CN115340749B - Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof - Google Patents

Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof Download PDF

Info

Publication number
CN115340749B
CN115340749B CN202210939125.5A CN202210939125A CN115340749B CN 115340749 B CN115340749 B CN 115340749B CN 202210939125 A CN202210939125 A CN 202210939125A CN 115340749 B CN115340749 B CN 115340749B
Authority
CN
China
Prior art keywords
epoxy resin
curing
curing agent
temperature
component epoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210939125.5A
Other languages
Chinese (zh)
Other versions
CN115340749A (en
Inventor
冯玉军
殷鸿尧
吕锟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN202210939125.5A priority Critical patent/CN115340749B/en
Publication of CN115340749A publication Critical patent/CN115340749A/en
Application granted granted Critical
Publication of CN115340749B publication Critical patent/CN115340749B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention discloses an underwater high-temperature slow-curing single-component epoxy resin system, a preparation method and application thereof. The single-component epoxy resin curing system comprises epoxy matrix resin, a curing agent and a diluent. The curing agent is a 4, 4-diaminodiphenyl methane derivative, and is prepared from an active hydrogen-containing compound, aldehyde and 4, 4-diaminodiphenyl methane through a Mannich reaction under the catalysis of protonic acid. The curing system formed by the curing agent, the epoxy resin monomer and the diluent has good fluidity, and can keep the fluidity for a long time at high temperature, namely has long pot life at high temperature. The cured product obtained by curing has good thermal performance and mechanical property, can work for a long time in a high-temperature environment under water, has ultra-long gel time and good thermal performance and mechanical property under high temperature under water, and can be used in the water shutoff and profile control field of the upstream of petroleum and natural gas industries.

Description

Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer material science, and particularly relates to an underwater high-temperature slow-curing single-component epoxy resin system.
Background
Epoxy resins (Epoxy resins) are polymeric prepolymers with no less than two Epoxy groups that form a three-dimensional crosslinked network under the action of a curing agent. Because of its excellent mechanical properties, electrical insulation properties, adhesion, heat resistance and corrosion resistance, and slight cure shrinkage, it has found wide application in various industrial fields including adhesives, coatings, aerospace, automotive, electronic and construction.
Most of the epoxy matrix materials are liquid prepolymers with fluidity at room temperature, have poor thermal performance and mechanical properties, and are required to be matched with a curing agent to generate a three-dimensional crosslinked network structure so as to show various excellent properties, thus becoming thermosetting resin materials with use value. The curing agent has an indispensable, decisive role in the application of the epoxy resin. Compounds containing two or more active bonds that can initiate an epoxy ring-opening reaction are typically used as curing agents, such as amines, imidazoles, anhydrides, phenols, and other compounds. In most practical applications, rapid curing at moderate to low temperatures in air is required, for which purpose a large number of highly reactive curing agents have been developed and even facilitated. While the high temperature curing process of epoxy curing systems has little research attention, not only has it prevented a thorough understanding of the mechanism by which epoxy resins are formed, but it has limited its use under a wider range of conditions. For example, some of the recently emerging applications have opposite requirements, such as slow cure at extremely high temperatures underwater during hydrocarbon production. When epoxy is used as a water shutoff, profile control material, slow curing in a high temperature water environment is required to ensure fluidity is maintained during injection so that curing occurs at the subsurface target location rather than in the wellbore. The mixture of matrix resin and curing agent is typically injected into the subsurface through the wellbore using a liquid delivery method and cured to plug the aqueous layer of the formation at a temperature greater than 120 ℃. But needless to say, high temperatures will speed up the curing process. Thus, achieving slow curing of epoxy resins in hot water is a great challenge.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and providing an underwater high-temperature slow-curing single-component epoxy resin system, a preparation method and application thereof, so as to obtain a flowable resin material with long pot life in a high-temperature environment, and the resin material has excellent thermal performance and mechanical property after curing.
