Epoxy hyperbranched polymer, epoxy adhesive and preparation method of epoxy hyperbranched polymer

Abstract

The invention discloses an epoxy hyperbranched polymer, an epoxy adhesive and a preparation method of the epoxy hyperbranched polymer. The epoxy hyperbranched polymer is prepared by reacting hydroxyl silicone oil and glycerol triglycidyl ether in a molar ratio of 1: (1.2-2); the epoxy adhesive is composed of a component A and a component B, wherein the component A is obtained by mixing raw materials of epoxy resin, a diluent and an epoxy hyperbranched polymer, and the component B is obtained by mixing raw materials of methyl tetrahydrophthalic anhydride and a curing accelerator. The epoxy hyperbranched polymer is added into an epoxy curing system, so that the toughness and the impact resistance of a cured product can be remarkably improved, the curing shrinkage and the internal stress of the system can be remarkably reduced, and the weather resistance and the dimensional stability are enhanced; therefore, the prepared epoxy adhesive has the excellent properties of high toughness, high bonding strength, good weather resistance and good hydrophobicity at the same time.

Description

Technical Field

[0001] The present invention belongs to the technical field of epoxy adhesives, and more specifically, the present invention relates to an epoxy-based hyperbranched polymer, an epoxy adhesive and a preparation method thereof. Background Art

[0002] In the field of high-performance bonding and composite materials, epoxy resins are widely used due to their excellent mechanical properties, adhesion and chemical stability. However, traditional epoxy systems usually show high brittleness and insufficient toughness after curing, and have poor weather resistance and hydrophobicity, which limits their application in high impact, dynamic load and harsh environments. Summary of the invention

[0003] Based on this, the object of the present invention is to provide an epoxy adhesive having excellent properties such as high toughness, strong adhesion, strong weather resistance, and strong hydrophobicity.

[0004] The specific technical solutions for achieving the above-mentioned invention objectives include the following.

[0005] The first aspect of the present invention provides an epoxy hyperbranched polymer, which is prepared by reacting hydroxy silicone oil and glycerol triglycidyl ether; the molar ratio of the hydroxy silicone oil to glycerol triglycidyl ether is 1:1.2-2.

[0006] The second aspect of the present invention provides a method for preparing an epoxy hyperbranched polymer, comprising the following steps: under the protection of an inert gas, adding a catalyst to propylene glycol triglycidyl ether and hydroxy silicone oil, and reacting at 80° C. to 120° C. for 4 to 12 hours to obtain the polymer.

[0007] The third aspect of the present invention provides an epoxy adhesive, comprising component A and component B, wherein component A is obtained by mixing the following components in parts by weight:

[0008] Epoxy resin 70-90 parts

[0009] 5 to 10 parts of diluent

[0010] 10 to 30 parts of epoxy hyperbranched polymer;

[0011] The B component is obtained by mixing the following components in parts by weight:

[0012] Methyltetrahydrophthalic anhydride 95 to 99 parts

[0013] 1 to 5 parts of curing accelerator.

[0014] A fourth aspect of the present invention provides a method for preparing an epoxy adhesive, comprising the following steps:

[0015] (1) uniformly mixing an epoxy resin, a diluent, and an epoxy-based hyperbranched polymer to obtain a component A;

[0016] (2) Methyltetrahydrophthalic anhydride and a curing accelerator are mixed uniformly to obtain component B.

