CN115160542B - Degradable water-absorbing epoxy resin and preparation method and application thereof - Google Patents
Degradable water-absorbing epoxy resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN115160542B CN115160542B CN202210949406.9A CN202210949406A CN115160542B CN 115160542 B CN115160542 B CN 115160542B CN 202210949406 A CN202210949406 A CN 202210949406A CN 115160542 B CN115160542 B CN 115160542B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- reaction system
- reaction
- absorbing
- degradable
- 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
Links
Images
Classifications
-
- 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
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- 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 a degradable water-absorbing epoxy resin, a preparation method and application thereof, wherein the degradable water-absorbing epoxy resin consists of hydantoin epoxy resin, a comonomer which can be selectively added, a cationic curing agent and a catalyst which can be selectively added; in the preparation process, the degradable water-absorbing epoxy resin can be directly pumped into the underground after a liquid mixture is obtained by mixing hydantoin epoxy resin, a comonomer, a cationic curing agent and a catalyst, so as to be used as a plugging agent to realize a cured plugging target layer, or after the liquid mixture is obtained by mixing hydantoin epoxy resin, the comonomer, the cationic curing agent and the catalyst, the solid which can be used as water-absorbing temporary plugging particles is obtained by re-curing, so that the plugging of stratum cracks is realized; the degradable water-absorbing epoxy resin has both water-absorbing performance and degradability under the action of sodium hydroxide, and has the advantages of simple preparation method, easily controlled conditions and low cost.
Description
Technical Field
The invention relates to the technical field of geothermal well development, in particular to degradable water-absorbing epoxy resin, a preparation method and application thereof.
Background
Degradable materials have important applications in geothermal well development. Among them, well plugging and stratum plugging are two important fields of application. The main reason for the leakage in drilling is that the formation cracks develop, so that the drilling fluid is leaked, and the reservoir is damaged.
Conventional plugging methods pump the gel rigid particles into the formation. Plugging is performed by the water absorption expansion effect of the hydrogel or by bridging the cracks by using rigid particles. However, conventional formation plugging agents have the disadvantage of being generally non-degradable, resulting in contamination of the formation and affecting subsequent recovery processes. Therefore, on the basis of the rigid particle plugging material, technicians develop degradable plugging materials, including degradable plugging gel and degradable rigid plugging materials; the degradable plugging gel mainly comprises guar gum type degradable natural polymers, and can be degraded under the action of biological enzymes, ammonium persulfate and other oxidizing agents; it is also reported in part that the degradable plugging material is a hydrogel formed by crosslinking a polyacrylamide polymer with a special crosslinking agent, and can be degraded under the action of ammonium persulfate; the degradable rigid plugging material mainly comprises polymers containing ester bonds in molecular chains such as polylactic acid, polyglycolic acid and the like, and is degraded through the rupture of the ester bonds under the action of strong alkali; it has also been reported in part that an ester bond can be introduced into an epoxy resin, for example, by reacting an anhydride-based curing agent with the epoxy resin to form an epoxy resin having an ester bond, or degradation can be performed under certain conditions.
For stratum plugging, the plugging principle is similar to plugging, and the degradable gel substance or the epoxy substance is pumped to the well to be solidified in the well shaft to form a rubber plug, so that the plugging of a target horizon is realized. The degradable gel and the degradable polymer containing ester bonds have the advantages that the degradable gel can absorb water and expand in the ground due to the fact that the degradable gel contains hydrophilic groups such as amide bonds, and therefore cracks with different sizes can be easily plugged. The following advantages are obtained for materials such as degradable epoxy resins and polyglycolic acid. First: the mechanical strength of the gel is far stronger than that of the degradable gel, but the gel is difficult to absorb a large amount of water and deform due to the fact that the gel contains a large amount of ester bonds, so that the gel meets the requirements of plugging cracks without size and morphology. Secondly, especially for epoxy polymers, due to the obvious thermal expansion and cold contraction phenomena, when the epoxy resin is used for filling and sealing in a shaft to seal a stratum, the epoxy polymer is very likely to be peeled off from the wall of the shaft in the use process due to the temperature difference generated in the construction process, so that the sealing is lost. In addition, mechanical vibrations generated during the construction process may also cause the epoxy resin to delaminate from the wellbore wall. Since bisphenol a type epoxy resin is generally insoluble in water, and a large amount of hydrophobic ester bonds are introduced to realize degradability, the rubber plug or the rigid plugging particles cannot absorb water and expand by utilizing water in the stratum or the shaft so as to realize plugging. Thirdly, gel substances are usually broken by using substances such as over ammonium persulfate, and the broken gel products are acidic and are easy to corrode a shaft at high temperature. And ester bonds, which can degrade under alkaline conditions.
Disclosure of Invention
The invention aims to provide a water-absorbing epoxy resin with degradability.
The invention also aims to provide a preparation method of the water-absorbing epoxy resin.
The invention also aims to provide an application of the water-absorbing epoxy resin as a degradable plugging agent.