The invention provides an underwater high-temperature slow-curing single-component epoxy resin system, which comprises epoxy matrix resin, a curing agent and a diluent; wherein the mass ratio of the epoxy matrix resin to the curing agent is 1 (0.3-1), the addition amount of the diluent is 5-20% of the mass of the epoxy matrix resin, and the curing agent is a beta-amino (carbonyl) compound based on 4, 4-diaminodiphenyl methane, and the chemical structure of the curing agent is shown in the following formula 1:
in formula 1, R 1 And R is 3 Is selected from one of hydrogen atom, phenyl, furyl and methyl, R 1 And R is 3 May be the same or different; r is R 2 And R is 4 One selected from acetonyl, o-hydroxyphenyl and benzoylmethyl, R 2 And R is 4 May be the same or different.
Further, the epoxy matrix resin is at least one of bisphenol A type epoxy resin E44, bisphenol A type epoxy resin E51, bisphenol F type epoxy resin and N, N, N ', N' -tetraepoxypropyl-4, 4-diaminodiphenylmethane.
Further, the diluent is at least one of n-butyl glycidyl ether and phenyl glycidyl ether, and more preferably n-butyl glycidyl ether.
The invention also provides an epoxy resin system curing agent, which is a beta-amino (carbonyl) compound based on 4, 4-diaminodiphenyl methane, and the chemical structure of the curing agent is shown in the following formula 1:
in formula 1, R 1 And R is 3 Is selected from one of hydrogen atom, phenyl, furyl and methyl, R 1 And R is 3 May be the same or different; r is R 2 And R is 4 One selected from acetonyl, o-hydroxyphenyl and benzoylmethyl, R 2 And R is 4 May be the same or different.
The invention provides a preparation method of an underwater high-temperature slow-curing single-component epoxy resin system, which is obtained by mechanically stirring epoxy matrix resin, a curing agent and a diluent according to mass ratio and removing bubbles by vacuum pumping; wherein the curing agent is prepared from a compound with active hydrogen, aldehyde and 4, 4-diaminodiphenyl methane through a Mannich reaction in one pot.
In the above method, further, the preparation method of the curing agent comprises the following steps:
(1) Fully dissolving 4, 4-diaminodiphenyl methane in an organic solvent under the ice bath condition (0-5 ℃) to obtain a solution;
(2) Slowly dripping aldehyde and a compound with active hydrogen into the solution obtained in the step (1) in sequence, and fully stirring and uniformly mixing;
(3) And (3) adding a catalyst into the mixture obtained in the step (2), reacting for 24-48 hours at room temperature, and performing post-treatment to obtain the curing agent.
In the method, further, the molar ratio of the compound with active hydrogen, aldehyde and 4, 4-diaminodiphenyl methane is (2-4): (2-2.2): 1, and the molar amount of the catalyst is 5-20% of the molar amount of 4, 4-diaminodiphenyl methane.
In the method, further, the compound with active hydrogen is at least one of acetone, acetophenone and phenol; acetone is preferred.
In the above method, further, the aldehyde is at least one of 37wt% formaldehyde aqueous solution, furfural, benzaldehyde and acetaldehyde; preferably furfural.
In the method, the catalyst is at least one of hydrochloric acid, sulfamic acid, bismuth chloride and anhydrous aluminum chloride; sulfamic acid is preferred.
In the above method, further, the organic solvent is at least one of absolute ethyl alcohol, tetrahydrofuran, 1, 4-dioxane, acetone and dimethyl sulfoxide; preferably 1, 4-dioxane.
The invention also provides a preparation method of the curing agent, which is the same as the preparation method of the curing agent.
The invention also provides an underwater high-temperature slow-curing single-component epoxy resin cured product, which is obtained by heating and curing the underwater high-temperature slow-curing single-component epoxy resin system.
The invention also provides application of the underwater high-temperature slow-curing single-component epoxy resin system in the fields of upstream of petroleum and natural gas industries, water shutoff, profile control and the like of high-temperature oil fields.
