Aliphatic amine-terminated modified sulfonated phenolic resin as well as preparation method and application thereof

Abstract

The invention provides a preparation method of fatty amine-terminated modified sulfonated phenolic resin. The preparation method comprises the following steps: S1) heating an aldehyde component and a secondary fatty amine component in water to react to obtain an intermediate reaction solution; s2) mixing the intermediate reaction liquid with a sulfomethylated phenolic resin aqueous solution, and heating to react to obtain a mixture; and S3) further heating the mixture obtained in the step S2) to react, and recombining the molecular structure of the product to obtain the fatty amine-terminated modified sulfonated phenolic resin. Compared with the prior art, the preparation method has the advantages that on the basis of sulfonated phenolic resin, the sulfonated phenolic resin is modified by utilizing the Mannich reaction among active sites, secondary aliphatic amine and aldehyde, the active sites of the sulfonated phenolic resin are regulated and controlled while amino groups are introduced, and adsorption groups and hydration groups are also introduced, so that the high-temperature adsorption capacity and hydration capacity of the product are improved; the compatibility of the sulfonated lignite and other materials, especially sulfonated lignite, under the high-temperature condition is regulated and controlled, so that the high-temperature resistance and salt resistance are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum drilling and oilfield chemistry, and in particular relates to a fatty amine-terminated modified sulfonated phenolic resin, a preparation method and application thereof. Background Art

[0002] During the drilling of ultra-deep wells, the drilling fluid often encounters complex situations due to the relatively deep reservoir burial, large changes in formation pressure, and complex and changeable lithology. Specifically, the downhole temperature and pressure are high, and sometimes ultra-high pressure salt water layers, complex salt-gypsum layers and gypsum mudstones are encountered, which are prone to salt-gypsum layer creep, unstable wellbore walls, easy blowouts and leaks, resistance during drilling and easy drill sticking, and other complex downhole accidents; when drilling with high-density drilling fluid, the drilling fluid has poor fluidity, thick mud cake, large filtration loss, and it is difficult to maintain the performance of the drilling fluid; especially in the "tri-sulfonate" and "polysulfonate" drilling fluids that are most commonly used for drilling in high-temperature and high-pressure formations, resin-based filtration reducers are very prone to high-temperature excessive cross-linking under high-temperature conditions, and are prone to precipitation under high-salinity conditions due to the presence of turbidity point salinity, resulting in treatment agent failure and deterioration of drilling fluid performance.

[0003] Sulfonated methylphenolic resin (also known as sulfonated phenolic resin, SMP) is a phenolic resin structure with sulfonic acid groups introduced into it. - ) has strong hydration effect and high bond energy of associated water, which improves the brittleness, adhesion and heat resistance of phenolic resin. It plays an important role in the fields of cationic resin, drilling operation, cementing operation, etc., especially sulfonated phenolic resin is the core treatment agent of "tri-sulfon" and "polysulfon" drilling fluid in deep well drilling, which can effectively reduce the water loss of drilling fluid under high temperature and high pressure, improve the lubricity of filter cake, stabilize the wellbore, and become an indispensable treatment agent in high-temperature deep well drilling fluid widely used in oil fields.

[0004] The review "Research Status and Development Direction of Ultra-High Temperature Water-Based Drilling Fluid Technology" (Oilfield Chemistry, Vol. 39, No. 3, 2022) points out that the difficulty of water-based drilling fluid in solving ultra-high temperature resistance lies in how to adjust and ensure that the drilling fluid can stably perform its performance under ultra-high temperature conditions, regulate the degradation and cross-linking of the treatment agent caused by ultra-high temperature conditions, and balance the effect of clay particles. The literature (Chem. World, 2019, 60 (11), 822-828) analyzes the high-temperature cross-linking reaction in the drilling fluid, how to control the rheology and filtration loss of the system, and discusses in detail the influencing factors of the cross-linking reaction of the treatment agent and the influence of the degree of cross-linking on the performance of the drilling fluid, such as temperature, time, pH value, polymer type, clay, etc., and puts forward the idea of ​​moderate cross-linking to improve the performance of the drilling fluid. However, sulfomethylphenol-formaldehyde resin (SMP) will inevitably have residual active sites during the production process. The structure diagram is shown in the figure. Figure 1As shown in the figure, the presence of active sites enables the resin to undergo cross-linking reactions under certain conditions, and is also the chemical basis for its performance in many fields of application. However, in high temperature / ultra-high temperature environments, excessive cross-linking of the resin will destroy the stability of the drilling fluid colloidal structure. Therefore, by using functional groups to occupy active sites, the cross-linking reaction of the resin fluid loss reducer under high temperature conditions can be controlled, and the adsorption capacity and hydrophilicity can be increased, thereby improving the product's temperature and salt resistance.

