CN113388077A - High-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement - Google Patents
High-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement Download PDFInfo
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- CN113388077A CN113388077A CN202110692036.0A CN202110692036A CN113388077A CN 113388077 A CN113388077 A CN 113388077A CN 202110692036 A CN202110692036 A CN 202110692036A CN 113388077 A CN113388077 A CN 113388077A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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Abstract
The invention discloses a high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement, which comprises the following preparation steps: (1) dissolving epoxy resin in N, N-dimethylformamide, introducing nitrogen, stirring, heating to 85 ℃; (2) dissolving benzoyl peroxide in acetone, then dropwise adding the acetone solution into the solution obtained in the step (1), heating to 95 ℃, and keeping the temperature for 30 min; (3) slowly adding a mixed aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and acrylamide into the reaction solution; reacting for 4 hours at constant temperature; (4) the solvent was removed by rotary evaporation, and the unreacted epoxy resin raw material was repeatedly washed with ethyl acetate to obtain a self-crosslinking aqueous epoxy resin. The self-crosslinking water-based epoxy resin is added into cement, so that the field slurry preparation step is simplified; the brittleness of the oil well cement can be improved, and the macroscopic mechanical property and compactness of the oil well cement can be effectively improved.
Description
Technical Field
The invention relates to the technical field of oil and gas field exploitation, in particular to a high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement.
Background
The well cementation is an operation of injecting cement slurry between a casing and a stratum annulus, forming oil well cement stones after the cement slurry is solidified, effectively packing the stratum and providing protection and support for the casing, and the quality of the well cementation is of great importance to subsequent drilling and oil gas exploitation. Along with the continuous deep exploration of oil and gas resources, the drilled stratum is more and more complex, which brings more severe examination to the well cementation quality. The traditional portland cement stone is an innate brittle material, is easy to shrink and poor in cementation, and the cement stone can crack due to different formation temperatures, casing expansion and soft and hard formation pressures, so that the effectiveness of formation packing is influenced, and the problem of channeling is further caused. Therefore, the improvement of the performance of the set cement, particularly the improvement of the toughness of the set cement is a fundamental measure for improving the complex stress resistance of the well cementation cement sheath, preventing the fluid channeling and ensuring the safe and efficient production of the oil-gas well.
The epoxy resin has the advantages of high bonding strength, high stability, low curing shrinkage rate, excellent chemical resistance and the like. The research of the epoxy resin for improving the performance of the well cementation cement stone is not deeply studied in the well cementation academic community, the oil-soluble epoxy resin is matched with the emulsifying agent and the curing agent for construction on site, the defects of complex formula, complex emulsion preparation and inconvenient application exist, the prepared emulsion system is unstable in performance and difficult to control the curing time, and potential safety hazards are brought to well cementation construction.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement. The water-based epoxy resin has stable construction performance, can resist the high-temperature environment of the stratum and can solve the problem of high brittleness of set cement.
The high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement is prepared by performing graft copolymerization on raw materials of epoxy resin, 2-acrylamide-2-methylpropanesulfonic acid and acrylamide under the action of an initiator benzoyl peroxide; the weight ratio of the epoxy resin, the 2-acrylamide-2-methylpropanesulfonic acid and the acrylamide is 100-110: 40-50: 4 to 6.
The preparation method comprises the following steps:
(1) dissolving epoxy resin in N, N-dimethylformamide, introducing nitrogen, stirring, heating to 85 ℃.
(2) And (2) dissolving benzoyl peroxide in acetone, then dropwise adding the acetone solution into the solution obtained in the step (1), heating to 95 ℃, and keeping the temperature for 30 min.
(3) Slowly adding a mixed aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and acrylamide into the reaction solution; reacting for 4 hours at constant temperature.
(4) The solvent was removed by rotary evaporation, and the unreacted epoxy resin raw material was repeatedly washed with ethyl acetate to obtain a self-crosslinking aqueous epoxy resin.
Preferably, the epoxy resin is epoxy resin E44.
Further preferably, the weight ratio of each raw material component is as follows: 100-110 parts of epoxy resin (E44); 40-50 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS); 4-6 parts of Acrylamide (AM); 3-5 parts of initiator Benzoyl Peroxide (BPO); 10-12 parts of acetone; 120-150 parts of N, N-Dimethylformamide (DMF).
The synthetic reaction mechanism of the high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement is as follows: and (2) taking Benzoyl Peroxide (BPO) as an initiator, abstracting tertiary hydrogen atoms on the main chain of the epoxy resin E44 to generate free radicals, and grafting the AM and the AMPS to tertiary carbon of main chain belt hydroxyl of the epoxy resin E44 by a graft copolymerization method. The grafting reaction mechanism is as follows:
compared with the prior art, the invention has the advantages that:
the self-crosslinking water-based epoxy resin has the advantages of temperature resistance, self-crosslinking property and self-emulsifying property.
