CN112979944A - Hydrophobic modified hyperbranched inhibitor for drilling fluid and preparation method thereof - Google Patents
Hydrophobic modified hyperbranched inhibitor for drilling fluid and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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Abstract
The invention discloses a hydrophobic modified hyperbranched inhibitor for drilling fluid and a preparation method thereof, wherein in the inhibitor, the center of the molecular structure is hyperbranched polyethyleneimine group, and the tail end of the molecular structure is introduced with long carbon chains, long fluorocarbon chains or phenyl groups, namely, hydrophobic groups are introduced, so that the hydrophobic modified hyperbranched inhibitor for drilling fluid is obtained. The inhibitor can change the hydrophilicity of the surface of the water-sensitive clay mineral, namely, the clay surface is changed from hydrophilicity to hydrophobicity, and the process of water molecules invading the clay is delayed, so that the aim of inhibiting the hydration of the clay is fulfilled.
Description
Technical Field
The invention belongs to the field of oilfield chemical additives, relates to a hyperbranched inhibitor, and particularly relates to a hydrophobic modified hyperbranched inhibitor for drilling fluid and a preparation method thereof.
Background
In recent years, high-performance water-based drilling fluid developed by adopting polyamine inhibitor has good inhibition performance, and has the technical advantages of low toxicity and controllable cost, so that the high-performance water-based drilling fluid is widely applied to water-sensitive shale well sections. Primary amine in polyamine molecules is partially protonated to generate quaternary ammonium groups, and after the quaternary ammonium groups enter clay layers, the quaternary ammonium groups bind adjacent clay layers under the action of electrostatic adsorption and hydrogen bonds, so that the expansion of clay layer intervals is hindered, and the inhibition of clay hydration expansion is realized. In addition, polyamine molecules with larger relative molecular mass are adsorbed on the outer surface of the clay to coat the clay, so that the invasion of water molecules in the drilling fluid is blocked, and the method is very favorable for inhibiting the hydration dispersion of the clay. Short carbon chains in polyamine molecules have certain hydrophobicity, namely a hydrophobic film can be formed on the surface of clay, and the progress of water molecules invading the interior of the clay is shortened to a certain extent.
In actual drilling construction, a drilling fluid engineer hopes that the drilling fluid can wrap shale debris which is just cut off, and the water-sensitive debris can be screened out through a vibrating screen before obvious hydration occurs, so that the drilling fluid is prevented from entering the drilling fluid after the debris is hydrated, and subsequent processing workload is increased for the drilling engineering. There is a need for a drilling fluid that has a good coating ability and can effectively prevent water molecules in the drilling fluid from invading the interior of shale within a certain period of time.
The use of amino hyperbranched polymers as shale inhibitors has been well documented. A large number of adsorption groups are distributed on the molecular branched chain of the amino hyperbranched polymer, so that more adsorption sites on the clay can be occupied, and the close adsorption between inhibitor molecules and the clay is realized. It can be said that the number of adsorption groups of the amino hyperbranched polymer as a coating inhibitor is sufficient. However, from the molecular structure of the amino hyperbranched polymer, except for the short carbon chain connected with 2-3 methylene groups, the molecular chain of the amino hyperbranched polymer does not have functional groups with obvious hydrophobicity. Therefore, when the hyperbranched polymer is used as a coating inhibitor, the hydrophobicity of the molecular film formed on the clay surface is not ideal.
Chinese patent CN106520085A discloses a dendritic shale inhibitor and a preparation method thereof, wherein the inhibitor is a dendritic polyether shale inhibitor obtained by the reaction of amine-terminated dendritic polymer and alkylene oxide, which is substantially obtained by introducing hydroxyl group into the molecular terminal of polypropyleneimine dendritic polymer (PPI) or polyamidoamine dendritic Polymer (PAMAM), so as to increase the number of adsorption groups, and the adsorption between the inhibitor molecules and clay is tighter, thereby facilitating the displacement of water molecules adsorbed on the clay surface. However, this patent is directed to converting primary amines to secondary amines in dendritic polyether inhibitors obtained by reacting primary amine groups at the ends of the molecular chain with alkylene oxides. From the mechanism, the amido is adsorbed on the clay surface by sharing hydrogen bonds, and the adsorption strength of primary amine is far higher than that of secondary amine; although hydroxyl groups are introduced at the molecular terminals, the hydroxyl groups are still weak adsorption groups compared with primary amines.
