Cage type oligomeric silsesquioxane as well as preparation method and application thereof

Abstract

The invention discloses polyhedral oligomeric silsesquioxane and a preparation method and application thereof, the preparation method comprises the following steps: (1) adding octa-halogenated polyhedral oligomeric silsesquioxane, iminodiacetic acid, an organic solvent and carbonate into a reactor, and reacting to obtain a reaction solution; (2) pouring the reaction liquid into water, filtering to obtain a precipitate, then washing with water, and carrying out vacuum drying to obtain an oligomeric silsesquioxane imino diacetic acid compound; and (3) adding the oligomeric silsesquioxane imidodiacetic acid compound prepared in the step (2) and acetic anhydride into a reactor, carrying out heating reaction, filtering, taking precipitate, and washing with water to obtain the cage type oligomeric silsesquioxane. The resin plugging agent has the beneficial effects that (1) the universality is good, the shrinkage rate of the resin plugging agent is greatly reduced, and the resin plugging agent has the advantages of low cost, easiness in popularization and the like; (2) the bonding force between the cured resin and an interface is improved; and (3) the heat resistance and the mechanical property of the resin plugging agent are effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of oil and gas field plugging materials, and particularly relates to a cage-shaped oligosilsesquioxane, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous deepening of oilfield development, due to the influence of factors such as production time, casing quality, steam injection thermal stress, formation stress, reservoir sand production, corrosion, etc., problems such as leakage, interlayer channeling, and external casing channeling of oil and water well casings have become increasingly prominent, resulting in imperfect well patterns and out-of-control reserves, seriously affecting the oilfield's production rate and recovery efficiency.

[0003] Currently, cement materials are often used in oil and water well casing leak plugging / channeling sealing in oilfields. For example, Chinese Patent Application CN107722955A discloses a variable density external casing channeling sealing and leak plugging agent and a preparation method thereof. The raw materials of the variable density external casing channeling sealing and leak plugging agent include G-grade sulfate-resistant cement, blast furnace slag powder, sepiolite powder, diatomite, and coal gangue powder. Among them, the variable density external casing channeling sealing and leak plugging agent is obtained by the following method: adding each raw material to clear water and mixing and stirring to obtain the variable density external casing channeling sealing and leak plugging agent. However, the dispersed particles of cement are easily washed and diluted by the well water, resulting in a decrease in concentration. After the hydration reaction, the volume shrinks, it is difficult to form a dense consolidated body, the strength is low (<8 MPa), the effective period is short (6 months), it is difficult for cement to form a consolidated body with a sufficient volume, and the plugging quality is poor; limited by the particle size, for low-permeability oil and water wells or wells with thread leakage, the injection pressure is high, and bridging is likely to occur, making it difficult to meet the plugging requirements of such leakage well conditions; the cement material cannot form an interpenetrating network structure, cannot quickly accumulate and stay, and has a large loss, making it difficult to plug the uncemented free section of the casing.

[0004] Limited by these performance defects of cement materials themselves, the success rate of oil and water well plugging measures is low, affecting the efficient development of oilfields. As an important thermosetting material in the modern materials industry, epoxy resin is liquid at room temperature and has the advantages of good fluidity, strong permeability, easy processing, etc. The liquid system ensures that it can enter the tiny fracture pores in the formation or outside the casing, and cures under the action of formation high temperature and the plugging agent to form a plugging agent cured body with high strength, high toughness, corrosion resistance, low shrinkage, and a long stable period. However, epoxy resin also has disadvantages such as shrinkage after curing, poor heat resistance, and rapid decline in mechanical properties at high temperatures, which greatly limits the application scenarios of epoxy resin in oil and water well channeling sealing and leak plugging.

[0005] In order to improve the properties of epoxy resin, a large number of researchers choose to add inorganic materials to epoxy resin to enhance relevant properties. For example, Chinese Patent Application CN 116265563A discloses a binary composite resin sealant, including bisphenol A epoxy resin and thermosetting phenolic resin; as well as a conditioner, a solvent, a plasticizer, a solvent and a curing agent. Among them, the bisphenol A epoxy resin includes bisphenol A epoxy resin E51 or bisphenol A epoxy resin E44; the thermosetting phenolic resin includes thermosetting phenolic resin YJDJ. Since inorganic materials have better thermal properties, mechanical properties, insulation properties, etc. compared with organic materials, such as graphene, silicate materials, silicon dioxide nanoparticles, etc., but adding inorganic materials to improve the properties of epoxy resin is cumbersome and complex, and the compatibility between inorganic materials and organic matrices is poor, and the dispersibility is not good.

