Temperature-controlled phase change water-resistance and air-permeability selective water shutoff agent and preparation method thereof

Abstract

The application discloses a temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent and a preparation method thereof, and belongs to the technical field of water shutoff agent preparation. The inorganic filler is used for toughening the polyester water shutoff agent, based on the curing mechanism of the thermosetting polyester material, the polyester water shutoff agent has good temperature resistance and high stability after being cured in the curing temperature range. The application is aimed at the high-temperature and high-salt reservoir conditions, the thermosetting polyester material is used to prepare the polyester base fluid, the pore-forming agent and the hydrophobic synergist are added into the system, the temperature-resistant and salt-resistant porous water-resisting and air-permeating polyester water shutoff agent system is formed, the water shutoff agent has a porous network pore structure, the gas flowability is increased and the liquid flowability is reduced, the gas selective passing capacity is improved, the hydrophobic association and the water-resisting and air-permeating effects are achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water plugging agent preparation, and particularly relates to a temperature-controlled phase change water plugging agent and a preparation method thereof. BACKGROUND

[0002] With the continuous exploration and development of oil and gas, efficient development of oil and gas fields with poor reservoir conditions (high temperature and high salinity) is an important development direction of the oil and gas industry. In high-temperature and high-salinity gas reservoirs, water exists in the form of edge-bottom water and condensate water. After water appears in the process of gas well production, water lock effect occurs in the near-wellbore area, which seriously affects the gas production. A large amount of water treatment also increases the production cost and even causes problems such as sand production, corrosion and scaling. Severe water production can also cause the gas well to be watered out and stop production, which seriously reduces the ultimate recovery of the gas well.

[0003] For the problem of bottom water coning and water production in high-temperature and high-salinity gas reservoir blocks, at present, low-position strong water drainage is mostly used to effectively control water invasion, showing the characteristics of water seal gas unsealing. For the problem of water plugging in interlayer development oil and gas reservoirs, mechanical plugging or conventional cement plugging is mainly used at the present stage, and the process technology is mature. However, for interlayer-free reservoirs or fractured reservoirs, water plugging materials and technologies are still blank. Therefore, it is necessary to actively develop water plugging agents for water control and gas production and to develop new water plugging agent systems to solve the problem of water production in gas reservoirs.

[0004] As for the water plugging system, the current water plugging system mainly has the following types: (1) frozen gel foam plugging agent: good resistance to washing, good plugging ability but difficult to inject into low-permeability reservoirs. (2) polymer water plugging agent: good selective plugging ability but high viscosity, not suitable for low-permeability formations. (3) polymer gel water plugging agent: good plugging strength and plugging ability but easy to cause gas layer misplugging, poor selective plugging ability. (4) functional nanofluid water control system: low viscosity, good gas-water selectivity but no systematic study, few field application cases. (5) phase permeability regulator: changes the gas-water wettability, has selectivity, small damage to the formation but few field application cases. (6) other plugging agents (hydrolyzed aluminum chloride gel / micro-expansion system): high plugging strength but poor gas-water selectivity, easy to cause misplugging.

[0005] At present, the method of adding nanomaterials to increase the strength of water plugging agents has become the main method for developing high-strength water plugging agent systems. Many documents report cases of adding nanomaterials or solid-phase materials (such as silicon dioxide, lithium soapstone, fly ash, fibers, starch, etc.) to the system to increase the strength of water plugging agents. However, most of these water plugging agents have molecular chains that are easily broken and degraded under high-temperature and high-salinity conditions, have poor stability and cannot effectively plug. SUMMARY

[0006] In order to overcome the above-mentioned prior art defects, the purpose of the present application is to provide a temperature-controlled phase change water-resistant and breathable selective water shutoff agent and a preparation method thereof, so as to solve the technical problems of poor stability and difficult effective plugging of the existing water shutoff agent.

[0007] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0008] The present application discloses a temperature-controlled phase change water-resistant and breathable selective water shutoff agent, which comprises, in mass percentage, 10-20% of thermosetting polyester, 15-25% of additive, 0.5-5% of pore-forming agent, 0.5-5% of hydrophobic synergist, 1-10% of inorganic filler, and the balance of water.