The invention also provides application of the curing agent in an epoxy resin system.
Compared with the prior art, the invention has the following beneficial effects:
1. the single-component epoxy resin system can be slowly cured in a high-temperature environment. The curing agent is modified based on 4, 4-diaminodiphenyl methane, furyl is introduced into amino through furfural, and nucleophilic reactivity of the amino is reduced through large steric hindrance effect and hydrogen bonding between oxygen atoms and amino hydrogen; the carbonyl with electron withdrawing effect is introduced through the acetone, so that the nucleophilicity of the amino is further reduced; finally, the effect of high-temperature slow solidification is achieved. Meanwhile, the curing agent is insoluble in water, and the curing process is less affected by water.
2. The one-component epoxy resin system has lower viscosity. The addition of the diluent n-butyl glycidyl ether greatly reduces the viscosity of the curing system, so that the curing system has good fluidity at normal temperature, is convenient to move in use, is a flowable resin material with long pot life in a high-temperature environment, and has excellent thermal performance and mechanical performance after curing.
3. The epoxy resin condensate cured by the single-component epoxy resin system has good thermal and mechanical properties. The introduction of benzene rings and furyl in the curing agent increases the thermal stability and the compression strength of the cured product, and the good thermal and mechanical properties enable the cured product of the epoxy resin to be used for a long time at high temperature, thereby having application prospects in the fields of water shutoff, profile control and the like in the high-temperature environment upstream of the petroleum and natural gas industry.
4. The synthesis process of the curing agent is green, simple and convenient, and the reaction condition is mild, so that the preparation of the single-component epoxy resin system is easy, and the curing agent is suitable for popularization and application.
5. The present invention provides a novel curing agent suitable for epoxy resin systems which enables the epoxy resin systems to be slowly cured at elevated temperatures.
Drawings
FIG. 1 is a molecular structure diagram of AFPA;
FIG. 2 is an infrared spectrum of AFPA;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of AFPA;
FIG. 4 is a flow chart of the water shutoff application of example 9;
FIG. 5 is a microscopic image at 4-fold and 10-fold magnification of the cross section of the curing system in example 9;
FIG. 6 is a non-isothermal solidification DSC of example 5;
FIG. 7 is a non-isothermal solidification DSC graph of comparative example 1;
FIG. 8 is a non-isothermal DSC plot of the cured product of example 5 and comparative example 1 at a temperature increase rate of 20℃min-1;
FIG. 9 is a graph of thermal weight loss for example 5 and comparative example 1;
fig. 10 is a graph of differential thermal weight loss for example 5 and comparative example 1.
Detailed Description
The one-component epoxy resin system according to the present invention will be further described with reference to examples and drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
The curing agent used in the following examples was synthesized by itself, and other materials were commercially available.
Examples 1 to 4
The raw materials and amounts used in examples 1 to 4 are shown in Table 1.
TABLE 1
In table 1, the preparation method of the curing agent AFPA is: 19.8g of 4, 4-diaminodiphenylmethane (0.1 mol) and 250mL of 1, 4-dioxane were added to a 500mL four-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, and placed in an ice bath (0 to 5 ℃). The mixture was stirred and the temperature was controlled below 10 ℃. When DDM (4, 4-diaminodiphenylmethane) was completely dissolved, 19.2g of furfural (0.2 mol) and 23.2g of acetone (0.4 mol) were added to the flask. After stirring the mixture for half an hour, 1.94g sulfamic acid (10 mol%,0.02 mol) was added and stirring was continued for a further 24 hours at 35 ℃. Thereafter, the mixture was poured into ethanol to precipitate a crude product. The crude product was filtered, washed (three times with ethanol, three times with ultrapure water) and dried under vacuum at 75 ℃ for 24 hours to give a red powder.