[0005] In order to improve the temperature and salt resistance of sulfonated phenolic resin, a Chinese patent with publication number CN109401736B discloses an ultra-high temperature drilling fluid loss reducer, which modifies SMP with hydroxyalkyl aldehyde and sulfonating reagent, increases the hydration group of the product, and synthesizes an ultra-high temperature drilling fluid loss reducer, which can effectively improve the temperature and salt resistance of resin-based fluid loss reducers. A Chinese patent with publication number CN109401738B discloses a high temperature and high salt water-based drilling fluid loss reducer and a preparation method thereof, which modifies SMP with melamine and then with polyacid and alcohol to improve the fluid loss reduction performance of sulfonated phenolic resin. The document "Development of Cationic Sulfonated Phenolic Resin Fluid Loss Reducer for Drilling Fluid" (Guangdong Chemical Industry, 2014, 41(08): 21-2) develops a zwitterionic SMP fluid loss reducer by modifying phenol with organic amine.

[0006] The above patent proves that controlling the active sites of sulfomethylphenolic resin (SMP) and introducing amine groups can help improve the performance of resin fluid loss reducers. Since primary amine (-NH2) has two reaction sites, primary amine derivatives, sodium p-aminobenzenesulfonate or melamine are used as raw materials (structure diagram as shown in the figure) Figure 2 As shown), they have 2, 4 and 6 reaction sites respectively. In production, the reaction conditions need to be controlled to avoid gelation or intramolecular cyclization reaction, and the remaining reaction sites in the product cannot be controlled, which is not conducive to significantly improving the performance of SMP. In order to further improve the temperature and salt resistance of sulfonated phenolic resin, the present invention is based on the structure of sulfonated methyl phenolic resin, utilizes the Mannich reaction between fatty secondary amine, formaldehyde and SMP, and introduces amino groups while regulating the active sites of the resin fluid loss reducer, thereby improving the temperature resistance, salt resistance and fluid loss reduction capabilities of the sulfonated phenolic resin. Summary of the invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a fatty amine-terminated modified sulfonated phenolic resin with high high-temperature adsorption capacity and hydration capacity and a preparation method thereof.

[0008] The invention provides a fatty amine-terminated modified sulfonated phenolic resin, a preparation method and an application thereof. The sulfonated phenolic resin is modified by the Mannich reaction of a sulfonated methyl phenolic resin with a secondary amine and formaldehyde, and while an amino group is introduced, the active site of a resin fluid loss reducer is regulated to improve the temperature resistance, salt resistance and fluid loss reduction capabilities of the sulfonated phenolic resin.

[0009] The purpose of the present invention is to solve the problem that the existing sulfonated phenolic resin has insufficient high temperature and salt resistance, and is prone to excessive cross-linking and thickening under high temperature and high salt conditions, resulting in uncontrollable rheology and filtration loss of drilling fluid.

[0010] The present invention provides a method for preparing a fatty amine-terminated modified sulfonated phenolic resin, comprising the following steps:

[0011] S1) heating the aldehyde component and the secondary fatty amine component in water to react to obtain an intermediate reaction liquid;

[0012] S2) mixing the intermediate reaction liquid with an aqueous solution of sulfomethylphenol-formaldehyde resin, and heating the mixture for reaction to obtain a mixture;

[0013] S3) the mixture obtained in step S2) is further heated to react, the molecular structure of the product is reorganized, and the fatty amine-terminated modified sulfonated phenolic resin is obtained.

[0014] Preferably, in step S1), the aldehyde component is selected from one or more of formaldehyde, paraformaldehyde, trioxymethylene, hydroxyacetaldehyde, 3-hydroxypropionaldehyde, 3-hydroxybutyraldehyde, 5-hydroxyvaleraldehyde and p-hydroxybenzaldehyde;

[0015] The secondary fatty amine is a low-order fatty amine;

[0016] The secondary fatty amine component is selected from chain fatty amines and / or cyclic fatty amines; the chain fatty amine is selected from one or more of dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, diisobutylamine and diethanolamine; the cyclic fatty amine is selected from one or more of tetrahydropyrrole, piperidine, 4-methylpiperidine, morpholine, N-methylpiperazine and N-ethylpiperazine.