[0009] The molecular weight of the thermosetting polyester is 400x10 4 mg / L.

[0010] The present application further discloses a preparation method of the above-mentioned temperature-controlled phase change water-resistant and breathable selective water shutoff agent, comprising the following steps:

[0011] S1: preparing thermosetting polyester by two-step method;

[0012] S2: adding inorganic filler into water to obtain a mixed solution;

[0013] S3: sequentially adding hydrophobic synergist, pore-forming agent, additive and thermosetting polyester into the mixed solution, and stirring to obtain polyester water shutoff agent mother liquor;

[0014] S4: obtaining a temperature-controlled phase change water-resistant and breathable selective water shutoff agent after high-temperature curing of the polyester water shutoff agent mother liquor;

[0015] The thermosetting polyester is 10-20% in mass percentage, the additive is 15-25% in mass percentage, the pore-forming agent is 0.5-5% in mass percentage, the hydrophobic synergist is 0.5-5% in mass percentage, the inorganic filler is 1-10% in mass percentage, and the balance is water.

[0016] Further, in S1, the thermosetting polyester is prepared by two-step method, comprising the following steps:

[0017] The itaconic acid, polyol and p-toluenesulfonic acid are mixed, and then pre-reacted in an oxygen-free environment until no water is generated in the whole reaction substrate, and then dibutyltin dilaurate is added for reaction, and the thermosetting polyester is obtained after the reaction is completed.

[0018] Further, the amount ratio of the itaconic acid and polyol is 1.2 mol:200 mL, and the amount of the p-toluenesulfonic acid and dibutyltin dilaurate is 0.05% of the mass of the mixed solution, respectively.

[0019] Further, the polyhydric alcohol is a mixture of ethylene glycol and 1,4-butanediol with a molar mass ratio of 0.975:0.025.

[0020] Further, the oxygen-free environment is nitrogen as a protective gas; the pre-reaction is to control the reaction temperature at 160-165 DEG C by using an oil bath device; and the stirring speed is 300-400 r / min.

[0021] Further, the reaction temperature is 160-165 DEG C, and the reaction time is 4-8 h.

[0022] Further, the auxiliary agent is one or more of triethanolamine, Tween 20, Tween 40, Tween 60, Tween 80, and Span 80.

[0023] Further, the pore-forming agent is one or more of sodium bicarbonate, ammonium bicarbonate, and ammonium carbamate.

[0024] Further, the hydrophobic synergist is one or both of hydrophobic nano-silica and heptadecafluorodecyltrimethoxysilane; and the inorganic filler is one or more of hydrophobic nano-silica, montmorillonite, and halloysite nanotube.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] The present application discloses a temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent, which is toughened by inorganic fillers to polyester water shutoff agent, and based on the curing mechanism of thermosetting polyester material (dehydration reaction of the hydroxymethyl on the phenolic nucleus and the ammonia on the phenolic nucleus of other hydroxymethyl phenol, or methine esterification between the hydroxymethyl on two hydroxymethyl phenols to form a three-dimensional network structure within the curing temperature range), the agent has good temperature resistance and high stability after curing within the curing temperature range. In addition, the main agent is generally insoluble in water, and the auxiliary agent is added to solve the problem, so that the main agent is better dissolved in water by the emulsifying effect of the auxiliary agent, which is beneficial to on-site construction.

[0027] The present application also discloses a preparation method of the temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent, which is prepared by using thermosetting polyester material to prepare polyester base liquid, and adding pore-forming agents and hydrophobic synergists to form a temperature-resistant and salt-resistant porous water-resisting and air-permeating polyester water shutoff agent system. The water shutoff agent has a porous network pore structure, which increases the air permeability and reduces the liquid permeability, improves the selective air permeability, and plays a role of hydrophobic association, water resistance and air permeation. The related experimental results prove that the temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent prepared by the present application plays a role of water control and gas production in high-temperature and high-salt gas wells, and has temperature resistance of above 170 DEG C, salt resistance of 20x10 4mg / L or more; the system has low initial viscosity, easy injection, long curing time at high temperature, high plugging strength, and good water control and air permeability selectivity. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 Preparation principle diagram of the temperature-controlled phase change water-resisting and air-permeability-selectivity plugging agent of the present application;

[0029] Figure 2 Post-curing state diagram of the temperature-controlled phase change water-resisting and air-permeability-selectivity plugging agent of the present application. DETAILED DESCRIPTION

[0030] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have the usual meanings understood by those skilled in the art of the present application, and in the event of a conflict, the definitions in the present specification shall prevail.