[0006] Cage-like oligosilsesquioxane (POSS) is an inorganic-organic hybrid structural material with excellent properties such as light weight, high strength, and high temperature resistance. It has the characteristics of small size and regular structure, and also has a combination of an inorganic internal cage structure and organic functional group branches. It can react with other substances simply and easily, and the distribution uniformity in the polymer matrix can reach the nanoscale and be connected to the polymer chain in the form of chemical bonds to obtain modified excellent functional materials with high temperature resistance, low density, high strength, etc. The excellent properties of cage-like oligosilsesquioxane have been widely used in high-precision industrial fields such as aerospace, national defense, military, and machining. The 8 organic functional groups of cage-like oligosilsesquioxane can be designed into epoxy groups, amino groups, hydroxyl groups, etc. Through these organic functional groups, it can combine with other organic polymers to form a cross-linked network structure. This property enables cage-like oligosilsesquioxane to be directly added to epoxy resin, so as to combine the excellent properties of the two, making epoxy resin have heat resistance, hardness and high-temperature mechanical properties, etc. For example, the addition of cage-like oligosilsesquioxane can greatly improve the heat resistance of epoxy resin, because the organic groups of cage-like oligosilsesquioxane are linked to inorganic molecules with very high heat resistance, so that the polymer added with cage-like oligosilsesquioxane can still maintain its original state at the degradation temperature of general polymers. Therefore, cage-like oligosilsesquioxane is very stable under high temperature conditions and generally degrades at 450-650 °C. Generally, more or less volume shrinkage occurs during the curing process of epoxy resin, and sometimes the volume shrinkage rate reaches more than 5%. The shrinkage of the resin volume generates shrinkage stress inside the resin. This stress is a potential destructive factor, which easily causes stress concentration inside the material, resulting in a decrease in the strength of the material and even causing problems such as material cracking and dimensional instability. How to solve the defects caused by volume shrinkage during resin curing has always been a problem that materials scientists are committed to solving.

[0007] There are currently two relatively common methods. The first method is to introduce a reactive swelling component. For example, Chinese Invention Patent CN106420366B discloses an ultra-low shrinkage composite resin and its preparation method. The ultra-low shrinkage composite resin is composed of a resin matrix and an inorganic filler. Among them: the resin matrix includes a polymerizable monomer system and an initiator system, and the inorganic filler includes an inorganic filler treated with surface silanization and calcium silicophosphate powder. The calcium silicophosphate powder undergoes volume expansion after hydration reaction, which can effectively compensate for the polymerization volume shrinkage of the composite resin and improve the volume stability of the composite resin. The second method is to use a swelling polymerizable monomer. Chinese Invention Patent CN112830934B discloses an unsaturated spiro orthocarbonate swelling monomer, its synthesis method and application. It provides an unsaturated spiro orthocarbonate swelling monomer, and its synthesis method includes the following steps: (1) Weigh 6,8-dihydroxy-1-nonene, dibutyltin oxide and toluene, add them to a reaction vessel and stir, and react at 150±2°C; (2) Cool the reaction solution in the reaction vessel to room temperature, then drop carbon disulfide into the reaction solution, and then heat the reaction solution to 110±2°C and continue the reaction; (3) Cool the reaction solution to room temperature, remove the toluene therein, then wash, recrystallize and vacuum dry to obtain the unsaturated spiro orthocarbonate swelling monomer. The above unsaturated spiro orthocarbonate swelling monomer can be used as an anti-curing shrinkage component of an organosilicon resin encapsulating material. The above two patents provide two different ways to maintain the volume of the polymer.

[0008] In addition, designing and synthesizing new polymerizable monomers can fundamentally solve the problem of resin volume shrinkage without the need to introduce swelling solvents (water, alcohols). Common swelling monomers mainly include six-membered cyclic carbonates, spiro orthocarbonates and spiro orthoesters, etc. The volume expansion rate of six-membered cyclic carbonates during polymerization is generally between 1.8% and 10.8%. 3,9-Dihydroxymethyl-1,5,7,11-tetraoxaspiro[5.5]undecane is used for photocuring bisphenol A glycidyl ether, and the volume expansion rate reaches 13%; subsequently, a tetrafunctional spiro orthocarbonate was synthesized for curing dicyclohexene oxide, and the volume expansion rate reached 2.18%. However, the common swelling monomers all have the following deficiencies: 1. High cost; 2. Poor universality. Summary of the Invention

[0009] Object of the Invention: Aiming at the technical problems of high cost and poor universality existing in common swelling monomers such as spiro orthocarbonates, the present invention provides a cage-type oligosilsesquioxane, its preparation method and application. The POSS cyclic anhydride monomer (i.e., cage-type oligosilsesquioxane) synthesized in the present invention can not only undergo ring-opening polymerization, but also react with resins such as epoxy resins and acrylic resins, and can well adapt to more complex and diverse resin systems, reducing the resin shrinkage rate.

[0010] Technical solution: A cage-shaped oligosilsesquioxane has the following structural formula:

[0011] Wherein: X is

[0012] The preparation method of the above-mentioned cage-shaped oligosilsesquioxane is as follows in terms of mole parts:

[0013] (1) Add 1 part of octahalogenated cage-shaped oligosilsesquioxane, 8 - 10 parts of iminodiacetic acid, an organic solvent, and a carbonate into a reactor, stir and react at a certain temperature for a period of time to obtain a reaction solution, wherein:

[0014] The mass ratio of the octahalogenated cage-shaped oligosilsesquioxane, the organic solvent, and the carbonate is 1:(5 - 15):(1 - 5);

[0015] (2) Pour the reaction solution into water, filter, take the precipitate, then wash it with water at least 3 times, and vacuum dry it for at least 24 hours to obtain an oligosilsesquioxane iminodiacetic acid compound;

[0016] (3) Add the oligosilsesquioxane iminodiacetic acid compound prepared in step (2) and 8 - 100 parts of acetic anhydride into a reactor, heat and react, filter, take the precipitate, and then wash it with water at least 3 times to obtain the cage-shaped oligosilsesquioxane.

[0017] Furthermore, the octahalogenated cage-shaped oligosilsesquioxane in step (1) is one of octachlorinated cage-shaped oligosilsesquioxane, octabrominated cage-shaped oligosilsesquioxane, and octaiodinated cage-shaped oligosilsesquioxane, and preferably octabrominated cage-shaped oligosilsesquioxane.

[0018] Furthermore, the organic solvent in step (1) is one or more of N,N-dimethylformamide and dimethyl sulfoxide.

[0019] Furthermore, the carbonate in step (1) is one of potassium carbonate, sodium carbonate, calcium carbonate, and magnesium carbonate, and preferably potassium carbonate.

[0020] Furthermore, the reaction temperature of the reaction in step (1) is 60 - 90 °C, and the reaction time is 6 - 12 hours.

[0021] Furthermore, the mass ratio of the octahalogenated cage-shaped oligosilsesquioxane, the organic solvent, and the carbonate in step (1) is 1:10:3.

[0022] Furthermore, the temperature of the vacuum drying in step (2) is 60 - 100 °C.

[0023] Furthermore, the water used in step (2) is distilled water or deionized water, preferably distilled water;

[0024] The water used in step (3) is distilled water or deionized water, preferably distilled water.

[0025] Furthermore, the reaction temperature of the reaction in step (3) is 110 - 130 °C, and the reaction time is 12 - 24 hours.

[0026] The cage - type oligosilsesquioxane is prepared by any of the above - mentioned preparation methods.

[0027] The application of the above - mentioned cage - type oligosilsesquioxane as a plugging agent in oil exploitation.

[0028] Beneficial effects: A cage - type oligosilsesquioxane, its preparation method and application disclosed by the present invention have the following beneficial effects:

[0029] (1) The cage - type oligosilsesquioxane synthesized by the present invention reduces the curing shrinkage rate through ring - opening polymerization of POSS cyclic anhydride monomers, solves the technical deficiencies such as high cost and poor compatibility of existing expanding monomers, has good universality in reacting with resins such as epoxy resin and acrylic resin, can well adapt to complex and diverse resin systems, greatly reduces the shrinkage rate of the resin plugging agent, and has the advantages of low cost and easy promotion;

[0030] (2) Due to the action of the cyclic anhydride monomers of the cage - type oligosilsesquioxane, the volume of the matrix resin does not shrink during the curing process, improves the adhesion between the cured resin and the interface, and ensures the bonding and plugging effect of the first and second interfaces;

[0031] (3) Due to the cage - like structure and functionalization of the cage - type oligosilsesquioxane, a good organic - inorganic hybrid system is provided, effectively improving the heat resistance and mechanical properties of the resin plugging agent. Description of the Drawings

[0032] Figure 1 It is a flow chart of a preparation method of a cage - type oligosilsesquioxane disclosed by the present invention.

[0033] Figure 2 It is an infrared spectrum of the cage - type oligosilsesquioxane prepared in Example 1.

[0034] Figure 3 It is a thermogravimetric decomposition curve of epoxy resin E - 51 with different contents of cage - type oligosilsesquioxane. Detailed Description of the Invention

[0035] The following is a detailed description of the specific implementation manners of the present invention.

[0036] Taking octabromo - cage - type oligosilsesquioxane as an example, the synthesis route of the present invention is as follows:

[0037]

[0038] For a better understanding of the present invention, the present invention will be further described below in conjunction with embodiments, but the embodiments of the present invention are not limited thereto.

[0039] Embodiment 1

[0040] A cage-type oligosilsesquioxane has the following structural formula:

[0041] Wherein: X is

[0042] The preparation method of the above-mentioned cage-type oligosilsesquioxane is as follows in parts by mole:

[0043] (1) Add 1 part of octabromo cage-type oligosilsesquioxane, 10 parts of iminodiacetic acid, an organic solvent and a carbonate into a reactor, stir and react at a certain temperature for a period of time to obtain a reaction solution, wherein:

[0044] The mass ratio of the octabromo cage-type oligosilsesquioxane, the organic solvent and the carbonate is 1:10:3;

[0045] (2) Pour the reaction solution into water, filter, take the precipitate, then wash it 3 times with water, and vacuum dry it for 24 hours to obtain an oligosilsesquioxane iminodiacetic acid compound;

[0046] (3) Add the oligosilsesquioxane iminodiacetic acid compound prepared in step (2) and 20 parts of acetic anhydride into a reactor, heat and react, filter, take the precipitate, and then wash it 3 times with water to obtain the cage-type oligosilsesquioxane.

[0047] Further, the organic solvent in step (1) is N,N-dimethylformamide.

[0048] Further, the carbonate in step (1) is potassium carbonate.

[0049] Further, the reaction temperature in step (1) is 80 °C and the reaction time is 12 hours.

[0050] Further, the temperature of the vacuum drying in step (2) is 80 °C.

[0051] Further, the water used in step (2) is distilled water;

[0052] The water used in step (3) is distilled water.

[0053] Further, the reaction temperature of the reaction in step (3) is 120 °C, and the reaction time is 18 hours.

[0054] The cage - type oligosilsesquioxane is prepared by any of the above - mentioned preparation methods.

[0055] The application of the above - mentioned cage - type oligosilsesquioxane as a plugging agent in oil exploitation.

[0056] The cage - type oligosilsesquioxane prepared in Example 1 was subjected to infrared spectroscopy test, and its infrared spectrum is as Figure 2 shown. From Figure 2 it can be seen that the peak at 1691 cm -1 is the carbonyl stretching vibration peak of the anhydride.

[0057] Example 2

[0058] A cage - type oligosilsesquioxane has the following structural formula:

[0059] Wherein: X is

[0060] The preparation method of the above - mentioned cage - type oligosilsesquioxane is as follows in terms of molar parts:

[0061] (1) Add 1 part of octahalogenated cage - type oligosilsesquioxane, 9 parts of iminodiacetic acid, an organic solvent and a carbonate into a reactor, stir and react at a certain temperature for a period of time to obtain a reaction solution, wherein:

[0062] The mass ratio of the octahalogenated cage - type oligosilsesquioxane, the organic solvent, and the carbonate is 1:15:5;

[0063] (2) Pour the reaction solution into water, filter, take the precipitate, then wash it with water 6 times, and vacuum - dry it for 48 hours to obtain an oligosilsesquioxane iminodiacetic acid compound;

[0064] (3) Add the oligosilsesquioxane iminodiacetic acid compound prepared in step (2) and 100 parts of acetic anhydride into a reactor, heat and react, then filter, take the precipitate, and wash it with water 5 times to obtain the cage - type oligosilsesquioxane.

