Dehydroabietyl Schiff base derivative as well as preparation method and application thereof

Abstract

The invention provides a dehydroabietyl Schiff base derivative as well as a preparation method and application thereof, and belongs to the technical field of oilfield exploitation, the dehydroabietyl Schiff base derivative has a structure as shown in a formula I. The dehydroabietyl Schiff base derivative provided by the invention contains a tricyclic phenanthrene rigid structure oleophylic skeleton of dehydroabietylamine; the water-in-oil emulsifying agent has an effect of emulsifying water in oil and is easy to stabilize a synthetic drilling fluid water-in-oil system. Meanwhile, the Schiff base derivative and the barite can form coordinate bond covalent bond acting force, and the problem that the barite is easy to settle is solved. The additive can improve the high-temperature stability of a synthetic drilling fluid system and the sedimentation stability of barite.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of oilfield exploitation, and relates to a dehydroabietyl Schiff base derivative and a preparation method and application thereof. BACKGROUND

[0002] The annual investment of oil and gas exploration funds in China is as high as nearly 8 billion yuan, accounting for about 80% of the total amount of national geological exploration funds. Drilling fluid is a medium for flushing in the hole during drilling and punching, and plays a key role in oil and gas exploration. Drilling fluid technology is the central technology of oil exploration and exploitation, and is also the fundamental factor of pollution. China consumes nearly 2 million tons of drilling fluid treatment agents every year, with a value of over 10 billion yuan. Most drilling fluid additives are high in cost, have certain toxicity and pollution, and the impact of cuttings generated from the stratum on the ecological environment is also difficult to recover. Therefore, it is of great economic and environmental significance to find safe and degradable natural plant additives with high cost performance.

[0003] As an important natural forest resource in China, the main component of rosin is small molecule resin acid with a unique tricyclic diterpene hydrophobic rigid skeleton and chiral center structure. This special structure makes rosin easy to build weak forces such as pi-pi stacking and specific spatial structure, and is an ideal raw material for preparing new small molecule gel materials. The abundant natural resource reserves and unique molecular structure advantages provide a broad development space and application potential for the research and development of small molecule gel materials. In the previous study, the amide bond was introduced into the rosin resin acid molecule, and rosin-based carbamide and sulfonamide organic gel materials were successfully prepared. It is found that they have excellent adsorption and response (temperature, pH) properties, and are tried to be used in the drilling fluid system of oil exploration, and it is found that they have good anti-settling performance.

[0004] Based on the previous research, in order to further enhance the fusion of gel molecules with drilling fluid and improve the tolerance of the product in high temperature environment (the application scene of drilling fluid is 150-200 DEG C high temperature condition), a rosin-based Schiff base derivative is developed, and the gel performance and application effect in drilling fluid are further explored, which is the research focus in the field. SUMMARY

[0005] In view of the shortcomings of the prior art, the purpose of the present application is to provide a dehydroabietyl Schiff base derivative and a preparation method and application thereof.

[0006] In order to achieve the purpose of the present application, the following technical solutions are adopted:

[0007] On the one hand, the present application provides a dehydroabietyl Schiff base derivative, which has the following structure as shown in formula I:

[0008]

[0009] wherein R1 is hydrogen or a linear C1-C20 alkyl group; and R2 is a substituted or unsubstituted C6-C12 aryl group, the substituents of the substituted C6-C12 aryl group being selected from the group consisting of a hydroxyl group, a halogen, a C6-C12 aryl group, or a C1-C5 alkyl group.

[0010] In the present application, the C1-C20 alkyl group can be a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20 alkyl group, the C6-C12 aryl group can be a C6, C7, C8, C9, C10, C11, or C12 aryl group, and the C1-C5 alkyl group can be a C1, C2, C3, C4, or C5 alkyl group.

