Epoxy-based hyperbranched polymers, epoxy adhesives, and methods of making the same

Abstract

The application discloses an epoxy-based hyperbranched polymer, an epoxy adhesive and a preparation method of the epoxy adhesive. The epoxy-based hyperbranched polymer is prepared by reacting hydroxyl silicone oil and glycerol triglycidyl ether with a molar ratio of 1:1.2-2; the epoxy adhesive is composed of an A component obtained by mixing raw materials of an epoxy resin, a diluent and the epoxy-based hyperbranched polymer and a B component obtained by mixing raw materials of methyltetrahydrophthalic anhydride and a curing accelerator. The addition of the epoxy-based hyperbranched polymer in an epoxy curing system can not only significantly improve the toughness and impact resistance of a cured product, but also significantly reduce the curing shrinkage and internal stress of the system, enhance the weather resistance and dimensional stability, so that the prepared epoxy adhesive simultaneously has excellent performances of high toughness, high bonding strength, good weather resistance and good hydrophobicity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of epoxy glue, and more particularly, the present application relates to an epoxy-based hyperbranched polymer, an epoxy adhesive and a preparation method thereof. BACKGROUND

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

[0003] Therefore, the purpose of the present application is to provide an epoxy adhesive with high toughness, strong adhesion, strong weather resistance and strong hydrophobicity.

[0004] The specific technical solutions to achieve the above-mentioned purposes include the following.

[0005] In a first aspect of the present application, an epoxy-based hyperbranched polymer is provided, which is prepared from hydroxyl silicone oil and glycerol triglycidyl ether; the molar ratio of the hydroxyl silicone oil to the glycerol triglycidyl ether is 1:1.2-2.

[0006] In a second aspect of the present application, a preparation method of an epoxy-based hyperbranched polymer is provided, comprising the following steps: under the protection of inert gas, a catalyst is added to glycerol triglycidyl ether and hydroxyl silicone oil, and then reacted at 80-120℃ for 4-12 hours to obtain the product.

[0007] In a third aspect of the present application, an epoxy adhesive is provided, which comprises component A and component B, wherein the component A is obtained by mixing the following components in the weight parts:

[0008] Epoxy resin 70-90 parts

[0009] Diluent 5-10 parts

[0010] Epoxy-based hyperbranched polymer 10-30 parts

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

[0012] Methyltetrahydrophthalic anhydride 95-99 parts

[0013] Curing accelerator 1-5 parts.

[0014] In a fourth aspect of the present application, a preparation method of an epoxy adhesive is provided, comprising the following steps:

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

[0016] (2) mixing methyltetrahydrophthalic anhydride, curing accelerator uniformly to obtain component B.

[0017] The present application first utilizes A2 monomer hydroxyl silicone oil and B3 monomer glycerol triglycidyl ether with a specific molar ratio to prepare an epoxy-based hyperbranched polymer. The hyperbranched polymer introduces a flexible silicon-oxygen chain segment and has high functionality and rich terminal groups, and has a highly branched three-dimensional network unit in a dendritic shape. Then the epoxy-based hyperbranched polymer of the present application 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 glue 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-based hyperbranched polymer ensure efficient reaction and uniform dispersion with epoxy groups, so that the cured product has multiple advantages such as balanced micro-phase distribution, weakened stress concentration, reduced shrinkage and improved dimensional stability. Therefore, adding the epoxy-based hyperbranched polymer 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 the weather resistance and dimensional stability, so that the prepared epoxy adhesive has excellent properties such as high toughness, high bonding strength, good weather resistance and good hydrophobicity. DETAILED DESCRIPTION

[0018] In order to facilitate the understanding of the present application, the present application will be described more fully below. The present application 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 application more thorough and comprehensive.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The use of the terms "and / or" includes a combination of one or more of the associated listed items.

[0020] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are commercially available unless otherwise specified.

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

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

[0023] In some embodiments, the hydroxyl silicone oil has a structural formula of n is a positive integer of 3-50.

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

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

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

[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 methyl imidazole and triethylamine.

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

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

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

[0032] In some embodiments, the reaction is carried out in the presence of a solvent. The addition of a solvent can serve to dilute the reaction, making it milder; the reaction can also be carried out without a solvent, but the process can be more complicated, such as requiring the dropwise addition of reactants to avoid local explosive polymerization leading to gelation.

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

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

[0035] In some embodiments, the solvent is added in an amount of 1.8-2.2 times the total mass of the glycerol triglycidyl ether and the hydroxyl silicone oil.