Chinese patent CN104017208A discloses a shale polyamine film-forming inhibitor and a preparation method thereof, wherein the inhibitor is a chain low-molecular-weight polyamine inhibitor synthesized by taking an amine compound and an epoxy compound as raw materials under the condition of adding a molecular weight regulator. The inhibitor can effectively inhibit the hydration expansion and hydration dispersion of the water-sensitive clay mineral, and has good oil-gas layer protection efficiency. This patent does not discuss and evaluate what is called film formation, nor does it analyze the mechanism of film formation. From the aspect of molecular structure, the structural characteristics of the inhibitor in film formation on the clay surface are not obvious, and the film formation may mean that a molecular chain can be tightly adsorbed on the clay surface under the action of hydrogen bonds.
The document 'development and application of novel polyamine shale hydration inhibitor' (Zhonghanyi, Qiu Zheng Song, Huang Wei an, etc.. Western An university of Petroleum institute (Nature science edition), 2013, 28 (2): 72-77.) relates to a chain oligomeric polyether amine as drilling fluid inhibitor SDPA. The inhibitor contains amido and ether bond, and can effectively inhibit hydration dispersion of clay. The influence of SDPA on the hydrophilicity of the clay surface is researched, and the wetting angle of the clay surface modified by SDPA can be increased from 26.95 degrees to 45.42 degrees, namely the hydrophobicity of the clay surface is enhanced after the SDPA is modified. The authors note that this is due to the fact that the polyoxypropylene chain in the molecule has some hydrophobicity. However, from the molecular structure of polyoxypropylene, the hydrophobicity of an alkyl chain formed by connecting 3 methylene groups is very limited.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a hydrophobic modified hyperbranched inhibitor, namely, a hydrophobic group is introduced at the molecular chain terminal of the hyperbranched polymer inhibitor, so that the hydrophobicity of an adsorption film on the surface of clay is enhanced, the surface of the clay is changed from hydrophilic to hydrophobic, and the progress of water molecules in drilling fluid invading the clay is slowed down.
In the invention, if the hydrophobic groups are introduced into the molecular chain of the hyperbranched polymer inhibitor, the thickness of a hydrophobic film formed on the surface of the clay by the inhibitor can be increased to a certain extent, the resistance of water molecules entering the clay is increased, and the hydration effect in the clay is delayed.
One of the objectives of the present invention is to provide a hydrophobic modified hyperbranched inhibitor for drilling fluid, wherein the central group of the molecular structure is a hyperbranched polyethyleneimine group, and the end group of the molecular structure is-NH2And a group of formula (I).
In a preferred embodiment, in formula (I), R is selected from the group consisting of structures represented by formula (I-1), formula (I-2), or formula (I-3):
in a more preferred embodiment, in the formulae (I-1) to (I-3), x is an integer of 3 to 17, y is an integer of 3 to 17, and R is1、R2、R3、R4And R5Each independently selected from-H, C1～C6Alkyl group of (1).
In a further preferred embodiment, in the formulae (I-1) to (I-3), x is an integer of 11 to 17, y is an integer of 11 to 17, R1、R2、R3、R4And R5Each independently selected from-H, -CH3or-CH2CH3。
Wherein, the hydrophobic modified hyperbranched inhibitor is modified hyperbranched polyethyleneimine, and the part at the tail end of the molecular structure of the modified hyperbranched polyethyleneimine is NH2Is substituted by a group shown as a formula (I) to form the hydrophobic modified hyperbranched inhibitor.
The molecular structure end of the inhibitor not only contains primary amine groups, but also contains long carbon chains, long fluorocarbon chains or substituted phenyl groups, wherein the primary amine groups can be combined with clay through hydrogen bond adsorption, and the groups shown in the formula (I) can endow the inhibitor with certain hydrophobicity.