[0011] In the present application, the dehydroabietyl Schiff base derivative has a tricyclic phenanthrene rigid structure lipophilic skeleton containing dehydroabietylamine in its structure, has strong lipophilicity, has excellent emulsification, and can generate a water-in-oil emulsion. The dehydroabietyl Schiff base derivative is easy to synthesize a base (oil-based) drilling fluid water-in-oil system. When R1 of the dehydroabietyl Schiff base derivative is hydrogen or an alkyl chain, the overall lipophilicity is ensured to be strong, and the compatibility with synthetic oil is increased. R2 has a very strong π electron structure, can form π-π electron conjugation with the Schiff base, and the substituents in R2 are also electron-donating groups such as alkane or hydroxyl, which have multiple electron empty p orbitals, enhance the electronegativity of R2 or form conjugate structures, promote, enhance, and assist the coordination of the Schiff base with barium sulfate barite, so that the barium sulfate can form a high-temperature-resistant chemical bond with the organic matter. At the same time, the Schiff base derivative itself has a relatively negative electron property. In the drilling fluid system, the Schiff base compound itself or with the synthetic base oil forms an electron accumulation, hydrogen bond, and intermolecular force, and the like weak force, and can form a network structure of a gel-like. Therefore, in the present application, the compound in the drilling fluid system not only has emulsification and coordination bond formation with barium sulfate, but also has gel weak force, which promotes the drilling fluid to form a stable emulsion gel structure with a certain flowability; ultimately promotes the formation of a stable emulsion and the anti-settling performance of barium sulfate, and the coordination of the Schiff base and barium sulfate has excellent high-temperature resistance, so the product can still maintain excellent performance after aging for 72 hours.

[0012] The dehydroabietyl Schiff base derivative of the present application can be dispersed at the oil-water interface in the drilling fluid system, reduce the surface tension, emulsify the oil-water system, the system is uniform, the dehydroabietyl Schiff base derivative molecules form a three-dimensional network structure in the emulsion oil phase under the hydrogen bond and electron accumulation, and the barite is uniformly dispersed in the three-dimensional network by forming a coordination bond with the Schiff base. The coordination bond has excellent high-temperature resistance and good anti-settling effect.

[0013] Preferably, R1 is hydrogen, methyl, ethyl, n-propyl, or isopropyl.

[0014] Preferably, R2 is substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, wherein the substituent is selected from hydroxyl or C1-C5 alkyl.

[0015] Preferably, the dehydroabietyl Schiff base derivative is any one of the following compounds:

[0016]

[0017]

[0018] In a second aspect, the present application provides a preparation method of the dehydroabietyl Schiff base derivative as described in the first aspect, and the preparation method comprises the following steps:

[0019] The dehydroabietyl amine shown in formula II reacts with the aldehyde or ketone compound shown in formula III to obtain the dehydroabietyl Schiff base derivative, and the reaction formula is as follows:

[0020] The dehydroabietyl amine shown in formula II reacts with the aldehyde or ketone compound shown in formula III to obtain the dehydroabietyl Schiff base derivative, and the reaction formula is as follows:

[0021]

[0022] Preferably, the molar ratio of the dehydroabietyl amine shown in formula II to the aldehyde compound shown in formula III is 0.8-1.2:0.8-1.2, for example, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1:0.8, 1:0.9, 1:1.1, 1:1.2, etc., and preferably 1:1.

[0023] Preferably, the solvent of the reaction is a polar organic solvent, preferably ethanol and / or methanol.

[0024] Preferably, the temperature of the reaction is 30-90°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or 90°C, and the reaction time is 0.5-6h, for example, 0.5h, 0.8h, 1h, 2h, 3h, 4h, 5h, or 6h.

[0025] In a third aspect, the present application provides a drilling fluid, and the drilling fluid comprises the dehydroabietyl Schiff base derivative as described in the first aspect as an additive.

[0026] As a preferred technical solution of the present application, the drilling fluid comprises an oil-based drilling fluid.

[0027] In a fourth aspect, the present application provides an application of the drilling fluid as described in the third aspect in oilfield exploitation.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] The dehydroabietyl Schiff base derivative provided by the present application contains a dehydroabietylamine tricyclic phenyl rigid structure oil-soluble skeleton, has water-in-oil emulsification, and is easy to be stably synthesized into a water-in-oil system of a synthetic base drilling fluid. The Schiff base and R2 form a conjugated structure, which enhances the coordination with barium sulfate barite, and solves the problem of easy sedimentation of barite. The additive can improve the high-temperature stability of the synthetic base drilling fluid system and the sedimentation stability of barite. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The Fourier transform infrared spectrum of DA, DNS, DHS and DIS.

[0031] Figure 2 The FT-IR spectrum of DNS prepared in Example 1. 1 H NMR spectrum.

[0032] Figure 3 The FT-IR spectrum of DNS prepared in Example 1. 13 C NMR spectrum.