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

[0037] In some embodiments of the present application, 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] Diluent 5-10 parts

[0040] Epoxy-based hyperbranched polymer 10-30 parts;

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

[0042] Methyltetrahydrophthalic anhydride 95-99 parts

[0043] Curing accelerator 1-5 parts.

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

[0045] Epoxy resin 70-80 parts

[0046] Diluent 5-10 parts

[0047] Epoxy-based hyperbranched polymer 10-15 parts;

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

[0049] Methyltetrahydrophthalic anhydride 95-99 parts

[0050] Curing accelerator 1-5 parts.

[0051] In some embodiments, the epoxy resin is one or more of glycidyl ether-based epoxy resin and glycidyl ester-based 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 the A component to the B component is 0.8-1.2:1.

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

[0058] In some embodiments of the present application, a preparation method of the epoxy adhesive is disclosed, comprising the following steps:

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

[0060] (2) mixing the methyltetrahydrophthalic anhydride and the curing accelerator uniformly to obtain the B component.

[0061] In the following embodiments of the present application, the epoxy-based hyperbranched polymer (epoxy-based HBP) is obtained by reacting hydroxyl silicone oil and glycerol triglycidyl ether as raw materials, and the reaction principle is as follows:

[0062]

[0063] wherein, represents hydroxyl silicone oil in the product represents " * ” represents the position of bond connection.

[0064] The present application will be described in detail below in combination with specific embodiments.

[0065] Embodiment 1

[0066] The epoxy adhesive of the present embodiment comprises the following preparation steps:

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

[0068] (1) Under nitrogen protection, hydroxyl silicone oil (A) and glycerol triglycidyl ether (B) are mixed in a molar ratio of 1:3 to obtain a mixture. In a three-necked flask containing GY-21A-50 and glycerol triglycidyl ether (molar ratio 1:1.2), 1% of the total mass of hydroxyl silicone oil and glycerol triglycidyl ether catalyst DBU was added, followed by twice the total mass of hydroxyl silicone oil and glycerol triglycidyl ether dimethylformamide (DMF); the mixture was refluxed at 90°C and stirred for 6 hours to obtain a mixture.

[0069] (2) Distill under reduced pressure and recover the solvent. Then add the recovered solvent and repeat the distillation under reduced pressure three times to obtain the epoxy hyperbranched polymer.

[0070] The infrared spectrum of the product shows that, compared to hydroxyl silicone oil, it exhibits higher performance at 3200 cm⁻¹. -1 ~3600cm -1 The product exhibits a relatively broad OH stretching vibration peak at 3400 cm⁻¹. -1 ~3500cm -1 The OH stretching vibration peaks are relatively concentrated; glycerol triglycidyl ether shows a peak at 910 cm⁻¹. -1 ~950cm -1 It exhibits strong CO stretching and epoxy characteristic peaks, and the product still has epoxy characteristic peaks, but the peak intensity is significantly reduced.

[0071] 2. Preparation of epoxy adhesive

[0072] According to the proportion of group A in Table 1, weigh the raw materials, stir and mix them evenly to obtain group A;

[0073] According to the proportion of group B in Table 1, weigh the raw materials and stir them evenly at 60℃ to obtain group B.

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

[0075] Table 1

[0076] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 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-based hyperbranched polymers (epoxy HBP)

[0080] (1) Under nitrogen protection, in a container filled with hydroxyl silicone oil ( In a three-necked flask containing GY-21A-50 and glycerol triglycidyl ether (molar ratio 1:1.3), 2% (by mass) of catalyst DBU (total mass of hydroxyl silicone oil and glycerol triglycidyl ether) was added, followed by twice the total mass of dimethylformamide (DMF). The mixture was refluxed at 100°C and stirred for 8 hours to obtain the final mixture.

[0081] (2) Distill under reduced pressure and recover the solvent. Then add the recovered solvent and repeat the distillation under reduced pressure three times to obtain the epoxy hyperbranched polymer.

[0082] 2. Preparation of epoxy adhesive

[0083] According to the proportion of group A in Table 2, weigh the raw materials, stir and mix them evenly to obtain group A;

[0084] According to the proportion of group B in Table 2, weigh the raw materials and stir them evenly at 60℃ to obtain group B.

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

[0086] Table 2

[0087] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 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-based hyperbranched polymers (epoxy HBP)

[0091] (1) Under nitrogen protection, in a container filled with hydroxyl silicone oil ( In a three-necked flask containing GY-21A-100 and glycerol triglycidyl ether (molar ratio 1:1.5), 1.5% of the total mass of hydroxyl silicone oil and glycerol triglycidyl ether catalyst DBU was added, followed by twice the total mass of hydroxyl silicone oil and glycerol triglycidyl ether dimethylformamide (DMF); the mixture was refluxed at 80°C and stirred for 4 hours to obtain a mixture.