The molecular structure and nuclear magnetism and infrared spectrograms of the prepared curing agent AFPA are respectively shown in figures 1, 2 and 3. Figure 2 shows a comparison of infrared spectra of furfural, 4-diaminodiphenylmethane and AFPA. By comparison, the peak value is 3425 cm -1 N-H stretching and 1680cm due to DDM primary amine -1 The peak at which the c=o stretch assigned to furfural disappeared, while the peak corresponding to the N-H stretch of the secondary amine appeared at 3320cm of the AFPA spectrum -1 Where it is located. Further utilize 1 H NMR spectra to confirm molecular structure as shown in fig. 3. The peak at 4.91ppm corresponds to the proton of N-CH and the peak at 2.12ppm corresponds to C-CH 3 Peaks at 2.89ppm and 3.57ppm correspond to-CH attached to carbonyl and benzene rings, respectively 2 The peaks at 4.88ppm correspond to protons of-CH-, the peaks at 6.21ppm and 6.32ppm correspond to protons on the benzene ring, and the peaks at 6.52ppm, 6.85ppm and 7.52ppm correspond to protons on the furan ring. In addition, the solvent and water peaks of deuterated dimethyl sulfoxide were at 2.5ppm and 3.33pmm, respectively.
In Table 1, the preparation method of the curing agent AFPA2 is different from the preparation method of AFPA in that the molar ratio of acetone, furfural and 4, 4-diaminodiphenylmethane is 3:2:1, and the rest of the operations are the same.
The preparation method of the medium single-component epoxy resin system in examples 1-4 comprises the following specific implementation steps: the epoxy resin, the curing agent and the diluent in table 1 are stirred at room temperature for 30min according to the proportion in the table to be uniformly mixed, and then are transferred into a vacuum oven to be vacuumized to remove bubbles, so that the single-component epoxy resin curing system of examples 1-4 is obtained.
The one-component epoxy resin curing system was put into ovens at 75 ℃, 90 ℃, 120 ℃ and 150 ℃ respectively for curing (curing in air), and the stringing condition of the curing system was observed every 1h to confirm whether the gel time was reached.
The gel time results for examples 1-4 are as follows: the gel times for examples 1 and 2 were all within 6-6.5 h at 75℃and for examples 3 and 4 were 48h and 30h, respectively, at 90 ℃. The results show that AFPA has a lower nucleophilic reactivity than AFPA2, so that the curing reaction with the epoxy resin takes longer to reach the gel point, since the primary amine remains at one end of AFPA2 compared to AFPA.
Examples 5 to 8
The raw materials and amounts used in examples 5 to 8 are shown in Table 2.
TABLE 2
The preparation method of the underwater high-temperature slow-curing single-component epoxy resin system in the embodiments 5 to 8 comprises the following specific implementation steps: stirring the epoxy resin, the curing agent and the diluent in the table at room temperature according to the proportion in the table for 30min to mix uniformly, transferring into a vacuum oven, and vacuumizing to remove bubbles to obtain the single-component epoxy resin curing system of examples 5-8.
In the measurement of the gel time, the curing system was placed in an oven at 60℃at 90℃at 120℃and 150℃for curing, respectively. Wherein, in table 2, curing in air means that the resin sample is directly put into a pressure-resistant glass bottle to be cured in an oven, curing in pure water means that the resin sample is transferred into the pressure-resistant glass bottle filled with 15-20 mL of water, and then the glass bottles are respectively put into the oven to be cured. In the curing process, the wiredrawing condition of the curing system is observed every 1h to confirm whether the gel time is reached.
Example 9
19g of 20 mesh ceramsite was packed into a glass funnel and used to simulate formation rock with cracks. Then, ultrapure water is continuously added into the funnel for flushing until the water flow reaches a stable state. Thereafter, 8mL of deionized water dyed with methylene blue was added to the funnel. The time for the water to flow completely out of the funnel was recorded. An appropriate amount of the resin samples of examples 5-6 was then added to the funnel, and the resin passed through and filled the cracks between the ceramsites. The funnel was moved to an oven at 120℃for 24 hours for solidification. After curing was complete, the funnel was removed and 8mL of methylene blue stained deionized water was added. The system was pressurized with a vacuum pump and a piston to test the plugging condition and the cross section was observed under magnification.
