Biodegradable epoxy resin pouring sealant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of biodegradable materials, and discloses a biodegradable epoxy resin pouring sealant as well as a preparation method and application thereof. The epoxy resin pouring sealant is prepared from the following raw materials: epoxy resin, acid anhydride, an antioxidant, an accelerant, filler and a coupling agent, the anhydride is selected from at least one of diethanol anhydride, dilactic anhydride, 2-hydroxybutyric anhydride and 2-hydroxy-3-methyl butyric anhydride; the biodegradable epoxy resin pouring sealant can be spontaneously degraded in natural environments such as seawater, soil and industrial compost, degradation products are nontoxic and harmless, and the problem of environmental pollution is solved. Meanwhile, by using the biodegradable anhydride curing agent, the biocompatibility of the epoxy resin material can be improved, so that the epoxy resin material can be applied to the field of biomedical treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to the technical field of green degradable epoxy resin materials, and specifically to a biodegradable epoxy resin potting adhesive and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a high-performance thermosetting polymer. Due to its excellent physical and chemical properties, it has shown wide application potential in coatings, adhesives, composite materials and other fields. However, during curing and subsequent treatment, traditional epoxy resins often volatilize environmentally harmful components, such as volatile organic compounds (VOCs), which pose a threat to the environment and human health. Therefore, green and biodegradable epoxy resin curing technology came into being to solve this environmental problem.

[0003] Green biodegradable epoxy resin materials refer to polymeric materials that have little impact on the environment and human health and can be biodegraded under natural conditions or through the action of microorganisms. The curing agents for this type of epoxy resin can be roughly divided into three categories: natural polymer-based, bio-based synthetic polymers, and degradable chemical synthesis. Natural polymer-based curing agents, such as starch and lignin, are derived from renewable resources and have good biocompatibility and degradability; bio-based synthetic polymer curing agents are polymers with specific functional groups obtained from biomass raw materials through microbial fermentation or chemical synthesis methods; and degradable chemical synthetic curing agents are designed with specific chemical structures to make them biodegradable while meeting performance requirements.

[0004] With the increasing global awareness of environmental protection and the advancement of sustainable development strategies, green biodegradable epoxy resin curing technology is gradually becoming a research hotspot. The application of green biodegradable materials is gradually expanding in the fields of coatings, adhesives, packaging materials, agricultural mulch films, biomedical materials, etc. In the future, with the continuous advancement of technology and further reduction of costs, green biodegradable epoxy resin curing technology is expected to be commercialized in a wider range of fields. Summary of the invention

[0005] The technical problem to be solved by the present invention is the problem of environmental pollution caused by the difficulty in degradation of epoxy resin materials used in the prior art. A biodegradable epoxy resin potting adhesive and a preparation method and application thereof, as well as a degradation method of the biodegradable epoxy resin potting adhesive are provided. The potting material has certain biocompatibility and can be degraded under the action of microorganisms and natural conditions. The degradation products are non-toxic and harmless, and have broad application prospects.

[0006] In order to solve the above technical problems, the first aspect of the present invention provides a biodegradable epoxy resin potting adhesive, wherein the raw materials for preparing the epoxy resin potting adhesive include: epoxy resin, acid anhydride, antioxidant, accelerator, filler and coupling agent;

[0007] The acid anhydride is selected from the compound shown in formula I:

[0008]

[0009] In formula I, R and R' are the same or different and are independently selected from hydrogen, C1-C10 straight-chain alkyl, and C3-C10 branched-chain alkyl.

[0010] According to some embodiments of the present invention, in Formula I, R, R' are the same or different, and are each independently selected from hydrogen, a C1-C6 straight-chain alkyl group, or a C3-C6 branched-chain alkyl group; preferably, R, R' are the same or different, and are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, or tert-butyl.

[0011] According to some embodiments of the present invention, the compound represented by Formula I is at least one selected from diglycolic anhydride, dilactic anhydride, 2-hydroxybutyric anhydride, and 2-hydroxy-3-methylbutyric anhydride.