[0017] Preferably, in step S1), the molar ratio of the aldehyde component to the secondary fatty amine component is (1.1-1.2):1.

[0018] Preferably, in step S1), the aldehyde component and the secondary fatty amine component are first mixed in water, and then the pH value of the mixed solution is adjusted to 9-10 with an alkali metal hydroxide, and then heated to react.

[0019] Preferably, the temperature of the heating reaction is 40° C. to 80° C.; and the time of the heating reaction is 1 to 3 hours.

[0020] Preferably, the mass concentration of sulfomethylphenol-formaldehyde resin in the sulfomethylphenol-formaldehyde resin aqueous solution in step S2) is 25% to 40%;

[0021] The molar ratio of the sulfomethylphenolic resin to the secondary fatty amine is (0.2-0.6):1;

[0022] The temperature of the heating reaction in step S2) is 70°C to 95°C.

[0023] Preferably, the temperature for continuing the heating reaction in step S3) is 90° C. to 120° C., and the time for continuing the heating reaction is 1 to 3 hours.

[0024] Preferably, after the temperature is continued to rise and the reaction is completed, the mixture is cooled and depressurized, and then spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin.

[0025] The invention also provides a fatty amine-terminated modified sulfonated phenolic resin prepared by the preparation method.

[0026] The present invention also provides a drilling fluid, comprising the fatty amine-terminated modified sulfonated phenolic resin prepared by the above preparation method.

[0027] The present invention provides a method for preparing a fatty amine-terminated modified sulfonated phenolic resin, comprising the following steps: S1) heating an aldehyde component and a secondary fatty amine component in water to react to obtain an intermediate (R 1 R 2 N-CH2OH) reaction liquid; S2) mixing the intermediate reaction liquid with a sulfomethylphenolic resin aqueous solution, heating the mixture for reaction; S3) further heating the mixture obtained in step S2) for reaction, reorganizing the product molecular structure, and obtaining a fatty amine-terminated modified sulfonated phenolic resin. Compared with the prior art, the present invention, on the basis of sulfonated phenolic resin, utilizes the Mancini reaction between the active site and the secondary fatty amine and aldehyde to modify the sulfonated phenolic resin, while introducing the amino group and regulating the active site of the sulfonated phenolic resin, and also introducing the adsorption group and the hydration group, thereby improving the high temperature adsorption capacity and hydration capacity of the product, regulating its compatibility with other materials, especially sulfonated lignite under high temperature conditions, and improving the high temperature resistance and salt resistance.

[0028] The test results show that the fatty amine-terminated modified sulfonated phenolic resin provided by the present invention can control the filtration loss to 25.0 mL at 220° C. and saturated salt conditions, which is helpful for the exploration and development of high and deep wells. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is the structural diagram of sulfonated phenolic resin (SMP);

[0030] Figure 2 is the primary amine reaction site diagram;

[0031] Figure 3 The diagram is the mechanism of Mannich reaction modification of sulfonated phenolic resin;

[0032] Figure 4 A synthetic route for Mannich reaction-modified sulfonated phenolic resins;

[0033] Figure 5 This is the infrared spectrum of the product. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0035] The invention provides a fatty amine-terminated modified sulfonated phenolic resin, which is obtained by aminating sulfonated methylphenolic resin with a secondary fatty amine in the presence of an aldehyde component.

[0036] In the present invention, the sulfomethylphenolic resin is preferably as shown in formula (I):

[0037]

[0038] Among them, m=0.2~0.6, n+x=0.4~0.8; m+n+x=1.

[0039] According to the present invention, the sulfonated methylphenolic resin is preferably a sulfonated phenolic resin SMP, more preferably a sulfonated phenolic resin SMP-1.

[0040] The present invention uses a secondary fatty amine as an amination reagent; the secondary fatty amine is preferably a low-grade fatty amine with a pK b The value (25°C) is 2.73-5.12, as shown in Table 1, and has the following three characteristics: ① The nucleophilicity of the α-carbon of the amine is greater than that of the phenolic compound, and it preferentially condenses with formaldehyde to obtain a methyleneamine cation intermediate, and finally generates a Mannich base, which is compared with the hydroxymethylation reaction with phenol, ketone or ester compounds; ② The nucleophilicity of the amine matches the nucleophilicity of the α-carbon of the phenolic compound, which is conducive to the smooth progress of the Mannich reaction; ③ The product structure is relatively stable, which promotes the reaction. The Mannich reaction intermediate N-hydroxymethyl compound or imine cation or Schiff base is electrically neutral or positively charged, and has a weak electrostatic repulsion with SMP, which is conducive to the modification of negatively charged SMP; in the present invention, the secondary fatty amine can be a fatty chain amine as shown in formula (II-1), or a cyclic amine as shown in formula (II-2); the general formula of the secondary fatty amine is preferably R 1 R2 NH, where R 1 and R 2 is a substituent of an amine group, representing that the organic amine used is a secondary amine, and the R 1 With R 2 Each is independently a C1-C4 alkyl group or a C1-C4 alkyl group substituted with a hydroxyl group, or R 1 With R 2 Connect into a ring.