The results are shown in fig. 4 and 5. The split allowed 5mL of water to pass within 20 seconds (fig. 4A). Meanwhile, when slight pressure is applied, the curing system can smoothly enter the pores among the ceramsite. When the resin was fully cured, water did not run out for 96 hours. The vacuum pump applied a pressure differential of 0.09MPa to the upper and lower spaces of the system, but water still was unable to flow out (fig. 4B). A piston is then used to apply pressure to the upper space of the system to check the plugging performance. Even if the air amount of the upper space is compressed by 73%, no water flows out (fig. 9). And calculating the internal pressure of 0.3Mpa by using an ideal gas state equation, namely, the breakthrough pressure of the blocking resin is at least 0.3Mpa. Fig. 10 shows images of the ceramsite and resin mixture at various magnifications, showing that the epoxy resin is tightly adhered to the ceramsite to form a whole.
Comparative example 1
Bisphenol A type epoxy resin E51, curing agent 4, 4-diaminodiphenylmethane and n-butyl glycidyl ether are prepared according to the following weight ratio of 10:2.2: and (3) stirring the mixture for 30min at room temperature in a mass ratio of 1 to uniformly mix, transferring the mixture into a vacuum oven, and vacuumizing the vacuum oven to remove bubbles to obtain the epoxy resin curing system of the comparative example 1.
When the gel time was measured, the prepared curing system was divided into a plurality of parts, and the parts were put into ovens at 60 ℃, 90 ℃, 120 ℃ and 150 ℃ respectively and cured in air, and the stringing condition of the curing system was observed every 10 minutes to confirm whether the gel time was reached.
The gel times for examples 5-8 and comparative example 1 are shown in Table 3. The temperature has a great influence on the gel time, and the lower the temperature is, the longer the gel time is. The gel time in air was as long as 80h for samples of examples 7-8 without n-Butyl Glycidyl Ether (BGE) at 60℃and decreased to 50h, 17h and 8h when the temperature was increased to 90 ℃, 120 ℃ and 150 ℃, respectively. Gel time reached 8h even at temperatures up to 150 ℃. This may be interpreted as the presence of BGE prevents contact of the amino and epoxy groups and thus gel time increases. But this effect becomes less pronounced at high temperatures, because in this case the molecular movement is very intense.
TABLE 3 Table 3
Performance testing
The curing behavior of the one-component epoxy resin curing system of example 5 and the epoxy resin curing system of comparative example 1 and their cured products after curing at 150℃for 12 hours were tested using a Differential Scanning Calorimeter (DSC). The test conditions are nitrogen atmosphere, and the temperature rising rates are 5, 10 and 20 ℃ min respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the Each sampling is 8-10 mg.
The thermal stability of the cured product was tested using a thermal weight loss analyzer (TGA). The test condition is nitrogen atmosphere, and the air flow is 60 mL.min -1 The temperature rising rate is 10 ℃ min -1 。
The compression strength of the cured product of the one-component epoxy resin curing system of example 5 was tested using a universal material tester. The tests were carried out at temperatures of 30, 90 and 120℃respectively, with compression rates of 5 mm.min -1 . The compressed sample was a cylindrical sample with a diameter of 10mm and a height of 10 mm.
The mechanical property test results show that the compression strength of the cured product of the single-component epoxy resin curing system of the embodiment 5 at 30, 60 and 120 ℃ is 122, 62 and 41Mpa respectively, and the cured product still has good compression strength at high temperature.