[0012] According to some embodiments of the present invention, the raw materials for preparing the epoxy resin potting glue include the following components in parts by weight: 100 parts of epoxy resin, 0.01 to 5 parts of antioxidant, 0.01 to 10 parts of accelerator, 1 to 100 parts of filler, 20 to 120 parts of acid anhydride, and 0.01 to 5 parts of coupling agent.

[0013] According to some embodiments of the present invention, the epoxy resin is selected from 2,3-epoxypropyl acrylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6'-methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, bis-(2,3-epoxycyclopentyl)-ether, 3,4-epoxycyclohexylmethyl-2',3'-epoxycyclohexyl ether, bis-(2,3-epoxycyclohexane), 1,2-bis-(2,3-epoxycyclohexyloxy)-ethane, bis-(2,3-epoxycyclohexyl)- At least one of 1,2-epoxycyclohexane-4,5-dicarboxylic acid epoxy resin, tetrahydrobenzene dimethyl ester epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and silicone modified epoxy resin.

[0014] According to some embodiments of the present invention, the bisphenol A epoxy resin includes at least one of Dow DER-330 (330 bisphenol A epoxy resin), DER-331 (331 bisphenol A epoxy resin), DER-332 (332 bisphenol A epoxy resin), DER-144 (144 bisphenol A epoxy resin), and DER-671 (671 bisphenol A epoxy resin).

[0015] According to some embodiments of the present invention, the bisphenol S epoxy resin includes at least one of DER-352 (352 bisphenol S epoxy resin), DER-353 (353 bisphenol S epoxy resin), and DER-354 (354 bisphenol S epoxy resin) produced by Dow Chemical.

[0016] According to some embodiments of the present invention, the organosilicon-modified epoxy resin includes at least one of EPSI-3201, EPSI-3202X, EPSI-6262, EPSI-3266, EPSI-6278, EPSI-3203X, EPSI-3866, EPSI-6862, EPSI-6878, EPSI-6200X and EPSI-6258X produced by Complex High-Tech Materials (Shanghai) Co., Ltd.

[0017] According to some embodiments of the present invention, the antioxidant is selected from at least one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis(β-(3,5-tert-butyl-4-methylphenyl) propionate), spiroglycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2-ethylenebis(4,6-di-tert-butylbenzene) fluorophosphorous acid, triphenyl phosphite, bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, trioctyl ester, tridecyl ester, tri(dodecanol) ester, tri(hexadecanol) ester, diphenylamine, p-phenylenediamine and dihydroquinoline.

[0018] According to some embodiments of the present invention, the accelerator is selected from at least one of aliphatic amines, aromatic amines, imidazoles and their derivatives, triazine compounds, organic phosphorus compounds, acetylacetonate metal salts, and rare earth metal complexes; preferably, the organic phosphorus compound is selected from triphenylphosphine and / or triethylphosphine.

[0019] According to some embodiments of the present invention, the particle size of the filler is 1 nm to 100 nm.

[0020] According to some embodiments of the present invention, the filler is selected from at least one of calcium carbonate, talc, barium sulfate, silicon dioxide, zinc oxide, titanium oxide, aluminum borate whiskers, aluminum oxide, sodium antimonate, antimony trioxide, apatite, attapulgite, barium metaborate, barium titanate, bentonite, bismuth oxide, boron oxide, calcium hydroxide, calcium sulfate, carbon black, ceramic microspheres, clay, diatomaceous earth, feldspar, hydrated calcium silicate, magnesium oxide, magnesium hydroxide, molybdenum disulfide, zinc borate and zinc sulfide.

[0021] According to some embodiments of the present invention, the coupling agent is selected from at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

[0022] The second aspect of the present invention provides a method for preparing the epoxy resin potting compound provided in the first aspect, comprising mixing the epoxy resin, anhydride, antioxidant, accelerator, filler and coupling agent in parts by weight, and removing bubbles in vacuum to obtain the epoxy resin potting compound.