[0092] (2) Distill under reduced pressure and recover the solvent. Then add the recovered solvent and repeat the distillation under reduced pressure three times to obtain the epoxy hyperbranched polymer.

[0093] 2. Preparation of epoxy adhesive

[0094] According to the proportion of group A in Table 3, weigh the raw materials, stir and mix them evenly to obtain group A;

[0095] According to the proportion of group B in Table 3, weigh the raw materials and stir them evenly at 60℃ to obtain group B.

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

[0097] Table 3

[0098] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 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-based hyperbranched polymers (epoxy HBP)

[0102] (1) Under nitrogen protection, in a container filled with hydroxyl silicone oil ( In a three-necked flask containing GY-21A-100 and glycerol triglycidyl ether (molar ratio 1:1.5), 1.5% of the total mass of hydroxyl silicone oil and glycerol triglycidyl ether, of catalyst DBU, was added, followed by twice the total mass of hydroxyl silicone oil and glycerol triglycidyl ether, of dimethylformamide (DMF). The mixture was refluxed at 90°C and stirred for 6 hours to obtain a mixture.

[0103] (2) Distill under reduced pressure and recover the solvent. Then add the recovered solvent and repeat the distillation under reduced pressure three times to obtain the epoxy hyperbranched polymer.

[0104] 2. Preparation of epoxy adhesive

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

[0106] According to the proportion of group B in Table 4, weigh the raw materials and stir them evenly at 60℃ to obtain group B.

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

[0108] Table 4

[0109] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 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-based hyperbranched polymers (epoxy HBP)

[0113] (1) Under nitrogen protection, in a container filled with hydroxyl silicone oil ( A three-necked flask with a stirrer, a thermometer, a dropping funnel and a reflux condenser, which was charged with hydroxyl silicone oil and glycerol triglycidyl ether (molar ratio 1:2), was added 1% of the total mass of the hydroxyl silicone oil and glycerol triglycidyl ether of catalyst DBU, and then added twice the total mass of the hydroxyl silicone oil and glycerol triglycidyl ether of dimethylformamide (DMF). The mixture was stirred at 95°C under constant temperature reflux for 6 hours to obtain a mixture;

[0114] (2) The solvent was recovered by distillation under reduced pressure, and then the recovered solvent was added and the distillation under reduced pressure was repeated 3 times to obtain the epoxy-based hyperbranched polymer.

[0115] 2. Preparation of the epoxy adhesive

[0116] The raw materials were weighed according to the allocation ratio of the A component in Table 5, and were stirred and mixed uniformly at 60°C to obtain the A component.

[0117] The raw materials were weighed according to the allocation ratio of the B component in Table 5, and were stirred and mixed uniformly at 60°C to obtain the B component.

[0118] In use, the A and B components were mixed uniformly at a mass ratio of 1:1.

[0119] Table 5

[0120] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 85 Methyltetrahydrophthalic anhydride 96 Butanediol glycidyl ether 10 Tetrabutylammonium bromide 4 Epoxy HBP 10

[0121] Comparative Example 1

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

[0123] The raw materials were weighed according to the allocation ratio of the A component in Table 6, and were stirred and mixed uniformly at 60°C to obtain the A component.

[0124] The raw materials were weighed according to the allocation ratio of the B component in Table 6, and were stirred and mixed uniformly at 60°C to obtain the B component.

[0125] In use, the A and B components were mixed uniformly at a mass ratio of 1:1.

[0126] Table 6

[0127] Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) 95 Methyltetrahydrophthalic anhydride 95 Butanediol glycidyl ether 5 Tetrabutylammonium bromide 5 Epoxy HBP Component A Parts by mass Component B Parts by mass Bisphenol A-type glycidyl ether (EEW 190) Methyltetrahydrophthalic anhydride Butanediol glycidyl ether Tetrabutylammonium bromide Epoxy HBP 0

[0128] Comparative Example 2

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

[0130] The raw materials were weighed according to the allocation ratio of the A component in Table 7, and were stirred and mixed uniformly at 60°C to obtain the A component.

[0131] The raw materials were weighed according to the allocation ratio of the B component in Table 7, and were stirred and mixed uniformly at 60°C to obtain the B component.

[0132] In use, the components A and B are mixed uniformly in a mass ratio of 1:1.