[0017] The present invention firstly uses a specific molar ratio of A2 monomer hydroxy silicone oil and B3 monomer propylene glycol triglycidyl ether to prepare an epoxy hyperbranched polymer, which introduces a flexible silicon oxygen segment, has high functionality and abundant terminal groups, and has a highly branched, dendrite-like three-dimensional network unit. Then the epoxy hyperbranched polymer of the present invention is added to an epoxy curing system to prepare an epoxy adhesive. On the one hand, the highly branched three-dimensional network unit including the silicon oxygen flexible segment can form a flexible network structure after the epoxy adhesive is cured, thereby effectively dispersing stress concentration points and improving fracture toughness and impact strength; on the other hand, the high-density functional groups of the epoxy hyperbranched polymer ensure efficient reaction and uniform dispersion with the epoxy group, so that the cured product has multiple advantages such as balanced microphase distribution, weakened stress concentration, reduced shrinkage and improved dimensional stability. Therefore, adding epoxy hyperbranched polymers to the epoxy curing system can not only significantly improve the toughness and impact resistance of the cured product, but also significantly reduce the curing shrinkage and internal stress of the system, enhance weather resistance and dimensional stability, so that the prepared epoxy adhesive has the excellent properties of high toughness, high bonding strength, weather resistance and good hydrophobicity. DETAILED DESCRIPTION

[0018] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0019] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items.

[0020] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used can be purchased from commercial channels unless otherwise specified.

[0021] In some embodiments of the present invention, an epoxy hyperbranched polymer is disclosed, which is prepared by reacting hydroxy silicone oil and glycerol triglycidyl ether; the molar ratio of the hydroxy silicone oil to glycerol triglycidyl ether is 1:1.2-2.

[0022] In some of the embodiments, the molar ratio of the hydroxy silicone oil to propylene glycol triglycidyl ether is 1:1.2-1.5.

[0023] In some embodiments, the structural formula of the hydroxy silicone oil is n is a positive integer ranging from 3 to 50.

[0024] In some embodiments, n=20-40.

[0025] In some embodiments, n=26-40.

[0026] In other embodiments of the present invention, a method for preparing an epoxy hyperbranched polymer is disclosed, comprising the following steps: under the protection of an inert gas, adding a catalyst to propylene glycol triglycidyl ether and hydroxy silicone oil, and reacting at 80° C. to 120° C. for 4 to 12 hours to obtain the polymer.

[0027] In some embodiments, the catalyst is a tertiary amine or an organic base.

[0028] In some embodiments, the tertiary amine is one or both of methylimidazole and triethylamine.

[0029] In some embodiments, the organic base is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0030] In some of the embodiments, the amount of the catalyst is 1-2% of the total mass of the glycerol triglycidyl ether and the hydroxy silicone oil.

[0031] In some of the embodiments, the amount of the catalyst used is 1-1.5% of the total mass of the glycerol triglycidyl ether and the hydroxy silicone oil.

[0032] In some embodiments, the reaction is carried out in the presence of a solvent. Adding a solvent can dilute the reaction and make it milder. The reaction can also be carried out without a solvent, but the reaction process will be more complicated, such as the need to dropwise add reactants to avoid local explosions that lead to gelation.

[0033] In some embodiments, the solvent is selected from one or more of acetone, butanone, ethylene dichloride, ethyl acetate, butyl acetate, dimethylformamide, toluene, and xylene.

[0034] In some of the embodiments, the amount of the solvent added is 1.5 to 2.5 times the total mass of the glycerol triglycidyl ether and the hydroxy silicone oil.

[0035] In some of the embodiments, the amount of the solvent added is 1.8 to 2.2 times the total mass of the propylene glycol triglycidyl ether and the hydroxy silicone oil.

[0036] In some of the embodiments, the preparation method of the epoxy hyperbranched polymer comprises the following steps: under the protection of inert gas, adding 1,8-diazabicyclo[5.4.0]undec-7-ene and dimethylformamide to propylene glycol triglycidyl ether and hydroxy silicone oil, reacting at 80° C. to 120° C. for 4 to 12 hours, and removing dimethylformamide to obtain the polymer.

[0037] In other embodiments of the present invention, an epoxy adhesive is disclosed, comprising a component A and a component B, wherein the component A is obtained by mixing the following components in parts by weight:

[0038] Epoxy resin 70-90 parts

[0039] 5 to 10 parts of diluent

[0040] 10 to 30 parts of epoxy hyperbranched polymer;

[0041] The B component is obtained by mixing the following components in parts by weight:

[0042] Methyltetrahydrophthalic anhydride 95 to 99 parts

[0043] 1 to 5 parts of curing accelerator.