[0023] According to some embodiments of the present invention, the curing conditions of the epoxy resin potting glue include: a curing temperature of 60° C. to 200° C., preferably 80° C. to 165° C., and a curing time of 1 h to 6 h.

[0024] The third aspect of the present invention provides the use of the epoxy resin potting compound described in the first aspect or the epoxy resin potting compound prepared by the preparation method described in the second aspect in the biomedical field, and can be particularly used for the preparation of medical electronic equipment, artificial heart components, orthopedic fixation materials, oral repair materials, etc.

[0025] In the present invention, the epoxy resin potting glue can also be used for electronic component packaging or for preparing coatings or for preparing engineering plastics, etc.

[0026] The fourth aspect of the present invention provides a method for degrading the epoxy resin potting compound described in the first aspect or the epoxy resin potting compound prepared by the preparation method described in the second aspect, wherein the epoxy resin potting material is placed in a pH buffer solution at a temperature of 90°C to 200°C for 5h to 24h; preferably, the pH value of the pH buffer solution is less than 2 or the pH is greater than 9.

[0027] In the present invention, the type of the pH buffer is not particularly limited; all of them are standard pH buffers that can be purchased commercially by those skilled in the art.

[0028] Beneficial effects:

[0029] The present invention aims at the environmental pollution problem caused by the difficulty in degradation of epoxy resin materials. By using a biodegradable anhydride curing agent, the prepared epoxy resin potting glue can be spontaneously degraded in natural environments such as seawater, soil, and industrial compost, and the degradation products are non-toxic and harmless, thereby solving the problem of environmental pollution. At the same time, the use of a biodegradable anhydride curing agent can improve the biocompatibility of the epoxy resin material, so that it can be applied in the biomedical field. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The data chart is a degradation performance test of the epoxy resin potting adhesive prepared in Examples 1-5 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0031] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0032] In the following examples and comparative examples of the present invention, unless otherwise specified, all raw materials used are commercially available.

[0033] In the following embodiments of the present invention, the compound represented by formula I can be prepared by a method comprising the following steps:

[0034] 1) In the presence of a solvent, aliphatic aldehyde and carbon monoxide are subjected to a carbonylation reaction under the action of an acid catalyst to obtain a reaction solution;

[0035] 2) Obtaining the compound represented by formula I by distilling the reaction solution under normal pressure.

[0036] The carbonylation reaction pathway in step 1) is shown as follows:

[0037]

[0038] According to some embodiments of the present invention, in step 1), the acid catalyst includes but is not limited to sulfuric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, heteropolyacid, phosphotungstic acid, ion exchange resin, and acidic molecular sieve.

[0039] According to some embodiments of the present invention, in step 1), during the carbonylation reaction, the carbon monoxide pressure is 3 MPa to 20 MPa, preferably 8 MPa to 12 MPa.

[0040] According to some embodiments of the present invention, in step 1), the temperature of the carbonylation reaction is 100°C to 250°C, preferably 140°C to 180°C.

[0041] According to some embodiments of the present invention, in step 1), the carbonylation reaction time is 0.5 h to 12 h, preferably 1 h to 4 h.

[0042] According to some embodiments of the present invention, in step 1), the solvent includes but is not limited to sulfolane, dioxane, methyl benzoate, cyclohexane, tetrahydrofuran, dichloromethane, and dimethyl sulfoxide.

[0043] According to some embodiments of the present invention, in step 1), the mass ratio of the fatty aldehyde to the solvent is 1:(5-125), preferably 1:(8-25).

[0044] According to some embodiments of the present invention, in step 1), the mass ratio of the acid catalyst to the fatty aldehyde is 1:(0.5-15), preferably 1:(1.25-5).