[0133] Table 7

[0134]

[0135] Comparative Example 3

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

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

[0138] (1) Under nitrogen protection, a three-necked flask containing hydroxyl silicone oil (trade name GY-21A-50) and pentaerythritol glycidyl ether (molar ratio 1:1.5) was added with 1% of catalyst DBU based on the total mass of the hydroxyl silicone oil and pentaerythritol glycidyl ether, and then twice the total mass of dimethylformamide (DMF) was added; under the condition of 90°C, constant temperature refluxing and stirring for 6 hours to obtain a mixture; (2) Vacuum distillation and recovery of the solvent, followed by repeated vacuum distillation 3 times with the recovered solvent to obtain an epoxy-based hyperbranched polymer.

[0139] 2. Preparation of epoxy adhesive

[0140] The same as Example 1.

[0141] Comparative Example 4

[0142] The epoxy adhesive of the present comparative example comprises the following preparation steps:

[0143] 1. Preparation of epoxy-based hyperbranched polymer (epoxy-based HBP)

[0144] (1) Under nitrogen protection, a three-necked flask containing hydroxyl silicone oil (trade name GY-21A-50) and pentaerythritol glycidyl ether (molar ratio 1:1.5) was added with 1% of catalyst DBU based on the total mass of the hydroxyl silicone oil and pentaerythritol glycidyl ether, and then twice the total mass of dimethylformamide (DMF) was added; under the condition of 90°C, constant temperature refluxing and stirring for 6 hours to obtain a mixture;

[0145] (2) Vacuum distillation and recovery of the solvent, followed by repeated vacuum distillation 3 times with the recovered solvent to obtain an epoxy-based hyperbranched polymer.

[0146] 2. Preparation of epoxy adhesive

[0147] The same as Example 1.

[0148] The same as Example 1. ​

[0149] Comparative Example 5

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

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

[0152] (1) Under nitrogen protection, a three-necked flask was charged with hydroxyl silicone oil (trade name GY-21A-50) and glycerol triglycidyl ether (molar ratio 1:2.5), 1% of the total mass of the hydroxyl silicone oil and glycerol triglycidyl ether was added as catalyst DBU, and twice the total mass of the hydroxyl silicone oil and glycerol triglycidyl ether was added as dimethylformamide (DMF); under the condition of 90°C, constant temperature reflux, and stirring for 6 hours, a mixture was obtained; (2) Distillation under reduced pressure, and recovery of the solvent, then repeated distillation under reduced pressure 3 times, to obtain the epoxy-based hyperbranched polymer.

[0153] 2. Preparation of epoxy adhesive

[0154] The same as Example 1.

[0155] The adhesives prepared in Comparative Examples 1-5 and Examples 1-5 were tested for the following properties:

[0156] (1) Shear strength: tested according to GB / T 7124 method.

[0157] (2) Coefficient of thermal expansion (CTE): TMA method.

[0158] (3) Impact toughness: tested according to GB / T 1043 method.

[0159] (4) Water absorption: dry and clean sample, weigh the mass change before and after soaking in pure water at 25°C.

[0160] (5) UV aging: after 7 days of UV lamp irradiation, test the retention rate according to the above shear strength method.

[0161] The results are shown in Table 8.

[0162] Table 8 Performance results of various epoxy adhesives

[0163]

[0164] As can be seen from Table 8, the epoxy adhesives prepared by adding the epoxy-based hyperbranched polymer of the present application (Examples 1-5) have high shear strength, impact toughness, aging retention rate, low coefficient of thermal expansion, and low water absorption.

[0165]

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

[0167] In Comparative Example 3, the epoxy-based hyperbranched polymer was prepared using hydroxyl 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 application, so when it was added to the epoxy system, the shear strength, impact toughness, aging retention rate, thermal expansion coefficient and water absorption rate were all poor.

[0168] In Comparative Example 4, the epoxy-based hyperbranched polymer was prepared using hydroxyl silicone oil and pentaerythritol glycidyl ether as raw materials. The polymer had gelled and hardened, and when it was added to the epoxy system, it could not function, and the shear strength, impact toughness, aging retention rate, thermal expansion coefficient and water absorption rate were all poor.

[0169] In Comparative Example 5, the epoxy-based hyperbranched polymer was prepared using hydroxyl silicone oil and pentaerythritol glycidyl ether as raw materials. The epoxy group in the polymer was too excessive, and after being added to the epoxy system, it led to a greater crosslinking density and an increase in brittleness, which had the opposite effect of toughening, so the comprehensive performance of the epoxy adhesive in Comparative Example 5 was poor.

[0170] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, but as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0171] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be noted that for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the present application should be subject to the appended claims.

Claims

1. An epoxy-based hyperbranched polymer, characterized in that, It is prepared by reacting hydroxyl silicone oil and glycerol triglycidyl ether; the molar ratio of the hydroxyl silicone oil to the glycerol triglycidyl ether is 1:1.2~2.