[0044] In some embodiments, the epoxy adhesive comprises component A and component B, wherein component A is obtained by mixing the following components in parts by weight:

[0045] Epoxy resin 70-80 parts

[0046] 5 to 10 parts of diluent

[0047] 10 to 15 parts of epoxy hyperbranched polymer;

[0048] The B component is obtained by mixing the following components in parts by weight:

[0049] Methyltetrahydrophthalic anhydride 95 to 99 parts

[0050] 1 to 5 parts of curing accelerator.

[0051] In some embodiments, the epoxy resin is one or more of glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0052] In some embodiments, the diluent is one or more of aliphatic glycidyl ether, aromatic glycidyl ether and alicyclic glycidyl ether.

[0053] In some embodiments, the diluent is butanediol glycidyl ether.

[0054] In some embodiments, the curing accelerator is one or more of a quaternary ammonium salt, a tertiary amine and a benzylamine.

[0055] In some embodiments, the curing accelerator is tetrabutylammonium bromide.

[0056] In some embodiments, the weight ratio of component A to component B is 0.8-1.2:1.

[0057] In some embodiments, the weight ratio of component A to component B is 0.9-1.1:1.

[0058] In other embodiments of the present invention, a method for preparing the above-mentioned epoxy adhesive is disclosed, comprising the following steps:

[0059] (1) uniformly mixing an epoxy resin, a diluent, and an epoxy-based hyperbranched polymer to obtain a component A;

[0060] (2) Methyltetrahydrophthalic anhydride and a curing accelerator are mixed uniformly to obtain component B.

[0061] In the following embodiments of the present invention, the epoxy hyperbranched polymer (epoxy HBP) ​​obtained by reacting hydroxy silicone oil and glycerol triglycidyl ether as raw materials has the following reaction principle:

[0062]

[0063] in, Hydroxyl silicone oil In the product express " * ” Represents the key connection location.

[0064] The present invention is described in detail below with reference to specific embodiments.

[0065] Example 1

[0066] The epoxy adhesive of this embodiment includes the following preparation steps:

[0067] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0068] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:1.2), 1% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU is added, and then twice the total weight of dimethylformamide (DMF) is added; under the condition of 90°C, the mixture is refluxed at a constant temperature and stirred for 6 hours to obtain a mixture;

[0069] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0070] The infrared spectrum of the product shows that compared with hydroxy silicone oil at 3200cm -1 ~3600cm -1 The relatively broad OH stretching vibration peak of the product is at 3400 cm -1 ~3500cm -1 The OH stretching vibration peaks are relatively concentrated; propylene glycol triglycidyl ether is at 910 cm -1 ~950cm -1 There are strong CO stretching and epoxy characteristic peaks. The product still has epoxy characteristic peaks, but the peak intensity is significantly weakened.

[0071] 2. Preparation of epoxy adhesive

[0072] According to the distribution ratio of Group A in Table 1, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0073] According to the distribution ratio of Group B in Table 1, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0074] When using, mix components A and B evenly in a mass ratio of 1:1.

[0075] Table 1

[0076] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 80 Methyltetrahydrophthalic anhydride 98 Butanediol Glycidyl Ether 5 Tetrabutylammonium bromide 2 Epoxy HBP 15

[0077] Example 2

[0078] The epoxy adhesive of this embodiment includes the following preparation steps:

[0079] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0080] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:1.3), add 2% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU, and then add twice the total weight of dimethylformamide (DMF) of hydroxy silicone oil and glycerol triglycidyl ether; reflux at a constant temperature at 100°C and stir for 8 hours to obtain a mixture;

[0081] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0082] 2. Preparation of epoxy adhesive

[0083] According to the distribution ratio of Group A in Table 2, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0084] According to the distribution ratio of Group B in Table 2, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0085] When using, mix components A and B evenly in a mass ratio of 1:1.