[0031] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, that is, the present application can be practiced without regard to any particular theory or mechanism.

[0032] Herein, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, amounts, contents and concentrations, are for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the range.

[0033] Herein, unless otherwise specified, “comprise”, “include”, “contain”, “have” or similar words encompass the meaning of “consist of” and “consist essentially of”, for example, “A comprises a” encompasses the meaning of “A comprises a and other” and “A comprises only a”.

[0034] Herein, for the sake of brevity, all possible combinations of the technical features in each embodiment or example are not described. Therefore, as long as the combinations of the technical features do not contradict each other, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope of the present specification.

[0035] The present invention proposes polyester water blocking agent system, strengthens the new idea of ​​water blocking agent system intensity by changing the concentration of host in water blocking system, namely by regulating the concentration control curing strength of host.Different from conventional nano material utilization to improve water blocking agent intensity, we toughen polyester water blocking agent by inorganic filler, because polyester water blocking agent is certain brittle after solidification.Simultaneously, based on the curing mechanism of thermosetting polyester material (within the curing temperature range, ammonia generation dehydration reaction on the phenol core of the hydroxyl group on the phenol core of other hydroxymethylphenols forms-CH2-key, or reacts between the hydroxyl groups on two hydroxymethylphenols and carries out methine esterification and obtains three-dimensional network structure), it not only has good temperature resistance after completing solidification within the curing temperature range, but also has higher stability.In addition, host is generally insoluble in water, and for solving this problem, we utilize the emulsification of auxiliary agent to make host better soluble in water, be conducive to on-site construction by adding auxiliary agent.

[0036] The design concept of porous water-blocking and breathable polyester water-blocking agent system is as follows Figure 1 As shown in the figure, based on the experimental idea, for the high temperature and high salt reservoir conditions, we screened and introduced thermosetting polyester materials to prepare polyester base liquid, and added porogens and hydrophobic enhancers into the system to form a temperature-resistant and salt-resistant porous water-blocking and breathable polyester water plugging agent system. The water plugging agent has a porous network pore structure, which increases the gas flowability while reducing the liquid flowability, improves the gas selective passage ability, and plays the role of hydrophobic association, water blocking and ventilation.

[0037] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0038] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0039] Example 1

[0040] A temperature-controlled phase-change water-blocking and air-permeable selective water-blocking agent, comprising the following steps:

[0041] S1: itaconic acid, 200 mL polyol (molar mass ratio of 0.975 of ethylene glycol, molar mass ratio of 0.025 of 1,4-butanediol) and mass ratio of 0.05% of p-methylbenzenesulfonic acid with a molar mass ratio of 1.2 were added to a four-necked flask with a magnetic stirrer, a condenser and a nitrogen inlet device, respectively, and nitrogen was used as a protective gas. First, nitrogen was passed for half an hour, and the remaining gas was removed. The reaction temperature was controlled at about 160°C by an oil bath device for pre-reaction. After the reaction, basically no water was generated. Then, a mass ratio of 0.05% of the catalyst dibutyltin dilaurate was added, and the temperature was controlled at 160°C. The system was maintained at this condition for 4h. Then, heating was stopped, and after cooling, the product was poured out to obtain a thermosetting polyester. The molecular weight of the thermosetting polyester was 400x10 4 mg / L or so;

[0042] S2: 5% hydrophobic nano-silica filler was added to water, and the inorganic filler was fully dispersed to obtain a mixed solution;

[0043] S3: 1.0% heptadecafluorodecyltrimethoxysilane was added to the mixed solution, and the hydrophobic synergist was fully dispersed. Then, 0.5% ammonium carbamate and 0.5% ammonium bicarbonate were added, and the pore-forming agent was fully dispersed. Then, 21.25% Tween 80 was added, and the stirring was mixed uniformly at a speed of 300-400r / min. Then, 15% of the prepared thermosetting polyester was added, and the stirring was fully mixed uniformly at a speed of 300-400r / min to obtain a polyester water plugging agent mother liquor.