The invention also aims to provide an application of the water-absorbing epoxy resin as a degradable temporary plugging agent.
For this purpose, the technical scheme of the invention is as follows:
a degradable water-absorbing epoxy resin, which comprises 2.7 parts of hydantoin epoxy resin, 0 to 0.3 part of comonomer, 0.081 to 0.054 part of cation curing agent and 0 to 0.027 part of catalyst by weight; wherein the comonomer is at least one of glucose, gluconolactone or isosorbide; the cationic curing agent is at least one of boron trifluoride and boron trifluoride ethylamine, boron trifluoride diethyl etherate; the catalyst is tertiary amine or quaternary ammonium salt.
Wherein, when the reaction system comprises the comonomer, the addition amount of the comonomer is 0.135 to 0.3 part.
Preferably, the tertiary amine is N, N-dimethylbenzylamine; the quaternary ammonium salt is tetrabutylammonium bromide.
The degradable water-absorbing epoxy resin has both water absorption and degradability after curing is completed, so that the degradable water-absorbing epoxy resin can be used as a degradable temporary plugging agent or a degradable plugging agent based on the special property.
When the degradable water-absorbing epoxy resin can be used as a degradable temporary plugging agent, the degradable water-absorbing epoxy resin can be prepared by the following three modes; in particular, the method comprises the steps of,
a preparation method 1 of degradable water-absorbing epoxy resin for degradable temporary plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent into the reaction system, and continuously stirring at 110-120 ℃ for 2-20 min to prepare a liquid mixture;
s3, pouring the liquid mixture prepared in the step S2 into a plurality of moulds, and placing the moulds in an oven at 110-120 ℃ for 10 hours to complete the curing reaction.
A preparation method 2 of degradable water-absorbing epoxy resin for degradable temporary plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent and a catalyst into the reaction system, and continuously stirring at 110-120 ℃ for at least 20min to prepare a liquid mixture;
s3, pouring the liquid mixture prepared in the step S2 into a plurality of moulds, and placing the moulds in an oven at 110-120 ℃ for 10 hours to complete the curing reaction.
A preparation method 3 of degradable water-absorbing epoxy resin for degradable temporary plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 100-120 ℃ to obtain an epoxy reaction system;
s2, adding a catalyst into the reaction system, and continuously stirring at 100-120 ℃ for 12-120 min to prepare a reddish brown liquid mixture;
s3, adding a cationic curing agent into the reaction system, and continuously stirring for 2min at 110-120 ℃ to prepare a reddish brown liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 110-120 ℃ for 10 hours to complete the curing reaction.
The degradable water-absorbing epoxy resin obtained based on the three preparation methods is used as a degradable temporary plugging agent, and the specific application method is as follows: the cured degradable water-absorbing epoxy resin is prepared into plugging agents with different particle sizes, the plugging agents are used for temporary plugging in a well with the temperature range of 80-200 ℃ in a particle grading mode, and alkali liquor is poured into the well after temporary plugging construction is completed to realize plugging removal.
When the degradable water-absorbing epoxy resin can be used as a degradable plugging agent, the degradable water-absorbing epoxy resin can be prepared by the following three modes; in particular, the method comprises the steps of,
a preparation method 1 of degradable water-absorbing epoxy resin for a degradable plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent into the reaction system, and continuously stirring at 110-120 ℃ for 2-20 min to obtain a liquid mixture.
A preparation method 2 of degradable water-absorbing epoxy resin for a degradable plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent and a catalyst into the reaction system, and continuously stirring at 110-120 ℃ for at least 20min to prepare a liquid mixture.
A preparation method 3 of degradable water-absorbing epoxy resin for a degradable plugging agent comprises the following preparation steps:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 100-120 ℃ to obtain an epoxy reaction system;
s2, adding a catalyst into the reaction system, and continuously stirring at 100-120 ℃ for 12-120 min to prepare a reddish brown liquid mixture;
s3, adding a cationic curing agent into the reaction system, and continuously stirring for 2min at 110-120 ℃ to obtain a reddish brown liquid mixture.
The degradable water-absorbing epoxy resin obtained based on the three preparation methods is used as a degradable plugging agent, and the specific application method is as follows: pumping the liquid mixture into a shaft at room temperature, solidifying the liquid mixture in the shaft with the underground environment temperature of 110-120 ℃ and plugging the shaft; after the construction is completed, lye is poured into the shaft to realize deblocking.
Compared with the prior art, the degradable water-absorbing epoxy resin has both water absorption performance and degradability under the action of sodium hydroxide, and the preparation method is simple, the conditions are easy to control, and the cost is low; when the degradable water-absorbing epoxy resin is used as a degradable liquid rubber plug, a curing and plugging target layer can be realized in a shaft at 110-120 ℃, and after curing, the rubber plug can be endowed with self-healing property by water-absorbing expansion after gaps appear between the rubber plug and the shaft wall, and alkali liquid is pumped to degrade the rubber plug after construction is finished; when the degradable water-absorbing epoxy resin is used as water-absorbing temporary plugging particles, the water-absorbing temporary plugging particles can be prepared into different particle sizes to meet the requirement of particle grading, and can be used for plugging formation cracks by water absorption expansion in the formation at 80-200 ℃, and after construction, alkali liquid is pumped to remove temporary plugging; in conclusion, the degradable water-absorbing epoxy resin has good market application and popularization prospects.