[0033] Figure 4 The FT-IR spectrum of DHS prepared in Example 2. 1 H NMR spectrum.

[0034] Figure 5 The FT-IR spectrum of DHS prepared in Example 2. 13 C NMR spectrum. DETAILED DESCRIPTION

[0035] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as specific limitations of the present application.

[0036] Example 1

[0037] Synthesis of dehydroabietyl naphthalene-2-hydroxy-1-naphthylmethyl Schiff base (DNS): 30.049 g (0.1 mol) of dehydroabietylamine (DA) was dissolved in 40 ml of ethanol solution, and then 0.1 mol of aldehyde solution (1-naphthaldehyde 18.63 ml) dissolved in 40 ml of ethanol was slowly added. The reaction was stirred at 80°C for 2h, and the precipitate was separated after standing for a period of time. The precipitate was dried to obtain a light yellow solid with a yield of 62.22%.

[0038] Example 2

[0039] Synthesis of Dehydroabietylamine and 2-hydroxy-1-naphthylmethyl Schiff base (DHS): 30.049 g (0.1 mol) of dehydroabietylamine was dissolved in 40 ml of ethanol solution, then 0.1 mol of aldehyde solution (2-hydroxy-1-naphthaldehyde 16.55 ml) dissolved in 40 ml of ethanol was slowly added, and the reaction was stirred at 80°C for 2 h. After standing for a period of time, the precipitate was dried to obtain a light yellow solid with a yield of 68.1%.

[0040] Example 3

[0041] Synthesis of Dehydroabietylamine and 2-hydroxy-1-naphthylmethyl Schiff base (DHS): 30.049 g (0.1 mol) of dehydroabietylamine was dissolved in 40 ml of ethanol solution, then 0.1 mol of aldehyde solution (2-hydroxy-1-naphthaldehyde 16.55 ml) dissolved in 40 ml of ethanol was slowly added, and the reaction was stirred at 80°C for 2 h. After standing for a period of time, the precipitate was dried to obtain a light yellow solid with a yield of 68.1%.

[0042] Example 4

[0043] Synthesis of Dehydroabietylamine and 2-hydroxy-1-naphthylmethyl Schiff base (DHS): 30.049 g (0.1 mol) of dehydroabietylamine was dissolved in 40 ml of ethanol solution, then 0.1 mol of aldehyde solution (2-hydroxy-1-naphthaldehyde 16.55 ml) dissolved in 40 ml of ethanol was slowly added, and the reaction was stirred at 80°C for 2 h. After standing for a period of time, the precipitate was dried to obtain a light yellow solid with a yield of 68.1%.

[0044] The synthesis reaction route of DNS, DHS and DIS in the above examples is as follows:

[0045]

[0046] The yield calculation formula in the above examples is as follows:

[0047]

[0048] Where m1 (unit: g) is the actual yield, and m2 (unit: g) is the theoretical yield.

[0049] In order to verify that the prepared dehydroabietyl Schiff base compound is obtained, raw material DA and products DNS, DHS and DIS are respectively subjected to infrared detection and mass spectrometry detection, and the detection results are shown in Table 1. Figure 1 .

[0050] Where, Figure 1 is the infrared spectrum of raw material DA and dehydroabietyl Schiff base compound, and 821 cm -1 and 1380 cm -1 are the vibration absorption peaks of the structure of rosin terpene; 2929 cm -1and the right side peaks are C-H stretching vibrations of -CH2and -CH3, indicating that both of them contain rosin skeleton functional groups. The 3392 cm -1 is the N-H stretching vibration of dehydroabietylamine; while the 1631-1645 cm -1 is the characteristic peak of the Schiff base C=N group, and the FT-IR results preliminarily confirm the successful synthesis of the Schiff base.

[0051] Figure 2 The13C NMR spectrum of DNS was recorded in deuterated chloroform as solvent (126 MHz, CDCl3), as shown in Figure 3 , and the specific information is as follows (δ / ppm): 123.58 (C-1), 124.21 (C-2), 145.16 (C-3), 134.72 (C-4), 126.64 (C-5), 147.30 (C-6), 37.51 (C-7), 46.06 (C-8, C-20), 18.80 (C-9), 30.33 (C-10), 38.40 (C-11), 19.38 (C-12), 38.03 (C-13), 33.24 (C-14), 36.77 (C-15), 23.80 (C-16, C-17), 25.41 (C-18, C-19), 160.32 (C-21), 124.41 (C-22), 125.06 (C-23), 125.73 (C-24), 128.36 (C-25), 133.68 (C-26), 130.57 (C-27), 131.56 (C-28), 131.13 (C-29), 128.91 (C-30), 126.85 (C-31). The carbon spectrum 13 C NMR) shows characteristic chemical shift signals, which fully confirm the successful synthesis of the compound.