Fig. 6 and 7 are non-isothermal curing DSC profiles of example 5 and comparative example 1, respectively. As shown in FIG. 6, the initial exothermic temperature of example 5 was about 190℃and the peak exothermic temperature was 5℃min -1 Reaching 254.3 ℃ at 10 ℃ for min -1 The temperature reaches 259.2 ℃ at 20 ℃ min -1 Reaching 273.3 deg.c. However, the initial exothermic temperature of comparative example 1 was about 100℃and was reduced by 90℃with heating rates of 5, 10 and 20℃min -1 The peak exothermic temperature at the time was only 151.5,163.8 and 192.9 ℃, as shown in fig. 7. Comparing the reaction exotherms of DDM and AFPA with the same epoxy resin, it can be concluded that the modified curative AFPA has higher onset and peak cure temperatures, indicating that AFPA has lower reactivity.
FIG. 8 is a DSC curve of the cured product of example 5 and comparative example 1. The glass transition temperatures of the cured products of example 5 and comparative example 1 were 123 and 145 ℃, respectively, indicating that the epoxy resin cured products obtained with AFPA as the curing agent had lower glass transition temperatures but were still at a higher level.
Fig. 9 and 10 are the thermogravimetric curves of example 5 and comparative example 1 and the differential thermogravimetric analysis curves thereof, respectively. FIG. 9 shows that the weight loss of example 5 starts at 130℃and its 5% (w/w) mass loss temperature is 233 ℃. The residual percentage of example 5 was 28.7% when the temperature reached 600 ℃. As a comparison, comparative example 1 starts weight loss at 300 ℃, its 5% mass loss temperature is 318 ℃, and the semicoke yield is 20.5% at 600 ℃. Example 5 reached the first maximum pyrolysis peak at 208℃with a peak value of 0.058%. Min -1 Comparative example 1, however, had no pyrolysis peak until the temperature reached 318 ℃. Example 5 reaches a second maximum pyrolysis peak at 373.7 ℃with a peak value of 0.68%. Min -1 . Comparative example 1 has a maximum pyrolysis rate of 0.89% min at 363.2C -1 Example 5 was 31% higher. Example 5 has a lower maximum pyrolysis temperature and maximum pyrolysis rate, indicating that example 5 decomposes more slowly and has better thermal stability.

Claims (10)

1. The single-component epoxy resin which is slowly solidified under water at high temperature is characterized by comprising epoxy matrix resin, a solidifying agent and a diluting agent, wherein the mass ratio of the epoxy matrix resin to the solidifying agent is 1 (0.3-1), the mass of the diluting agent is 5-20% of the mass of the epoxy matrix resin, the chemical structure of the solidifying agent is shown as a formula 1,
in the formula 1, the components are mixed,R 1 and R is 3 Selected from one of phenyl, furyl and methyl, R 1 And R is 3 The same; r is R 2 And R is 4 One selected from acetonyl, o-hydroxyphenyl and benzoylmethyl, R 2 And R is 4 May be the same or different; the curing agent is prepared by the following method:
(1) Fully dissolving 4, 4-diaminodiphenyl methane in an organic solvent under ice bath condition to obtain a solution;
(2) Sequentially dripping aldehyde and a compound with active hydrogen into the solution obtained in the step (1), and fully stirring and uniformly mixing; the molar ratio of the compound with active hydrogen, aldehyde and 4, 4-diaminodiphenyl methane is (2-4): 2-2.2): 1;
(3) And (3) adding a catalyst into the mixture obtained in the step (2), reacting for 24-48 hours at room temperature, and performing post-treatment to obtain the curing agent.
2. The underwater high temperature slow curing one-component epoxy resin of claim 1, wherein the epoxy matrix resin is at least one of bisphenol a type epoxy resin E44, bisphenol a type epoxy resin E51, bisphenol F type epoxy resin, N' -tetraepoxypropyl-4, 4-diaminodiphenyl methane and glycidylamine type epoxy resin; the diluent is at least one of n-butyl glycidyl ether and phenyl glycidyl ether.