[0041]

[0042] In the present invention, specifically, the chain aliphatic amine includes but is not limited to one or more of dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, diisobutylamine and diethanolamine; the cyclic aliphatic amine includes but is not limited to one or more of tetrahydropyrrole, piperidine, 4-methylpiperidine, morpholine, N-methylpiperazine and N-ethylpiperazine.

[0043] Table 1 pK of amination reagent raw materials b Value (25℃)

[0044] Serial number amine Chemical formula <![CDATA[pK b Value]]> 1 ammonia <![CDATA[NH3]]> 4.77 2 Dimethylamine <![CDATA[(CH3)2NH2]]> 3.32 3 Diethylamine <![CDATA[(CH3CH2)2NH]]> 3.06 4 Dipropylamine <![CDATA[(CH3CH2CH2)2NH]]> 3.06 5 Dibutylamine <![CDATA[(CH3CH2CH2CH2)2NH]]> 2.75 6 Diisobutylamine <![CDATA[((CH3)2CHCH2)2NH]]> 2.93 7 Diethanolamine <![CDATA[(HOCH2CH2)2NH]]> 5.12 8 Tetrahydropyrrole <![CDATA[C4H9N]]> 2.73 9 Piperidine <![CDATA[C5H 11 N]]> 2.75 10 4-Methylpiperidine <![CDATA[C6H 13 N]]> 2.77 11 Piperidine <![CDATA[C5H 11 N]]> 2.75 12 Morpholine <![CDATA[C4H9NO]]> 5.67 13 N-Methylpiperazine <![CDATA[C5H 12 N2]]> 4.91 14 N-Ethylpiperazine <![CDATA[C6H 14 N2]]> 4.73 15 N-Butylpiperazine <![CDATA[C8H 18 N2]]> 4.73

[0045] In the present invention, the aldehyde component is preferably one or more of alkyl aldehydes, polyaldehydes and hydroxyalkyl aldehydes; specifically, formaldehyde, paraformaldehyde, trioxymethylene, etc. can be selected, and hydroxyalkyl aldehydes such as hydroxyacetaldehyde, 3-hydroxypropionaldehyde, 3-hydroxybutyraldehyde, 5-hydroxyvaleraldehyde, and p-hydroxybenzaldehyde can also be selected. The characteristic is that the steric hindrance of the adjacent groups of the aldehyde group is small, and it can form an active intermediate with the secondary amine, and undergo a Mannich reaction with the active site of the SMP to connect the amine group to the active site of the SMP. The reaction formula for the intermediate N-hydroxymethyl compound generated by the amine and the aldehyde component in the Mannich reaction is:

[0046]

[0047] The OH (NC-OH) on the N-hydroxymethyl compound undergoes an intermolecular elimination reaction with the H (CH) of the SMP benzene ring unit to remove a molecule of water, and the amine group is connected to the benzene ring unit of SMP through a methylene (-CH2-) or a methine (-CHR-). The reaction formula is:

[0048]

[0049] Since the intermediate N-hydroxymethyl compound is electrically neutral, compared with the Chinese patent with publication number CN109401736B (a kind of ultra-high temperature drilling fluid loss reducer), which uses the negatively charged intermediate of hydroxymethyl sulfonate formed by hydroxyalkyl aldehyde and sulfonating agent to modify SMP, the electrostatic repulsion is smaller and is more conducive to the deep modification of SMP; the introduction of amine groups can increase the group diversity of SMP and improve the adsorption capacity and hydration capacity of SMP; the amine groups are introduced through the active sites of SMP, which can regulate the cross-linking effect of SMP at high temperature, which is conducive to the development of temperature-resistant SMP products.