[0065] Further, the octahalogenated cage - type oligosilsesquioxane in step (1) is octachlorinated cage - type oligosilsesquioxane.

[0066] Further, the organic solvent in step (1) is dimethyl sulfoxide.

[0067] Further, the carbonate in step (1) is sodium carbonate.

[0068] Further, the reaction temperature of the reaction in step (1) is 90 °C, and the reaction time is 11 hours.

[0069] Further, the temperature of the vacuum drying in step (2) is 60 °C.

[0070] Further, the water used in step (2) is deionized water;

[0071] The water used in step (3) is deionized water.

[0072] Further, the reaction temperature of the reaction in step (3) is 130 °C, and the reaction time is 12 hours.

[0073] The cage-shaped oligosilsesquioxane is prepared by any one of the above preparation methods.

[0074] The application of the above cage-shaped oligosilsesquioxane as a plugging agent in oil exploitation.

[0075] Example 3

[0076] A cage-shaped oligosilsesquioxane has the following structural formula:

[0077] Wherein: X is

[0078] The preparation method of the above cage-shaped oligosilsesquioxane is as follows in terms of mole parts:

[0079] (1), Add 1 part of octahalogenated cage-shaped oligosilsesquioxane, 8 parts of iminodiacetic acid, an organic solvent and a carbonate into a reactor, stir and react at a certain temperature for a period of time to obtain a reaction solution, wherein:

[0080] The mass ratio of the octahalogenated cage-shaped oligosilsesquioxane, the organic solvent and the carbonate is 1:5:1;

[0081] (2), Pour the reaction solution into water, filter, take the precipitate, then wash it 4 times with water, and vacuum dry it for 36 hours to obtain an oligosilsesquioxane iminodiacetic acid compound;

[0082] (3), Add the oligosilsesquioxane iminodiacetic acid compound prepared in step (2) and 25 parts of acetic anhydride into a reactor, heat and react, filter, take the precipitate, and then wash it 4 times with water to obtain the cage-shaped oligosilsesquioxane.

[0083] Further, the octahalogenated cage-shaped oligosilsesquioxane in step (1) is octaiodinated cage-shaped oligosilsesquioxane.

[0084] Further, the organic solvent in step (1) is a mixture of N,N-dimethylformamide and dimethyl sulfoxide with an equal volume ratio.

[0085] Further, the carbonate in step (1) is calcium carbonate.

[0086] Further, the reaction temperature of the reaction in step (1) is 60 °C and the reaction time is 2 hours.

[0087] Further, the temperature of the vacuum drying in step (2) is 100 °C.

[0088] Further, the water used in step (2) is distilled water;

[0089] The water used in step (3) is distilled water.

[0090] Further, the reaction temperature of the reaction in step (3) is 110 °C and the reaction time is 24 hours.

[0091] The cage-shaped oligosilsesquioxane is prepared by any one of the above preparation methods.

[0092] The application of the above cage-shaped oligosilsesquioxane as a plugging agent in oil exploitation.

[0093] Example 4

[0094] It is substantially the same as Example 3, except that: the carbonate in step (1) is magnesium carbonate.

[0095] Performance verification

[0096] 1. Shrinkage

[0097] To verify the contribution of the prepared cage-shaped oligosilsesquioxane to the properties of epoxy resin, the cage-shaped oligosilsesquioxane prepared in Example 1 was introduced into epoxy resin E-51 to replace part of the methylhexahydrophthalic anhydride plugging agent, and the ratio of anhydride to epoxy group was calculated according to the stoichiometric ratio. The cage-shaped oligosilsesquioxane was 0%, 5%, 10%, 15%, 20%, and 25% of the mass of epoxy resin E-51, respectively. The volume change of the cured product is shown in Table 1:

[0098] Table 1

[0099]

[0100]

[0101] By comparing the thermogravimetric curves in a nitrogen atmosphere, the heating range was from 40 °C to 550 °C, and the heating rate was 10 °C / min. The results are as Figure 3As shown, compared with the E-51 epoxy resin composite without added cage oligomeric silsesquioxane, the addition of cage oligomeric silsesquioxane significantly improves the decomposition residual mass of E-51 epoxy resin.

[0102] 2. Compressive Strength Test

[0103] To verify the contribution of the prepared cage oligomeric silsesquioxane to the properties of epoxy resin, the cage oligomeric silsesquioxane prepared in Example 1 was introduced into epoxy resin E-51 to replace part of the methylhexahydrophthalic anhydride curing agent. The ratio of anhydride to epoxy group was calculated according to the stoichiometric ratio. The cage oligomeric silsesquioxane was 0%, 5%, 10%, 15%, 20%, and 25% of the mass of epoxy resin E-51, respectively. The pressure changes of the cured products are shown in Table 2:

[0104] Table 2

[0105]

[0106]

[0107] The samples with different amounts of cage oligomeric silsesquioxane were subjected to compressive strength tests. It can be seen from Table 2 that the compressive strength is the largest when the content of cage oligomeric silsesquioxane reaches 20%, which is 88 MPa, an increase of 42 MPa compared with the epoxy resin without added cage oligomeric silsesquioxane.

[0108] The above has made a detailed description of the embodiments of the present invention. However, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the scope of knowledge possessed by those of ordinary skill in the art.

Claims

1. A cage-type oligomeric silsesquioxane, characterized in that: The structural formula is as follows: in: X is 2. A method for preparing the cage-type oligomeric silsesquioxane according to claim 1, characterized in that: In terms of molar parts, the steps are as follows: (1) Add 1 part of octahalogenated cage-type oligomeric silsesquioxane, 8-10 parts of iminodiacetic acid, an organic solvent and a carbonate into a reactor, and stir the reaction at a certain temperature for a period of time to obtain a reaction solution, wherein: The mass ratio of the octahalogenated cage-type oligomeric silsesquioxane, the organic solvent, and the carbonate is 1:(5-15):(1-5); (2) pouring the reaction solution into water, filtering, taking the precipitate, then washing with water at least 3 times, and vacuum drying for at least 24 hours to obtain an oligomeric half-siloxane iminodiacetic acid compound; (3) Add the oligomeric half silsesquioxane iminodiacetic acid compound prepared in step (2) and 8-100 parts of acetic anhydride into a reactor, heat for reaction, filter, take out the precipitate, and then rinse with water for at least 3 times to obtain a cage-type oligomeric silsesquioxane.

3. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that: The octahalogenated cage oligomeric silsesquioxane in step (1) is one of octachloro cage oligomeric silsesquioxane, octabromo cage oligomeric silsesquioxane and octaiodo cage oligomeric silsesquioxane, preferably octabromo cage oligomeric silsesquioxane.

4. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The organic solvent in step (1) is one or more of N,N-dimethylformamide and dimethyl sulfoxide.

5. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The carbonate in step (1) is one of potassium carbonate, sodium carbonate, calcium carbonate and magnesium carbonate, preferably potassium carbonate.

6. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The reaction temperature of the reaction in step (1) is 60-90° C., and the reaction time is 6-12 hours.

7. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that In step (1), the mass ratio of the octahalogenated cage-type oligomeric silsesquioxane, the organic solvent and the carbonate is 1:10:

3.

8. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The vacuum drying temperature in step (2) is 60-100°C.

9. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The water used in step (2) is distilled water or deionized water, preferably distilled water; The water used in step (3) is distilled water or deionized water, preferably distilled water.

10. The method for preparing a cage-type oligomeric silsesquioxane according to claim 2, characterized in that The reaction temperature of the reaction in step (3) is 110-130° C., and the reaction time is 12-24 hours.

11. A cage-type oligomeric silsesquioxane, characterized in that: It is prepared by the preparation method according to any one of claims 2 to 10.

12. Use of the cage-type oligomeric silsesquioxane according to claim 1 or claim 11 as a plugging agent in oil production.

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