In a preferred embodiment, the ratio of the total molar amount of the terminal groups of the molecular structure to the molar amount of the groups of formula (I) is 1: (0.01-0.5).
Wherein the total molar amount of the terminal groups of the molecular structure is the molar amount of the group shown in the formula (I) and-NH2Sum of the molar amounts of (a).
In a further preferred embodiment, the ratio of the total molar amount of the terminal groups of the molecular structure to the molar amount of the groups of formula (I) is 1: (0.02-0.12).
The group represented by the formula (I) can endow the inhibitor with a certain degree of hydrophobicity, but the content of the group represented by the formula (I) in the end group of the inhibitor is also required, because the content is too small, the hydrophobic effect is poor, and the content is too large, the content of the primary amine group at the end of the molecular structure is correspondingly reduced, and the combination of the inhibitor and clay is further weakened.
For example, the hydrophobically modified hyperbranched inhibitor may be represented by formula (I'):
wherein, the molecular weight of the hyperbranched polyethyleneimine raw material used for synthesizing the inhibitor shown in the formula (I') is 1481.34g/mol, and the primary amine: secondary amine: tertiary amine 14: 9: 12, the number of terminal amine groups is 14. The molecular structural formula shown in formula (I') is merely illustrative, and is one embodiment of the hydrophobically modified hyperbranched inhibitor of the present invention.
In a preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine groups at the center of the inhibitor molecular structure is 1200 to 750000 g/mol.
In a further preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine group at the center of the inhibitor molecular structure is 20000 to 750000 g/mol.
In a further preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine groups at the center of the inhibitor molecular structure is 60000-750000 g/mol.
Wherein, the molecular weight can not be too small or too large, when the molecular weight is too low, a better hyperbranched structure can not be obtained, and when the molecular weight is too high, the problem of difficult dissolution can occur, thereby influencing the reaction efficiency.
The second purpose of the invention is to provide a preparation method of the hydrophobic modified hyperbranched inhibitor for drilling fluid, which comprises the following steps of taking substituted isocyanate shown in a formula (II) and hyperbranched polyethyleneimine as raw materials, and reacting to obtain:
R-N ═ C ═ O formula (II).
In a preferred embodiment, in formula (II), R is selected from the group consisting of structures represented by formula (I-1), formula (I-2), or formula (I-3):
in a more preferred embodiment, in the formulae (I-1) to (I-3), x is an integer of 3 to 17, y is an integer of 3 to 17, and R is1、R2、R3、R4And R5Each independently selected from-H, C1～C6Alkyl group of (1).
In a further preferred embodiment, in the formulae (I-1) to (I-3), x is an integer of 11 to 17, y is an integer of 11 to 17, R1、R2、R3、R4And R5Each independently selected from-H, -CH3or-CH2CH3。
In the molecular structure of the hydrophobic modified hyperbranched inhibitor, a long carbon chain, a long fluorocarbon chain or substituted phenyl is introduced at the tail end of a molecule, namely a hydrophobic group is introduced. The introduced hydrophobic groups improve the hydrophobicity of the molecular membrane, increase the repulsion between clay particles and water molecules, reduce the speed of the water molecules entering the interior of the clay, and delay the time of the water molecules entering the interior of the clay.
In a preferred embodiment, the molar ratio of the hyperbranched polyethyleneimine to the substituted isocyanate is 1: (0.01-0.5), wherein the molar weight of the hyperbranched polyethyleneimine is NH at the tail end of the molecular structure2Based on the molar amount of (a).
In a further preferred embodiment, the molar ratio of the hyperbranched polyethyleneimine to the substituted isocyanate is 1: (0.02-0.12), wherein the molar weight of the hyperbranched polyethyleneimine is NH at the tail end of the molecular structure2Based on the molar amount of (a).
In a preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine is 1200-750000 g/mol.
In a further preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine is 20000 to 750000 g/mol.
In a further preferred embodiment, the relative molecular mass of the hyperbranched polyethyleneimine is 60000-750000 g/mol.