2. The epoxy-based hyperbranched polymer according to claim 1, characterized in that, The molar ratio of the hydroxyl silicone oil to glycerol triglycidyl ether is 1:1.2~1.

5.

3. The epoxy-based hyperbranched polymer according to claim 1, characterized in that, The structural formula of the hydroxyl silicone oil is as follows: n is a positive integer from 3 to 50.

4. The epoxy-based hyperbranched polymer according to claim 3, characterized in that, The n = 20~40.

5. The epoxy-based hyperbranched polymer according to claim 4, characterized in that, The n=26~40.

6. A method for preparing the epoxy-based hyperbranched polymer according to any one of claims 1 to 5, characterized in that, Includes the following steps: Under inert gas protection, a catalyst is added to glycerol triglycidyl ether and hydroxyl silicone oil, and the reaction is carried out at 80℃~120℃ for 4 to 12 hours to obtain the product.

7. The method for preparing the epoxy-based hyperbranched polymer according to claim 6, characterized in that, The catalyst is an organic base.

8. The method for preparing the epoxy-based hyperbranched polymer according to claim 7, characterized in that, The organic base is methylimidazolium, triethylamine, or 1,8-diazabicyclo[5.4.0]undec-7-ene.

9. The method for preparing the epoxy-based hyperbranched polymer according to claim 6, characterized in that, The amount of catalyst used is 1% to 2% of the total mass of the glycerol triglycidyl ether and hydroxy silicone oil.

10. The method for preparing the epoxy-based hyperbranched polymer according to claim 9, characterized in that, The amount of catalyst used is 1% to 1.5% of the total mass of the glycerol triglycidyl ether and hydroxy silicone oil.

11. The method for preparing the epoxy-based hyperbranched polymer according to claim 6, characterized in that, The reaction is carried out in the presence of a solvent.

12. The method for preparing the epoxy-based hyperbranched polymer according to claim 11, characterized in that, The solvent is selected from one or more of acetone, butanone, dichloroethane, ethyl acetate, butyl acetate, dimethylformamide, toluene, and xylene.

13. The method for preparing the epoxy-based hyperbranched polymer according to claim 11, characterized in that, The amount of solvent added is 1.5 to 2.5 times the total mass of the glycerol triglycidyl ether and hydroxyl silicone oil.

14. The method for preparing the epoxy-based hyperbranched polymer according to claim 13, characterized in that, The amount of solvent added is 1.8 to 2.2 times the total mass of the glycerol triglycidyl ether and hydroxyl silicone oil.

15. The method for preparing the epoxy-based hyperbranched polymer according to claim 6, characterized in that, Includes the following steps: Under inert gas protection, 1,8-diazabicyclo[5.4.0]undec-7-ene and dimethylformamide are added to glycerol triglycidyl ether and hydroxy silicone oil, and the mixture is reacted at 80℃~120℃ for 4 to 12 hours to remove dimethylformamide, thus obtaining the final product.

16. An epoxy adhesive, characterized in that, It includes component A and component B, wherein component A is obtained by mixing the following components in parts by weight: 70-90 parts epoxy resin 5 to 10 parts diluent 10 to 30 parts of the epoxy-based hyperbranched polymer according to any one of claims 1 to 5; Component B is obtained by mixing the following components in parts by weight: 95-99 parts of methyltetrahydrophthalic anhydride 1 to 5 parts of curing accelerator.

17. The epoxy adhesive according to claim 16, characterized in that, Component A is obtained by mixing the following components in parts by weight: 70-80 parts epoxy resin 5 to 10 parts diluent 10 to 15 parts of epoxy-based hyperbranched polymer; Component B is obtained by mixing the following components in parts by weight: 95-99 parts of methyltetrahydrophthalic anhydride 1 to 5 parts of curing accelerator.

18. The epoxy adhesive according to claim 16 or 17, 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; And / or, the curing accelerator is one or more of quaternary ammonium salts, tertiary amines, and benzylamine; And / or, the weight ratio of component A to component B is 0.8~1.2:

1.

19. The epoxy adhesive according to claim 18, characterized in that, The diluent is butylene glycol glycidyl ether; the curing accelerator is tetrabutylammonium bromide; the weight ratio of component A to component B is 0.9~1.1:

1.

20. A method for preparing the epoxy adhesive according to any one of claims 16-19, characterized in that, Includes the following steps: (1) Mix epoxy resin, diluent, and epoxy hyperbranched polymer evenly to obtain component A; (2) Mix methyltetrahydrophthalic anhydride and curing accelerator evenly to obtain component B.

Images