[0052] Figure 3 The high-resolution mass spectrum of DNS is shown in the figure, and the theoretical calculation value of C31H32N is 418, and the test value is 418.25. The above shows that the synthesis product is DNS.

[0053] The13C NMR spectrum of DHS was recorded in deuterated chloroform as solvent (126 MHz, CDCl3). As shown in Figure 4The specific information is shown as follows (δ / ppm): 122.70 (C-1), 124.03 (C-2), 145.67 (C-3), 134.35 (C-4), 126.17 (C-5), 146.74 (C-6), 37.81 (C-7), 64.30 (C-8), 19.01 (C-9), 30.27 (C-10), 38.19 (C-11), 18.60 (C-12), 46.19 (C-13), 33.47 (C-14), 36.26 (C-15), 24.00 (C-16, C-17), 25.37 (C-18), 25.47 (C-19), 65.14 (C-20), 158.36 (C-21), 133.88 (C-22), 117.67 (C-23), 177.19 (C-24), 124.37 (C-25), 128.01 (C-26), 129.31 (C-27), 137.51 (C-28), 125.15 (C-29), 126.90 (C-30), 106.47 (C-31). The carbon spectrum 13 The C NMR) all show characteristic chemical shift signals, confirming the successful synthesis of the compound.

[0054] Figure 5 The high resolution mass spectrum of DHS is shown in Figure 1, and the C 31 H 32 The theoretical calculation value of ON is 434, and the test value is 438.27. Based on the above, it is shown that the synthesized product is DHS.

[0055] Application Example

[0056] Preparation of synthetic oil-based drilling fluid base slurry

[0057] In a high-speed stirring cup, 240 mL of synthetic oil was added, and 24 g of main emulsifier HT-MUL, 7.5 g of organic clay, 60 mL of 20% CaCl2 aqueous solution, 6 g of CaO, 12 g of oxidized asphalt fluid loss additive, 480 g of barite with a density of 1.8 g / cm 3 The stirring time was 20 min, then 6 g of the product prepared in Example 1-3 was added as an additive, and stirred for 10 min, until all the raw materials were added together and stirred for 40 min to obtain the oil-based drilling fluid base fluid.

[0058] Comparative Example 1

[0059] The difference between the application example and the comparative example is that the high-temperature-resistant terpene synthetic oil-based drilling fluid additive in the comparative example is dehydroabietic acid.

[0060] Comparative Example 2

[0061] Unlike the application example, the comparative example is a high-temperature-resistant terpene synthetic oil-based drilling fluid additive that is dehydroabietylamine.

[0062] Comparative Example 3

[0063] Unlike the application example, the comparative example is a high-temperature-resistant terpene synthetic oil-based drilling fluid additive that is dehydroabietylamine.

[0064] Comparative Example 4

[0065] Unlike the application example, the comparative example uses a structurally similar amidine, R1 = H, R2 = NH2.

[0066] The performance of the oil-based drilling fluid base fluid is evaluated, including the following:

[0067] (1) High-temperature aging test

[0068] The oil-based drilling fluid base fluid prepared in the application example and the comparative example is loaded into a high-temperature stainless steel tank, filled with 1.0 MPa of nitrogen, and placed in a digital roller heating furnace. The sample is rolled at different temperatures (as shown in Table 1) for 16 h, and then cooled to 25°C.

[0069] (2) Rheological property test

[0070] The prepared drilling fluid sample is tested at room temperature using a six-rotation-rate viscometer before and after aging (180°C, 72 h). The stable readings of Φ600 are recorded at different rotation rates. The apparent viscosity: AV = ηapp = Φ600 / 2 mPa·s.

[0071] (3) Barite settling test method

[0072] The barite settling test method is established for different settling conditions, such as simulated static conditions, dynamic conditions, inclination angles, flow loops, high temperatures and high pressures, etc. The static settling test method is used.