Wherein, the molecular weight can not be too low or too high, when the molecular weight is too low, a better hyperbranched structure can not be obtained, and when the molecular weight is too high, the problem of difficult dissolution can occur, thereby influencing the reaction efficiency.
In a preferred embodiment, the preparation method comprises the following steps:
step 1, dispersing hyperbranched polyethyleneimine in an organic solvent to obtain a dispersion liquid;
step 2, adding a catalyst and substituted isocyanate shown in a formula (II) into the dispersion liquid under a protective atmosphere, and stirring for reaction to obtain a crude product;
and 3, carrying out post-treatment on the crude product to obtain the hydrophobic modified hyperbranched inhibitor.
In a preferred embodiment, in step 1, the organic solvent is selected from one or more of tetrahydrofuran, acetone, N-methylpyrrolidone, 1, 4-dioxane, N-dimethylformamide, N-dimethylacetamide.
In a preferred embodiment, in step 1, the hyperbranched polyethyleneimine is present in the dispersion at a weight concentration of 0.5 wt% to 20.0 wt%.
In a further preferred embodiment, in step 1, the hyperbranched polyethyleneimine is present in a concentration by weight of 2.0 to 8.0% by weight in the dispersion.
In a preferred embodiment, in step 2, the protective atmosphere is selected from nitrogen and/or an inert gas.
In a further preferred embodiment, in step 2, the protective atmosphere is selected from nitrogen and/or helium, for example nitrogen.
In a preferred embodiment, in step 2, the catalyst is selected from dibutyl tin dilaurate and/or stannous octoate, preferably dibutyl tin dilaurate.
In a further preferred embodiment, the catalyst is used in an amount of 0.01 to 0.10% by weight, based on 100% by weight of the substituted isocyanate of formula (II).
In a further preferred embodiment, the catalyst is used in an amount of 0.02 to 0.08% by weight, based on 100% by weight of the substituted isocyanate of formula (II).
In a preferred embodiment, in step 2, the temperature of the reaction is 40 to 80 ℃.
In a further preferred embodiment, in step 2, the temperature of the reaction is controlled to be 45 to 65 ℃.
The temperature may be controlled before the reaction in step 2, or may be controlled when the dispersion is prepared in step 1, as long as the temperature is controlled to be 40 to 80 ℃, preferably 45 to 65 ℃ during the reaction.
In a preferred embodiment, in step 2, the reaction is carried out for 5 to 30 hours, preferably 12 to 24 hours.
In a preferred embodiment, in step 3, the post-treatment is distillation under reduced pressure to remove the solvent.
Compared with the prior art, the invention has the following beneficial effects: in the molecular structure of the hydrophobic modified hyperbranched inhibitor, a long carbon chain, a long fluorocarbon chain or phenyl is introduced at the tail end of a molecule, namely a hydrophobic group is introduced. When the inhibitor molecules are adsorbed with clay, a molecular film can be formed on the surface of the clay. The introduced hydrophobic groups improve the hydrophobicity of the molecular membrane, increase the repulsion between clay particles and water molecules, reduce the speed of the water molecules entering the interior of the clay, and delay the time of the water molecules entering the interior of the clay. In actual drilling construction, the hydration time of the water-sensitive clay minerals is delayed, and favorable conditions are provided for screening out the water-sensitive rock debris through a vibrating screen, so that favorable conditions are provided for maintaining the performance of the drilling fluid.