[0045] In the examples and comparative examples of the present invention, the preparation method of the diglycolic anhydride is as follows:

[0046] 15 parts of trioxymethylene, 3 parts of phosphotungstic acid, and 125 parts of cyclopentane sulfone were placed in a reaction kettle, 8MPa of CO gas was introduced, the stirring speed was 1000r / min, and the reaction was carried out at a temperature of 160°C for 2h to obtain a reaction solution. Then the obtained reaction solution was subjected to atmospheric distillation, and the effluent at 120°C to 140°C was collected. The effluent was cooled, crystallized, washed, and dried to obtain diglycolic anhydride powder with a purity of 95.6%.

[0047] In the embodiments and comparative examples of the present invention,

[0048] 3,4-Epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester was purchased from Daicel Corporation of Japan, model number 2021P;

[0049] DER-331 epoxy resin was purchased from The Dow Chemical Company;

[0050] DER-144 epoxy resin was purchased from The Dow Chemical Company;

[0051] 2,6-di-tert-butyl-4-methylphenol was purchased from Hubei Jiufenglong Chemical Co., Ltd.;

[0052] Triphenyl phosphite was purchased from Wuhan Jiyesheng Chemical Co., Ltd.;

[0053] Triphenylphosphine was purchased from Huainan Derui Chemical Co., Ltd.;

[0054] Spherical nano-silica (50 nm) was purchased from Xuancheng Jingrui New Materials Co., Ltd., model VK-SP50;

[0055] γ-Mercaptopropyltrimethoxysilane was purchased from Wuhan Xinweiye Chemical Co., Ltd.;

[0056] Methylhexahydrophthalic anhydride was purchased from Hubei Jiufenglong Chemical Co., Ltd.;

[0057] Methyltetrahydrophthalic anhydride was purchased from Wuhan Jiyesheng Chemical Co., Ltd.;

[0058] Phthalic anhydride was purchased from Kangdisi Chemical (Hubei) Co., Ltd.

[0059] Example 1

[0060] This embodiment is used to illustrate the biodegradable epoxy resin potting adhesive and its preparation method of the present invention.

[0061] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 50 parts of diglycolic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly, and vacuum degassed to obtain the epoxy resin potting glue.

[0062] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0063] Example 2

[0064] This embodiment is used to illustrate the biodegradable epoxy resin potting adhesive and its preparation method of the present invention.

[0065] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 80 parts of diglycolic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed evenly, and vacuum degassed to obtain the epoxy resin potting glue.

[0066] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0067] Example 3

[0068] This embodiment is used to illustrate the biodegradable epoxy resin potting adhesive and its preparation method of the present invention.

[0069] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 100 parts of diglycolic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly and vacuum degassed to obtain the epoxy resin potting glue.

[0070] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0071] Example 4

[0072] This embodiment is used to illustrate the biodegradable epoxy resin potting adhesive and its preparation method of the present invention.

[0073] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 20 parts of diglycolic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly, and vacuum degassed to obtain the epoxy resin potting glue.

[0074] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0075] Example 5

[0076] This embodiment is used to illustrate the biodegradable epoxy resin potting adhesive and its preparation method of the present invention.

[0077] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 120 parts of diglycolic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly, and vacuum degassed to obtain the epoxy resin potting glue.

[0078] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0079] Comparative Example 1

[0080] This comparative example is used to illustrate the biodegradable epoxy resin potting adhesive and the preparation method thereof of the present invention.

[0081] 70 parts of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 100 parts of methyltetrahydrophthalic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly, and vacuum degassed to obtain the epoxy resin potting glue.

[0082] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0083] Comparative Example 2

[0084] This comparative example is used to illustrate the biodegradable epoxy resin potting adhesive and the preparation method thereof of the present invention.

[0085] 70 parts of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 100 parts of methylhexahydrophthalic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly and vacuum degassed to obtain the epoxy resin potting glue.

[0086] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0087] Comparative Example 3

[0088] This comparative example is used to illustrate the biodegradable epoxy resin potting adhesive and the preparation method thereof of the present invention.

