high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0017] Furthermore, the reaction time is 2-4 hours.

[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 undergo a click reaction to introduce a tertiary amine group and an acyl chloride group, thereby obtaining tertiary amine-modified benzoyl chloride; the tertiary amine group in the tertiary amine-modified benzoyl chloride reacts with the bromine group in 3-pentadecanylphenoxyethyl bromide to generate a quaternary ammonium salt group, thereby obtaining modified cashew phenol; the acyl chloride group in the modified cashew phenol reacts with the phenolic hydroxyl group in the benzenesulfonic acid-modified phenolic resin to obtain a high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0020] The quaternary ammonium salt groups and cashew phenol in high-temperature sulfonated phenolic resin can reduce filtration loss and improve salt resistance. Quaternary ammonium salts can adsorb onto clay particles or formation minerals to form a dense filter cake, reducing drilling fluid penetration into the formation. The hydrophobic long chains of cashew phenol can enhance the filter cake's resistance to high temperatures and salt, reducing filtration loss under high temperature and pressure. Furthermore, the combination of modified cashew phenol with benzenesulfonic acid-modified phenolic resin can form a more stable network structure, further reducing filtration loss. The abundant sulfonic acid groups and benzene ring structure in high-temperature sulfonated phenolic resin can improve the drilling fluid's high-temperature resistance, salt resistance, and reduce filtration loss. Attached Figure Description

[0021] Figure 1 It is the reaction formula for modified cashew phenol. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

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

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

[0026]

[0027] Example 1

[0028] The preparation method of 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, stir and disperse, then add 0.9 g of 3-(dimethylamino)-1-propanethiol and 0.02 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 25 °C for 2 h, centrifuge after the irradiation, wash and dry to obtain tertiary amine-modified benzoyl chloride;

[0030] S2. Add 2g of 3-pentadecanylphenol to 5mL of 1,2-bromoethane, then add 0.51g of potassium hydroxide, heat to 62℃ and react for 3h. After the reaction is completed, column chromatography is used to separate the 3-pentadecanylphenoxyethyl bromide.

[0031] S3. Add 1.1 mmol of tertiary amine-modified benzoyl chloride and 1.26 mmol of 3-pentadecanylphenoxyethyl bromide to 40 mL of N,N-dimethylformamide solvent, stir and mix, react at 80 °C for 6 h, distill under reduced pressure, filter, and dry to obtain modified cashew phenol.

[0032] S4. Dissolve 3.7 g of o-aminobenzenesulfonic acid, 6.3 g of glyoxal and 3.1 g of p-hydroxybenzenesulfonic acid in 40 mL of dimethyl sulfoxide solution containing sulfuric acid, mix well, and then transfer the mixture to a 200 mL polytetrafluoroethylene reactor. React at 115 °C for 42 h. After the reaction, wash the product with anhydrous ethanol and deionized water to obtain intermediate 1. Add 1 g of intermediate 1 to a reactor containing 25 mL of toluene, and then add 3.1 g of 1,3-propanesulfonic acid lactone dropwise. React at 105 °C for 45 h. After the reaction, filter to obtain 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. After stirring and dissolving, add 5 parts by weight of modified cashew phenol and react at 60°C for 2 hours. After the reaction is completed, distill under reduced pressure and filter to obtain 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, stir and disperse, then add 1.2 g of 3-(dimethylamino)-1-propanethiol and 0.03 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 40 °C for 3 h, centrifuge after the irradiation, wash and dry to obtain tertiary amine-modified benzoyl chloride;

[0037] S2. Add 2.3 g of 3-pentadecanylphenol to 6 mL of 1,2-bromoethane, then add 0.53 g of potassium hydroxide, heat to 68 °C and react for 4 h. After the reaction is complete, column chromatography is used to separate 3-pentadecanylphenoxyethyl bromide.

[0038] S3. Add 1.3 mmol of tertiary amine-modified benzoyl chloride and 1.41 mmol of 3-pentadecanylphenoxyethyl bromide to 50 mL of N,N-dimethylformamide solvent, stir and mix, react at 90 °C for 9 h, distill under reduced pressure, filter, and dry to obtain modified cashew phenol.