Drawings
FIG. 1 shows the hydration condition of sodium bentonite in clear water, which is 0.5h, 4h and 16h from left to right (a/b/c) in sequence;
FIG. 2 shows the hydration of sodium bentonite in 0.5% hyperbranched polyethyleneimine (relative molecular mass is 60000g/mol, respectively), from left to right (a/b/c) for 0.5h, 4h and 16h in sequence;
FIG. 3 shows the hydration of sodium bentonite in 0.5% hyperbranched polyethyleneimine (with a relative molecular mass of 100000g/mol, respectively), which is 0.5h, 4h and 16h from left to right (a/b/c);
FIG. 4 shows the hydration of sodium bentonite in 0.5% hyperbranched polyethyleneimine (relative molecular mass is 200000g/mol, respectively), from left to right (a/b/c) for 0.5h, 4h and 16h in sequence;
FIG. 5 shows the hydration of sodium bentonite in 0.5% hyperbranched polyethyleneimine (with a relative molecular mass of 500000g/mol, respectively) for 0.5h, 4h and 16h in sequence from left to right (a/b/c);
FIG. 6 shows the hydration of sodium bentonite in 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in example 1, from left to right (a/b/c) for 0.5h, 4h and 16h in that order;
FIG. 7 shows the hydration of sodium bentonite in 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in example 2, from left to right (a/b/c) for 0.5h, 4h and 16h in that order;
FIG. 8 shows the hydration of sodium bentonite in 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in example 3, from left to right (a/b/c) for 0.5h, 4h and 16h in that order;
FIG. 9 shows the hydration of sodium bentonite in 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in example 4 for 0.5h, 4h and 16h from left to right (a/b/c) in that order;
FIG. 10 shows the hydration of sodium bentonite in 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in example 5, from left to right (a/b/c) for 0.5h, 4h and 16h in that order.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
120g of hyperbranched polyethyleneimine (0.002mol, relative molecular mass of 60000g/mol and number of terminal amine groups of about 360 +/-20) was dissolved in 2000g N-methylpyrrolidone in a sealed reaction vessel, and temperature was controlled to 45 ℃; then in N2Under the protection of (1), after 0.006g of dibutyltin dilaurate is added, 21.276g of octadecyl isocyanate (0.072mol, the molar concentration ratio of primary amine groups in the hyperbranched polyethyleneimine to octadecyl isocyanate is about 1: 0.1) is added, and the mixture is reacted for 12 hours under the condition of continuous stirring to obtain pale yellow viscous liquid. And distilling under reduced pressure to remove the N-methyl pyrrolidone to obtain the hydrophobic modified hyperbranched inhibitor.
Nuclear magnetic characterization of the product obtained in example 1 [ (CD)3)2SO，25℃]Knot ofAs shown in table 1.
Table 1:
[ example 2 ]
Dissolving 200g of hyperbranched polyethyleneimine (0.002mol, the relative molecular mass is 100000g/mol, and the number of terminal amine groups is about 420 +/-20) in 2300g of 1, 4-dioxane in a sealed reaction vessel, and controlling the temperature to 50 ℃; then in N2Under the protection of (1), after adding 0.005g of dibutyltin dilaurate, 8.57g of phenyl isocyanate (0.072mol, the molar concentration ratio of primary amine groups in the hyperbranched polyethyleneimine to the phenyl isocyanate is about 1: 0.1) is added, and the mixture is reacted for 16 hours under the condition of continuous stirring to obtain a light yellow viscous liquid. And distilling under reduced pressure to remove the 1, 4-dioxane to obtain the hydrophobic modified hyperbranched inhibitor.
Nuclear magnetic characterization of the product obtained in example 2 [ (CD)3)2SO，25℃]The results are shown in Table 2.
Table 2:
| δ | attribution |
| 5.13 | —N*H2 |
| 2.61，2.50 | —C*H2—C*H2—NH2 |
| 2.01 | —CH2—N*H—CH2— |
| 6.00 | —N*H—CO—N*H— |
| 7.61，7.43，7.19 | H on the benzene ring |
[ example 3 ]
200g of hyperbranched polyethyleneimine (0.002mol, 100000g/mol of relative molecular mass and approximately 420. + -. 20 of the number of terminal amine groups) are dissolved in 2800g of tetrahydrofuran in a sealed reaction vessel and the temperature is controlled to 50 ℃; then in N2Under the protection of (1), after 0.005g of dibutyltin dilaurate was added, 9.89g of 3, 5-dimethylphenyl isocyanate (0.0672mol, the molar concentration ratio of primary amine groups in the hyperbranched polyethyleneimine to 3, 5-dimethylphenyl isocyanate was about 1: 0.08) was added, and the mixture was reacted for 16 hours under continuous stirring to obtain a pale yellow viscous liquid. And distilling under reduced pressure to remove tetrahydrofuran to obtain the hydrophobic modified hyperbranched inhibitor.