[0044] S4: set the temperature of the double constant temperature oven to 170°C with a temperature fluctuation of ±2°C; place the polyester water plugging agent mother liquor into the double constant temperature oven for high temperature curing at 170°C to obtain a temperature-controlled phase change water resistance and air permeability selective water plugging agent.

[0045] The performance test results of the obtained temperature-controlled phase change water resistance and air permeability selective water plugging agent are shown in Table 1:

[0046] Table 1: performance test results of the water plugging agent in Example 1

[0047] Item Result Initial viscosity (25°C), mPa-s 2.29 Curing time, min 240 Curing strength, MPa 4.8 Compressive strength (170°C aging), MPa 4.2 Water plugging rate, % 91.18 Gas plugging rate, % 23.13

[0048] Example 2

[0049] A temperature-controlled phase change water resistance and air permeability selective water plugging agent, comprising the following steps:

[0050] S1: the molar mass ratio of 1.2 itaconic acid, 200 mL polyol (molar mass ratio of 0.975 ethylene glycol, molar mass ratio of 0.025 1,4-butanediol) and mass ratio of 0.05% p-toluenesulfonic acid are added to a four-necked flask with magnetic stirrer, condenser and nitrogen inlet device, respectively, and nitrogen is used as protective gas. First, nitrogen is passed for half an hour, and the remaining gas is removed. The reaction temperature is controlled at about 160℃ by an oil bath device for pre-reaction. When the reaction basically generates no water, a catalyst dibutyltin dilaurate with a mass ratio of 0.05% is added, and the temperature is controlled at 160℃. The system is kept under this condition for 4h, and then the heating is stopped. After cooling, the product is poured out to obtain a thermosetting polyester; the molecular weight of the thermosetting polyester is 400×10 4 mg / L or so;

[0051] S2: 3% halloysite nanotubes are added to water, and the inorganic filler is fully dispersed to obtain a mixed solution;

[0052] S3: 0.7% heptadecafluorodecyltrimethoxysilane is added to the mixed solution, and the hydrophobic synergist is fully dispersed; then 0.7% sodium bicarbonate is added, and the pore-forming agent is fully dispersed; then 22.5% triethanolamine is added, and the stirring is mixed uniformly at a speed of 300-400r / min; then 10% of the prepared thermosetting polyester is added, and the stirring is fully mixed uniformly to obtain a polyester water plugging agent mother liquor, and the stirring speed is set to 300-400r / min to obtain the polyester water plugging agent mother liquor;

[0053] S4: set the temperature of the double constant temperature oven to 170℃, and the temperature fluctuation is ±2℃; the polyester water plugging agent mother liquor is placed in the double constant temperature oven for high temperature curing at 170℃ to obtain a temperature-controlled phase change water resistance and air permeability selective water plugging agent.

[0054] The performance test results of the obtained temperature-controlled phase change water resistance and air permeability selective water plugging agent are shown in Table 2:

[0055] Table 2: Performance test results of the water plugging agent in Example 2

[0056]

[0057]

[0058] Example 3

[0059] A temperature-controlled phase change water resistance and air permeability selective water plugging agent, comprising the following steps:

[0060] S1: itaconic acid, 200 mL polyol (molar mass ratio of 0.975 of ethylene glycol, molar mass ratio of 0.025 of 1,4-butanediol) and mass ratio of 0.05% of p-methylbenzenesulfonic acid with a molar mass ratio of 1.2 were added to a four-necked flask with magnetic stirrer, condenser and nitrogen inlet device, respectively, and nitrogen was used as protective gas. First, nitrogen was passed for half an hour, and the remaining gas was removed. The reaction temperature was controlled at about 160°C by an oil bath device for pre-reaction. When no water was generated, 0.05% of the catalyst dibutyltin dilaurate was added, and the temperature was controlled at 160°C. The system was kept at this condition for 4h, and then the heating was stopped. After cooling, the product was poured out to obtain a thermosetting polyester. The molecular weight of the thermosetting polyester was 400×10 4 mg / L or so;