[0086] Table 2

[0087] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 85 Methyltetrahydrophthalic anhydride 97 Butanediol Glycidyl Ether 5 Tetrabutylammonium bromide 3 Epoxy HBP 10

[0088] Example 3

[0089] The epoxy adhesive of this embodiment includes the following preparation steps:

[0090] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0091] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-100) and glycerol triglycidyl ether (molar ratio 1:1.5), 1.5% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU is added, and then twice the total weight of dimethylformamide (DMF) is added; under the condition of 80°C, the mixture is refluxed at a constant temperature and stirred for 4 hours to obtain a mixture;

[0092] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0093] 2. Preparation of epoxy adhesive

[0094] According to the distribution ratio of Group A in Table 3, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0095] According to the distribution ratio of Group B in Table 3, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0096] When using, mix components A and B evenly in a mass ratio of 1:1.

[0097] Table 3

[0098] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 75 Methyltetrahydrophthalic anhydride 99 Butanediol Glycidyl Ether 10 Tetrabutylammonium bromide 1 Epoxy HBP 15

[0099] Example 4

[0100] The epoxy adhesive of this embodiment includes the following preparation steps:

[0101] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0102] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-100) and glycerol triglycidyl ether (molar ratio 1:1.5), add 1.5% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU, and then add twice the total weight of dimethylformamide (DMF) of hydroxy silicone oil and glycerol triglycidyl ether; reflux at a constant temperature at 90°C and stir for 6 hours to obtain a mixture;

[0103] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0104] 2. Preparation of epoxy adhesive

[0105] According to the distribution ratio of Group A in Table 4, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0106] According to the distribution ratio of Group B in Table 4, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0107] When using, mix components A and B evenly in a mass ratio of 1:1.

[0108] Table 4

[0109] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 70 Methyltetrahydrophthalic anhydride 95 Butanediol Glycidyl Ether 5 Tetrabutylammonium bromide 5 Epoxy HBP 25

[0110] Example 5

[0111] The epoxy adhesive of this embodiment includes the following preparation steps:

[0112] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0113] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing 1% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether (brand name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:2), add 1% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU, and then add twice the total weight of dimethylformamide (DMF) of the hydroxy silicone oil and glycerol triglycidyl ether; reflux at a constant temperature of 95°C and stir for 6 hours to obtain a mixture;

[0114] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0115] 2. Preparation of epoxy adhesive

[0116] According to the distribution ratio of Group A in Table 5, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0117] According to the distribution ratio of Group B in Table 5, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0118] When using, mix components A and B evenly in a mass ratio of 1:1.

[0119] Table 5

[0120] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 85 Methyltetrahydrophthalic anhydride 96 Butanediol Glycidyl Ether 10 Tetrabutylammonium bromide 4 Epoxy HBP 10

[0121] Comparative Example 1

[0122] The epoxy adhesive of this comparative example comprises the following preparation steps:

[0123] According to the distribution ratio of Group A in Table 6, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0124] According to the distribution ratio of Group B in Table 6, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0125] When using, mix components A and B evenly in a mass ratio of 1:1.

[0126] Table 6

[0127] Component A Mass Component B Mass Bisphenol A glycidyl ether (EEW190) 95 Methyltetrahydrophthalic anhydride 95 Butanediol Glycidyl Ether 5 Tetrabutylammonium bromide 5 Epoxy HBP 0

[0128] Comparative Example 2

[0129] The epoxy adhesive of this comparative example comprises the following preparation steps:

[0130] According to the distribution ratio of Group A in Table 7, weigh the raw materials, stir and mix them evenly to obtain Component A;

[0131] According to the distribution ratio of Group B in Table 7, weigh the raw materials, stir and mix them evenly at 60°C to obtain Group B.

[0132] When using, mix components A and B evenly in a mass ratio of 1:1.

[0133] Table 7

[0134]

[0135] Comparative Example 3

[0136] The epoxy adhesive of this comparative example comprises the following preparation steps:

[0137] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0138] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-50) and pentaerythritol glycidyl ether (molar ratio 1:1.5), 1% of the total weight of hydroxy silicone oil and pentaerythritol glycidyl ether as catalyst DBU is added, and then twice the total weight of dimethylformamide (DMF) is added; under the condition of 90°C, the mixture is refluxed at a constant temperature and stirred for 6 hours to obtain a mixture;

[0139] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0140] 2. Preparation of epoxy adhesive

[0141] Same as Example 1.

