A triple shape memory material and its preparation method and application

Abstract

The application provides a kind of triple shape memory material and its preparation method and application, belong to the technical field of intelligent plugging in well drilling.The triple shape memory material is a high-temperature, triple shape memory epoxy polymer material containing covalent crosslinking and dynamic crosslinking of disulfide bond, which is made of epoxy monomer, polyamine curing agent, disulfide bond-containing curing agent and other additives by gradient temperature curing;The epoxy polymer material has two transition temperatures (Tg1 90-145 DEG C, Tg2 120-170 DEG C), and has high strength and toughness, after pressing according to procedure, then cutting, crushing into granular, combined with calcium carbonate particles, fiber, graphite material to prepare plugging agent, gradually expands at high temperature, realizes the effective pressure containment plugging of large crack.The triple shape memory material prepared by the application can meet the pressure containment plugging demand of deep, high-temperature formation.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of intelligent plugging in drilling, and particularly relates to a triple shape memory material and a preparation method and application thereof. BACKGROUND

[0002] Well leakage is a frequent and malignant accident in oil and gas drilling development. For a long time, people have been committed to developing various plugging technologies. Conventional bridging plugging materials have poor adaptability to crack size, are prone to aging failure at high temperature, have low plugging efficiency for complex strata with uncertain crack size, and are prone to repeated leakage. Temperature stimulation responsive shape memory polymer materials have the advantages of easy processing, large recoverable deformation, high strength, etc. At the transition temperature, the fixed deformation is compressed, and the stratum temperature is stimulated to excite the recovery to the original expansion state, so as to realize effective bridging and dense pressure sealing at the stratum cracks. The use of temperature-sensitive shape memory materials with conventional plugging materials can reduce the cost and improve the dense pressure capacity of the plugging fluid. Therefore, temperature-sensitive shape memory polymer materials have good application and development prospects in the field of drilling plugging.

[0003] At present, there are some studies on plugging using temperature-sensitive shape memory polymer materials.

[0004] In the patent CN201611203352.2 "Shape memory type plugging agent", the shape memory type plugging agent is composed of shape memory foam, fibrous plugging material, filling material and suspension stabilizer. The shape memory foam is one or a combination of polyurethane shape memory foam, styrene shape memory foam and poly-norbornene shape memory foam. It is directly used, and the preparation of shape memory foam material and the high temperature excitation transition temperature are not involved.

[0005] In the patent CN201911398748.0 "Temperature control rigid expansion plugging working fluid for drilling fluid", a temperature control rigid expansion plugging agent is included, which is one or a blend of shape memory polymer type temperature control rigid expansion plugging agent or shape memory alloy type temperature control rigid expansion plugging agent. The shape memory polymer type temperature control rigid expansion plugging agent includes any one or several of shape memory polyurethane, shape memory polylactic acid and shape memory cross-linked vinyl chloride, and the activation temperature is 70-100℃, which cannot meet the plugging application at higher temperature.

[0006] In the patent CN202010195263.8 "a shape memory plugging agent, preparation method and application thereof", shape memory particles, foam particles and composite particles are used as shape memory type plugging agent. The shape memory polymer particles include shape memory polystyrene particles, shape memory epoxy resin particles or shape memory cyanate ester particles. The reinforcing body in the particles includes at least one of glass fiber, Kevlar fiber, carbon fiber, continuous fiber, carbon nanotube, carbon black, graphene, silicon dioxide and clay. The shape memory epoxy resin particles have a deformation temperature in the range of 60-170℃. The synthesis and preparation method of shape memory epoxy resin particles are not involved. When used as a plugging agent, the content of shape memory plugging agent is as high as 25-35%, which is not economical. The performance cannot meet the demand of efficient plugging.

[0007] In the paper "Development and Performance Evaluation of Temperature-sensitive Expandable Plugging Agent Based on Shape Memory Epoxy Resin Polymer", a thermoset shape memory epoxy resin is prepared by reacting epoxy and aromatic amine curing agent. By controlling the amount of crosslinking agent to 17% and 19%, shape memory plugging materials with transition temperature-Tg of 77.6 and 84.1℃ are obtained. The sand bed evaluation plugging pressure is 5.52MPa. The obtained shape memory epoxy material has high mechanical properties and high temperature resistance, but poor toughness, which is not conducive to later hot pressing.

[0008] In the paper "Preparation Technology of Shape Memory Polymer Temperature-controlled Swellable Plugging Agent SDP", when anhydride is used to cure epoxy resin, polyglycerol ether toughening agent is added to improve the toughness of the material. However, the glass transition temperature and tensile strength decrease with the increase of the content of toughening agent. The trigger transition temperature is 73-85℃. By using hyperbranched toughening agent and controlling the concentration of crosslinking agent and the degree of curing, shape memory epoxy plugging materials with trigger transition temperature of 75-105℃ can be obtained, but the trigger temperature is still not high enough.

[0009] In the paper "Preparation and Application of Shape Memory Polymer Temperature-controlled Swellable Plugging Agent", the use of hyperbranched toughening agent improves the toughness of the material while prolonging the memory recovery-expansion time, and the expansion delay time decreases with the increase of the environmental temperature. The main method is to adjust the expansion time by environmental temperature, rather than from the structure design of the material.

[0010] The epoxy materials obtained in the above related technologies have only one glass transition temperature and can only undergo double shape change. The problems of the existing technology include low trigger temperature (rarely higher than 110℃), difficulty in balancing strength and toughness, and difficulty in adjusting the swelling state from composition and structure design. High glass transition temperature (Tg) plugging materials can be triggered and recovered at high temperature to realize effective sealing of large cracks and meet the demand of efficient plugging under high temperature conditions. The glass transition temperature of the triple shape memory material in the existing technology is low, which cannot meet the pressure plugging demand of deep and high temperature formations. SUMMARY

[0011] The present application provides a triple shape memory material, a preparation method and application thereof to solve the problems in the prior art. The triple shape memory material is a high-temperature triple shape memory epoxy polymer material containing covalent cross-linking and dynamic cross-linking of disulfide bonds, which is prepared by gradient temperature curing of an epoxy monomer, a polyamine curing agent, a disulfide bond-containing curing agent and other additives; the epoxy polymer material has two high transition temperatures (Tg1 90-145℃, Tg2 120-170℃), and has high strength and toughness. After being pressed according to a procedure, the material is cut and crushed into granules, combined with calcium carbonate particles, fibers and graphite materials to prepare a lost circulation material which gradually expands at high temperature to effectively plug large cracks. The triple shape memory material prepared by the present application can meet the pressure plugging requirements of deep and high-temperature formations.

[0012] To achieve the above-mentioned object, in a first aspect, the present application provides a triple shape memory material, which comprises the following raw materials by weight percentage: epoxy monomer 55-75%, curing agent 24-40%, and additive 1-5%; wherein the curing agent is selected from a polyamine curing agent and / or a disulfide bond-containing curing agent.

[0013] In a preferred embodiment, the epoxy monomer is a monomer containing 2-4 epoxy groups; more preferably, the epoxy monomer is selected from one or more of bisphenol A diglycidyl ether E51, bisphenol A diglycidyl ether E44, trimethylolpropane triglycidyl ether TGE, and 4.4-diamino diphenyl methane tetraglycidyl amine TGDDM.

[0014] In a preferred embodiment, the polyamine curing agent is selected from one or more of polyether amine D230, diaminodiphenyl methane DDM, 4,4-diamino diphenyl sulfone DDS, and 4,4'-diamino diphenyl ether OBA.

[0015] In a preferred embodiment, the disulfide bond-containing curing agent is selected from one or more of a disulfide bond-containing carboxylic acid curing agent, a disulfide bond-containing hydroxyl curing agent, and a disulfide bond-containing diamine curing agent.

[0016] In a preferred embodiment, the disulfide bond-containing carboxylic acid curing agent includes 2,2'-dithiodibenzoic acid DTSA; the disulfide bond-containing hydroxyl curing agent includes 4,4'-dihydroxydiphenyl disulfide TBP; and the disulfide bond-containing diamine curing agent includes dithiodianiline TDA.

[0017] In a preferred embodiment, the mass percentage of the disulfide bond-containing curing agent is 5-15%.

[0018] In a preferred embodiment, the additive is barite powder.

[0019] In a second aspect, the present application further provides a preparation method of the triple shape memory material, comprising the following steps:

[0020] 1) Weigh a certain amount of epoxy monomer, heat to 80-120℃ in oil bath, and stir;

[0021] 2) Weigh a certain amount of curing agent and additive, heat to 80-120℃ in oil bath, and stir, then add to the epoxy monomer in step 1) and mix evenly;

[0022] 3) Pour the mixture obtained in step 2) into a mold for temperature rising curing to obtain a cured product;

[0023] 4) Determine the glass transition temperatures Tg1, Tg2 of the prepared shape memory epoxy polymer material, and Tg2>Tg1.

[0024] In a preferred embodiment, step 3) is to pour the mixture of the obtained epoxy monomer, curing agent and additive into a mold for temperature rising curing, and the temperature rising curing is at 95-105℃ for 1-2h, 120-140℃ for 1-3h, 140-160℃ for 1-3h, and 170-190℃ for 1-2h.

[0025] In a preferred embodiment, step 4) is to test the glass transition temperature of the obtained cured product by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA).

[0026] The glass transition temperature Tg1 of the obtained cured product is 90-145℃, and the glass transition temperature Tg2 is 120-170℃; the temperature of 5% weight loss in thermogravimetric analysis is 300-400℃; and the rubbery storage modulus at 150-170℃ is 10-20MPa in DMA test analysis.

[0027] In a third aspect, the present application further provides the use of the triple shape memory material in a plugging agent.

[0028] In a fourth aspect, the present application further provides a plugging agent composition, which comprises the triple shape memory material 4-8 parts, calcium carbonate 8-15 parts, basalt fiber 0.2-0.4 parts, and graphite 3-5 parts by weight fraction.

[0029] In a fifth aspect, the present application further provides a preparation method of the plugging agent composition, comprising the following steps:

[0030] 1) heating the triple shape memory material to T1 temperature, T1 = Tg2 + (10-20)℃, pressing; keeping the pressed state to cool to T2 temperature, T2 = Tg1 + (10-20)℃, T2 < Tg2, continuing to press; keeping the pressed state to cool to T3 temperature, T3 = room temperature < Tg1, obtaining sheet triple shape memory material;

[0031] 2) cutting and crushing the sheet triple shape memory material obtained in step 1) into granular shape, as shape memory plugging agent;

[0032] 3) preparing the shape memory plugging agent obtained in step 2) into plugging agent composition with calcium carbonate, fiber and graphite.

[0033] Using the plugging agent composition for crack plugging test, the plugging agent gradually expands at its excited transition temperature Tg1 and Tg2, and adaptively plugs the cracks. Figure 1 As shown in the attached figure, the cured sample is bent at T1 temperature in oil bath, keeping the shape to cool to T2 temperature, continuing to bend into C shape, keeping the shape to cool to T3 temperature; then, warming from T3 temperature to Tg1, and further warming to Tg2, the sample returns to the initial state from C shape.

[0034] As shown in the attached figure, the cured sample is bent at T1 temperature in oil bath, keeping the shape to cool to T2 temperature, continuing to bend into C shape, keeping the shape to cool to T3 temperature; then, warming from T3 temperature to Tg1, and further warming to Tg2, the sample returns to the initial state from C shape. Figure 1 As shown in the attached figure, the cured sample is bent at T1 temperature in oil bath, keeping the shape to cool to T2 temperature, continuing to bend into C shape, keeping the shape to cool to T3 temperature; then, warming from T3 temperature to Tg1, and further warming to Tg2, the sample returns to the initial state from C shape.

[0035] Adding the plugging agent composition into 4% bentonite base slurry to form experimental test slurry; using long slit plugging experimental device to test the plugging performance of the experimental slurry containing the plugging agent at room temperature and high temperature 120-150, the cracks are long and narrow cracks with opening of 2*1mm, 3*2mm and 4*3mm, the experimental slurry completely leaks at room temperature, and the experimental slurry can bear pressure of 5-9MPa and the leakage amount is less than 200ml at 150.

[0036] The beneficial effects of the present application are:

[0037] 1) The present application designs and prepares epoxy polymer with soft-hard crosslinking network and dynamic reversible disulfide crosslinking network structure, so that the hard network provides strength, and the soft network and dynamic reversible crosslinking network provide toughness; different crosslinking networks have different glass transition temperatures, so that the triple shape memory epoxy material with two high transition temperatures (Tg1 90-145℃, Tg2 120-170℃) and step-by-step recovery expansion is obtained.

[0038] 2. The plugging agent composition prepared by the present invention gradually expands at a high temperature of 120 - 150 °C, can effectively withstand pressure and plug large cracks, and can meet the requirements of pressure-bearing plugging in deep and high-temperature formations. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 is the preparation process of the sheet-shaped triple shape memory material of the present invention; wherein, I - heating to T1 = Tg2 + 10 - 20 °C, deforming, maintaining the deformation and cooling to T2 = Tg1 + 10 - 20 °C < Tg2; II - at T2, deforming, maintaining the deformation and cooling to T3 = room temperature < Tg1; III - heating from T3 at room temperature to Tg1; IV - heating from Tg1 to Tg2. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] It should be noted that the raw materials used in the present invention are all ordinary commercially available products, and no specific limitation is made on their sources.

[0041] Example 1

[0042] The preparation process of the triple shape memory material is as follows:

[0043] 1) Weigh epoxy monomer E51 (55%) in a beaker, heat and stir in an oil bath at 100 °C;

[0044] 2) Weigh curing agent diaminodiphenylmethane - DDM (25%), diphenylamine disulfide - TDA (15%) and barite (H2SO4) (5%) in another beaker, heat and stir in an oil bath at 100 °C, and add them to the epoxy monomer in step 1), and mix evenly;

[0045] 3) Pour the mixture obtained in 2) into a mold, cure at 100 °C for 1.5 h, 130 °C for 2 h, 150 °C for 2 h, and 180 °C for 1.5 h; obtain a cured product.

[0046] The DSC results show that the glass transition temperatures of the obtained cured product are 90 °C and 120 °C, the temperature of 5% thermal weight loss is < 300 °C, the rubbery state storage modulus at 150 - 170 °C in the DMA test is 10 MPa, and the expansion rate of the sample after program pressing is 20% when heated from room temperature to 90 °C and 90% when heated to 120 °C.

[0047] The preparation process of the plugging agent composition is as follows:

[0048] 1) Heat the triple shape memory material to temperature T1, T1 = Tg2 + 15, and press; maintain the pressing state and cool to temperature T2, T2 = Tg1 + 15, T2 < Tg2, and continue to press; maintain the pressing state and cool to temperature T3, T3 = room temperature < Tg1, to obtain a sheet-shaped triple shape memory material;

[0049] 2) The sheet-shaped triple shape memory material obtained in step 1) is cut and crushed into granules as a shape memory plugging agent;

[0050] 3) The shape memory plugging agent (4 g) obtained in step 2) is prepared into a plugging agent composition together with calcium carbonate particles (15 g), basalt fibers (0.4 g), and graphite (5 g), and is added into 1.5 L of 4% bentonite base slurry. The plugging performance of the plugging agent is tested by using a long crack (2 x 1 mm, 3 x 2 mm) plugging experimental device. The results are as follows: room temperature test - complete leakage, 150°C test - pressure bearing 9 MPa, 8 MPa, leakage amount 150 ml, 200 ml.

[0051] Example 2

[0052] The preparation process of the triple shape memory material is as follows:

[0053] The formula of the triple shape memory material is as follows: epoxy monomer E44 (35%) and 4.4-diamino diphenyl methane tetraglycidyl amine-TGDDM (40%), curing agent polyetheramine D230 (5%), 4,4-diamino diphenyl sulfone-DDS (9%), and 2,2'-dithiodibenzoic acid-DTSA (9%), and barite (2%). The preparation process is as shown in Example 1.

[0054] The DSC result shows that the glass transition temperature of the obtained cured product is 145°C and 170°C, the temperature at 5% weight loss is 400°C, the rubbery storage modulus at 150-170°C is 20 MPa by DMA test, the sample is pressed by program and then the sample is heated from room temperature to 145°C, the expansion rate is 30%, and the sample is heated to 120°C, the expansion rate is 60%.

[0055] The preparation process of the plugging agent composition is as follows:

[0056] The preparation process of the shape memory plugging agent is as shown in Example 1. The obtained shape memory plugging agent (8 g) is prepared into a plugging agent composition together with calcium carbonate particles (8 g), basalt fibers (0.2 g), and graphite (3 g), and is added into 1.5 L of 4% bentonite base slurry. The plugging performance of the plugging agent is tested by using a long crack (3 x 2 mm) plugging experimental device. The results are as follows: room temperature test - complete leakage, 150°C test - pressure bearing 5 MPa, leakage amount 160 ml.

[0057] Example 3

[0058] The preparation process of the triple shape memory material is as follows:

[0059] The formulation of the triple shape memory material is: epoxy monomer is E51 (35%) and trimethylolpropane triglycidyl ether-TGE (35%), curing agent is 4,4'-diamino diphenyl ether-OBA (16%) and 4,4'-dihydroxy diphenyl disulfide-TBP (10%), and barite (4%), and the preparation process is as shown in Example 1.

[0060] The DSC result shows that the glass transition temperature of the obtained cured product is 118°C, 164°C, the temperature of 5% thermal weight loss is 350°C, the rubbery storage modulus at 150-170°C is 12 MPa by DMA test, the sample expands by 50% when heated from room temperature to 118°C, and expands by 50% when heated to 120°C.

[0061] The preparation process of the plugging agent composition is as follows:

[0062] The preparation process of the shape memory plugging agent is the same as that of Example 1, the obtained shape memory plugging agent (8 g) is mixed with calcium carbonate particles (12 g), basalt fiber (0.4 g), and graphite (5 g) to prepare a plugging agent composition, which is added to a 1.5 L 4% bentonite base slurry, and the plugging performance of the plugging agent is tested by using a long crack (4x3 mm) sealing experiment device, the results show that at room temperature, the complete loss occurs, and at 150°C, the pressure bearing is 8 MPa, and the loss amount is 120 ml.

[0063] Example 4

[0064] The preparation process of the triple shape memory material is as follows:

[0065] The formulation of the triple shape memory material is: epoxy monomer is E51 (35%) and 4.4-diamino diphenyl methane tetraglycidyl amine-TGDDM (36%), curing agent is 4,4-diamino diphenyl sulfone-DDS (20%) and dithiodiaminophenyl-TDA (5%), and barite (4%), and the preparation process is as shown in Example 1.

[0066] The DSC result shows that the glass transition temperature of the obtained cured product is 121°C, 154°C, the temperature of 5% thermal weight loss is 350°C, the rubbery storage modulus at 150-170°C is 17 MPa by DMA test, the sample expands by 48% when heated from room temperature to 121°C, and expands by 76% when heated to 154°C.

[0067] The preparation process of the plugging agent composition is as follows:

[0068] The preparation process of the shape memory plugging agent is the same as that of Example 1. The obtained shape memory plugging agent (8 g) is prepared into a plugging agent composition together with calcium carbonate particles (12 g), basalt fibers (0.4 g) and graphite (5 g), and is added into 1.5 L of 4% bentonite base slurry. The plugging performance of the plugging agent is tested by using a long crack (3x2 mm) sealing experiment device. The results are as follows: complete leakage at room temperature, 9 MPa pressure and 170 ml leakage at 150°C.

[0069] Example 5

[0070] The preparation process of the triple shape memory material is as follows:

[0071] The formula of the triple shape memory material is as follows: epoxy monomer E51 (53%) and 4,4-diamino diphenyl methane tetraglycidyl amine-TGDDM (20%), curing agent polyether amine D230 (5%), diamino diphenyl methane-DDM (10%) and dithiodiaminophenyl-TDA (9%), and barite (3%). The preparation process is as described in Example 1.

[0072] The DSC result shows that the glass transition temperature of the obtained cured product is 108°C and 141°C, the temperature at 5% weight loss is 330°C, the rubbery storage modulus at 150-170°C is 10 MPa by DMA test, the sample expands by 43% when heated from room temperature to 108°C, and expands by 91% when heated to 141°C after program compression.

[0073] The preparation process of the plugging agent composition is as follows:

[0074] The preparation process of the shape memory plugging agent is the same as that of Example 1. The obtained shape memory plugging agent (8 g) is prepared into a plugging agent composition together with calcium carbonate particles (10 g), basalt fibers (0.3 g) and graphite (4 g), and is added into 1.5 L of 4% bentonite base slurry. The plugging performance of the plugging agent is tested by using a long crack (3x2 mm) sealing experiment device. The results are as follows: complete leakage at room temperature, 8.5 MPa pressure and 140 ml leakage at 150°C.

[0075] Comparative Example 1

[0076] The preparation process of the shape memory material is as follows:

[0077] The formula of the shape memory material is as follows: epoxy monomer E51 (55%), and curing agent replaced by sebacic acid SA (25%) and 4,4'-dithiodibutyric acid (DTBA) (15%), and barite (5%). The other preparation process is as described in Example 1.

[0078] DSC results show that the glass transition temperature of the cured product is 62°C, 93°C, the temperature of 5% thermal weight loss is 305°C, the rubbery storage modulus is 6 MPa at 150-170°C by DMA test, the sample expands by 30% when heated from room temperature to 65°C and expands by 50% when heated to 95°C after programmed compression.

[0079] The preparation process of the lost circulation material composition is as follows:

[0080] The preparation process of the shape memory lost circulation material is the same as that in Example 1. The obtained shape memory lost circulation material (4 g) is prepared into a lost circulation material composition together with calcium carbonate particles (15 g), basalt fibers (0.4 g) and graphite (5 g), and is added into a 1.5 L 4% bentonite base slurry to test the plugging performance of the lost circulation material by using a long crack (3x2 mm) plugging experimental device. The test at room temperature shows complete loss, the test at 150°C shows plugging failure and the pressure bearing is 0, and the lost circulation material mainly seals the door, i.e., is plugged at the crack door.

[0081] Comparative Example 2

[0082] The preparation process of the shape memory material is as follows:

[0083] The formulation of the shape memory material is as follows: the epoxy monomer is E51 (53%) and 4.4-diaminodiphenyl methane tetraglycidyl amine-TGDDM (20%), the curing agent is sebacic acid SA (15%) and 4,4'-dithiodibutyric acid (DTBA) (9%), and the barite (3%), and the preparation process is as in Example 5.

[0084] DSC results show that the glass transition temperature of the cured product is 112°C, the temperature of 5% thermal weight loss is 315°C, the rubbery storage modulus is 8.6 MPa at 150-170°C by DMA test, and the sample expands by 38% when heated from room temperature to 115°C after programmed compression.

[0085] The preparation process of the lost circulation material composition is as follows:

[0086] The preparation process of the shape memory lost circulation material is the same as that in Example 5. The obtained shape memory lost circulation material (8 g) is prepared into a lost circulation material composition together with calcium carbonate particles (10 g), basalt fibers (0.3 g) and graphite (4 g), and is added into a 1.5 L 4% bentonite base slurry to test the plugging performance of the lost circulation material by using a long crack (3x2 mm) plugging experimental device. The test at room temperature shows complete loss, the test at 150°C shows that the pressure bearing is 4.5 MPa and the loss amount is 280 ml, and the lost circulation material partially seals the door.

[0087] As can be seen from comparative example 1 and comparative example 2, and example 5, the triple shape memory material prepared in example 1 and example 5 has two high transition temperatures (Tg190-145℃, Tg2120-170℃), and has significantly better high-temperature plugging performance, while the shape memory materials of comparative examples 1-2 cannot meet the high-temperature plugging requirements.

[0088] The technical scheme of the present application is not limited to the technical means disclosed in the above technical means, but also includes technical schemes composed of any combination of the above technical features. The above is a specific implementation of the present application, and it should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which are also considered within the scope of protection of the present application.

Claims

1. A method of preparing a lost circulation material composition, characterized in that, The method comprises the following steps: 1) heating the triple shape memory material to T1 temperature, T1 = Tg2 + (10-20) ℃, pressing; keeping the pressed state to cool to T2 temperature, T2 = Tg1 + (10-20) ℃, T2 < Tg2, continue to press; keeping the pressed state to cool to T3 temperature, T3 = room temperature < Tg1, to obtain a sheet-shaped triple shape memory material; the Tg1 and Tg2 are glass transition temperatures of the triple shape memory material, Tg2 > Tg1; 2) cutting and crushing the sheet-shaped triple shape memory material obtained in the step 1) into granular shape, as a shape memory plugging agent; 3) preparing the shape memory plugging agent obtained in the step 2) into a plugging agent composition with calcium carbonate, basalt fiber and graphite; The plugging agent composition comprises, in terms of weight fraction, 4-8 parts of the triple shape memory material, 8-15 parts of calcium carbonate, 0.2-0.4 parts of basalt fiber and 3-5 parts of graphite. The triple shape memory material comprises, in terms of weight percentage, the following raw materials: 55-75% of an epoxy monomer, 24-40% of a curing agent and 1-5% of an additive; wherein the curing agent is selected from a polyamine curing agent and a curing agent containing a disulfide bond.

2. The production method according to claim 1, characterized by, The epoxy monomer is a monomer containing 2-4 epoxy groups.

3. The preparation method according to claim 1, characterized in that, The polyamine curing agent is selected from one or more of polyetheramine D230, diamino diphenyl methane DDM, 4,4-diamino diphenyl sulfone DDS and 4,4'-diamino diphenyl ether OBA.

4. The method of claim 1, wherein, The curing agent containing a disulfide bond is selected from one or more of a disulfide bond-containing carboxylic acid curing agent, a disulfide bond-containing hydroxyl curing agent and a disulfide bond-containing diamine curing agent; the disulfide bond-containing carboxylic acid curing agent comprises 2,2'-dithiodibenzoic acid DTSA; the disulfide bond-containing hydroxyl curing agent comprises 4,4'-dihydroxydiphenyl disulfide TBP; and the disulfide bond-containing diamine curing agent comprises dithiodianiline TDA; the mass percentage of the curing agent containing a disulfide bond is 5-15%.

5. The preparation method according to claim 1, characterized in that, The additive is barite powder.

6. The method of claim 1, wherein, The preparation method of the triple shape memory material comprises the following steps: 1) weighing a certain amount of epoxy monomer, heating to 80-120 ℃ in an oil bath and stirring; 2) weighing a certain amount of a curing agent and an additive, heating to 80-120 ℃ in an oil bath and stirring, adding to the epoxy monomer in the step 1) and mixing uniformly; 3) pouring the mixture obtained in the step 2) into a mold for temperature rising curing to obtain a cured product; 4) determining the glass transition temperatures Tg1 and Tg2 of the prepared shape memory epoxy polymer material, Tg2 > Tg1.

7. The production method according to claim 6, wherein The mixture of the epoxy monomer, the curing agent and the additive is poured into a mold for temperature rising curing, the temperature rising curing is carried out at 95-105 ℃ for 1-2 h, at 120-140 ℃ for 1-3 h, at 140-160 ℃ for 1-3 h and at 170-190 ℃ for 1-2 h; and the glass transition temperature of the obtained cured product is tested by differential scanning calorimetry DSC or dynamic mechanical analysis DMA.

Images