(1) Acrylamide monomer and 2-acrylamide-2-methyl propanesulfonic acid monomer are introduced into the molecular chain of epoxy resin at the same time, and the proportion is adjusted, so that the epoxy resin can realize self-emulsification and self-crosslinking without adding emulsifier and curing agent.
(2) The decomposition temperature of the modified epoxy resin is 310 ℃, and the modified epoxy resin can resist the high temperature of 180 ℃ of the stratum; the emulsion has good stability and is convenient to store and transport.
(3) When the single-component self-crosslinking waterborne epoxy resin is applied to oil well cement, a curing agent is not required to be added, the step of on-site slurry preparation is simplified, and the potential safety hazard of construction caused by an external curing agent is avoided.
(4) The problems of high compactness and brittleness of the oil well cement are solved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an infrared spectrum of a self-crosslinking aqueous epoxy resin prepared in example 1 of the present invention.
FIG. 2 is a curing diagram of a self-crosslinking aqueous epoxy resin.
FIG. 3 is a thermogravimetric analysis of a self-crosslinking aqueous epoxy resin.
FIG. 4 shows the flexural strength of the resin set cement.
FIG. 5 shows compressive strength of resin set cement.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A preparation method of high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement comprises the following steps:
(1) dissolving 105g of epoxy resin E44 in 135g of N, N-dimethylformamide, transferring the mixture into a three-neck flask with a condensing tube and a constant-pressure dropping funnel, introducing nitrogen, stirring by a magnetic stirrer, and heating to 85 ℃;
(2) using 4g of benzoyl peroxide as an initiator, dissolving the benzoyl peroxide in 11g of acetone, then dropwise adding an acetone solution into a three-neck flask, heating the system to 95 ℃, and reacting at a constant temperature for 30 min;
(3) dissolving 45g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 5g of Acrylamide (AM) in 40g of water to form a mixed aqueous solution; then slowly adding the mixed aqueous solution into a three-neck flask, and reacting for 4 hours at constant temperature;
(4) after the reaction, the solvent was removed by a rotary evaporator, and the unreacted epoxy resin raw material was repeatedly washed with ethyl acetate to obtain a self-crosslinking aqueous epoxy resin sample.
The following performance characterizations and tests were performed on the self-crosslinking waterborne epoxy resin prepared in example 1:
(1) FIG. 1 is an infrared spectrum of a self-crosslinking aqueous epoxy resin prepared in example 1. As can be seen from FIG. 1, 3324cm-1introducing-SO on side chain of epoxy resin3Superposing a stretching vibration absorption peak of-OH and a stretching vibration peak of-NH on H; 1666cm-1The compound should be secondary amide in AMPS and AM>S is a superposed absorption peak caused by O stretching vibration; 1190cm-1In AMPS>O-asymmetric stretching vibration absorption peak, 1114cm-1In AMPS>S is equal to O and is symmetrical to expand and contract to shake and absorb the peak; 769cm-1Corresponds to-NH2A vibration absorption peak; at the same time, 914cm-1And 829cm-1The absorption peaks of (A) correspond to-C-H asymmetric stretching vibration and deformation vibration on the epoxy group respectively, which shows that the epoxy group is not participated in the reaction to be reserved, and the reaction is mainly carried out in a grafting copolymerization mode by AMPS and AM.
(2) The self-crosslinking water-based epoxy resin prepared in example 1 and water are mixed according to a mass ratio of 1: 3 preparing emulsion, adjusting the pH to 12-13 (the pH of a cement paste system), and curing for 5 hours at the temperature of 80 ℃ to obtain the self-crosslinking product shown in figure 2.
(3) The thermal stability analysis of the self-crosslinking waterborne epoxy resin prepared in example 1 by using a thermogravimetric analyzer showed that the initial decomposition temperature of the sample was 310 ℃, the thermal stability was good, and the downhole operation was satisfied, as shown in fig. 3.
(4) The method comprises the steps of adding a certain mass fraction of the aqueous epoxy resin sample prepared in the example 1 into Jiahua G-grade cement, preparing cement slurry according to a GBT 19139-. The formula of the cement paste is as follows: 600G of Jiahua G-grade cement, self-crosslinking water-based epoxy resin, 1% of fluid loss additive, 0.5% of dispersing agent and 0.44% of defoaming agent (water-cement ratio).