[0039] S4. Dissolve 4.1 g of o-aminobenzenesulfonic acid, 6.7 g of glyoxal and 3.4 g of p-hydroxybenzenesulfonic acid in 50 mL of dimethyl sulfoxide solution containing sulfuric acid, mix well, and then transfer the mixture to a 200 mL polytetrafluoroethylene reactor. React at 120 °C for 48 h. After the reaction, wash the product with anhydrous ethanol and deionized water to obtain intermediate 1. Add 2 g of intermediate 1 to a reactor containing 30 mL of toluene, and then add 3.6 g of 1,3-propanesulfonic acid lactone dropwise. React at 110 °C for 48 h. After the reaction, filter to obtain benzenesulfonic acid modified phenolic resin.

[0040] S5. Add 65 mL of N,N-dimethylformamide solvent, 4 parts by weight of benzenesulfonic acid modified phenolic resin, and 0.02 parts by weight of pyridine to the reactor. After stirring and dissolving, add 10 parts by weight of modified cashew phenol and react at 68°C for 4 hours. After the reaction is completed, distill under reduced pressure and filter to obtain high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0041] Example 3

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

[0043] S1. Add 1.7 g of 4-vinylbenzoyl chloride to 42 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.1 g of 3-(dimethylamino)-1-propanethiol and 0.025 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 35 °C for 2 h, centrifuge after the irradiation, wash and dry to obtain tertiary amine-modified benzoyl chloride;

[0044] S2. Add 2.1 g of 3-pentadecanylphenol to 6 mL of 1,2-bromoethane, then add 0.52 g of potassium hydroxide, heat to 65 °C and react for 4 h. After the reaction is complete, column chromatography is used to separate the 3-pentadecanylphenoxyethyl bromide.

[0045] S3. Add 1.2 mmol of tertiary amine-modified benzoyl chloride and 1.34 mmol of 3-pentadecanylphenoxyethyl bromide to 45 mL of N,N-dimethylformamide solvent, stir and mix, react at 85 °C for 8 h, distill under reduced pressure, filter, and dry to obtain modified cashew phenol.

[0046] S4. Dissolve 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal and 3.2 g of p-hydroxybenzenesulfonic acid in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mix well, and then transfer the mixture to a 200 mL polytetrafluoroethylene reactor. React at 117 °C for 45 h. After the reaction, wash the product with anhydrous ethanol and deionized water to obtain intermediate 1. Add 1.5 g of intermediate 1 to a reactor containing 28 mL of toluene, and then add 3.3 g of 1,3-propanesulfonic acid lactone dropwise. React at 107 °C for 46 h. After the reaction, filter to obtain benzenesulfonic acid modified phenolic resin.

[0047] S5. Add 55 mL of N,N-dimethylformamide solvent, 3 parts by weight of benzenesulfonic acid modified phenolic resin, and 0.015 parts by weight of pyridine to the reactor. After stirring and dissolving, add 6 parts by weight of modified cashew phenol and react at 64°C for 3 hours. After the reaction is completed, distill under reduced pressure and filter to obtain high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0048] Comparative Example 1

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

[0050] S1. Dissolve 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal and 3.2 g of p-hydroxybenzenesulfonic acid in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mix well, and then transfer the mixture to a 200 mL polytetrafluoroethylene reactor. React at 117 °C for 45 h. After the reaction, wash the product with anhydrous ethanol and deionized water to obtain intermediate 1. Add 1.5 g of intermediate 1 to a reactor containing 28 mL of toluene, and then add 3.3 g of 1,3-propanesulfonic acid lactone dropwise. React at 107 °C for 46 h. After the reaction, filter to obtain benzenesulfonic acid modified phenolic resin.

[0051] S2. Add 3 parts by weight of benzenesulfonic acid-modified phenolic resin to the reactor to obtain high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0052] Comparative Example 2

[0053] S1. Add 1.7 g of 4-vinylbenzoyl chloride to 42 mL of N,N-dimethylformamide solvent, stir and disperse, then add 1.1 g of 3-(dimethylamino)-1-propanethiol and 0.025 g of benzoin dimethyl ether photoinitiator, irradiate with 365 nm ultraviolet light at 35 °C for 2 h, centrifuge after the irradiation, wash and dry to obtain tertiary amine-modified benzoyl chloride;

[0054] S2. Dissolve 3.9 g of o-aminobenzenesulfonic acid, 6.5 g of glyoxal and 3.2 g of p-hydroxybenzenesulfonic acid in 45 mL of dimethyl sulfoxide solution containing sulfuric acid, mix well, and then transfer the mixture to a 200 mL polytetrafluoroethylene reactor. React at 117 °C for 45 h. After the reaction, wash the product with anhydrous ethanol and deionized water to obtain intermediate 1. Add 1.5 g of intermediate 1 to a reactor containing 28 mL of toluene, and then add 3.3 g of 1,3-propanesulfonic acid lactone dropwise. React at 107 °C for 46 h. After the reaction, filter to obtain benzenesulfonic acid modified phenolic resin.