[0142] Comparative Example 4

[0143] The epoxy adhesive of this comparative example comprises the following preparation steps:

[0144] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0145] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:1), add 1% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU, and then add twice the total weight of dimethylformamide (DMF) of hydroxy silicone oil and glycerol triglycidyl ether; reflux at a constant temperature at 90°C and stir for 6 hours to obtain a mixture;

[0146] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0147] 2. Preparation of epoxy adhesive

[0148] Same as Example 1.

[0149] Comparative Example 5

[0150] The epoxy adhesive of this comparative example comprises the following preparation steps:

[0151] 1. Preparation of epoxy hyperbranched polymer (epoxy HBP)

[0152] (1) Under nitrogen protection, in a container filled with hydroxy silicone oil ( In a three-necked flask containing hydroxy silicone oil (brand name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:2.5), 1% of the total weight of hydroxy silicone oil and glycerol triglycidyl ether as catalyst DBU is added, and then twice the total weight of dimethylformamide (DMF) is added; under the condition of 90°C, the mixture is refluxed at a constant temperature and stirred for 6 hours to obtain a mixture;

[0153] (2) distilling under reduced pressure and recovering the solvent, then adding the recovered solvent and repeating the distillation under reduced pressure for 3 times to obtain an epoxy hyperbranched polymer.

[0154] 2. Preparation of epoxy adhesive

[0155] Same as Example 1.

[0156] The adhesives prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were subjected to the following performance tests:

[0157] (1) Shear strength: tested according to GB / T 7124 method.

[0158] (2) Coefficient of thermal expansion (CTE): TMA method.

[0159] (3) Impact toughness: tested according to GB / T 1043 method.

[0160] (4) Water absorption: Weigh the mass change of the dry and clean sample before and after immersion in 25°C pure water.

[0161] (5) UV aging: After 7 days of UV irradiation, the retention rate was tested using the above shear strength method.

[0162] The results are shown in Table 8.

[0163] Table 8 Performance results of various epoxy adhesives

[0164]

[0165] It can be seen from Table 8 that the epoxy adhesives prepared by adding the epoxy hyperbranched polymers of the present invention (Examples 1 to 5) have higher shear strength, impact toughness, aging retention rate, and lower thermal expansion coefficient and water absorption rate.

[0166] Compared with Example 4, the epoxy adhesive prepared without adding the epoxy hyperbranched polymer of the present invention (Comparative Example 1) or the epoxy adhesive prepared with adding linear polysiloxane diol (Comparative Example 2) has significantly reduced shear strength, impact toughness, and aging retention rate, while significantly increased thermal expansion coefficient and water absorption rate.

[0167] In Comparative Example 3, an epoxy hyperbranched polymer was prepared using hydroxy silicone oil and pentaerythritol glycidyl ether as raw materials. Due to excessive branching, the polymer was a gel or had hardened and could not provide further applications. Therefore, when it was added to the epoxy system, the shear strength, impact toughness, aging retention rate, thermal expansion coefficient and water absorption performance were all poor.

[0168] In Comparative Example 4, an epoxy hyperbranched polymer was prepared using hydroxy silicone oil and propylene glycol triglycidyl ether in a molar ratio of 1:1 as raw materials. The polymer had already gelled and solidified. When it was added to the epoxy system, it could not function. Its shear strength, impact toughness, aging retention rate, thermal expansion coefficient and water absorption performance were all poor.

[0169] In Comparative Example 5, an epoxy hyperbranched polymer was prepared using hydroxy silicone oil and propylene glycol triglycidyl ether in a molar ratio of 1:2.5 as raw materials. There were too many excess epoxy groups in the polymer. After being added to the epoxy system, the cross-linking density was higher and the brittleness was increased accordingly, which had the opposite effect of toughening. Therefore, the overall performance of the epoxy adhesive in Comparative Example 5 was poor.

[0170] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0171] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An epoxy hyperbranched polymer, characterized in that The invention is prepared by reacting hydroxy silicone oil and glycerol triglycidyl ether; the molar ratio of the hydroxy silicone oil to glycerol triglycidyl ether is 1:1.2-2, preferably 1:1.2-1.

5.

2. The epoxy hyperbranched polymer according to claim 1, characterized in that The structural formula of the hydroxy silicone oil is n is a positive integer of 3-50, preferably n=20-40, more preferably 26-40.

3. A method for preparing an epoxy hyperbranched polymer according to claim 1 or 2, characterized in that: The following steps are involved: Under the protection of inert gas, add catalyst to propylene glycol triglycidyl ether and hydroxy silicone oil, and react at 80°C-120°C for 4-12 hours to obtain the product.

4. The method for preparing an epoxy hyperbranched polymer according to claim 3, wherein The catalyst is a tertiary amine or an organic base; Preferably, the tertiary amine is one or both of methylimidazole and triethylamine, and the organic base is 1,8-diazabicyclo[5.4.0]undec-7-ene; Preferably, the amount of the catalyst used is 1% to 2% of the total mass of the glycerol triglycidyl ether and the hydroxy silicone oil, preferably 1% to 1.5%.

5. The method for preparing an epoxy hyperbranched polymer according to claim 3, wherein The reaction is carried out in the presence of a solvent; Preferably, the solvent is selected from one or more of acetone, butanone, ethylene dichloride, ethyl acetate, butyl acetate, dimethylformamide, toluene, and xylene; Preferably, the amount of the solvent added is 1.5 to 2.5 times, preferably 1.8 to 2.2 times, the total mass of the glycerol triglycidyl ether and the hydroxy silicone oil.

6. The method for preparing an epoxy hyperbranched polymer according to claim 3, characterized in that: The following steps are involved: Under the protection of inert gas, add 1,8-diazabicyclo[5.4.0]undec-7-ene and dimethylformamide to propylene glycol triglycidyl ether and hydroxy silicone oil, react at 80°C to 120°C for 4 to 12 hours, and remove dimethylformamide to obtain the product.

7. An epoxy adhesive, characterized in that: The invention comprises component A and component B, wherein component A is obtained by mixing the following components in parts by weight: Epoxy resin 70-90 parts 5 to 10 parts of diluent 10 to 30 parts of the epoxy hyperbranched polymer according to claim 1 or 2; The B component is obtained by mixing the following components in parts by weight: Methyltetrahydrophthalic anhydride 95 to 99 parts 1 to 5 parts of curing accelerator.

8. The epoxy adhesive according to claim 7, characterized in that: The A component is obtained by mixing the following components in parts by weight: Epoxy resin 70-80 parts 5 to 10 parts of diluent 10 to 15 parts of epoxy hyperbranched polymer; The B component is obtained by mixing the following components in parts by weight: Methyltetrahydrophthalic anhydride 95 to 99 parts 1 to 5 parts of curing accelerator.

9. The epoxy adhesive according to claim 7 or 8, characterized in that: The epoxy resin is one or more of glycidyl ether epoxy resin and glycidyl ester epoxy resin; And / or, the diluent is one or more of aliphatic glycidyl ether, aromatic glycidyl ether and alicyclic glycidyl ether; preferably butanediol glycidyl ether; And / or, the curing accelerator is one or more of a quaternary ammonium salt, a tertiary amine and benzylamine; preferably tetrabutylammonium bromide; And / or, the weight ratio of component A to component B is 0.8-1.2:1; preferably 0.9-1.1:

1.

10. A method for preparing the epoxy adhesive according to any one of claims 7 to 9, characterized in that: The following steps are involved: (1) uniformly mixing an epoxy resin, a diluent, and an epoxy-based hyperbranched polymer to obtain a component A; (2) Methyltetrahydrophthalic anhydride and a curing accelerator are mixed uniformly to obtain component B.

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