The flexural strength test result is shown in fig. 4, and it can be seen that the flexural strength of the cement stone modified by the high temperature resistant self-crosslinking waterborne epoxy resin is obviously higher than that of blank cement stone, and when the addition amount is 2-6%, the flexural strength of the cement stone is increased along with the increase of the addition amount of the waterborne epoxy resin; however, when the amount is more than 6%, the amount of the aqueous epoxy resin is increased, and the flexural strength is reduced. Therefore, the optimal mixing amount of the water-based epoxy resin is 6%, the breaking strength is 8.9MPa, and the breaking strength is improved by 48.3%.
The results of the compressive strength test are shown in fig. 5, and it can be seen that the strength of the cement stone modified by the self-crosslinking waterborne epoxy resin of the present invention is obviously increased compared with the strength of the blank cement stone. There is also an optimum resin addition of 6% for compressive strength improvement, where the compressive strength is 34.6MPa and the compressive strength is increased by 38.4%.
(5) Comparative test of compression resistance of self-crosslinking waterborne epoxy resin prepared in example 1 and conventional epoxy resin
The self-crosslinking water-based epoxy resin prepared in example 1 and the conventional epoxy resin E44 before modification were added to set cement separately to perform a compression and bending test (6% addition) and the results are shown in Table 1 and Table 2.
TABLE 1 compressive Strength of resin blended Cement before and after modification
| Compressive strength (MPa) | 1 | 2 | 3 | Mean value of |
| Example 1 epoxy resin | 34.7 | 34.4 | 34.7 | 34.6 |
| Conventional epoxy resin E44 | 26.4 | 26.6 | 26.2 | 26.4 |
TABLE 2 flexural Strength of resin-doped Cement before and after modification
| Flexural strength (MPa) | 1 | 2 | 3 | Mean value of |
| Example 1 epoxy resin | 9.0 | 8.8 | 8.9 | 8.9 |
| Conventional epoxy resin E44 | 6.2 | 6.5 | 6.5 | 6.4 |
The data in the two tables show that the compressive strength of the conventional epoxy resin E44 directly added into the cement is 26.4 MPa; when the self-crosslinking water-based epoxy resin in the embodiment 1 is added into cement paste, the compression strength of the set cement is 34.6MPa, and the compression strength is improved by 31.1 percent. The conventional epoxy resin E44 is directly added into the cement, and the flexural strength is 6.4 MPa; when the self-crosslinking water-based epoxy resin in the embodiment 1 is added into cement paste, the compression strength of the set cement is 8.9MPa, and the compression strength is improved by 39.1 percent. After the self-crosslinking aqueous epoxy resin modified by the method is added into the set cement, the pore structure in the set cement is reduced, the compactness of the set cement is improved, and meanwhile, the self-crosslinking film forming of the aqueous epoxy resin is an important reason for enabling the compression strength/rupture strength of the set cement to be higher than that of the epoxy resin E44 directly added into the cement paste.
In conclusion, the invention provides the high-temperature-resistant self-crosslinking water-based epoxy resin for the oil well, which is mainly applied to the field of well cementation engineering. The epoxy resin has self-emulsifying and self-crosslinking properties; meanwhile, the grafted sulfonic acid group enables the resin to have high temperature resistance, and is beneficial to being applied to a cement paste system. The amide group connected to the side chain of the self-crosslinking waterborne epoxy resin can react and be connected with the epoxy group on the main chain of the other waterborne epoxy resin to form a film-shaped and crosslinked net-shaped substance which is crosslinked with each other, thereby improving the compactness and the mechanical property of the set cement.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. The high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement is characterized by being prepared by performing graft copolymerization on raw materials of epoxy resin, 2-acrylamide-2-methylpropanesulfonic acid and acrylamide under the action of an initiator benzoyl peroxide; the weight ratio of the epoxy resin, the 2-acrylamide-2-methylpropanesulfonic acid and the acrylamide is 100-110: 40-50: 4 to 6.
2. The high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) dissolving epoxy resin in N, N-dimethylformamide, introducing nitrogen, stirring, heating to 85 ℃;
(2) dissolving benzoyl peroxide in acetone, then dropwise adding the acetone solution into the solution obtained in the step (1), heating to 95 ℃, and keeping the temperature for 30 min;
(3) slowly adding a mixed aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid and acrylamide into the reaction solution; reacting for 4 hours at constant temperature;
(4) and after the reaction is finished, removing the solvent by rotary evaporation, and repeatedly washing and removing unreacted epoxy resin raw materials by using ethyl acetate to obtain the high-temperature-resistant self-crosslinking waterborne epoxy resin.
3. The high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement as claimed in claim 2, wherein the epoxy resin is epoxy resin E44, and the weight ratio of the epoxy resin E44 to the N, N-dimethylformamide is 100-110: 120-150.
4. The high-temperature-resistant self-crosslinking water-based epoxy resin for oil well cement as claimed in claim 2, wherein in the step (2), the dosage weight ratio of benzoyl peroxide to acetone is 3-5: 10 to 12.
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