3. The preparation method of the underwater high-temperature slow-curing single-component epoxy resin is characterized in that the single-component epoxy resin is obtained by mechanically stirring epoxy matrix resin, curing agent and diluent according to mass ratio and removing bubbles by vacuum pumping; the preparation method of the curing agent comprises the following steps of:
(1) Fully dissolving 4, 4-diaminodiphenyl methane in an organic solvent under ice bath condition to obtain a solution;
(2) Sequentially dripping aldehyde and a compound with active hydrogen into the solution obtained in the step (1), and fully stirring and uniformly mixing;
(3) And (3) adding a catalyst into the mixture obtained in the step (2), reacting for 24-48 hours at room temperature, and performing post-treatment to obtain the curing agent.
4. The application of the underwater high-temperature slow-curing single-component epoxy resin in the field of water shutoff and profile control of high-temperature oil fields.
5. An epoxy resin system curing agent is characterized in that the chemical structure of the curing agent is shown in the following formula 1:
in formula 1, R 1 And R is 3 Is selected from one of hydrogen atom, phenyl, furyl and methyl, R 1 And R is 3 May be the same or different; r is R 2 And R is 4 One selected from acetonyl, o-hydroxyphenyl and benzoylmethyl, R 2 And R is 4 May be the same or different;
the curing agent is prepared by the following method:
(1) Fully dissolving 4, 4-diaminodiphenyl methane in an organic solvent under ice bath condition to obtain a solution;
(2) Sequentially dripping aldehyde and a compound with active hydrogen into the solution obtained in the step (1), and fully stirring and uniformly mixing; the molar ratio of the compound with active hydrogen, aldehyde and 4, 4-diaminodiphenyl methane is (2-4): 2-2.2): 1;
(3) And (3) adding a catalyst into the mixture obtained in the step (2), reacting for 24-48 hours at room temperature, and performing post-treatment to obtain the curing agent.
6. The use of the curing agent of claim 5 in an epoxy resin system.
7. The method for preparing the curing agent according to claim 5, wherein the method for preparing the curing agent comprises the following steps:
(1) Fully dissolving 4, 4-diaminodiphenyl methane in an organic solvent under ice bath condition to obtain a solution;
(2) Sequentially dripping aldehyde and a compound with active hydrogen into the solution obtained in the step (1), and fully stirring and uniformly mixing;
(3) And (3) adding a catalyst into the mixture obtained in the step (2), reacting for 24-48 hours at room temperature, and performing post-treatment to obtain the curing agent.
8. The process according to claim 7, wherein the molar amount of catalyst is 5 to 20% of the molar amount of 4, 4-diaminodiphenylmethane.
9. The method of claim 7, wherein the active hydrogen-bearing compound is at least one of acetone, acetophenone, and phenol; the aldehyde is at least one of formaldehyde aqueous solution with the mass concentration of 37%, furfural, benzaldehyde and acetaldehyde; the catalyst is at least one of hydrochloric acid, sulfamic acid, bismuth chloride and anhydrous aluminum chloride; the organic solvent is at least one of absolute ethyl alcohol, tetrahydrofuran, 1, 4-dioxane, acetone and dimethyl sulfoxide.
10. A one-component epoxy resin cured product is characterized in that the one-component epoxy resin cured product is obtained by heating and curing the underwater high-temperature slow-curing one-component epoxy resin according to claim 1.