[0055] S3. Add 55 mL of N,N-dimethylformamide solvent, 3 parts by weight of benzenesulfonic acid modified phenolic resin, and 0.015 parts by weight of pyridine to the reactor. After stirring and dissolving, add 6 parts by weight of tertiary amine modified benzoyl chloride. React at 64°C for 3 hours. After the reaction is completed, distill under reduced pressure and filter to obtain high-temperature resistant sulfonated phenolic resin for drilling fluid.

[0056] Performance testing

[0057] Preparation of saturated brine-based slurry: Add 350 mL of water to a high-speed mixing cup, add 0.49 g of sodium carbonate and 14 g of sodium bentonite for testing while stirring, stir at high speed for 20 min, seal and let stand for 24 h to obtain 4% fresh water-based slurry.

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

[0059] The experimental slurry was aged at 220℃ for 16 hours and then cooled and removed. Its rheological properties and medium-pressure filtration loss (FL) were determined according to GB / T16783.1-2014 "Field Testing of Drilling Fluids for Petroleum and Natural Gas Industry - Part 1: Water-based Drilling Fluids". API and high temperature and high pressure filtration loss FL HTHP (Test temperature 180℃, pressure 3.45MPa), including rheological properties testing: apparent viscosity AV and plastic viscosity PV, the test results are shown in Table 1.

[0060]

[0061] As shown in Table 1, the high-temperature resistant sulfonated phenolic resins for drilling fluids of the present invention in Examples 1-3 have better temperature and salt resistance than comparative examples 1-2, and significantly reduce filtration loss under high temperature and high pressure, while also exhibiting better rheological properties.

[0062] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0063] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0064] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments.

Claims

1. A high-temperature resistant sulfonated phenolic resin for drilling fluid, characterized in that it 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 3-pentadecanylphenol. The preparation method of the benzenesulfonic 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 and mixed evenly. Then the mixture is transferred to a 200mL polytetrafluoroethylene reactor and reacted at 115-120℃ for 42-48h. After 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, and then 1,3-propanesulfonic acid lactone is added dropwise and reacted at 105-110℃ for 45-48h. After the reaction, the mixture is filtered to obtain benzenesulfonic acid modified phenolic resin. The ratio of intermediate 1, toluene, and 1,3-propanesulfonic acid lactone is 1-2g: 25-30mL: 3.1-3.6g; The method for preparing the modified 3-pentadecanylphenol is as follows: 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 with 365nm ultraviolet light at 25-40℃ for 2-3h, centrifuge, wash and dry to obtain tertiary amine-modified benzoyl chloride; S2. Add 2-2.3 g of 3-pentadecanylphenol to 5-6 mL of 1,2-bromoethane, then add 0.51-0.53 g of potassium hydroxide, heat the mixture for 3-4 h, and then separate the reaction by column chromatography to obtain 3-pentadecanylphenoxyethyl bromide. S3. Add 1.1-1.3 mmol of tertiary amine-modified benzoyl chloride and 1.26-1.41 mmol of 3-pentadecanylphenoxyethyl bromide to 40-50 mL of N,N-dimethylformamide solvent, stir and mix, react at 80-90 °C, distill under reduced pressure after reaction, filter, and dry to obtain modified 3-pentadecanylphenol. The 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; The reaction temperature in S2 is 62-68℃; The reaction time in S3 is 6-9 hours.

2. A method for preparing a high-temperature resistant sulfonated phenolic resin for drilling fluid as described in claim 1, characterized in that, The preparation method of the high-temperature resistant sulfonated phenolic resin for drilling fluid is as follows: 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 are added to a reactor. After stirring and dissolving, 5-10 parts by weight of modified 3-pentadecanylphenol are added. The reaction is carried out at 60-68℃. After the reaction is completed, the mixture is distilled under reduced pressure and filtered to obtain the high-temperature resistant sulfonated phenolic resin for drilling fluid.

3. The method for preparing high-temperature resistant sulfonated phenolic resin for drilling fluid according to claim 2, characterized in that, The reaction time is 2-4 hours.

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