[0089] 70 parts of 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 100 parts of phthalic anhydride, 1 part of 2,6-di-tert-butyl-4-methylphenol, 0.5 parts of triphenyl phosphite, 0.5 parts of triphenylphosphine, 30 parts of spherical nano-silica (50 nm), and 0.1 parts of γ-mercaptopropyltrimethoxysilane are stirred and mixed uniformly and vacuum degassed to obtain the epoxy resin potting glue.

[0090] After the epoxy resin potting glue is injected into the mold, it is first cured at 130° C. for 1 hour and then cured at 150° C. for 4 hours to obtain a cubic cured product with a side length of 1 cm.

[0091] To further illustrate the advancement of the present invention, the biodegradable epoxy resin potting adhesives prepared in the above Examples 1-5 and Comparative Examples 1-3 are tested and evaluated for their performance using the following method.

[0092] (i) The solidified cubic bodies with a side length of 1 cm prepared in Examples 1-5 of the present invention and Comparative Examples 1-3 were respectively placed in a boric acid buffer solution with a pH value of 10.5 (purchased from Shanghai Shangbao Biotechnology Co., Ltd.), and heated to 120° C. for degradation. The remaining mass percentage (%) of the epoxy resin potting glue after degradation for 10 h was recorded. The results are shown in Table 1.

[0093] Table 1

[0094]

[0095]

[0096] It can be seen from the results in Table 1 above that the epoxy resin potting glue prepared by the present invention has excellent biodegradability, the residual mass ratio of the epoxy resin potting glue after 10 hours is significantly lower than that of comparative examples 1-3, and the epoxy resin potting glue prepared by the present invention can be completely degraded within 24 hours.

[0097] (II) Mechanical testing

[0098] Tensile test: The epoxy resin potting glue obtained in Examples 1-5 of the present invention and Comparative Examples 1-3 was respectively cured (first cured at 130°C for 1 h and then cured at 150°C for 4 h) to prepare strips with a length of 165 mm, a width of 13 mm, and a thickness of 3.2 mm. The tensile test was performed using an Instron Legend 2367 tensile testing machine. The tensile rate was set to 5 mm / min, and the maximum tensile load that the strips could withstand was read.

[0099] Bending test: The epoxy resin potting glue obtained in Examples 1-5 of the present invention and Comparative Examples 1-3 was cured (first cured at 130° C. for 1 h and then cured at 150° C. for 4 h) to form a 165 mm long, 13 mm wide, and 3.2 mm thick specimen, and a three-point bending test was performed using an FL universal material testing machine, with the distance between the two support points being 60 mm, and the maximum stress borne by the specimen under the bending load was recorded. The statistical results of the tensile test and the bending test are shown in Table 2.

[0100] Table 2

[0101]

[0102]

[0103] It can be seen from the results in Table 2 that the epoxy resin potting adhesive prepared by the present invention has excellent biodegradability while maintaining good mechanical properties; there is no obvious decrease in mechanical properties, and the application range is wide.

[0104] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A biodegradable epoxy resin potting adhesive, characterized in that: The raw materials for preparing the epoxy resin potting glue include: epoxy resin, acid anhydride, antioxidant, accelerator, filler and coupling agent; The acid anhydride is selected from the compound shown in formula I: In formula I, R and R' are the same or different and are independently selected from hydrogen, C1-C10 straight-chain alkyl, and C3-C10 branched-chain alkyl.

2. The epoxy resin potting adhesive according to claim 1, characterized in that: In Formula I, R, R' are the same or different, and are independently selected from hydrogen, C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl; preferably, R, R' are the same or different, and are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl; Further preferably, the compound represented by formula I is at least one selected from diglycolic anhydride, dilactic anhydride, 2-hydroxybutyric anhydride, and 2-hydroxy-3-methylbutyric anhydride.

3. The epoxy resin potting adhesive according to claim 1 or 2, characterized in that: The raw materials for preparing the epoxy resin potting glue include the following components in parts by weight: 100 parts of epoxy resin, 0.01 to 5 parts of antioxidant, 0.01 to 10 parts of accelerator, 1 to 100 parts of filler, 20 to 120 parts of acid anhydride, and 0.01 to 5 parts of coupling agent.

4. The epoxy resin potting adhesive according to any one of claims 1 to 3, characterized in that: The epoxy resin is selected from 2,3-epoxypropyl acrylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6'-methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, bis-(2,3-epoxycyclopentyl)-ether, 3,4-epoxycyclohexylmethyl-2',3'-epoxycyclohexyl ether, bis-(2,3-epoxycyclohexane), 1,2-bis-(2,3-epoxycyclohexyloxy)-ethane, bis-(2,3-epoxycyclohexyl) ether, 1, At least one of 1-bis(2',3'-epoxycyclohexyloxymethyl)-3,4-epoxycyclohexane, diglycidyl phthalate, 4,4-dihydroxydiphenyl sulfone diglycidyl ether, tetraphenol ethane tetraglycidyl ether, resorcinol diglycidyl ether, pyrogallol glycidyl, resorcinol acetal tetraglycidyl ether, p-aminophenol epoxy resin, 4,4'diaminodiphenylmethane tetraglycidylamine, 1,2-epoxycyclohexane-4,5-dicarboxylic acid epoxy resin, tetrahydrobenzene dimethyl ester epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and silicone modified epoxy resin.

5. The epoxy resin potting adhesive according to any one of claims 1 to 4, characterized in that: The antioxidant is selected from at least one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-methylphenol, bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis(β-(3,5-tert-butyl-4-methylphenyl) propionate), spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2-ethylenebis(4,6-di-tert-butylbenzene) fluorophosphorous acid, triphenyl phosphite, bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, trioctyl ester, tridecyl ester, tri(dodecanol) ester, tri(hexadecanol) ester, diphenylamine, p-phenylenediamine and dihydroquinoline; And / or, the accelerator is selected from at least one of aliphatic amines, aromatic amines, imidazoles and their derivatives, triazine compounds, organic phosphorus compounds, acetylacetonate metal salts, and rare earth metal complexes; preferably, the organic phosphorus compound is selected from triphenylphosphine and / or triethylphosphine.

6. The epoxy resin potting adhesive according to any one of claims 1 to 5, characterized in that: The filler is selected from at least one of calcium carbonate, talc, barium sulfate, silicon dioxide, zinc oxide, titanium oxide, aluminum borate whisker, aluminum oxide, sodium antimonate, antimony trioxide, apatite, attapulgite, barium metaborate, barium titanate, bentonite, bismuth oxide, boron oxide, calcium hydroxide, calcium sulfate, carbon black, ceramic microspheres, clay, diatomaceous earth, feldspar, hydrated calcium silicate, magnesium oxide, magnesium hydroxide, molybdenum disulfide, zinc borate and zinc sulfide; And / or, the particle size of the filler is 1 nm to 100 nm.

7. The epoxy resin potting adhesive according to any one of claims 1 to 6, characterized in that: The coupling agent is selected from at least one of γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

8. A method for preparing the epoxy resin potting adhesive according to any one of claims 1 to 7, characterized in that: include: The epoxy resin, anhydride, antioxidant, accelerator, filler and coupling agent in parts by weight are mixed, and bubbles are removed by vacuum to obtain the epoxy resin potting glue.

9. Use of the epoxy resin potting adhesive according to any one of claims 1 to 7 or the epoxy resin potting adhesive prepared by the preparation method according to claim 8 in the biomedical field.

10. A method for degrading the epoxy resin potting adhesive according to any one of claims 1 to 7 or the epoxy resin potting adhesive prepared by the preparation method according to claim 8, characterized in that: The epoxy resin encapsulating material is placed in a pH buffer solution at a temperature of 90° C. to 200° C. for 5 h to 24 h; preferably, the pH value of the pH buffer solution is less than 2 or the pH value is greater than 9.

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