[0061] S2: 5% hydrophobic nano-silica was added to water, and the inorganic filler was fully dispersed to obtain a mixed solution;

[0062] S3: 1% heptadecafluorodecyltrimethoxysilane was added to the mixed solution, and the hydrophobic synergist was fully dispersed. Then 1% ammonium carbamate was added, and the pore former was fully dispersed. Then 20% Tween 80 was added, and the stirring was mixed uniformly at a speed of 300-400 r / min. Then 20% of the prepared thermosetting polyester was added, and the stirring was fully mixed uniformly to obtain a polyester water plugging agent mother liquor. The stirring speed was set to 300-400 r / min to obtain the polyester water plugging agent mother liquor;

[0063] S4: set the temperature of the double constant temperature oven to 170°C with a temperature fluctuation of ±2°C; put the polyester water plugging agent mother liquor into the double constant temperature oven for high temperature curing at 170°C to obtain a temperature-controlled phase change water resistance and air permeability selective water plugging agent.

[0064] The performance test results of the obtained temperature-controlled phase change water resistance and air permeability selective water plugging agent are shown in Table 3:

[0065] Table 3: performance test results of the water plugging agent in Example 3

[0066]

[0067]

[0068] Example 4

[0069] A temperature-controlled phase change water resistance and air permeability selective water plugging agent, comprising the following steps:

[0070] S1: itaconic acid, 200 mL polyol (molar mass ratio of 0.975 of ethylene glycol, molar mass ratio of 0.025 of 1,4-butanediol) and mass ratio of 0.05% of p-methylbenzenesulfonic acid with a molar mass ratio of 1.2 were added to a four-necked flask with a magnetic stirrer, a condenser and a nitrogen inlet device, respectively, and nitrogen was used as a protective gas. First, nitrogen was passed for half an hour, and the remaining gas was removed. The reaction temperature was controlled at about 160°C by an oil bath device for pre-reaction. After the reaction, basically no water was generated. Then, a mass ratio of 0.05% of the catalyst dibutyltin dilaurate was added, and the temperature was controlled at 160°C. The system was maintained at this condition for 4h. Then, heating was stopped, and after cooling, the product was poured out to obtain a thermosetting polyester. The molecular weight of the thermosetting polyester was 400 x 10 4 mg / L or so;

[0071] S2: 2% hydrophobic nano-silica and 3% heptadecafluorodecyltrimethoxysilane were added to water, and the inorganic filler was fully dispersed to obtain a mixed solution;

[0072] S3: 5% hydrophobic nano-silica was added to the mixed solution, and the hydrophobic synergist was fully dispersed. Then, 1% ammonium carbamate was added, and the pore former was fully dispersed. Then, 25% Span 80 was added, and the stirring was mixed uniformly at a speed of 300-400 r / min. Then, 20% of the prepared thermosetting polyester was added, and the stirring was fully mixed uniformly to obtain a polyester water plugging agent mother liquor. The stirring speed was set to 300-400 r / min to obtain the polyester water plugging agent mother liquor.

[0073] S4: the temperature of the double constant temperature oven was set to 170°C with a temperature fluctuation of ±2°C. The polyester water plugging agent mother liquor was placed in the double constant temperature oven for high temperature curing at 170°C to obtain a temperature-controlled phase change water resistance and air permeability selective water plugging agent.