CN202210939125.5A 2022-08-05 2022-08-05 Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof Active CN115340749B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210939125.5A CN115340749B (en) 2022-08-05 2022-08-05 Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210939125.5A CN115340749B (en) 2022-08-05 2022-08-05 Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115340749A CN115340749A (en) 2022-11-15
CN115340749B true CN115340749B (en) 2023-08-01

Family

ID=83950121

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210939125.5A Active CN115340749B (en) 2022-08-05 2022-08-05 Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115340749B (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3600362A (en) * 1969-06-12 1971-08-17 Furane Plastics Epoxy resin cured with liquid resinous amine curing agents
JP4463345B2 (en) * 1999-06-18 2010-05-19 関西ペイント株式会社 Paint composition
CN101348563B (en) * 2008-09-17 2010-11-10 中昊晨光化工研究院 Tough mannich base curing agent and preparation thereof
JP5093904B2 (en) * 2009-01-29 2012-12-12 日本化薬株式会社 Epoxy resin and production method thereof
CN102093671B (en) * 2010-12-30 2012-12-26 株洲南车时代电气股份有限公司 Epoxy resin composite and pouring method thereof
CN102504670A (en) * 2011-10-27 2012-06-20 北京东方雨虹防水技术股份有限公司 Permeable epoxy resin waterproof coating for concrete
CN102617983B (en) * 2012-04-11 2014-01-29 中科院广州化灌工程有限公司 Environment-friendly high-performance furfural-free epoxy chemical grouting material, preparation method and application
CN103819144A (en) * 2013-12-30 2014-05-28 天津科技大学 Preparation method of epoxy mortar for filling ocean oil and gas pipeline
CN107151114A (en) * 2017-05-02 2017-09-12 中水电第十工程局（郑州）有限公司 A kind of preparation method of epoxy concrete for underwater concrete defect repair
WO2019185567A1 (en) * 2018-03-30 2019-10-03 Evonik Degussa Gmbh Phenalkamine epoxy curing agents and epoxy resin compositions containing the same

Also Published As

Publication number Publication date
CN115340749A (en) 2022-11-15

Similar Documents

Publication Publication Date Title
Li et al. Thermally reversible and self‐healing novolac epoxy resins based on Diels–Alder chemistry
CN109438712B (en) Boron modified polycarbosilane resin and preparation method thereof
CN109852241A (en) A kind of heat-resisting selfreparing polysiloxanes-epoxy resin composite material coating and preparation method thereof
CN113292719B (en) Polyamide resin containing imide structure and preparation method thereof
CN116283835B (en) Biomass epoxy monomer, self-curing epoxy resin and preparation method thereof
CN110591091A (en) Main chain type benzoxazine containing daidzein group and preparation method thereof
CN105001824A (en) Room temperature curing ultralow temperature epoxy sealant and preparation method thereof
CN113683777A (en) Preparation method of epoxy-terminated hyperbranched polyether sulfone and application of epoxy-terminated hyperbranched polyether sulfone in salt spray-resistant epoxy resin
CN115340749B (en) Underwater high-temperature slow-curing single-component epoxy resin system and preparation method and application thereof
CN113174031B (en) Internal toughening nanoparticle curing agent, epoxy resin matrix and preparation method of internal toughening nanoparticle curing agent
CN111925780B (en) Preparation method of high-temperature-resistant high-strength plugging agent for plugging of oil and gas well
CN113717339A (en) Curing agent for reducing volatile matters of adhesive
CN116445144B (en) Low-shrinkage high-strength plant-based resin plugging agent and preparation method thereof
CN116789618A (en) Biomass epoxy monomer, biomass self-repairing epoxy resin and preparation method
Chen et al. Synthesis of self‐healing soybean oil‐based waterborne polyurethane based on Diels–Alder reaction
Tian et al. Investigation of structure/property relationships of polytriazoles
CN111826117B (en) Two-component polyurethane sealing heat-insulating glue
CN115386066A (en) High-performance bio-based thermosetting epoxy resin and preparation method thereof
CN112898516B (en) Phenolic aldehyde modified amine and preparation method thereof
CN113480727A (en) Preparation method of modified polyether amine epoxy resin curing agent
CN110862652B (en) Low-shrinkage resin cured at room temperature and preparation method thereof
Rashid et al. A vanillin-derived hardener for recyclable, degradable and self-healable high-performance epoxy vitrimers based on transimination
TWI743759B (en) Preparation of novel five-carbon ring heterobifunctional epoxy monomers and polypenta-carbon ring polymer oligomers with epoxy side chains from dicyclopentadiene
CN116333586B (en) High heat-resistant impregnating varnish and preparation method and application thereof
CN116606410A (en) High-free-volume high-heat-resistance benzoxazine resin and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant