Preparation method of high heat-resistant and low-fragmentation-rate epoxy resin fracturing proppant

Abstract

The present application relates to a method for preparing a high heat-resistant, low-fragmentation epoxy resin fracturing proppant. The first aspect of the present application relates to an epoxy resin composition, which comprises: a) an epoxide; b) a curing agent; c) an auxiliary agent; wherein the auxiliary agent is selected from thiols containing two or more thiol groups, anhydride polymers, maleimide and its derivatives, and any combination thereof. The second aspect of the present application relates to a method for curing the epoxy resin composition described in the first aspect of the present application, the method comprising the following steps: 1) mixing the epoxy resin composition and silicone oil; 2) curing the epoxy resin composition. The third aspect of the present application relates to an article formed by curing the epoxy resin composition described in the first aspect of the present application.

Description

Technical Field

[0001] The present application relates to the technical field of oil and natural gas extraction, and in particular to a method for preparing a high-heat-resistant, low-fragmentation-rate, low-density epoxy resin fracturing proppant. Background Art

[0002] With the continuous development of social industry, human energy demand continues to grow, but oil and gas reserves are gradually decreasing. Conventional fossil energy such as oil and natural gas is increasingly unable to meet human development needs, and the contradiction between energy supply and demand is constantly intensifying.

[0003] In order to ease the contradiction between energy supply and demand, it is imperative to efficiently exploit oil and gas in unconventional reservoirs. Shale oil and gas, as a new type of unconventional natural gas resource, has received more and more attention. However, due to the low porosity and low permeability of its reservoirs, industrial development of shale oil and gas is difficult and the output is low. Fracturing technology is needed to increase oil well production. In the process of oil extraction, after the high closure pressure and low permeability deposits are treated by fracturing, the oil and gas rock formations are cracked, and the proppant enters the formation along with the high-pressure fracturing fluid and fills the cracks to prevent the cracks from closing, maintain high conductivity, and thus increase the output of oil and gas wells.

[0004] Fracturing proppant is a key material in hydraulic fracturing technology, and its performance directly affects the production of oil and gas wells. The most ideal fracturing proppant needs to have the characteristics of full suspension, durability and economy. At present, fracturing proppant can be roughly divided into three categories: quartz sand proppant, ceramsite proppant and coated proppant. Among them, quartz sand proppant and ceramsite proppant are the most widely used. However, their common disadvantages are poor anti-crushing ability, high density, and must be pressed and exported with fracturing fluid. In addition, the fracturing fluid used has great environmental pollution, complex process, high equipment requirements, and great construction difficulty. Coated proppant is a proppant prepared by coating a layer of 5-20μm resin on the surface of aggregates such as quartz sand and ceramsite. The outer layer of coated resin can wrap the crushed quartz sand or ceramsite inside to prevent the crushed fine particles from blocking the fracture channel, so its conductivity is better than that of quartz sand proppant and ceramsite proppant. However, since the aggregate inside is quartz sand or expanded clay, its density is still relatively high, and it also requires the use of high-molecular viscous fracturing fluid, making the construction process more difficult.

[0005] At present, quartz sand proppants, ceramsite proppants and coated proppants have the disadvantage of high density, so polymer proppants have attracted widespread attention. Epoxy resin is a thermosetting resin with high reactivity, good temperature resistance and excellent mechanical properties. Patent applications CN109321226A, CN109321227A, and CN112048294A reported a series of epoxy resin proppants. These proppants have low density, strong rigidity, strong compressive resistance and strong corrosion resistance. They are not only conducive to improving the carrying capacity of fracturing fluids, but also can maintain long-term stability in crustal cracks, which is conducive to improving the conductivity of cracks and is expected to increase oil and gas production. However, these epoxy resin proppants currently also have some problems. Their glass transition temperature is lower than 160°C, which is not conducive to their application in high-temperature deep wells.

[0006] Therefore, it is still of great significance to develop thermosetting epoxy resin proppants with high heat resistance, low breakage rate and low density. Summary of the invention

[0007] One of the purposes of the present application is to provide a thermosetting epoxy resin proppant with high heat resistance, low breakage rate and low density.

[0008] The first aspect of the present application relates to an epoxy resin composition, comprising:

[0009] a) epoxides;

[0010] b) curing agent;

[0011] c) additives;

[0012] The auxiliary agent is selected from mercaptans containing two or more mercapto groups, acid anhydride polymers, maleimide and its derivatives, and any combination thereof.

[0013] The second aspect of the present application relates to a method for curing the epoxy resin composition described in the first aspect of the present application, the method comprising the following steps:

[0014] 1) mixing the epoxy resin composition and silicone oil;

[0015] 2) curing the epoxy resin composition.

[0016] The third aspect of the present application relates to the following article, which is formed by curing the epoxy resin composition described in the first aspect of the present application through the method described in the second aspect of the present application.

[0017] The applicant unexpectedly discovered that by adding an auxiliary agent to the epoxy resin composition described in the first aspect of the present application, a thermosetting epoxy resin proppant with a high glass transition temperature, a low breakage rate, and a low density can be obtained, thereby achieving the inventive purpose of the present application.

[0018] Applicants have further unexpectedly discovered that if a multi-stage curing is used, a synergistic effect can be formed with the adjuvant to obtain an epoxy resin proppant with further improved properties.

[0019] The invention of the present application will become more clear to those skilled in the art through the following specific implementation modes and examples. DETAILED DESCRIPTION

[0020] "Scope" disclosed herein is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following range can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" are listed in this document, and "0 to 5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0021] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0022] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0023] In the present application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0024] In this application, unless otherwise specified, the terms "include" and "comprising" mentioned herein may be open-ended or closed-ended. For example, the terms "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0025] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number itself, and "several" in "one or several" means two or more.

[0026] In the description herein, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0027] Herein, unless otherwise specified, percentage (%) or part refers to percentage by weight or part by weight relative to the composition.

[0028] Herein, unless otherwise stated, the sum of the contents of the various components in the composition is 100%.

[0029] Herein, unless otherwise specified, the sum of the parts of each component in the composition may be 100 parts by weight.

[0030] In this context, unless otherwise specified, "a combination thereof" means a multi-component mixture of the elements described, for example a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0031] If not specifically stated, the terms "a" or "an" used in the present specification means "at least one".

[0032] Unless otherwise specified herein, all reactions are carried out at normal temperature and pressure.

[0033] The products obtained in this application have achieved improvements in at least the following aspects:

[0034] Roundness, which can be measured by SY / T 5108-2014 standard.

[0035] Sphericity, which can be measured by SY / T 5108-2014 standard.

[0036] Density, which can be measured by SY / T 5108-2014 standard.

[0037] Glass transition temperature T g , which can be measured by differential scanning calorimetry.

[0038] The breakage rate can be measured by SY / T 5108-2014 standard.

[0039] Particle size, which can be measured by GB / T 19077-2016 standard.

[0040] The present application will now be described in more detail in conjunction with the following specific embodiments. However, those skilled in the art will appreciate that the following specific embodiments are provided for illustrative purposes only and are not intended to limit the present application in any way.

[0041] The first aspect of the present application relates to an epoxy resin composition, the epoxy resin composition comprising

[0042] a) epoxides;

[0043] b) curing agent;

[0044] c) additives;

[0045] The auxiliary agent is selected from mercaptans containing two or more mercapto groups, acid anhydride polymers, maleimide and its derivatives, and any combination thereof.

[0046] Epoxide

[0047] The epoxy resin composition described in the first aspect of the present application comprises a) epoxide.

[0048] The a) epoxides that can be used in the present application are not particularly limited. Those skilled in the art can select the specific epoxide to be used according to the properties of the desired product.

[0049] According to one embodiment, a) the epoxide that can be used in the epoxy resin composition of the first aspect of the present application is selected from: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and any combination thereof.

[0050] According to one embodiment, the bisphenol A epoxy resin that can be used in the present application is selected from: E-51, E-44, E-20, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether (DGEBA) and its alicyclic hydrogenated derivatives, tetrabromobisphenol A diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, and any combination thereof. However, those skilled in the art know that the bisphenol A epoxy resin that can be used in the present application is by no means limited thereto.

[0051] According to one embodiment, the bisphenol F epoxy resin that can be used in the present application is selected from: NPEF170, bisphenol F diglycidyl ether, and any combination thereof. However, those skilled in the art know that the bisphenol F epoxy resin that can be used in the present application is by no means limited thereto.

[0052] According to one embodiment, the novolac epoxy resin that can be used in the present application is selected from: F-44, F-51, and any combination thereof. However, those skilled in the art know that the novolac epoxy resin that can be used in the present application is by no means limited thereto.

[0053] According to yet another embodiment, the a) epoxides useful in the present application may be selected from:

[0054] -AG-80, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexene dioxide, 4,4'-bis(1,2-epoxyethyl)diphenyl ether, 4,4'-(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane, resorcinol diglycidyl ether, phloroglucinol diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 2-(3,4-epoxy)cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane-dicarboxamide), diepoxide compounds containing hydantoin rings;

[0055] - hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl esters of dicarboxylic acids such as glycidyl terephthalate, or epoxidized dienes (dienes) or fatty acids having diepoxidized olefinic unsaturation (unsaturated groups), 1,2-cyclohexanedicarboxylic acid diglycidyl ether;

[0056] p-Aminophenol triglycidyl ether, polyaryl glycidyl ether, 1,3,5-tri(1,2-epoxy)benzene, 2,2',4,4'-tetraglycidyloxybenzophenone, tetraglycidyloxytetraphenylethane, polyglycidyl ethers of phenol / formaldehyde resins of the novolac type (polyepoxidized novolacs), epoxidized polybutadiene, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, tetraglycidyl-4,4'-diaminodiphenylmethane;

[0057] and any combination of the above.

[0058] However, those skilled in the art will appreciate that the a) epoxides that can be used in the present application are by no means limited to the specific compounds listed above.

[0059] Curing agent

[0060] The epoxy resin composition described in the first aspect of the present application comprises b) a curing agent.

[0061] The curing agent that can be used in the present application is not particularly limited. Those skilled in the art can select the curing agent that can be used in the present application according to the desired properties of the final product.

[0062] According to one embodiment, the curing agent is selected from amines, derivatives obtained by the reaction of urea and polyamines, anhydrides, organic acids, organic phosphates, polyols, imidazole compounds, phenolic resins, and any combination thereof.

[0063] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the amine that can be used as a curing agent is selected from:

[0064] - aliphatic amines, such as cyclohexylamine, linear ethylenepolyamines such as ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA);

[0065] - cycloaliphatic amines, such as 1,2-diaminocyclohexane, isophoronediamine, N,N'-diisopropylisophoronediamine and hexamine;

[0066] - aromatic amines, such as benzylamine, diethyltoluenediamine (DETDA), metaphenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenyl sulfone (DDS), 4,4'-diaminodiphenyl sulfone, 4,4'-methylenedianiline, 4,4'-methylenebis(o-chloroaniline) (MBOCA);

[0067] - dicyandiamide;

[0068] and any combination of the above amines.

[0069] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the derivative obtained by the reaction of urea and polyamine is selected from: 1-(2-aminoethyl)imidazolidinone (also known as 1-(2-aminoethyl)imidazolin-2-one (UDETA)), 1-(2-hydroxyethyl)imidazolidinone (HEIO), 1-(2-[(2-aminoethyl)amino]ethyl)imidazolidinone (UTETA), 1-[(2-{2-[(2-aminoethyl)amino]ethyl}amino)ethyl]imidazoline (UTEPA), N-(6-aminohexyl)-N'-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea (UPy), and any combination thereof.

[0070] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the acid anhydride used as a curing agent is selected from: phthalic anhydride, dichlorophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride (MTHPA, such as Aradur 917 from Huntsman), methylhexahydrophthalic anhydride (HHPA), methylnadic anhydride (MNA), dodecenylsuccinic anhydride (DDSA), maleic anhydride, and any combination thereof.

[0071] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the organic acid used as a curing agent is selected from: oxalic acid, succinic acid, citric acid, tartaric acid, adipic acid, sebacic acid, perchloric acid and phosphoric acid, isophthalic acid, p-toluenesulfonic acid, methanedisulfonyl chloride, methanedisulfonic acid, and any combination thereof.

[0072] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the organic phosphate used as a curing agent is selected from: monomethyl orthophosphate, monoethyl orthophosphate, monobutyl orthophosphate, monopentyl orthophosphate, and any combination thereof.

[0073] According to one embodiment, in the epoxy resin composition described in the first aspect of the present application, the polyol as a curing agent is selected from: glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyols (for example, those obtained by condensation of alkylene oxides or mixtures of alkylene oxides with glycerol, ethylene glycol, trimethylolpropane, pentaerythritol) and polyester polyols (for example, those obtained from polycarboxylic acids, especially oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, isophthalic acid and terephthalic acid with glycerol, ethylene glycol, trimethylolpropane and pentaerythritol); and any combination thereof.

[0074] According to a preferred embodiment, the curing agent used in the epoxy resin composition described in the first aspect of the present application is selected from: dicyandiamide, imidazole, phthalic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or phenolic resin, and any combination thereof.

[0075] In the epoxy resin composition described in the first aspect of the present application, the amount of the curing agent can be adjusted according to the desired properties, quality, shape, etc. of the final product, as is clear to those skilled in the art.

[0076] According to one embodiment, the mass of the curing agent of component b) is 5 to 120%, or 5% to 110% of the mass of the epoxy of component a).

[0077] As a limiting embodiment, the mass of component b) curing agent is 5%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 100%, or 105%, or 110%, or 115%, or 120% of the mass of component a) epoxide.

[0078] Additives

[0079] The epoxy resin composition described in the first aspect of the present application comprises c) an auxiliary agent; wherein the auxiliary agent is selected from thiols containing two or more mercapto groups, acid anhydride polymers, maleimide and its derivatives, and any combination thereof.

[0080] In the context of this application, the term "auxiliary agent" is understood to be a substance which helps to increase the degree of curing of the epoxy resin.

[0081] According to one embodiment, the thiol containing two or more thiol groups is selected from aliphatic thiols, aromatic thiols, heterocyclic thiols, and any combination thereof.

[0082] According to one embodiment, the aliphatic thiol is selected from 2,2'-(ethylenedioxy)-diethanethiol (triethylene glycol-dithiol) and ethanedithiol, and any combination thereof.

[0083] According to one embodiment, the aromatic thiol is selected from phenylenediol

[0084] According to one embodiment, the heterocyclic thiol is selected from 2,4,6-trimercapto-1,3,5-triazine

[0085] According to one embodiment, the anhydride polymer is a styrene-anhydride copolymer.

[0086] According to one embodiment, the styrene-anhydride copolymer is a styrene-maleic anhydride copolymer. For example, the styrene-maleic anhydride copolymer may be SMA-1000.

[0087] According to one embodiment, the maleimide derivative is an N-substituted maleimide

[0088] According to a preferred embodiment, the substituent in the N-substituted maleimide is selected from C1-C 16 Alkyl, C2-C 16 Alkenyl, C2-C 16 Alkynyl, C3-C 16 Cycloalkyl, C3-C 16 Heterocyclic group, C5-C 16 Aryl, C3-C 16Heterocycloalkyl, and any combination thereof.

[0089] According to a more preferred embodiment, the N-substituted maleimide is N-methylmaleimide.

[0090] Those skilled in the art will appreciate that the amount of component c) auxiliary agent used can be adjusted according to the desired final properties of the product.

[0091] According to one embodiment, the mass of the auxiliary agent of component c) is 0.1 to 5%, or 0.5 to 4%, or 0.5 to 3% of the mass of the epoxide of component a).

[0092] According to a non-limiting embodiment, the mass of the component c) auxiliary agent is 0.1%, or 0.2%, or 0.3%, or 0.4%, or 0.5%, or 0.6%, or 0.7%, or 0.8%, or 0.9%, or 1.0%, or 1.1%, or 1.2%, or 1.3%, or 1.4%, or 1.5%, or 1.6%, or 1.7%, or 1.8%, or 1.9%, or 2.0%, or 2.1%, or 2.2%, or 2.3%, or 2.4%, or 2.5%, or 2.6%, or 2.7%, or 2.8%, or 2.9%, or 3.0%, or 3.1%, or 3.2%, or 3.4%, or 3.5%, or 3.6%, or 3.7%, or 3.8%, or 3.9%, or 4.0%, or 4.1%, or 4.2%, or 4.3%, or 4.4%, or 4.5%, or 4.6%, or 4.7%, or 4.8%, or 4.9%, or 5.0%, or 5.0%, or 5.0%, or 5.1%, or 5.2%, or 5. .3%, or 2.4%, or 2.5%, or 2.6%, or 2.7%, or 2.8%, or 2.9%, or 3.0%, or 3.1%, or 3.2%, or 3.3%, or 3.4%, or 3.5%, or 3.6%, or 3.7%, or 3.8%, or 3.9%, or 4.0%, or 4.1%, or 4.2%, or 4.3%, or 4.4%, or 4.5%, or 4.6%, or 4.7%, or 4.8%, or 4.9%, or 5.0%.

[0093] Accelerator

[0094] According to a preferred embodiment, the epoxy resin composition described in the first aspect of the present application further comprises component d) an accelerator, wherein the accelerator is selected from tertiary amines, ureas, imidazole compounds, and any combination thereof.

[0095] In the context of this application, the term "accelerator" means an agent that is capable of accelerating or catalyzing the curing of epoxy resins.

[0096] According to one embodiment, the urea used as the accelerator is selected from: phenyldimethylurea, 2,4-toluenebisdimethylurea, and any combination thereof.

[0097] According to one embodiment, the tertiary amine used as the accelerator is selected from: DMP-30, N,N-dimethylbenzylamine, triethanolamine, and any combination thereof.

[0098] According to one embodiment, the imidazole compound used as the accelerator is selected from: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole, and any combination thereof.

[0099] However, those skilled in the art will appreciate that other promoters may also be used.

[0100] The amount of component d) the accelerator is not particularly limited. The amount of component d) can be adjusted according to the desired properties, shape, quality, etc. of the final product, as is clear to those skilled in the art.

[0101] According to one embodiment, the mass of the accelerator of component d) is 0.1 to 15%, or 0.1 to 12%, of the mass of the epoxide of component a).

[0102] According to a non-limiting embodiment, the mass of the accelerator of component d) is 0.1%, or 0.2%, or 0.3%, or 0.4%, or 0.5%, or 0.6%, or 0.7%, or 0.8%, or 0.9%, or 1.0%, or 1.1%, or 1.2%, or 1.3%, or 1.4%, or 1.5%, or 1.6%, or 1.7%, or 1.8%, or 1.9%, or 2.0%, or 2.1%, or 2.2%, or 2.3%, or 2.4%, or 2.5%, or 2.6%, or 2.7%, of the epoxide of component a). or 2.8%, or 2.9%, or 3.0%, or 3.1%, or 3.2%, or 3.3%, or 3.4%, or 3.5%, or 3.6%, or 3.7%, or 3.8%, or 3.9%, or 4.0%, or 4.1%, or 4.2%, or 4.3%, or 4.4%, or 4.5%, or 4.6%, or 4.7%, or 4.8%, or 4.9%, or 5.0%, or 5.1%, or 5.2%, or 5.3%, or 5.4%, or 5.5%, or 5.6%, or 5.7%, or 5.8%, or 5.9%, or 6.0%, or 6.1%, or 6.2%, or 6.3%, or 6.4%, or 6.5%, or 6.6%, or 6.7%, or 6.8%, or 6.9%, or 7.0%, or 7.1%, or 7.2%, or 7.3%, or 7.4%, or 7.5%, or 7.6%, or 7.7%, or 7.8%, or 7.9%, or 8.0%, or 8.1%, or 8.2%, or 8.3%, or 8.4%, or 8.5%, or 8.6%, or 8.7%, or 8.8%, or 8.9%, or 9.0%, or 9.1%, or 9. .2%, or 9.3%, or 9.4%, or 9.5%, or 9.6%, or 9.7%, or 9.8%, or 9.9%, or 10.0%, or 10.1%, or 10.2%, or 10.3%, or 10.4%, or 10.5%, or 10.6%, or 10.7%, or 10.8%, or 10.9%, or 11.0%, or 11.1%, or 11.2%, or 11.3%, or 11.4%, or 11.5%, or 11.6%, or 11.7%, or 11.8%, or 11.9%, or 12.0%.

[0103] The second aspect of the present application relates to a method for curing the epoxy resin composition described in the first aspect of the present application, the method comprising the following steps:

[0104] 1) mixing the epoxy resin composition and silicone oil;

[0105] 2) curing the epoxy resin composition.

[0106] Step 1)

[0107] According to one embodiment, step 1) is performed at a stirring speed of 50 to 500 rpm. It should be understood that those skilled in the art can adjust the rotation speed used in step 1) according to the size, properties, quality, morphology, etc. of the desired product.

[0108] According to non-limiting embodiments, step 1) can be carried out at 50 rpm, or 60 rpm, or 70 rpm, or 80 rpm, or 90 rpm, or 100 rpm, or 110 rpm, or 120 rpm, or 130 rpm, or 140 rpm, or 150 rpm, or 160 rpm, or 170 rpm, or 180 rpm, or 190 rpm, or 200 rpm, or 210 rpm, or 220 rpm, or 230 rpm, or 240 rpm, or 250 rpm, or 260 rpm, or 270 rpm. The stirring speed is 200rpm, 280rpm, 290rpm, 300rpm, 310rpm, 320rpm, 330rpm, 340rpm, 350rpm, 360rpm, 370rpm, 380rpm, 390rpm, 400rpm, 410rpm, 420rpm, 430rpm, 440rpm, 450rpm, 460rpm, 470rpm, 480rpm, 490rpm, or 500rpm.

[0109] In the above step 1), the epoxy resin composition and the silicone oil are mixed.

[0110] Those skilled in the art will appreciate that the mass ratio of the epoxy resin composition and the silicone oil is not particularly limited and may be adjusted according to desired properties, quality, size, etc. of the final product.

[0111] According to one embodiment, the mass ratio of the epoxy resin composition to the silicone oil is 1:2 to 1:20, or 1:2 to 1:15, or 1:2 to 1:10.

[0112] According to non-limiting embodiments, the mass ratio of the epoxy resin composition to the silicone oil may be 1:2, or 1:2.2, or 1:2.4, or 1:2.6, or 1:2.8, or 1:3.0, or 1:3.2, or 1:3.4, or 1:3.6, or 1:3.8, or 1:4.0, or 1:4.2, or 1:4.4, or 1:4.6, or 1:4.8, or 1:5.0, or 1:5.2, or 1:5.4, or 1:5.6, or 1:5.8, or 1:6.0, or 1:6.2, or 1:6.4, or 1:6.6, or 1:6.8, or 1:7.0, or 1:7.2, or 1:7.4, or 1:7.6, or 1:7.8, or 1:8.0, or 1:8.2, or 1:8.4, or 1:8.6, or 1:8.8, or 1:9.0, or 1:9.2, or 1:9.4, or 1:9.6, or 1:9.8, or 1:10.0, or 1:10.2, or 1:10.4, or 1:10.6, or 1:10.8, or 1:11.0, or 1:1 1.2, or 1:11.4, or 1:11.6, or 1:11.8, or 1:12.0, or 1:12.2, or 1:12.4, or 1:12.6, or 1:12.8, or 1:13.0, or 1:13.2, or 1:13.4, or 1:13.6, or 1:13.8, or 1:14.0, or 1:14.2, or 1:14.4, or 1:14.6, or 1:14.8, or 1:15.0, or 1:15.2, or 1:15.4, or 1:15. 6, or 1:15.8, or 1:16.0, or 1:16.2, or 1:16.4, or 1:16.6, or 1:16.8, or 1:17.0, or 1:17.2, or 1:17.4, or 1:17.6, or 1:17.8, or 1:18.0, or 1:18.2, or 1:18.4, or 1:18.6, or 1:18.8, or 1:19.0, or 1:19.2, or 1:19.4, or 1:19.6, or 1:19.8, or 1:20.0.

[0113] The silicone oil that can be used in the method described in the second aspect of the present application is not particularly limited.

[0114] According to one embodiment, the silicone oil is modified by an alkyl group, an aryl group, or a polyether.

[0115] According to one embodiment, the silicone oil is selected from methyl silicone oil, phenyl silicone oil, and any combination thereof.

[0116] Step 2)

[0117] The method of the second aspect of the present application comprises step 2) curing the epoxy resin composition.

[0118] The step 2) can be carried out in a single stage or in multiple stages. Those skilled in the art will appreciate that the manner in which step 2) is carried out can be adjusted according to the desired final properties of the product.

[0119] According to one embodiment, step 2) is performed in only one stage.

[0120] In the case where step 2) is performed in only one stage, step 2) is performed at a temperature of 90 to 200°C, or 100 to 180°C, or 110 to 160°C.

[0121] For example, in the case where step 2) is performed only in one stage, step 2) is performed at a temperature of 90°C, or 100°C, or 110°C, or 120°C, or 130°C, or 140°C, or 150°C, or 160°C, or 170°C, or 180°C, or 190°C, or 200°C.

[0122] In case step 2) is performed in only one stage, the duration of step 2) may be 1 to 10 hours, or 2 to 8 hours, or 3 to 6 hours.

[0123] For example, in the case where step 2) is performed only in one stage, the duration of step 2) may be 1 hour, or 1.5 hours, or 2 hours, or 2.5 hours, or 3 hours, or 3.5 hours, or 4 hours, or 4.5 hours, or 5 hours, or 5.5 hours, or 6 hours, or 6.5 hours, or 7 hours, or 7.5 hours, or 8 hours, or 8.5 hours, or 9 hours, or 9.5 hours, or 10 hours.

[0124] According to an alternative embodiment, step 2) is carried out in n stages, where n>1, and the nth stage is cured at a temperature T n Next duration t n .

[0125] According to a preferred embodiment, n is greater than or equal to 3, wherein T1 is at least 70°C to less than 120°C, T2 is at least 120°C to less than 180°C, and T3 is at least 180°C to less than 220°C.

[0126] According to non-limiting embodiments, T1 may be 70°C, or 72°C, or 74°C, or 76°C, or 78°C, or 80°C, or 82°C, or 84°C, or 86°C, or 88°C, or 90°C, or 92°C, or 94°C, or 96°C, or 98°C, or 100°C, or 102°C, or 104°C, or 106°C, or 108°C, or 110°C, or 112°C, or 114°C, or 116°C, or 118°C, or 119°C.

[0127] According to non-limiting embodiments, T2 may be 120°C, or 122°C, or 124°C, or 126°C, or 128°C, or 130°C, or 132°C, or 134°C, or 136°C, or 138°C, or 140°C, or 142°C, or 144°C, or 146°C, or 148°C, or 150°C, or 152°C, or 154°C, or 156°C, or 158°C, or 160°C, or 162°C, or 164°C, or 166°C, or 168°C, or 170°C, or 172°C, or 174°C, or 176°C, or 178°C, or 179°C.

[0128] According to non-limiting embodiments, T3 may be 180°C, or 182°C, or 184°C, or 186°C, or 188°C, or 190°C, or 192°C, or 194°C, or 196°C, or 198°C, or 200°C, or 202°C, or 204°C, or 206°C, or 208°C, or 210°C, or 212°C, or 214°C, or 216°C, or 218°C, or 219°C.

[0129] In case step 2) is performed in n stages (n>1), the duration of each stage can be adjusted according to the desired quality of the final product.

[0130] For example, when n is greater than or equal to 3:

[0131] -t1 may be 0.1 to 4 hours, or 0.1 to 3 hours. For example, t1 may be 0.1 hour, or 0.2 hour, or 0.4 hour, or 0.6 hour, or 0.8 hour, or 1.0 hour, or 1.2 hour, or 1.4 hour, or 1.6 hour, or 1.8 hour, or 2.0 hour, or 2.2 hour, or 2.4 hour, or 2.6 hour, or 2.8 hour, or 3.0 hour, or 3.2 hour, or 3.4 hour, or 3.6 hour, or 3.8 hour, or 4.0 hour.

[0132] -t2 can be 0.1 to 4 hours, or 0.1 to 3 hours. For example, t2 can be 0.1 hour, or 0.2 hour, or 0.4 hour, or 0.6 hour, or 0.8 hour, or 1.0 hour, or 1.2 hour, or 1.4 hour, or 1.6 hour, or 1.8 hour, or 2.0 hour, or 2.2 hour, or 2.4 hour, or 2.6 hour, or 2.8 hour, or 3.0 hour, or 3.2 hour, or 3.4 hour, or 3.6 hour, or 3.8 hour, or 4.0 hour.

[0133] -t3 may be 0.1 to 5 hours, or 0.1 to 4 hours, or 0.1 to 3 hours. For example, t3 may be 0.1 hour, or 0.2 hour, or 0.4 hour, or 0.6 hour, or 0.8 hour, or 1.0 hour, or 1.2 hour, or 1.4 hour, or 1.6 hour, or 1.8 hour, or 2.0 hour, or 2.2 hour, or 2.4 hour, or 2.6 hour, or 2.8 hour, or 3.0 hour, or 3.2 hour, or 3.4 hour, or 3.6 hour, or 3.8 hour, or 4.0 hour, or 4.2 hour, or 4.4 hour, or 4.6 hour, or 4.8 hour, or 5.0 hour.

[0134] The third aspect of the present application relates to the following product, which is formed by curing the epoxy resin composition described in the first aspect of the present application through the method described in the second aspect of the present application.

[0135] The type of the product is not particularly limited. According to a preferred embodiment, the product described in the third aspect of the present application is a fracturing proppant.

[0136] The size of the product of the third aspect of the present application can be adjusted according to actual needs. According to a preferred embodiment, the number average particle size of the product is 100 to 5000 μm.

[0137] According to a non-limiting embodiment, the number average particle size of the product of the third aspect of the present application is 100 μm, or 150 μm, or 200 μm, or 250 μm, or 300 μm, or 350 μm, or 400 μm, or 450 μm, or 500 μm, or 550 μm, or 600 μm, or 650 μm, or 700 μm, or 750 μm, or 800 μm, or 850 μm, or 900 μm, or 950 μm, or 1000 μm, or 1100 μm, or 1200 μm, or 1300 μm, or 1400 μm, or 1500 μm, or 1600 μm, or 1700 μm, or 1800 μm, or 1900 μm, or 2000 μm, or 2100μm, or 2200μm, or 2300μm, or 2400μm, or 2500μm, or 2600μm, or 2700μm, or 2800μm, or 2900μm, or 3000μm, or 3100μm, or 3200μm, or 3300μm, or 3400μm, or 3500μm, or 3600μm, or 3700μm, or 3800μm, or 3900μm, or 4000μm, or 4100μm, or 4200μm, or 4300μm, or 4400μm, or 4500μm, or 4600μm, or 4700μm, or 4800μm, or 4900μm, or 5000μm.

[0138] The particle size test method is well known in the art. For example, the average particle size of the product of the third aspect of the present application can be tested by a laser particle size analyzer using the method described in standard GB / T 19077-2016.

[0139] According to one embodiment, the sphericity of the product described in the third aspect of the present application is greater than or equal to 0.9.

[0140] According to one embodiment, the roundness of the product described in the third aspect of the present application is greater than or equal to 0.9.

[0141] The above-mentioned sphericity and roundness test methods are well known in the art. For example, the sphericity and roundness of the product of the third aspect of the present application can be tested by a microscope using the method in standard SY / T5108-2014.

[0142] According to one embodiment, the apparent density of the product described in the third aspect of the present application is 1.0 to 1.5 g / cm 3 For example, the apparent density of the product described in the third aspect of the present application may be 1.0 g / cm 3 , or 1.05g / cm 3 , or 1.1 g / cm 3 , or 1.15 g / cm 3 , or 1.2 g / cm 3 , or 1.25g / cm 3 , or 1.3 g / cm 3 , or 1.35 g / cm 3 , or 1.4 g / cm 3 , or 1.45g / cm 3 , or 1.5g / cm 3 .

[0143] The test method of apparent density is well known in the art. For example, the method described in standard SY / T 5108-2014 can be used to test the apparent density of the product of the third aspect of the present application by using a density bottle.

[0144] According to one embodiment, the glass transition temperature T g Greater than 150°C, or greater than 160°C.

[0145] The test method of glass transition temperature is well known in the art. For example, the glass transition temperature of the product can be tested using a DSC device at a heating rate of 10 K / min.

[0146] The present invention will be further described below in conjunction with specific embodiments.

[0147] Example

[0148] The reagents used in the examples of this application are shown in Table 1

[0149] Table 1 Manufacturers and brands of reagents used in the examples

[0150]

[0151]

[0152] The test methods for the apparent density, crushing rate and compressive strength of the products in the examples of the present application are as described in the standard SY / T5108-2014. In the examples, the glass transition temperature is measured using DSC at 10K / min.

[0153] Each embodiment is completed in the following manner:

[0154] Example 1

[0155] A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-51; 80 g of phthalic anhydride; 3 g of DMP-30; and 1 g of phenylenedithiol.

[0156] At 50°C, epoxy resin, phthalic anhydride and phenylenedithiol were mixed uniformly to obtain a first mixture. DMP-30 was then added to the first mixture to obtain a second mixture. The second mixture was then added to 1000 g of methyl silicone oil preheated to 150°C at a uniform rate over 10 minutes and cured for 5 hours. The reaction system was filtered and washed to obtain a product as a fracturing proppant.

[0157] Example 2

[0158] A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-51; 80 g of phthalic anhydride; 3 g of DMP-30; and 1 g of phenylenedithiol.

[0159] At 50°C, epoxy resin, phthalic anhydride and phenylenedithiol are uniformly mixed to obtain a first mixture. DMP-30 is then added to the first mixture to obtain a second mixture. Then, within 10 minutes, the second mixture is uniformly added to 1000g of methyl silicone oil preheated to 90°C and cured for 2 hours. Then the temperature is raised to 150°C and the curing is continued for 2 hours. The reaction system is filtered and washed to obtain a crude product. Finally, the crude product is cured in an oven at 200°C for 1 hour to obtain a product as a fracturing proppant.

[0160] Example 3

[0161] Repeat Example 2, except that:

[0162] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-44; 80 g of phthalic anhydride; 3 g of DMP-30; and 1 g of ethanedithiol.

[0163] (2) Use 500g of methyl silicone oil.

[0164] Example 4

[0165] Repeat Example 2, except that:

[0166] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: epoxy resin E-44; 100 g of methyltetrahydrophthalic anhydride; 3 g of DMP-30; and 1 g of ethanedithiol.

[0167] (2) Use 500g of methyl silicone oil.

[0168] Example 5

[0169] Repeat Example 2, except that:

[0170] (1) A product using an epoxy resin composition comprising the following raw materials as a fracturing proppant: 100 g of phenolic epoxy resin F-51; 80 g of phthalic anhydride; 3 g of N,N-dimethylbenzylamine; and 1 g of phenylenediol.

[0171] Example 6

[0172] Repeat Example 2, except that:

[0173] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of phenolic epoxy resin F-51; 80 g of phthalic anhydride; 1 g of N,N-dimethylbenzylamine; and 1 g of phenylenediol.

[0174] Example 7

[0175] Repeat Example 2, except that:

[0176] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of phenolic epoxy resin F-51; 80 g of phthalic anhydride; 10 g of N,N-dimethylbenzylamine; and 1 g of phenylenediol.

[0177] Example 8

[0178] Repeat Example 2, except that:

[0179] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin F-44; 80 g of phthalic anhydride; 3 g of N,N-dimethylbenzylamine; and 2 g of phenylenediol.

[0180] Example 9

[0181] Repeat Example 2, except that:

[0182] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-51; 20 g of dicyandiamide; 1 g of phenyldimethylurea; and 1 g of SMA-1000.

[0183] Example 10

[0184] Repeat Example 2, except that:

[0185] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-51; 10 g of imidazole; and 1 g of N,N′-(4,4′-methylenediphenyl)bismaleimide.

[0186] Embodiment 11

[0187] Repeat Example 2, except that:

[0188] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin F-51; 53 g of succinic anhydride; 3 g of DMP-30; and 1 g of N-methylmaleimide.

[0189] Example 12

[0190] Repeat Example 2, except that:

[0191] (1) A product used as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin F-51; 80 g of phthalic anhydride; 3 g of DMP-30; and 2 g of phenylenediol.

[0192] Comparative Example 1

[0193] A product as a fracturing proppant was prepared using an epoxy resin composition comprising the following raw materials: 100 g of epoxy resin E-51; 80 g of phthalic anhydride; 3 g of DMP-30;

[0194] At 50°C, epoxy resin and acid anhydride were uniformly mixed to obtain a first mixture. DMP-30 was then added to the first mixture to obtain a second mixture. The second mixture was then added to 1000 g of methyl silicone oil preheated to 150°C at a uniform rate over 10 minutes and cured for 5 hours. The reaction system was filtered and washed to obtain a product as a fracturing proppant.

[0195] Comparative Example 2

[0196] Comparative Example 1 was repeated, except that the process was as follows:

[0197] At 50°C, epoxy resin E-51 and phthalic anhydride were mixed uniformly, and then DMP-30 was added to the mixture. Then, within 10 minutes, the mixture was uniformly added to 1000g of methyl silicone oil preheated to 90°C, and cured for 2 hours. Then the temperature was raised to 150°C and the curing was continued for 2 hours. The reaction system was filtered and washed to obtain a crude product. The crude product was then cured in an oven at 200°C for 1 hour to obtain a product as a fracturing proppant.

[0198] The properties of the epoxy resin product obtained are shown in Table 2.

[0199] Table 2 Properties of epoxy resin products obtained in the examples and comparative examples

[0200]

[0201] As can be seen from Table 2, by using the epoxy resin composition described in the first aspect of the present application and the method described in the second aspect of the present application, an epoxy resin product with high glass transition temperature, low breakage rate and low density as a fracturing proppant can be obtained, thereby achieving the purpose of the present application.

[0202] This can be confirmed by comparing Example 1 with Comparative Example 1. The only difference between Example 1 and Comparative Example 1 is that an auxiliary agent is used in Example 1 (conforming to the first aspect of the present application), while the epoxy resin composition of Comparative Example 1 does not contain an auxiliary agent (conforming to the first aspect of the present application). The results show that when no auxiliary agent is used, the T g It is significantly lower than Example 1 (Example 1 is 163°C, and Comparative Example 1 is only 147°C), and the crushing rate D% is higher than Example 1 (Example 1 has a crushing rate of 6.5%, and Comparative Example 1 has a crushing rate of 7.8%).

[0203] Further, the synergistic effect of the additive and the three-stage curing process can be seen from Table 1. This can be confirmed from the comparison of Example 1, Example 1, and Comparative Examples 1 to 2.

[0204] No additives were used in the comparative example and the comparative example 2. The only difference between the comparative example 1 and the comparative example 2 is that the comparative example 2 uses a three-stage curing, while the comparative example 2 uses a single-stage curing. The results in Table 1 show that by using the three-stage curing, the T of the final proppant can be increased. g When the temperature rises by 3℃, the breakage rate decreases by 1.5%, that is:

[0205] ΔT g (Stage 3) = 3°C

[0206] ΔD% (three stages) = -1.5%

[0207] The difference between Example 1 and Comparative Example 1 is as described above. The auxiliary agent is used to make the T of the final proppant g When the temperature rises by 16℃, the breakage rate decreases by 1.3%, that is:

[0208] ΔT g (Auxiliary agent) = 16°C

[0209] ΔD%(auxiliary agent)=1.3%

[0210] It is therefore expected that, if there is no synergistic effect, the use of both the additive and the three-stage curing process will result in a proppant with a T g When the temperature rises by 19℃, the breakage rate decreases by 2.8%.

[0211] ΔT g (Three stages) + ΔT g (Auxiliary agent) = 19°C

[0212] ΔD% (three stages) + ΔD% (additive) = 2.8%

[0213] However, if we compare Example 2 (using both the additive and the three-stage curing process) with Comparative Example 1 (neither the additive nor the three-stage curing process was used, but the single-stage curing was used in Comparative Example 1), we can find that Example 2 increases the T of the fracturing proppant. g The temperature rose by 27℃ and the breakage rate decreased by 4.7%, which is significantly higher than the linear sum of the technical effects of using additives and the three-stage curing process, that is,

[0214] ΔT g (three-stage + additive) = 27°C

[0215] ΔD% (three-stage + additive) = 4.7%

[0216] and

[0217] ΔT g (three-stage + additive)>ΔT g (Three stages) + ΔT g (Additives)

[0218] ΔD%(three-stage + additives)>ΔD%(three-stage)+ΔD%(additives)

[0219] This synergistic effect was unexpected.

[0220] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An epoxy resin composition comprising a) epoxides; b) curing agent; c) additives; The auxiliary agent is selected from mercaptans containing two or more mercapto groups, acid anhydride polymers, maleimide and its derivatives, and any combination thereof.

2. The epoxy resin composition according to claim 1, having one or more of the following characteristics: (1) The epoxide is selected from: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and any combination thereof; Preferably: - the bisphenol A type epoxy resin is selected from: E-51, E-44, E-20, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether and its alicyclic hydrogenated derivatives, tetrabromobisphenol A diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, and any combination thereof; and / or The bisphenol F type epoxy resin is selected from: NPEF170, bisphenol F diglycidyl ether, and any combination thereof; and / or The phenolic epoxy resin is selected from: F-44, F-51, and any combination thereof; (2) The epoxide is selected from: -AG-80, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexene dioxide, 4,4'-bis(1,2-epoxyethyl)diphenyl ether, 4,4'-(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane, resorcinol diglycidyl ether, phloroglucinol diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 2-(3,4-epoxy)cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane-dicarboxamide), diepoxide compounds containing hydantoin rings; - hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl esters of dicarboxylic acids such as terephthalic acid glycidyl ether, or epoxidized dienes or fatty acids having bis-epoxidized olefinic unsaturation, 1,2-cyclohexanedicarboxylic acid diglycidyl ether; p-Aminophenol triglycidyl ether, polyaryl glycidyl ether, 1,3,5-tri(1,2-epoxy)benzene, 2,2',4,4'-tetraglycidyloxybenzophenone, tetraglycidyloxytetraphenylethane, polyglycidyl ethers of phenol / formaldehyde resins of the novolac type, epoxidized polybutadiene, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, tetraglycidyl-4,4'-diaminodiphenylmethane; and any combination thereof.

3. The epoxy resin composition according to claim 1, wherein the curing agent is selected from the group consisting of amines, derivatives obtained by reaction of urea and polyamines, anhydrides, organic acids, organic phosphates, polyols, imidazole compounds, phenolic resins, and any combination thereof; Preferably, the curing agent has one or more of the following characteristics: (1) The amine used as the curing agent is selected from: - aliphatic amines, such as cyclohexylamine, linear ethylenepolyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; - cycloaliphatic amines, such as 1,2-diaminocyclohexane, isophoronediamine, N,N'-diisopropylisophoronediamine and hexamine; - aromatic amines, such as benzylamine, diethyltoluenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-methylenedianiline, 4,4'-methylenebis(o-chloroaniline); - dicyandiamide; and any combination thereof; (2) The derivative obtained by the reaction of urea with polyamine is selected from the group consisting of: 1-(2-aminoethyl)imidazolidinone, 1-(2-hydroxyethyl)imidazolidinone, 1-(2-[(2-aminoethyl)amino]ethyl)imidazolidinone, 1-[(2-{2-[(2-aminoethyl)amino]ethyl}amino)ethyl]imidazoline, N-(6-aminohexyl)-N'-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea, and any combination thereof; (3) the acid anhydride as the curing agent is selected from the group consisting of phthalic anhydride, dichlorophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, and maleic anhydride, and any combination thereof; (4) the organic acid used as a curing agent is selected from the group consisting of oxalic acid, succinic acid, citric acid, tartaric acid, adipic acid, sebacic acid, perchloric acid and phosphoric acid, isophthalic acid, p-toluenesulfonic acid, methanedisulfonyl chloride or methanedisulfonic acid, and any combination thereof; (5) the organic phosphate as a curing agent is selected from the group consisting of monomethyl orthophosphate, monoethyl orthophosphate, monobutyl orthophosphate, monopentyl orthophosphate, and any combination thereof; (6) the polyol as a curing agent is selected from the group consisting of glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyol, polyester polyol, and any combination thereof; (7) The curing agent is selected from the group consisting of: dicyandiamide, imidazole, phthalic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or phenolic resin, and any combination thereof.

4. The epoxy resin composition according to claim 1, having one or more of the following characteristics: (1) The mass of the curing agent is 5 to 120%, or 5 to 110% of the mass of the epoxide; (2) The mass of the auxiliary agent is 0.1 to 5% of the mass of the epoxide; (3) The mass of the accelerator is 0.1 to 15% of the mass of the epoxide.

5. The epoxy resin composition according to claim 1, wherein the auxiliary agent has one or more of the following characteristics: (1) The thiol containing two or more thiol groups is selected from: aliphatic thiols, aromatic thiols, heterocyclic thiols, and any combination thereof; Preferably: The aliphatic thiol is selected from: 2,2'-(ethylenedioxy)-diethanethiol, ethanedithiol, and any combination thereof; and / or The aromatic thiol is selected from phenylenedithiol; and / or The heterocyclic thiol is selected from 2,4,6-trimercapto-1,3,5-triazine; (2) The anhydride polymer is a styrene-anhydride copolymer; Preferably, the styrene-anhydride copolymer is a styrene-maleic anhydride copolymer; More preferably, the styrene-maleic anhydride copolymer is SMA-1000; (3) The maleimide derivative is N-substituted maleimide; Preferably, the substituent in the N-substituted maleimide is selected from C1-C 16 Alkyl, C2-C 16 Alkenyl, C2-C 16 Alkynyl, C3-C 16 Cycloalkyl, C3-C 16 Heterocyclic group, C5-C 16 Aryl, C3-C 16 Heterocycloalkyl, and any combination thereof; More preferably, the N-substituted maleimide is N-methylmaleimide.

6. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further comprises d) an accelerator, wherein the accelerator is selected from the group consisting of: tertiary amines, ureas, imidazole compounds, and any combination thereof; Preferably, the promoter has one or more of the following characteristics: (1) Urea as an accelerator is selected from: phenyldimethylurea, 2,4-toluenebisdimethylurea, and any combination thereof; (2) the tertiary amine as a promoter is selected from: DMP-30, N,N-dimethylbenzylamine, triethanolamine, and any combination thereof; (3) The imidazole compound used as the accelerator is selected from the group consisting of: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and any combination thereof.

7. A method for curing the epoxy resin composition according to any one of claims 1 to 6, the method comprising the steps of: 1) mixing the epoxy resin composition and silicone oil; 2) curing the epoxy resin composition; Preferably, the method has one or more of the following features: (1) Step 1) is carried out at a stirring speed of 50 to 500 rpm; (2) In step 1), the mass ratio of the epoxy resin composition to the silicone oil is 1:2 to 1:20; (3) The silicone oil is modified by alkyl, aryl or polyether; preferably, the silicone oil is selected from methyl silicone oil, phenyl silicone oil, and any combination thereof; (4) Step 2) is performed in at least one stage; preferably Step 2) is carried out at a temperature of 90 to 200°C, or 100 to 180°C, or 110 to 160°C, and / or Step 2) is performed for 1 to 10 hours, or 2 to 8 hours, or 3 to 6 hours; (5) Step 2) is divided into n stages, n>1, and the nth stage is cured at temperature T n Next duration t n ; Preferably n is greater than or equal to 3, and wherein T1 is at least 70 to less than 120°C, T2 is at least 120 to less than 180°C, and T3 is at least 180C to less than 220°C; More preferably: t1 is from 0.1 to 4 hours, and / or t2 is from 0.1 to 4 hours; and / or t3 is from 0.1 to 5 hours.

8. An article, wherein the article is formed by curing the epoxy resin composition according to any one of claims 1 to 6 by the method according to claim 7; Preferably, the article has one or more of the following features: (1) The product is a fracturing proppant; (2) The product is a granule; Preferably, the number average particle size of the product is 100 to 5000 μm; and / or The sphericity of the article is greater than or equal to 0.9; and / or The roundness of the article is greater than or equal to 0.9; and / or The apparent density of the product is 1.0 to 1.5 g / cm 3 ; (3) The glass transition temperature of the product is greater than 150°C.

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