[0074] The performance test results of the obtained temperature-controlled phase change water resistance and air permeability selective water plugging agent are shown in Table 4:

[0075] Table 4: performance test results of the water plugging agent in Example 4

[0076]

[0077]

[0078] Example 5

[0079] A temperature-controlled phase change water resistance and air permeability selective water plugging agent, comprising the following steps:

[0080] S1: itaconic acid with a molar mass ratio of 1.2, 200 mL of polyol (ethylene glycol with a molar mass ratio of 0.975, 1,4-butanediol with a molar mass ratio of 0.025) and p-toluenesulfonic acid with a mass ratio of 0.05% are respectively added into a four-necked flask with a magnetic stirrer, a condenser and a nitrogen inlet device, nitrogen is used as a protective gas, nitrogen is first passed for half an hour, the remaining gas is removed, the reaction temperature is controlled at about 160 DEG C through an oil bath device for pre-reaction, the reaction is basically no water generation, then a catalyst dibutyltin dilaurate with a mass ratio of 0.05% is added, the temperature is controlled at 160 DEG C, the system is kept under this condition for 4h, then heating is stopped, after cooling, the product is poured out, and a thermosetting polyester is obtained; the molecular weight of the thermosetting polyester is about 400x10 4 mg / L;

[0081] S2: 15% montmorillonite is added in water, and the inorganic filler is fully dispersed to obtain a mixed solution;

[0082] S3: 0.5% hydrophobic nano-silicon dioxide is added in the mixed solution, and the hydrophobic synergist is fully dispersed; then 10% ammonium carbamate is added, and the pore former is fully dispersed; then 15% Tween 60 is added, and the stirring is uniformly mixed at a speed of 300-400r / min; then 15% of the prepared thermosetting polyester is added, and the stirring is fully mixed and uniformly mixed to obtain a polyester water plugging agent mother liquor, and the stirring speed is set to 300-400r / min to obtain the polyester water plugging agent mother liquor;

[0083] S4: the temperature of a double constant temperature oven is set to 170 DEG C, and the temperature fluctuation is ±2 DEG C; the polyester water plugging agent mother liquor is placed in the double constant temperature oven for high temperature curing at 170 DEG C to obtain a temperature-controlled phase change water resistance and air permeability selective water plugging agent.

[0084] Example 6

[0085] A temperature-controlled phase change water resistance and air permeability selective water plugging agent, comprising the following steps:

[0086] S1: itaconic acid with a molar mass ratio of 1.2, 200 mL of polyol (ethylene glycol with a molar mass ratio of 0.975, 1,4-butanediol with a molar mass ratio of 0.025) and p-toluenesulfonic acid with a mass ratio of 0.05% are respectively added into a four-necked flask with a magnetic stirrer, a condenser and a nitrogen inlet device, nitrogen is used as a protective gas, nitrogen is first passed for half an hour, the remaining gas is removed, the reaction temperature is controlled at about 160 DEG C through an oil bath device for pre-reaction, the reaction is basically no water generation, then a catalyst dibutyltin dilaurate with a mass ratio of 0.05% is added, the temperature is controlled at 165 DEG C, the system is kept under this condition for 4h, then heating is stopped, after cooling, the product is poured out, and a thermosetting polyester is obtained; the molecular weight of the thermosetting polyester is about 400x10 4 mg / L.

[0087] S2: Add 15% montmorillonite in water, and wait for the inorganic filler to be fully dispersed to obtain a mixed solution;

[0088] S3: Add 0.5% hydrophobic nano-silicon dioxide in the mixed solution, and wait for the hydrophobic synergist to be fully dispersed; then add 10% ammonium carbamate, and wait for the pore-forming agent to be fully dispersed; then add 15% Tween 60, and wait for stirring and mixing to be uniform, with a set speed of 300-400 r / min; then add the prepared 15% thermosetting polyester, and wait for stirring and mixing to be fully uniform to obtain a polyester water plugging agent mother liquor, with a set speed of 300-400 r / min, to obtain the polyester water plugging agent mother liquor;

[0089] S4: Set the temperature of the double constant temperature oven to 170℃, with a temperature fluctuation of ±2℃; place the polyester water plugging agent mother liquor in the double constant temperature oven for high-temperature curing at 170℃ to obtain a temperature-controlled phase change water-resisting and air-permeating selective water plugging agent.