Nuclear magnetic characterization of the product obtained in example 3 [ (CD)3)2SO，25℃]The results are shown in Table 3.
Table 3:
| δ | attribution |
| 5.14 | —N*H2 |
| 2.61，2.50 | —C*H2—C*H2—NH2 |
| 2.03 | —CH2—N*H—CH2— |
| 6.02 | —N*H—CO—N*H— |
| 7.39，7.09 | H on the benzene ring |
| 2.35 | Ph-C*H3 |
[ example 4 ]
In a sealed reaction vessel, 200g of hyperbranched polyethyleneimine (0.001mol, relative molecular mass of 200000g/mol, number of terminal amine groups of about 780 +/-40) was dissolved in 1000g of a mixed solution of acetone and 8800g N, N-dimethylformamide, and temperature was controlled to 65 ℃; then in N2Under the protection of (1), after 0.008g of dibutyltin dilaurate is added, 10.31g of perfluorododecyl isocyanate (0.0156mol, the molar concentration ratio of primary amine groups in the hyperbranched polyethyleneimine to the perfluorododecyl isocyanate is about 1: 0.02) is added, and the mixture is reacted for 24 hours under the condition of continuous stirring to obtain a light yellow viscous liquid. And distilling under reduced pressure to remove acetone and N, N-dimethylformamide to obtain the hydrophobic modified hyperbranched inhibitor.
Nuclear magnetic characterization of the product obtained in example 4 [ (CD)3)2SO，25℃]The results are shown in Table 4.
Table 4:
| δ | attribution |
| 5.11 | —N*H2 |
| 2.69，2.50 | —C*H2—C*H2—NH2 |
| 2.00 | —CH2—N*H—CH2— |
| 6.05 | —N*H—CO—N*H— |
[ example 5 ]
200g of hyperbranched polyethyleneimine (0.0004mol, 500000g/mol relative to the molecular mass and approximately 1280 +/-80 of the number of terminal amine groups) are dissolved in 2800g N-methylpyrrolidone in a sealed reaction vessel, and the temperature is controlled to 60 ℃; then in N2Under the protection of (1), after 0.005g of dibutyltin dilaurate is added, 12.98g of dodecyl isocyanate (0.06144mol, the molar concentration ratio of primary amine groups in hyperbranched polyethyleneimine to N-methylpyrrolidone is about 1: 0.12) is added, and the mixture is reacted for 20 hours under the condition of continuous stirring to obtain a light yellow viscous liquid. And distilling under reduced pressure to remove the N-methyl pyrrolidone to obtain the hydrophobic modified hyperbranched inhibitor.
Nuclear magnetic characterization of the product obtained in example 5 [ (CD)3)2SO，25℃]The results are shown in Table 5.
Table 5:
[ Experimental example 1 ] Effect of Hydrophobically modified hyperbranched inhibitor on the hydrophilicity of clay surface
0.5 percent of hyperbranched polyethyleneimine adopted in example 1 or 0.5 percent of the hydrophobic modified hyperbranched inhibitor prepared in any one of examples 1 to 5 and 5.0 percent of sodium bentonite are quantitatively added into 400mL of tap water, the mixture is stirred at a high speed for 30min, after the mixture is respectively heated and rolled for 16h at 60 ℃, 90 ℃ and 120 ℃, a proper amount of suspension is transferred onto a clean glass slide, and the glass slide is placed in a vacuum drying oven to be dried under the condition of room temperature, so that a layer of bentonite film is formed on the surface of the glass slide. The change of the wetting angle of water molecules after the clay adsorbs different hydrophobic modified hyperbranched inhibitors is tested by adopting a drop stopping method and a JA-200 type contact angle tester (the test method refers to Zhonghanyi, Qiuzong, Huangweian, and the like. the research and the application of the novel polyamine shale hydration inhibitor [ J ]. Western An college of Petroleum (Nature science edition), 2013, 28(2), 72-77.). The test results are shown in table 6:
table 6: wetting Angle (. degree) of different inhibitors
As can be seen from table 6: under the same temperature condition, the wetting angle of the bentonite added with the hydrophobic modified hyperbranched inhibitor prepared in the examples 1 to 5 is obviously larger than that of the bentonite without any added clay sample, and similarly, the wetting angle of the bentonite added with the hydrophobic modified hyperbranched inhibitor prepared in the examples 1 to 5 is also obviously larger than that of the bentonite added with the hyperbranched polyethyleneimine in the synthetic raw material of the corresponding example. Therefore, after the hydrophobic modified hyperbranched inhibitor obtained in the embodiments 1 to 5 is adsorbed on the clay surface, the clay surface can be effectively changed from hydrophilic to hydrophobic, which is very favorable for preventing water molecules from invading the clay interior and delaying hydration.