[0050] The invention provides a method for preparing the above-mentioned fatty amine-terminated modified sulfonated phenolic resin, comprising the following steps: S1) heating an aldehyde component and a secondary fatty amine component in water to react to obtain an intermediate reaction liquid; S2) mixing the intermediate reaction liquid with a sulfomethylphenolic resin aqueous solution, heating to react to obtain a mixture; S3) further heating the mixture obtained in step S2) to react, reorganizing the product molecular structure, and obtaining the fatty amine-terminated modified sulfonated phenolic resin.

[0051] The present invention modifies sulfonated phenolic resin (SMP) by Mannich reaction. The structure of sulfonated phenolic resin (SMP) is shown in FIG. Figure 1 As shown, compared with primary amines, there are two reaction sites, such as Figure 2 As shown, the tertiary amine has one reaction site, and the reaction mechanism is shown in Figure 3 As shown, the modification formula and reaction process are shown in Figure 4 As shown. Among them, R 1 and R 2 is a substituent of an amine group, indicating that the amine used is a secondary amine; R 1 With R 2 Each is independently selected from a C1-C4 alkyl group or a C1-C4 alkyl group substituted with a hydroxyl group; or R 1 With R 2 The bridges are connected into rings to form aliphatic cyclic amines. The Mannich reaction intermediates N-hydroxymethyl compounds or iminium cations or Schiff bases are electrically neutral or positively charged, and have weak electrostatic repulsion with SMP, which is conducive to the modification of negatively charged SMP.

[0052] The present invention has no particular limitation on the sources of all raw materials, and any raw materials available on the market can be used.

[0053] The aldehyde component and the secondary fatty amine component are mixed in water; the aldehyde component is preferably one or more of alkyl aldehydes, polyaldehydes and hydroxyalkyl aldehydes; the alkyl aldehyde is preferably formaldehyde; the polyaldehyde is selected from paraformaldehyde and / or triformaldehyde; the hydroxyalkyl aldehyde is selected from one or more of hydroxyacetaldehyde, 3-hydroxypropionaldehyde, 3-hydroxybutyraldehyde, 5-hydroxyvaleraldehyde and p-hydroxybenzaldehyde; the secondary fatty amine is preferably a chain fatty amine and / or a cyclic fatty amine; the chain fatty amine is selected from one or more of dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, diisobutylamine and diethanolamine; the cyclic fatty amine is preferably tetrahydrofuran One or more of pyrrole, piperidine, 4-methylpiperidine, morpholine, N-methylpiperazine and N-ethylpiperazine; the secondary fatty amine used in the present invention is a low-order fatty amine, which has the following three characteristics: 1) The nucleophilicity of the α-carbon of the amine is greater than that of the phenolic compound, and it preferentially condenses with formaldehyde to obtain a methyleneamine cation intermediate, and finally generates a Mannich base, which reacts with phenol, ketone or ester compounds for hydroxymethylation; 2) The nucleophilicity of the amine matches the nucleophilicity of the α-carbon of the phenolic compound, which is conducive to the smooth progress of the Mannich reaction; 3) The product structure is relatively stable, which promotes the reaction. The molar ratio of the aldehyde reagent to the secondary fatty amine is preferably (1.1-1.2): 1; the concentration of the secondary fatty amine in the mixed solution is preferably 0.5-2 mol / L, more preferably 1-2 mol / L.

[0054] Then, the pH value of the mixed solution is preferably adjusted to alkaline, and then heated to react to obtain the intermediate (R 1 R 2 N-CH2OH) reaction solution; in the present invention, an alkali metal hydroxide is preferably used to adjust the pH value of the mixed solution; the alkali metal hydroxide is any alkali metal hydroxide known to those skilled in the art, and there is no special limitation. In the present invention, sodium hydroxide and / or potassium hydroxide are preferably used; the pH value of the mixed solution is preferably adjusted to 9 to 10; in order to promote the reaction of formaldehyde with the secondary fatty amine to generate the reaction intermediate R 1 R 2 N-CH2OH, the temperature of the heating reaction is preferably 40°C to 80°C, more preferably 50°C to 60°C; the time of the heating reaction is preferably 1 to 3 hours, more preferably 2 to 3 hours.

[0055] The intermediate reaction liquid is mixed with a sulfomethylphenolic resin aqueous solution, and heated to react to obtain a mixture; the molar ratio of the sulfomethylphenolic resin to the secondary fatty amine is preferably (0.2-0.6):1, and more preferably (0.3-0.5):1; the mass concentration of the sulfomethylphenolic resin in the sulfomethylphenolic resin aqueous solution is preferably 25%-40%, more preferably 30%-40%, and more preferably 35%-40%; in the present invention, the temperature of the heating reaction is preferably 70°C-95°C, more preferably 75°C-90°C, and more preferably 80°C-90°C; the time of the heating reaction is preferably 1.5-4h; the reaction is first carried out at a lower temperature to inhibit side reactions such as phenolic condensation and polycondensation to increase the conversion rate of the secondary fatty amine.