[0090] Example 7

[0091] A temperature-controlled phase change water-resisting and air-permeating selective water plugging agent, comprising the following steps:

[0092] S1: Add itaconic acid with a molar mass ratio of 1.2, 200 mL of a polyhydric alcohol (ethylene glycol with a molar mass ratio of 0.975 and 1,4-butanediol with a molar mass ratio of 0.025), and 0.05% p-toluenesulfonic acid by mass into a four-necked flask of a magnetic stirrer, a condenser, and a nitrogen inlet device respectively, with nitrogen as a protective gas, first pass nitrogen for half an hour to remove the remaining gas, and control the reaction temperature at about 160℃ through an oil bath device for pre-reaction, then add 0.05% of a catalyst, dibutyltin dilaurate, by mass, control the temperature at 165℃, keep the system under this condition for 5h, then stop heating, and after cooling, pour out the product to obtain a thermosetting polyester; the molecular weight of the thermosetting polyester is about 400×10 4 mg / L;

[0093] S2: Add 15% montmorillonite in water, and wait for the inorganic filler to be fully dispersed to obtain a mixed solution;

[0094] S3: Add 0.5% hydrophobic nano-silicon dioxide in the mixed solution, and wait for the hydrophobic synergist to be fully dispersed; then add 10% ammonium carbamate, and wait for the pore-forming agent to be fully dispersed; then add 15% Tween 60, and wait for stirring and mixing to be uniform, with a set speed of 300-400 r / min; then add the prepared 15% thermosetting polyester, and wait for stirring and mixing to be fully uniform to obtain a polyester water plugging agent mother liquor, with a set speed of 300-400 r / min, to obtain the polyester water plugging agent mother liquor;

[0095] S4: set the temperature of the double thermostat to 170℃, with a temperature fluctuation of ±2℃; place the polyester water shutoff agent mother liquor into the double thermostat for high-temperature curing at 170℃ to obtain a temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent.

[0096] Example 8

[0097] A temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent, comprising the following steps:

[0098] S1: respectively add itaconic acid with a molar mass ratio of 1.2, 200 mL of a polyhydric alcohol (ethylene glycol with a molar mass ratio of 0.975 and 1,4-butanediol with a molar mass ratio of 0.025), and 0.05% by mass of p-toluenesulfonic acid into a four-necked flask of a magnetic stirrer, a condenser, and a nitrogen inlet device, with nitrogen as a protective gas, first pass nitrogen for half an hour to remove the remaining gas, and pre-react by controlling the reaction temperature at about 160℃ through an oil bath device, until basically no water is generated, then add 0.05% by mass of a catalyst, dibutyltin dilaurate, control the temperature at 165℃, keep the system under this condition for 5.5 h, then stop heating, and after cooling, pour out the product to obtain a thermosetting polyester; the molecular weight of the thermosetting polyester is 400×10 4 mg / L or so;

[0099] S2: add 15% of montmorillonite to water, and after the inorganic filler is fully dispersed, a mixed solution is obtained;

[0100] S3: add 0.5% of heptadecafluorodecyltrimethoxysilane to the mixed solution, and after the hydrophobic synergist is fully dispersed, add 10% of ammonium carbamate, and after the pore-forming agent is fully dispersed, add 15% of Tween 60, and after stirring and mixing uniformly, set the rotation speed to 300-400 r / min; then add 15% of the prepared thermosetting polyester, and after stirring and fully mixing uniformly, set the rotation speed to 300-400 r / min to obtain a polyester water shutoff agent mother liquor;

[0101] S4: set the temperature of the double thermostat to 170℃, with a temperature fluctuation of ±2℃; place the polyester water shutoff agent mother liquor into the double thermostat for high-temperature curing at 170℃ to obtain a temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent.

[0102] Example 9

[0103] A temperature-controlled phase change water-resisting and air-permeating selective water shutoff agent, comprising the following steps:

[0104] S1: Itaconic acid with a molar mass ratio of 1.2, 200 mL of polyol (ethylene glycol with a molar mass ratio of 0.975, 1,4-butanediol with a molar mass ratio of 0.025) and p-toluenesulfonic acid with a mass ratio of 0.05% were added to a magnetic stirrer, a condenser and a four-necked flask with a nitrogen device, respectively. Nitrogen was used as a protective gas. First, nitrogen was passed through for half an hour to remove the remaining gases. The reaction temperature was controlled at about 160°C by an oil bath device for pre-reaction. The reaction was carried out until almost no water was produced. Then, a catalyst dibutyltin dilaurate with a mass ratio of 0.05% was added, the temperature was controlled at 165°C, and the system was kept under this condition for 8 hours. Then, the heating was stopped. After cooling, the product was poured out to obtain a thermosetting polyester; the molecular weight of the thermosetting polyester was 400×10 4 mg / L or so;