Drawings
FIG. 1 is a flow chart of the preparation of the degradable water-absorbing epoxy resin of the present invention;
FIG. 2 (a) is a photograph of the degradable water absorbing epoxy resin of example 4 of the present invention when degraded in 20wt.% sodium hydroxide solution at 120℃for 0 h;
FIG. 2 (b) is a photograph of the degradable water absorbing epoxy resin of example 4 of the present invention when degraded in 20wt.% sodium hydroxide solution at 120℃for 8 hours;
FIG. 2 (c) is a photograph of the degradable water absorbing epoxy resin of example 4 of the present invention when degraded in a 20wt.% sodium hydroxide solution at 120℃for 12 hours;
FIG. 2 (d) is a photograph of the degradable water absorbing epoxy resin of example 4 of the present invention when degraded in 20wt.% sodium hydroxide solution at 120℃for 16 hours;
FIG. 3 is a photograph showing the degradable water-absorbing epoxy resin of example 5 of the present invention after swelling at 200℃for 4 hours with water absorption, and degradation at 200℃for 4 hours.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific examples, which are in no way limiting.
Example 1
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin into a reaction bottle at room temperature, and under the stirring condition, raising the temperature of the reaction system to 120 ℃ to obtain an epoxy reaction system;
among them, hydantoin epoxy resin, namely 5, 5-dimethyl-1, 3-di (oxiranylmethyl) imidazolidine-2, 4-dione, specifically hydantoin epoxy resin (epoxy value of 0.7-0.74) supplied by Shenzhen Kagaku chemical Co., ltd was used, and the following examples and comparative examples were the same.
S2, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to dissolve the boron trifluoride monoethylamine into the epoxy system to prepare a pale yellow liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a yellow cylindrical product.
Example 2
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of glucose into a reaction bottle at room temperature, and raising the temperature of a reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring for 20min at 120 ℃ to prepare a reddish brown liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold had lost fluidity at the curing temperature, and cured to form a reddish brown cylindrical product indicating that caramelization had occurred during the reaction.
Example 3
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of glucose into a reaction bottle at room temperature, and raising the temperature of a reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.081g of boron trifluoride monoethylamine and 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 20min at 120 ℃ to prepare a reddish brown liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold had lost fluidity at the curing temperature, and cured to form a reddish brown cylindrical product, indicating that caramelization was emitted during the reaction.
Example 4
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of glucose into a reaction bottle at room temperature, and raising the temperature of a reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 40min at 120 ℃ to prepare a reddish brown liquid intermediate product;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to prepare a reddish brown liquid intermediate product;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Example 5
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of glucose into a reaction bottle at room temperature, and raising the temperature of a reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 120min at 120 ℃ to prepare a reddish brown liquid intermediate product;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to prepare a reddish brown liquid intermediate product;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours for curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Example 6
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin into a reaction bottle at room temperature, and under the stirring condition, raising the temperature of the reaction system to 120 ℃ to obtain an epoxy reaction system;
s2, adding 0.054g of boron trifluoride monoethylamine into the reaction system, and continuously stirring for 2min at 120 ℃ to dissolve the boron trifluoride monoethylamine into the epoxy system to prepare a liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a yellow cylindrical product.
Example 7
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 3.31g of hydantoin epoxy resin and 0.5517g of glucose into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.0331g of N, N-dimethylbenzylamine into the reaction system, and continuously stirring at 120 ℃ for 12min to obtain a reddish brown liquid mixture;
s3, adding 0.0993g of boron trifluoride monoethylamine into the reaction system, and continuously stirring for 2min at 120 ℃ to obtain a reddish brown liquid mixture
S4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Example 8
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.135g of gluconolactone into a reaction bottle at room temperature, and raising the temperature of the reaction system to 100 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.0135g of tetrabutylammonium bromide into the reaction system, and continuously stirring at 100 ℃ for 100min to obtain a reddish brown liquid mixture;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to obtain a reddish brown liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Example 9
An epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of isosorbide into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.081g of boron trifluoride monoethylamine and 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 2min at 120 ℃ to prepare a yellow liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a yellow cylindrical product.
Example 10
An epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of isosorbide into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 20min at 120 ℃ to prepare yellow homogeneous liquid;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to prepare a yellow liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a yellow cylindrical product.
Example 11
A degradable water-absorbing epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.135g of glucose into a reaction bottle at room temperature, and raising the temperature of a reaction system to 110 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 14min at 110 ℃ to obtain a reddish brown liquid mixture;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 110 ℃ for 2min to obtain a reddish brown liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 110 ℃ for 10 hours to complete the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Comparative example 1
An epoxy resin is prepared by the following method:
s1, adding 2.7g of bisphenol A diglycidyl ether (epoxy value 0.51) and 0.2186g of glucose into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the condition of stirring to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 40min at 120 ℃ to obtain a reddish brown liquid mixture;
s3, adding 0.081g of boron trifluoride monoethylamine into the reaction system, and continuously stirring at 120 ℃ for 2min to prepare a liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S4, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a reddish brown cylindrical product.
Comparative example 2
An epoxy resin is prepared by the following method:
s1, adding 2.7g of bisphenol A diglycidyl ether (with an epoxy value of 0.51) and 0.2186g of isosorbide into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the condition of stirring to obtain an epoxy reaction system;
s2, adding 0.081g of boron trifluoride monoethylamine and 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 2min at 120 ℃ to prepare a yellow liquid mixture;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to finish the curing reaction; through step S3, the liquid in each mold has lost fluidity at the curing temperature, and is cured to form a yellow cylindrical product.
Comparative example 3
An epoxy resin is prepared by the following method:
s1, adding 1.0g of hydantoin epoxy resin, 1.2g of methyl hexahydrophthalic anhydride and 0.02g of N, N-dimethylbenzylamine into a reaction bottle at room temperature, and stirring for 5min at room temperature to prepare a homogeneous solution;
s2, pouring the liquid prepared in the step S1 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S2, the liquid in each mold loses fluidity and solidifies to form a cylindrical product.
Comparative example 4
An epoxy resin is prepared by the following method:
s1, adding 1.0g of bisphenol A diglycidyl ether (epoxy value is 0.51), 0.8g of methyl hexahydrophthalic anhydride and 0.02g of N, N-dimethylbenzylamine into a reaction bottle at room temperature, and stirring for 5min at room temperature to prepare a homogeneous solution;
s2, pouring the liquid prepared in the step S1 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S2, the liquid in each mold loses fluidity and solidifies to form a cylindrical product.
Comparative example 5
An epoxy resin is prepared by the following method:
s1, adding 2.0g g bisphenol A diglycidyl ether (epoxy value 0.51) and 0.06g boron trifluoride monoethylamine into a reaction bottle at room temperature, and stirring for 5min at room temperature to prepare a homogeneous solution;
s2, pouring the liquid prepared in the step S1 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 10 hours to complete the curing reaction; through step S2, the liquid in each mold loses fluidity and solidifies to form a cylindrical product.
Comparative example 6
An epoxy resin is prepared by the following method:
s1, adding 2.7g of hydantoin epoxy resin and 0.3g of isosorbide into a reaction bottle at room temperature, and raising the temperature of the reaction system to 120 ℃ under the stirring condition to obtain an epoxy reaction system;
s2, adding 0.027g of tetrabutylammonium bromide into the reaction system, and continuously stirring for 40min at 120 ℃ to prepare a reddish brown homogeneous liquid;
s3, pouring the liquid prepared in the step S2 into a plurality of moulds, and placing the moulds in a baking oven at 120 ℃ for 40 hours, wherein the product still has fluidity, i.e. the curing reaction cannot occur due to lack of curing agent.
Comparative example 7
An epoxy resin is prepared by the following method:
s1, stirring 2mL of dimethyl sulfoxide, 0.3g of glucose and 0.027g of tetrabutylammonium bromide for 5min at room temperature to prepare colorless transparent liquid, heating to 120 ℃ while stirring, and reacting for 20min; the color of the reaction system is not changed in the whole process of the step;
s2, adding 2.7g of hydantoin epoxy resin into the reaction system, and continuously reacting for 15min at 120 ℃. The reaction system turned reddish brown.
Comparative example 8
2.7g of hydantoin epoxy resin and 0.3g of glucose are added into a reaction bottle at room temperature, the temperature of the reaction system is increased to 120 ℃ under the stirring condition, and the reaction is carried out for 20min without change of the reaction system.
Performance test:
(one) Water absorption test:
taking any one of the cylindrical products prepared in examples 1 to 11 and comparative examples 1 to 5 and measuring the diameter thereof, then vertically placing the cylindrical product into a sample bottle with an inner diameter of 20mm, and adding clear water into the sample bottle to submerge the cylindrical product with the clear water; then, placing the sample bottle into a high-pressure reaction kettle, and placing the sample bottle at a specified degradation temperature to perform water absorption swelling reaction; in the process, the autoclave is cooled every 4 hours, so as to take out the cylindrical product in the reaction bottle and measure the diameter, and then the product is vertically put back into the sample bottle and is continuously put back into the autoclave, and the reaction is continuously carried out at the same temperature until the designed reaction time is reached.
The specific test results are shown in table 1 below.
Table 1:
from the test results of table 1 above, it can be seen that the cured hydantoin epoxy resin has a certain water absorption capacity. It can be seen that the degradable epoxy resin prepared by the method has water absorption. In addition, in the case of comparative example 3 and comparative example 4 in which hydantoin epoxy resin or other epoxy resin was used and the degradable function was expected to be increased by introducing a large amount of ester bonds, the product prepared in this way did not have water absorption property because the ester bonds were hydrophobic.
In addition, in order to further determine the applicable temperature range of the degradable water-absorbing epoxy resin, the degradable water-absorbing epoxy resin prepared in the example 5 is subjected to a water-absorbing swelling experiment in an environment of 80 ℃; specifically, taking any one of the prepared cylindrical products and measuring the diameter of the cylindrical products, vertically placing the cylindrical products into a sample bottle with the inner diameter of 20mm, and adding clear water into the sample bottle to submerge the cylindrical products by the clear water; then, placing the sample bottle in a water bath kettle with the temperature of 80 ℃ to enable the sample bottle to be subjected to water absorption swelling reaction at a specified degradation temperature, taking out a cylindrical product in the reaction bottle after water absorption for 11 hours, and measuring the diameter; through testing, the diameter of the cylindrical solid before the experiment is 7.8mm, and after 11 hours, the diameter of the cylindrical solid is increased to 8.6mm, so that the degradable water-absorbing epoxy resin can also show water-absorbing swelling property at 80 ℃.
(II) degradation test:
taking any one of the cylindrical products prepared in examples 1 to 11 and comparative examples 1 to 5 as a test sample, measuring the diameter of each test sample, vertically placing the cylindrical product into a sample bottle with an inner diameter of 20mm, and adding a sufficient amount of 20wt.% NaOH aqueous solution into the sample bottle to enable the NaOH aqueous solution to just submerge the cylindrical product; then, placing the sample bottle into a high-pressure reaction kettle, and placing the sample bottle at a specified degradation temperature for degradation reaction; in the degradation process, cooling the high-pressure reaction kettle every 4 hours to take out a cylindrical product in the reaction bottle and measure the diameter, then vertically returning the product to the sample bottle and continuously returning the product to the high-pressure reaction kettle, and continuously carrying out degradation reaction at the same degradation temperature; among them, for the product of example 5, a sample having a diameter of 9.4mm was used which swelled by water absorption at 200℃for 4 hours. In addition, for the solid products prepared in comparative examples 4 and 5, similar testing methods are adopted for different degradation solutions, but different degradation solutions are adopted, and in comparative example 4, a mixed degradation solution prepared by 15g of water and 5g of dimethyl sulfoxide and a mixed degradation solution prepared by 15g of 20wt.% NaOH solution and 5g of dimethyl sulfoxide are adopted respectively; comparative example 5 used a mixed degradation solution of 15g of 20wt.% NaOH solution with 5g of dimethyl sulfoxide.
The specific test results are shown in table 2 below.
Table 2:
from the test results of Table 2 above, it can be seen that the products prepared in examples 1-11 all degraded under the action of 20wt.% aqueous NaOH.
Meanwhile, it can also be seen from the test results of Table 2 that the product of example 1 was reduced from 7.8mm to 7.7mm in diameter after 8 hours of degradation, and the product of example 2 was reduced from 7.9mm to 7.7mm in diameter after 4 hours of degradation, and it was found that the degradation rate of the product of example 2 was significantly faster than that of example 1, which indicated that the degradation performance of the cured and formed degradable epoxy resin was better after the hydantoin epoxy resin was structurally modified with glucose.
The product preparation of example 3 was different from the product preparation of example 4; wherein, the product of the example 2 is obtained by adding boron trifluoride monoethylamine into an epoxy reaction system and then curing, the product of the example 3 is obtained by simultaneously adding boron trifluoride monoethylamine and tetrabutylammonium bromide into the same epoxy reaction system and then curing, and the product of the example 4 is obtained by adding tetrabutylammonium bromide into the same epoxy reaction system and then adding boron trifluoride monoethylamine and then curing; from the performance test of the three products, it can be seen that the performances of the three products obtained by different preparation modes are different. The water-swelling properties of the products of example 2 and example 3 were almost the same, while the water-swelling properties of the product of example 4 were significantly better than those of the products of example 2 and example 3; whereas the degradation rates of the products of example 2, example 3 and example 4 were progressively faster in terms of degradation performance, it can be seen that the degradation performance of the product of example 4 is better than that of example 2, and that of example 2 is better than that of example 3; meanwhile, compared with comparative example 5, when tetrabutylammonium bromide is only added in the preparation process of the product and boron trifluoride monoethylamine is not added, corresponding degradable epoxy resin cannot be obtained by curing; in summary, in the preparation process of the degradable epoxy resin, boron trifluoride monoethylamine is taken as a cationic curing agent, both boron trifluoride monoethylamine and hydantoin epoxy resin are the necessary components for preparing the product, tetrabutylammonium bromide is taken as an anionic catalyst and is a component which can be selectively added, but the degradation performance of the epoxy resin can be obviously improved by adding tetrabutylammonium bromide, and compared with the method that the method is simultaneously added into an epoxy reaction system, the degradation performance of the product obtained by adding tetrabutylammonium bromide into the epoxy reaction system for stirring and then adding boron trifluoride monoethylamine for stirring and curing is better.
FIG. 2 (a) is a photograph showing a product of the degradable water-absorbing epoxy resin prepared in example 4 before degradation, from which it can be seen that the degradable water-absorbing epoxy resin is a reddish brown cylindrical solid; as shown in fig. 2 (b), which is a photograph of the degradable water-absorbing epoxy resin prepared in example 4 when it is degraded for 8 hours, it can be seen from the figure that the diameter of the degradable water-absorbing epoxy resin is significantly reduced; FIG. 2 (c) is a photograph showing the degradable water-absorbing epoxy resin prepared in example 4 degraded for 12 hours, from which it can be seen that the diameter of the degradable water-absorbing epoxy resin continues to decrease; as shown in FIG. 2 (d), which is a photograph showing the degradation of the degradable water-absorbing epoxy resin prepared in example 4 for 16 hours, it can be seen that the degradable water-absorbing epoxy resin is hardly reduced, and the main component in the sample bottle is reddish brown liquid.
As a further experimental study of example 4, the stirring reaction time of example 5 after tetrabutylammonium bromide is added in the preparation process of the degradable epoxy resin, and the water absorption swelling performance and degradation performance of the corresponding prepared product are better, because after the step S2 of example 4 is finished, no glucose remains at the bottom of the reaction bottle, a homogeneous liquid mixture is completely formed, a plurality of hydroxyl groups exist on the glucose molecular structure, and according to the reaction addition, it can be deduced that only part of hydroxyl groups in the glucose molecule react at the moment, so that along with the extension of the reaction time, epoxy groups still react with the hydroxyl groups on glucose continuously, thereby giving the product better water absorption and degradation performance. Meanwhile, as a comparative reference, the product of example 5, which was soaked in clear water at 200 ℃ for 4 hours to be swelled by water absorption, was used as a test sample, and a degradation experiment was performed in an aqueous sodium hydroxide solution at 200 ℃ so that the product was completely degraded and disappeared after 4 hours, and the degradation liquid was reddish brown.
The degradation property of the degradable water-absorbing epoxy resin prepared in example 5 at 80 ℃ was also investigated in the same way as the water-absorbing swelling property test; specifically, taking any one of the prepared cylindrical products as a test sample, measuring the diameter of each test sample, vertically placing the cylindrical product into a sample bottle with the inner diameter of 20mm, and adding a sufficient amount of 20wt.% NaOH aqueous solution into the sample bottle to enable the NaOH aqueous solution to just submerge the cylindrical product; then, placing the sample bottle into a water bath kettle, and placing the sample bottle at a specified degradation temperature for degradation reaction; after degradation for 11 hours, taking out the cylindrical product in the reaction bottle and measuring the diameter; through experiments, the initial diameter of the cylindrical product is 7.8mm, and the diameter of the cylindrical product is reduced to 6.9mm after 11h degradation in 20wt.% NaOH aqueous solution at 80 ℃, so that the application range of the degradable water-absorbing epoxy resin can be enlarged to 80-200 ℃ when the degradable water-absorbing epoxy resin is used as a temporary plugging agent.
In example 6, the boron trifluoride monoethylamine was reduced in the amount and the water absorption and degradation properties were hardly changed when boron trifluoride monoethylamine was small as compared with example 1.
Compared with example 4, in the degradable epoxy resin prepared in example 7, tetrabutylammonium bromide is replaced by N, N-dimethylbenzylamine, the stirring time of the N, N-dimethylbenzylamine in an epoxy reaction system is slightly shortened, the product has water swelling property and degradability, and the water swelling property and degradability are greatly improved compared with those of example 4.
In comparison with example 4, the degradable epoxy resin prepared in example 8, in which glucose is replaced with gluconolactone, has both water-swelling property and degradability, and has water-swelling property slightly lower than that of the product of example 4, and degradability slightly better than that of the product of example 4.
In the degradable epoxy resins prepared in example 9 and example 10, glucose was replaced with isosorbide, and the corresponding obtained products had both water swelling property and degradability; the products of the degradable epoxy resins prepared in example 9 and example 10 were yellow in color compared to the glucose modified products. Degradation performance is reduced. In addition, when the degradable epoxy resin was modified with isosorbide as compared with example 2 and example 4, it was used to add only boron trifluoride monoethylamine to the epoxy reaction system and cure it to obtain a product whose degradability was superior to that of the product obtained by adding tetrabutylammonium bromide first and then boron trifluoride monoethylamine to the same epoxy reaction system and curing it.
In the epoxy resins prepared in comparative examples 1 and 2, hydantoin epoxy resin is replaced by bisphenol A diglycidyl ether, and after the corresponding prepared products are degraded for 8 hours, the degradation solution is still colorless and transparent, and after the degradation is continued for a period of time, no new change exists, so that the products cannot be degraded in a NaOH aqueous solution at 120 ℃.
Comparative example 3 and comparative example 4 epoxy resins were prepared by modifying hydantoin epoxy resin and bisphenol a diglycidyl ether with methylhexahydrophthalic anhydride and curing them, respectively, i.e., the objective of increasing degradability was achieved by introducing a large amount of ester bonds, however, the modified products had degradability but no significant diameter change in the water-swelling experiments.
In the epoxy resin prepared in comparative example 5, bisphenol a diglycidyl ether was reacted with boron trifluoride monoethylamine to effect cure molding, but the product was not degradable in strong sodium oxide solution.
In the hydantoin epoxy resin prepared in comparative example 6, boron trifluoride monoethylamine was not added, and the product of the reaction at 120℃for a long time could not be cured.
Comparative example 7 and comparative example 8 it can be seen that tetrabutylammonium bromide alone does not allow glucose to react at 120 c, only when glucose is present with hydantoin epoxy resin; in addition, tetrabutylammonium bromide alone cannot cure the epoxy resin, and boron trifluoride monoethylamine alone can not only cause glucose to undergo a color change reaction at 120 ℃, but also cure the epoxy resin.
Claims (10)
1. The degradable water-absorbing epoxy resin is characterized by comprising 2.7 parts by weight of hydantoin epoxy resin, 0 to 0.3 part by weight of comonomer, 0.081 to 0.054 part by weight of cationic curing agent and 0 to 0.027 part by weight of catalyst; wherein the comonomer is at least one of glucose, gluconolactone or isosorbide; the cationic curing agent is at least one of boron trifluoride and boron trifluoride ethylamine, boron trifluoride diethyl etherate; the catalyst is tertiary amine or quaternary ammonium salt.
2. The degradable water-absorbing epoxy resin of claim 1, wherein the tertiary amine is N, N-dimethylbenzylamine; the quaternary ammonium salt is tetrabutylammonium bromide.
3. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent into the reaction system, and continuously stirring at 110-120 ℃ for 2-20 min to prepare a liquid mixture;
s3, pouring the liquid mixture prepared in the step S2 into a plurality of moulds, and placing the moulds in an oven at 110-120 ℃ for 10 hours to complete the curing reaction.
4. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent and a catalyst into the reaction system, and continuously stirring at 110-120 ℃ for at least 20min to prepare a liquid mixture;
s3, pouring the liquid mixture prepared in the step S2 into a plurality of moulds, and placing the moulds in an oven at 110-120 ℃ for 10 hours to complete the curing reaction.
5. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 100-120 ℃ to obtain an epoxy reaction system;
s2, adding a catalyst into the reaction system, and continuously stirring at 100-120 ℃ for 12-120 min to prepare a liquid mixture;
s3, adding a cationic curing agent into the reaction system, and continuously stirring for 2min at 110-120 ℃ to prepare a liquid mixture;
s4, pouring the liquid prepared in the step S3 into a plurality of moulds, and placing the moulds in a baking oven at 110-120 ℃ for 10 hours to complete the curing reaction.
6. Use of the degradable water-absorbing epoxy resin prepared by the preparation method of the degradable water-absorbing epoxy resin according to any one of claims 3 to 5 as a degradable temporary plugging agent, wherein the cured degradable water-absorbing epoxy resin is prepared into plugging agents with different particle sizes and is used for temporary plugging in a well with the temperature range of 80-200 ℃ in a particle grading manner; after temporary plugging construction is completed, alkali liquor is poured into the well to realize plugging removal.
7. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent into the reaction system, and continuously stirring at 110-120 ℃ for 2-20 min to obtain a liquid mixture.
8. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 110-120 ℃ to obtain an epoxy reaction system;
s2, adding a cationic curing agent and a catalyst into the reaction system, and continuously stirring at 110-120 ℃ for at least 20min to prepare a liquid mixture.
9. A process for the preparation of a degradable water-absorbing epoxy resin according to claim 1 or 2, characterized by the steps of:
s1, adding hydantoin epoxy resin into a reaction bottle or adding hydantoin epoxy resin and a comonomer into the reaction bottle at room temperature, and under the stirring condition, raising the temperature of a reaction system to 100-120 ℃ to obtain an epoxy reaction system;
s2, adding a catalyst into the reaction system, and continuously stirring at 100-120 ℃ for 12-120 min to prepare a liquid mixture;
s3, adding a cationic curing agent into the reaction system, and continuously stirring for 2min at 110-120 ℃ to prepare a liquid mixture.