[ Experimental example 2 ] mud ball immersion experiment
The mud ball immersion experiment can visually observe the hydration effect caused by the invasion of the experimental slurry into the mud ball. The method for preparing the rock sample (used for simulating water-sensitive rock debris from the stratum) by adopting the bentonite indoors comprises the following steps: weighing 10.0g of bentonite, placing the bentonite in a pre-cleaned mould cup, and stabilizing the pressure for 30min under the pressure of 41.3685MPa (6000Psi) (the test method refers to Xuzhou, Zhang Qian. novel aminopolyol collapse inhibitor research [ J ]. drilling and production process, 2010, 33(1), 93-95.).
Bentonite rock samples are randomly selected and respectively put into clear water, 0.5% of the hyperbranched polyethyleneimine (the relative molecular mass is 60000g/mol, 100000g/mol, 200000g/mol and 500000g/mol) adopted in the examples 1 to 5 and 0.5% of the hydrophobically modified hyperbranched inhibitor solution prepared in the examples 1 to 5, and the hydration condition of sodium bentonite at different time is observed, and the result is shown in fig. 1 to 10.
As can be seen from fig. 1 to 10, when the soaking time is 0.5h, the periphery of the rock sample soaked in the clear water begins to be blurred, that is, the bentonite contacted with the clear water begins to be hydrated, and at this time, the core placed in the 0.5% hyperbranched polyethyleneimine and 0.5% hydrophobically modified hyperbranched inhibitor solutions prepared in examples 1 to 5 is still intact; when the soaking time is 4 hours, the periphery of the core soaked in the 0.5% hyperbranched polyethyleneimine solution becomes fuzzy, the hydration sign is obvious, and the core soaked in the 0.5% hydrophobically modified hyperbranched inhibitor solution prepared in the examples 1-5 is still intact; when the soaking time reaches 16 hours, the core soaked in clear water is completely disintegrated, only the central part of the core soaked in the 0.5% hyperbranched polyethyleneimine solution is still intact, the appearance of the core soaked in the 0.5% hydrophobically modified hyperbranched inhibitor solution prepared in the examples 1-5 is still intact, and only the outer edge part of the core begins to become fuzzy. The above experiment results show that the hydrophobic modified hyperbranched inhibitor prepared in examples 1-5 can delay the hydration of the water-sensitive clay mineral.
Claims (12)
1. A hydrophobically modified hyperbranched inhibitor for drilling fluid has a central group of a molecular structure of a hyperbranched polyethyleneimine group and a terminal group of a molecular structure of-NH2And a group of formula (I):
wherein, in the formula (I), R is selected from the structures shown in formula (I-1), formula (I-2) or formula (I-3):
wherein x is an integer of 3 to 17, y is an integer of 3 to 17, R1、R2、R3、R4And R5Each independently selected from-H, C1～C6Alkyl group of (1).
2. The hydrophobically modified hyperbranched inhibitor for drilling fluid as claimed in claim 1, wherein x is an integer of 11 to 17, y is an integer of 11 to 17, and R is1、R2、R3、R4And R5Each independently selected from-H, -CH3or-CH2CH3。
3. The hydrophobically modified hyperbranched inhibitor for drilling fluids according to claim 1, wherein the ratio of the total molar amount of the terminal groups of the molecular structure to the molar amount of the groups of formula (I) is 1: (0.01 to 0.5), preferably (0.02 to 0.12).