[0056] The obtained mixture is then subjected to a further temperature-raising reaction to reorganize the molecular structure of the product; the temperature of the temperature-raising reaction is preferably 90°C to 120°C, more preferably 95°C to 120°C; the time of the temperature-raising reaction is preferably 3 to 12 hours; in the embodiments provided in the present invention, the time of the temperature-raising reaction is specifically 3 hours, 5 hours, 8 hours, 10 hours or 12 hours.

[0057] After the temperature continues to rise and the reaction is finished, the mixture is cooled and depressurized, and then spray-dried to obtain a powdery fatty amine-terminated modified sulfonated phenolic resin.

[0058] The invention is based on sulfonated phenolic resin, utilizes the Mancini reaction between active sites and secondary fatty amines and aldehydes, controls the active sites of the sulfonated phenolic resin and introduces adsorption groups and hydration groups at the same time, improves the high-temperature adsorption capacity and hydration capacity of the product, regulates the compatibility of the product with other materials, especially sulfonated lignite, under high temperature conditions, and improves the high temperature resistance and salt resistance.

[0059] The present invention also provides an application of the fatty amine-terminated modified sulfonated phenolic resin as a fluid loss reducing agent.

[0060] The present invention also provides a drilling fluid, comprising the fatty amine-terminated modified sulfonated phenolic resin prepared by the above method.

[0061] In order to further illustrate the present invention, the present invention provides a fatty amine-terminated modified sulfonated phenolic resin and a preparation method thereof, which are described in detail below in conjunction with examples.

[0062] The reagents used in the following examples are all commercially available, among which sulfonated phenolic resin SMP-1 (Lankao County Desheng Mud Treatment Agent Factory) is used.

[0063] Example 1

[0064] Add formaldehyde (37.0%, 32.4g, 0.40mol) to a mixture of dimethylamine solution (40.0%, 56.4g, 0.50mol) and 283.9g of water, stir to make the mixture uniform, heat to 60°C and react for 1h, then add the reaction solution to a sulfonated phenolic resin aqueous solution (100g sulfonated phenolic resin, 200g water), heat to 60°C and react for 4 hours; continue to heat the obtained mixture and react at 120°C for 1h; after the reaction time is reached, a brown liquid is obtained, which is cooled; the liquid is spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin 1.

[0065] Example 2

[0066] Hydroxyacetaldehyde (12.0 g, 0.20 mol) and 3-hydroxypropionaldehyde (29.6 g, 0.40 mol) were added to a mixture of diisobutylamine (77.5 g, 0.60 mol) and 457.5 g of water, stirred to make the mixture uniform, added NaOH (0.5 g, 12.5 mmol) to adjust the pH value to 9-10, heated to 50° C. and reacted for 2 h, then the reaction solution was added to a sulfonated phenolic resin aqueous solution (100 g sulfonated phenolic resin, 200 g water), heated to 80° C. and reacted for 2 hours; the obtained mixture was further heated and reacted at 110° C. for 5 h; after the reaction time was reached, a brown liquid was obtained, which was cooled; the liquid was spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin 2.

[0067] Example 3

[0068] Add paraformaldehyde (polymerization degree 2-8, 15.0 g) to a mixture of di-n-butylamine (12.9 g, 0.1 mol), 4-methylpiperidine (42.4 g, 0.43 mol), N-methylpiperazine (20.0 g, 0.2 mol) and 244.2 g of water, stir to make the mixture uniform, add NaOH (0.5 g, 12.5 mmol) to adjust the pH value to 9-10, heat to 40°C and react for 3 hours, then add the reaction solution to a sulfonated phenolic resin aqueous solution (100 g sulfonated phenolic resin, 200 g water), heat to 90°C and react for 3 hours; continue to heat the obtained mixture and react at 105°C for 2 hours; after the reaction time is reached, a brown liquid is obtained, which is cooled; the liquid is spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin 3.