[0073] The static settling test is a method for evaluating the settling trend of drilling fluid under static conditions in the wellbore. The drilling fluid is added to a stainless steel tank and statically placed at a specific temperature for a period of time. The density of the upper part of the drilling fluid column (the lower layer of free liquid) ρtop and the density of the bottom ρbottom are measured. The calculation formula of the static settling factor SF is as follows.

[0074] SF = ρbottom / (ρbottom+ρtop)

[0075] SF is 0.50, which indicates that static settling does not occur, and SF is greater than 0.52, which indicates that the static settling stability is poor. The operation method is simple and suitable for field use. However, the dewatering shrinkage is not considered when calculating the static settling factor, that is, the upper layer of free liquid is not involved in the calculation, and there is a certain deviation between the experimental results and the true value.

[0076] The rheological parameters of the drilling fluid are tested according to the national standard GB / T 29170-2012 Laboratory Testing of Drilling Fluids for Petroleum and Natural Gas Industry.

[0077] The results are shown in Table 1.

[0078] Table 1

[0079]

[0080] As shown in Table 1, after adding the product of the embodiments, the rheological parameters of the drilling fluid before and after aging change less compared to the base slurry, indicating that the temperature resistance of the product of the embodiments is excellent, and the drilling fluid has low viscosity and viscosity stability; the demulsification voltage is as high as 1000V or more, indicating that the emulsion has strong stability. The settling factor SF is about 0.502, which has very good effect of preventing barite from settling.

[0081] In Comparative Examples 1-3, terpene amide is replaced by using raw material carboxylic acid, structural analogue rosin amine and rosin ester, wherein the demulsification voltage of the rosin ester is sharply reduced to below 400V, proving that the emulsion structure of the system is destroyed, and the drilling fluid cannot be normally used.

[0082] The preliminary experimental data show that the pure double-interval amine has a demulsification voltage of 332V after aging, which is significantly lower than that of Examples 1-3 (all greater than 1500V), and the reason is presumed to be:

[0083] 1. The strong polarity of the amino group leads to intermolecular hydrogen bonding, affecting the performance;

[0084] 2. Lack of π-π conjugated system of benzene ring, reducing the coordination bonding force with barium ions.

[0085] The applicant declares that the dehydroabietyl Schiff base derivative, the preparation method and the application thereof of the present application are illustrated by the above embodiments, but the present application is not limited to the above embodiments, that is, it does not mean that the present application must rely on the above embodiments to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the selected raw materials, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A dehydroabietyl Schiff base derivative, characterized in that: The dehydroabietyl Schiff base derivative has a structure shown in the following formula I: Wherein R1 is hydrogen or C1-C20 alkyl; R2 is substituted or unsubstituted C6-C12 aryl, and the substituent in the substituted C6-C12 aryl is selected from hydroxyl, halogen, C6-C12 aryl or C1-C5 alkyl.

2. The dehydroabietyl Schiff base derivative according to claim 1, characterized in that R1 is hydrogen, methyl, ethyl, n-propyl or isopropyl; Preferably, R2 is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenyl group, wherein the substituent is selected from a hydroxyl group or a C1-C5 alkyl group.

3. The dehydroabietyl Schiff base derivative according to claim 1 or 2, characterized in that The dehydroabietyl Schiff base derivative is any one of the following compounds:

4. A method for preparing the dehydroabietyl-containing Schiff base derivative according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: The dehydroabietylamine represented by formula II reacts with the aldehyde or ketone compound represented by formula III to obtain the dehydroabietyl Schiff base derivative, and the reaction formula is as follows:

5. The preparation method according to claim 4, characterized in that The molar ratio of dehydroabietylamine represented by formula II to the aldehyde compound represented by formula III is 0.8-1.2:0.8-1.

2.

6. The preparation method according to claim 4, characterized in that The solvent for the reaction is a polar organic solvent, preferably ethanol and / or methanol.

7. The preparation method according to claim 4, characterized in that The reaction temperature is 30-90° C., and the reaction time is 0.5-6 h.

8. A drilling fluid, characterized in that: The drilling fluid comprises the dehydroabietyl Schiff base derivative according to any one of claims 1 to 3 as an additive.

9. The drilling fluid according to claim 8, characterized in that The drilling fluid includes oil-based drilling fluid.

10. Use of the drilling fluid according to claim 8 in oil field production.

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