[0105] S2: Add 15% montmorillonite to water and wait until the inorganic filler is fully dispersed to obtain a mixed solution;

[0106] S3: Add 0.5% hydrophobic nano-silica to the mixed solution and wait for the hydrophobic synergist to be fully dispersed; then add 10% ammonium carbamate and wait for the porogen to be fully dispersed; then add 15% Tween 40 and stir until mixed evenly, setting the speed to 300-400 r / min; then add 15% of the prepared thermosetting polyester and stir until mixed evenly to obtain a polyester water plugging agent mother liquor, setting the speed to 300-400 r / min to obtain a polyester water plugging agent mother liquor;

[0107] S4: Setting the temperature of the double constant temperature box to 170°C with a temperature fluctuation of ±2°C; placing the polyester water blocking agent mother liquor in the double constant temperature box for high temperature curing at 170°C to obtain a temperature-controlled phase-change water-blocking and breathable selective water blocking agent.

[0108] Figure 2 The figure shows the cured state of the temperature-controlled phase-change water-blocking and breathable selective water-blocking agent of the present invention. The figure shows that after curing, it not only exhibits excellent temperature resistance but also high stability. The water-blocking agent has a porous network structure, which increases gas flow while reducing liquid flow, improving gas selective permeability, and achieving hydrophobic association, water blocking, and air permeability.

[0109] The above content is only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water-blocking agent, characterized in that: The following steps are involved: S1: Preparation of thermosetting polyester using a two-step process; S2: adding an inorganic filler to water to obtain a mixed solution; S3: adding a hydrophobic synergist, a porogen, an additive, and a thermosetting polyester to the mixed solution in sequence, and stirring the mixture to obtain a polyester water plugging agent mother solution; S4: curing the polyester water-blocking agent mother liquor at high temperature to obtain a temperature-controlled phase-change water-blocking and air-permeable selective water-blocking agent; Calculated by mass percentage, thermosetting polyester 10% to 20%, additive 15% to 25%, porogen 0.5% to 5%, hydrophobic synergist 0.5% to 5%, inorganic filler 1% to 10% and the balance water; The molecular weight of the thermosetting polyester is 400×10 4 mg / L; In S1, the two-step method for preparing the thermosetting polyester comprises the following steps: After itaconic acid, polyol, and p-toluenesulfonic acid are mixed, a pre-reaction is carried out in an oxygen-free environment until no water is produced in the entire reaction base, and then dibutyltin dilaurate is added to react. After the reaction is completed, a thermosetting polyester is obtained; The polyol is obtained by mixing ethylene glycol and 1,4-butanediol in a molar mass ratio of 0.975:0.

025.

2. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The dosage ratio of itaconic acid to polyol is 1.2 mol:200 mL; the dosage of p-toluenesulfonic acid and dibutyltin dilaurate is 0.05% of the mass of the mixed solution respectively.

3. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The oxygen-free environment uses nitrogen as the protective gas; the pre-reaction uses an oil bath device to control the reaction temperature at 160-165° C.; and the stirring speed is 300-400 r / min.

4. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The reaction temperature is 160-165° C., and the reaction time is 4-8 hours.

5. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The auxiliary agent is one or more of triethanolamine, Tween 20, Tween 40, Tween 60, Tween 80, Span 80 and the like.

6. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The porogen is one or more of sodium bicarbonate, ammonium bicarbonate and ammonium carbamate.

7. The method for preparing a temperature-controlled phase-change water-blocking and air-permeable selective water blocking agent according to claim 1, characterized in that: The hydrophobic synergist is one or two of hydrophobic nano-silica and heptadecafluorodecyltrimethoxysilane; and the inorganic filler is one or more of hydrophobic nano-silica, montmorillonite and halloysite nanotubes.

Images