[0069] Example 4

[0070] Trioxymethylene (3.0 g, 0.1 mol), 3-hydroxybutyraldehyde (8.8 g, 0.1 mol) and 4-hydroxybutyraldehyde (12.2 g, 0.14 mol) are added to a mixture of diethylamine (7.3 g, 0.1 mol), tetrahydropyrrole (7.1 g, 0.1 mol), 1-butylpiperazine (14.2 g, 0.1 mol) and 83.5 g of water, stirred to make the mixture uniformly mixed, heated to 50° C. for reaction for 1 h, and then the reaction solution is added to a sulfonated phenolic resin aqueous solution (100 g sulfonated phenolic resin, 200 g water), heated to 95° C., and reacted for 1.5 hours; the obtained mixture is further heated and reacted at 100° C. for 3 h; after the reaction time is reached, a brown liquid is obtained, which is cooled; the liquid is spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin 4.

[0071] Example 5

[0072] Hydroxyacetaldehyde (6.0 g, 0.1 mol) and 5-hydroxyvaleraldehyde (14.3 g, 0.14 mol) are added to a mixture of diethanolamine (10.5 g, 0.1 mol), morpholine (8.7 g, 0.1 mol) and 9.3 g of water, stirred to make the mixture uniformly mixed, and NaOH (0.5 g, 12.5 mmol) is added to adjust the pH value to 9-10, and the temperature is raised to 40° C. for reaction for 3 h. The reaction solution is then added to a sulfonated phenolic resin aqueous solution (100 g of sulfonated phenolic resin and 200 g of water), and the temperature is raised to 70° C. for reaction for 3 hours. The obtained mixture is further heated and reacted at 95° C. for 1 h. After the reaction time is reached, a brown liquid is obtained, which is cooled. The liquid is spray-dried to obtain a powdered fatty amine-terminated modified sulfonated phenolic resin 5.

[0073] The performance of the fatty amine-terminated modified sulfonated phenolic resin products obtained in Examples 1 to 5 was evaluated in saturated salt water-based slurry, as follows:

[0074] Preparation of saturated salt water base slurry: Add 350 mL of water to a high-speed stirring cup, add 0.49 g of sodium carbonate and 14 g of test sodium bentonite while stirring, stir at high speed for 20 min, seal and place for 24 h to obtain 4% fresh water base slurry, add 105 g of NaCl while stirring to obtain saturated salt water base slurry.

[0075] Preparation of experimental slurry: Under high-speed stirring, add 8% sulfonated lignite (SMC) + 10% fatty amine-terminated modified sulfonated phenolic resins 1 to 5 prepared in the embodiment to 4% fresh water-based slurry, stir at high speed for 20 minutes, and add 105g NaCl under stirring to obtain experimental slurry.

[0076] The saturated salt water base slurry and the experimental slurry were aged at 220℃ / 16h and then cooled and taken out. The rheological properties and medium pressure filtration loss FL were measured according to GB / T16783.1.API and high temperature and high pressure filtration loss FL HTHP (Test temperature 180°C, pressure 3.45MPa), wherein the rheological properties include apparent viscosity AV, plastic viscosity PV and yield value YP, and the test results are shown in Table 1.

[0077] Table 1 Performance evaluation of products in saturated salt water slurry

[0078]

[0079] It can be seen from the experimental results that the fatty amine-terminated modified sulfonated phenolic resin has good rheology and low filtration loss after high-temperature aging at 220℃ / 24h in saturated salt water-based slurry. The high-temperature and high-pressure filtration loss can be controlled within 25.0mL. The product has good high-temperature and salt resistance and the ability to control high-temperature and high-pressure filtration loss.

[0080] The aliphatic amine-terminated modified sulfonated phenolic resin obtained in Example 1 and Example 5 was analyzed by infrared spectroscopy to obtain its infrared spectrum, as shown in FIG. Figure 5 In SMP, 3427.6cm -1 It is the characteristic absorption peak of phenolic hydroxyl group (OH); 3007cm -1 The weaker absorption peak originates from the -CH vibration on the aromatic ring; 2922.4cm -1 The antisymmetric stretching vibration peak of methylene is 2853.7 cm -1 It is the symmetric stretching vibration absorption peak of methylene, and at 1478.3cm -1 It is the asymmetric deformation vibration (bending vibration) peak of methylene; 1626.8cm -1 Sulfonylmethyl (-CH2SO3 - ) The characteristic absorption peak of the CS bond stretching vibration of the group is 1186.5cm -1 、1130.6cm -1 Sulfonic acid group (-SO3 - ) Asymmetric stretching vibration characteristic absorption peak, 1042.5cm -1 It is the characteristic absorption peak produced by the symmetric stretching vibration of the sulfonic acid group, 700~500cm -1 The absorption peaks are caused by the deformation vibration of CS and SO bonds; the vibration of the benzene ring skeleton is generally at 1600cm -1 、1580cm -1 There is absorption nearby, overlapping with the CS characteristic peak, 882.8cm -1 、767.9cm -1 、626.8cm -1 It is the shear vibration of CH in C6H6.