10. Use of a degradable water-absorbing epoxy resin prepared by the method for preparing a degradable water-absorbing epoxy resin according to any one of claims 7-9 as a degradable plugging agent, characterized in that a liquid mixture is pumped into a well bore at room temperature, cured and plugged in the well bore at an ambient temperature of 110-120 ℃ downhole; after the construction is completed, lye is poured into the shaft to realize deblocking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210949406.9A CN115160542B (en) | 2022-08-09 | 2022-08-09 | Degradable water-absorbing epoxy resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210949406.9A CN115160542B (en) | 2022-08-09 | 2022-08-09 | Degradable water-absorbing epoxy resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115160542A CN115160542A (en) | 2022-10-11 |
| CN115160542B true CN115160542B (en) | 2023-05-23 |
Family
ID=83479928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210949406.9A Active CN115160542B (en) | 2022-08-09 | 2022-08-09 | Degradable water-absorbing epoxy resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115160542B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964780A (en) * | 2012-12-11 | 2013-03-13 | 蓝星(北京)化工机械有限公司 | Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN106564240A (en) * | 2016-11-07 | 2017-04-19 | 北京新福润达绝缘材料有限责任公司 | Manufacturing method of glass fiber mat laminated plate high in proof tracking index |
| CN111040382A (en) * | 2019-12-27 | 2020-04-21 | 四川东材科技集团股份有限公司 | Melamine-epoxy glass fiber pipe and preparation method thereof |
| CN113637293A (en) * | 2021-08-30 | 2021-11-12 | 中海油能源发展股份有限公司 | Modified resin and application thereof in plugging agent, high-temperature plugging agent and application thereof in high-temperature abandoned well plugging |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9441152B2 (en) * | 2013-06-04 | 2016-09-13 | Halliburton Energy Services, Inc. | Wellbore servicing compositions and methods of making and using same |
-
2022
- 2022-08-09 CN CN202210949406.9A patent/CN115160542B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964780A (en) * | 2012-12-11 | 2013-03-13 | 蓝星(北京)化工机械有限公司 | Epoxy resin composition for vacuum introduction formation of fibre reinforced composite material and preparation method of epoxy resin composition |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN106564240A (en) * | 2016-11-07 | 2017-04-19 | 北京新福润达绝缘材料有限责任公司 | Manufacturing method of glass fiber mat laminated plate high in proof tracking index |
| CN111040382A (en) * | 2019-12-27 | 2020-04-21 | 四川东材科技集团股份有限公司 | Melamine-epoxy glass fiber pipe and preparation method thereof |
| CN113637293A (en) * | 2021-08-30 | 2021-11-12 | 中海油能源发展股份有限公司 | Modified resin and application thereof in plugging agent, high-temperature plugging agent and application thereof in high-temperature abandoned well plugging |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115160542A (en) | 2022-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vidil et al. | Control of reactions and network structures of epoxy thermosets | |
| US4485875A (en) | Process for selectively plugging permeable zones in a subterranean formation | |
| US6311773B1 (en) | Resin composition and methods of consolidating particulate solids in wells with or without closure pressure | |
| CN111484578B (en) | Water-soluble AA-AM-NVP-NGD quadripolymer temporary plugging agent for fracturing and synthesis method thereof | |
| CN111995994B (en) | High-pressure-bearing plugging agent for oil production casing pipe and processing technology thereof | |
| CN109735315B (en) | Environment-friendly delayed crosslinking profile control agent for oil extraction and preparation method and application thereof | |
| CN110591676A (en) | Temperature-sensitive expandable shape memory plugging agent, and preparation method and application thereof | |
| CN115160542B (en) | Degradable water-absorbing epoxy resin and preparation method and application thereof | |
| US5061387A (en) | Aqueous gel system of partially methylated melamine-formaldehyde resin and polyvinyl alcohol | |
| CN107011879A (en) | A kind of high temperature resistance and high strength composite crosslinking frozen glue packing agent and preparation method | |
| CN114560996B (en) | Degradable biological epoxy resin prepared by tannic acid curing and high Wen Dulou application thereof | |
| CN111434699B (en) | Modified nano-silica cross-linking agent, self-unblocking rubber plug and preparation method | |
| CN112280249A (en) | Low-viscosity underwater quick-setting elastic epoxy plugging grouting material and application thereof | |
| CN106565636A (en) | Fluorine-containing polyfunctional group epoxy resin, and preparation method and application of fluorine-containing polyfunctional group epoxy resin | |
| CN116445144B (en) | Low-shrinkage high-strength plant-based resin plugging agent and preparation method thereof | |
| CN113045719A (en) | Plugging agent suitable for water plugging of high-temperature high-salinity clastic rock oil reservoir and preparation method thereof | |
| CN115322301B (en) | Polyurethane modified splitting, penetrating, reinforcing and grouting material, preparation method and application | |
| CN111393779A (en) | Low-expansion high-strength physical crosslinked gel particles and preparation method and application thereof | |
| CN113174018A (en) | Oil and gas well plugging fluid and preparation method thereof | |
| CN111393614B (en) | Resin underwater curing agent and preparation method thereof | |
| CN111909671A (en) | Preparation method and application of phenolic resin cross-linking agent | |
| CN105237956A (en) | Water-swellable epoxy material | |
| CN115612469A (en) | Temperature and mineralization response type low-initial-viscosity weak gel system and preparation method thereof | |
| CN114573792A (en) | Dynamic crosslinking degradable epoxy resin, preparation method and high-temperature plugging application thereof | |
| CN109851988B (en) | High-strength rubber plug system capable of being stored for long time at room temperature and preparation method 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 |