4. The hydrophobically modified hyperbranched inhibitor for drilling fluid according to any one of claims 1 to 3, wherein the hyperbranched polyethyleneimine group at the center of the inhibitor molecular structure has a relative molecular mass of 1200 to 750000g/mol, preferably 20000 to 750000g/mol, and more preferably 60000 to 750000 g/mol.
5. A preparation method of the hydrophobic modified hyperbranched inhibitor for the drilling fluid, disclosed by any one of claims 1-4, comprises the following steps of taking substituted isocyanate shown as a formula (II) and hyperbranched polyethyleneimine as raw materials, and reacting to obtain the inhibitor:
R-N ═ C ═ O formula (II).
6. The process according to claim 5, wherein in the formula (II), R is selected from the group consisting of the structures represented by the formula (I-1), the formula (I-2) and the formula (I-3):
wherein x is an integer of 3 to 17, y is an integer of 3 to 17, R1、R2、R3、R4And R5Each independently selected from-H, C1～C6Alkyl groups of (a); preferably, x is an integer of 11 to 17, y is an integer of 11 to 17, R1、R2、R3、R4And R5Each independently selected from-H, -CH3or-CH2CH3。
7. The preparation method according to claim 5, wherein the molar ratio of the hyperbranched polyethyleneimine to the substituted isocyanate is 1: (0.01 to 0.5), preferably 1: (0.02-0.12), wherein the molar weight of the hyperbranched polyethyleneimine is NH at the tail end of the molecular structure2Based on the molar amount of (a).
8. The preparation method according to claim 5, wherein the relative molecular mass of the hyperbranched polyethyleneimine is 1200-750000 g/mol, preferably 20000-750000 g/mol, and more preferably 60000-750000 g/mol.
9. The method according to any one of claims 5 to 8, wherein the method comprises the steps of:
step 1, dispersing hyperbranched polyethyleneimine in an organic solvent to obtain a dispersion liquid;
step 2, adding a catalyst and substituted isocyanate shown in a formula (II) into the dispersion liquid under a protective atmosphere, and stirring for reaction to obtain a crude product;
and 3, carrying out post-treatment on the crude product to obtain the hydrophobic modified hyperbranched inhibitor.
10. The production method according to claim 9, wherein, in step 1,
the organic solvent is one or more selected from tetrahydrofuran, acetone, N-methylpyrrolidone, 1, 4-dioxane, N-dimethylformamide and N, N-dimethylacetamide; and/or
In the dispersion, the weight concentration of the hyperbranched polyethyleneimine is 0.5 wt% to 20.0 wt%, preferably 2.0 wt% to 8.0 wt%.
11. The production method according to claim 9, wherein, in step 2,
the protective atmosphere is selected from nitrogen and/or an inert gas, preferably nitrogen; and/or
In step 2, the catalyst is selected from dibutyl tin dilaurate and/or stannous octoate, preferably dibutyl tin dilaurate, more preferably, the amount of the catalyst is 0.01 wt% to 0.10 wt%, preferably 0.02 wt% to 0.08 wt%, based on 100 wt% of the substituted isocyanate represented by formula (II).
12. The production method according to claim 9, wherein, in step 2,
the reaction temperature is 40-80 ℃, and preferably 45-65 ℃; and/or
The reaction is carried out for 5-30 h, preferably 12-24 h.
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| CN106634881A (en) * | 2016-08-25 | 2017-05-10 | 中国石油大学(北京) | Additive composition applicable to viscosity reduction of oil-based drilling fluid and application thereof, and oil-based drilling fluid and application thereof |
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| CN106634881A (en) * | 2016-08-25 | 2017-05-10 | 中国石油大学(北京) | Additive composition applicable to viscosity reduction of oil-based drilling fluid and application thereof, and oil-based drilling fluid and application thereof |
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