[0081] In the dimethylamine-modified sulfomethylphenolic resin, the main structure peaks are similar, but the characteristic absorption peak of the CS bond stretching vibration of the sulfonic acid group is 1626.8 cm -1 Redshift to 1606.7 cm -1 ; 1352.9cm -1 A new peak appears, which is attributed to the scissoring vibration of the CH of the methyl group. The bond length remains unchanged, but the bond angle changes periodically. The stretching vibration of the CN bond is generally at 1190cm -1 It overlaps with the characteristic absorption peak of asymmetric stretching vibration of sulfonic acid group; the shear vibration of CH in C6H6 is 626.8cm -1 The peak blue shifted to 621.6 cm -1 .

[0082] In the diethanolamine-modified sulfomethylphenolic resin, the main structure peaks are similar, but the characteristic absorption peak of the CS bond stretching vibration of the sulfonic acid group is 1626.8 cm -1 Blue shift to 1658.9cm -1 , and at 1602.8cm -1 There are obvious vibration peaks of the benzene ring skeleton; the stretching vibration of the CN bond is generally at 1190cm -1 It overlaps with the characteristic absorption peak of asymmetric stretching vibration of sulfonic acid group; the shear vibration peak of CH in C6H6 is 626.8cm -1 Blue shift to 611.9cm -1 .

[0083] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a fatty amine-terminated modified sulfonated phenolic resin, characterized in that: The following steps are involved: S1) heating the aldehyde component and the secondary fatty amine component in water to react to obtain an intermediate reaction liquid; S2) mixing the intermediate reaction liquid with an aqueous solution of sulfomethylphenol-formaldehyde resin, and heating the mixture for reaction to obtain a mixture; S3) the mixture obtained in step S2) is further heated to react, the molecular structure of the product is reorganized, and the fatty amine-terminated modified sulfonated phenolic resin is obtained.

2. The preparation method according to claim 1, characterized in that: In step S1), the aldehyde component is selected from one or more of formaldehyde, paraformaldehyde, trioxymethylene, hydroxyacetaldehyde, 3-hydroxypropionaldehyde, 3-hydroxybutyraldehyde, 5-hydroxyvaleraldehyde and p-hydroxybenzaldehyde; The secondary fatty amine is a low-order fatty amine; The secondary fatty amine component is selected from chain fatty amines and / or cyclic fatty amines; the chain fatty amine is selected from one or more of dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, diisobutylamine and diethanolamine; the cyclic fatty amine is selected from one or more of tetrahydropyrrole, piperidine, 4-methylpiperidine, morpholine, N-methylpiperazine and N-ethylpiperazine.

3. The preparation method according to claim 1, characterized in that: In the step S1), the molar ratio of the aldehyde component to the secondary fatty amine component is (1.1-1.2):

1.

4. The preparation method according to claim 1, characterized in that: In the step S1), the aldehyde component and the secondary fatty amine component are first mixed in water, and then the pH value of the mixed solution is adjusted to 9-10 with an alkali metal hydroxide, and then heated to react.

5. The preparation method according to claim 1, characterized in that: The temperature of the heating reaction is 40° C. to 80° C.; the time of the heating reaction is 1 to 3 hours.

6. The preparation method according to claim 1, characterized in that: The mass concentration of sulfonyl phenolic resin in the sulfonyl phenolic resin aqueous solution in step S2) is 25% to 40%; The molar ratio of the sulfomethylphenolic resin to the secondary fatty amine is (0.2-0.6):1; The temperature of the heating reaction in step S2) is 70°C to 95°C.

7. The preparation method according to claim 1, characterized in that: The temperature for continuing the heating reaction in step S3) is 90° C. to 120° C.; and the time for continuing the heating reaction is 1 to 3 hours.

8. The preparation method according to claim 1, characterized in that: After the temperature continues to rise and the reaction is finished, the mixture is cooled and depressurized, and then spray-dried to obtain a powdery fatty amine-terminated modified sulfonated phenolic resin.

9. The fatty amine-terminated modified sulfonated phenol-formaldehyde resin prepared by the preparation method according to any one of claims 1 to 8.

10. A drilling fluid comprising the fatty amine-terminated modified sulfonated phenolic resin prepared by the preparation method according to any one of claims 1 to 8.

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