Modifier containing beta hydroxyl-carbamate group as well as preparation method and application of modifier

Abstract

The invention provides a modifier containing a beta hydroxyl-carbamate group, a preparation method of the modifier and application of the modifier to an epoxy resin adhesive. Specifically, the modifier is prepared by carrying out a ring-opening reaction on cyclic carbonate containing monofunctionality and a primary amino compound containing Si-O, and the preparation method is simple and easy to operate. Besides, the modifier is added into an epoxy resin system through a physical bonding method, beta-site hydroxyl and carbamate groups in the structure of the modifier can effectively adjust the interface bonding capacity between an epoxy resin curing product and a base material, and meanwhile the toughness of the epoxy resin curing product can be further improved. And in the use process of the epoxy resin adhesive, the modifier can interact with hydroxyl in the surface of an inorganic base material as well as a long molecular chain in an organic polymer, so that materials with different properties are coupled, the aim of improving the adhesion of the materials is achieved, and the actual requirements are met.

Description

Technical Field

[0001] The invention relates to a modifier and a preparation method thereof, in particular to a modifier containing a beta hydroxy-carbamate group and a preparation method and application thereof, belonging to the technical field of polymer materials. Background Art

[0002] Epoxy resin adhesive is an adhesive composed of epoxy resin matrix, curing agent and other additives. It has excellent bonding performance, temperature resistance, corrosion resistance and wear resistance. It can be used to bond metal, plastic, glass, wood, stone, rubber, leather and other materials, and is widely used in automobile, furniture, electronics, machinery, construction and other industries. Common types of epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic epoxy resin. Affected by their structural characteristics, the corresponding epoxy resin adhesive cured products have the following defects: First, the cross-linking density of the cured product is too large, and the rigid group content is high, resulting in poor toughness and impact resistance. Second, its adhesion to substrates with low polarity, such as polycarbonate sheets, is poor. These two defects seriously limit the application scope of epoxy resin adhesives. In order to solve these defects, researchers have proposed many modification methods. Among them, the most commonly used method is to introduce modifiers into epoxy resin adhesives through "physical bonding" or "chemical bonding", which can improve the toughness of the adhesive and improve the adhesion between the adhesive and the substrate to a certain extent.

[0003] At present, the most commonly used modification method is to introduce polar groups such as -O- and -COO- into the structure of the epoxy resin matrix through the use of toughening agents, thereby adjusting the content of its polar groups to a certain extent. At the same time, the toughening agent can form microphase separation in the epoxy resin matrix, thereby improving the stress concentration inside the epoxy adhesive and hindering the transmission of internal stress and plastic deformation.

[0004] Prior art CN115637125A discloses "an environmentally friendly epoxy resin adhesive and its preparation method", wherein the chain bonding containing the flexible group "-NHCOO-" is introduced into the epoxy resin adhesive system by the "non-isocyanate" method, and the adhesive prepared by this method has good adhesion and excellent toughness. However, this method has certain limitations in the specific implementation process, such as: the raw material cyclic carbonate used is not a conventional general raw material, and its synthesis method is relatively cumbersome, that is, it is difficult to achieve large-scale use to a certain extent. CN113861421A discloses "a polyimide-type epoxy resin toughener and its preparation method", wherein, it includes preparing a polyamic acid solution containing phenolic hydroxyl groups and a polyamic acid solution not containing phenolic hydroxyl groups respectively, then mixing the two polyamic acid solutions, stirring, and then converting the polyamic acid into polyimide by chemical imidization or thermal imidization to obtain a polyimide-type epoxy resin toughener. Although the toughened epoxy resin product prepared by this method has good strength and toughness, the synthesis of the toughening agent involves the use of N-methylpyrrolidone solvent, and the synthesis steps are relatively cumbersome. CN102516717A discloses "Thermoplastic elastomer toughened epoxy resin, preparation and application". In this method, the thermoplastic elastomer, compatibilizer and auxiliary agent need to be pre-mixed at 120-180°C, and then mixed with the epoxy resin, and at the same time, the compatibilizer and curing agent are mixed. The toughening agent and epoxy resin in the epoxy resin cured product prepared by this method have poor compatibility. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention proposes a modifier containing a β-hydroxy-carbamate group, a preparation method and an application thereof. The preparation method involved is simple and easy to operate; and the modifier can give the epoxy resin adhesive good adhesion to the interface with weak polarity, while satisfying the improvement of its toughness.

[0006] In order to achieve the above technical objectives, the following technical solutions are proposed: The first purpose of the technical solution is to propose: a modifier containing a β-hydroxy-carbamate group, wherein the structural formula of the modifier is as shown in formula (I) or formula (II): ; Wherein, R1 is -CH3 or -CH2CH3; R2 is an alkane group containing -H, -OH or C2 to C6; R3 is an alkane group containing -H, -OH or C2-C6.

[0007] The second object of the technical scheme is to propose: a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: subjecting a monofunctional cyclic carbonate to a ring-opening reaction with a primary amine compound containing Si-O to obtain a compound as shown in formula (I) or formula (II), i.e., a modifier containing a β-hydroxy-carbamate group; Among them, the structural formula of the monofunctional cyclic carbonate is as follows: The structural formula of the primary amine compound containing Si-O is as follows: ; And the reaction involved is as follows: ; The structural formulas of the compounds represented by formula (I) and formula (II) are as follows: ; R1 is -CH3 or -CH2CH3; R2 is an alkane group containing -H, -OH or C2 to C6; R3 is an alkane group containing -H, -OH or C2-C6.

[0008] Preferably, the primary amine compound containing Si-O is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, ureapropyltrimethoxysilane or ureapropyltriethoxysilane.

[0009] Preferably, the molar ratio of the monofunctional cyclic carbonate to the primary amine compound containing Si—O is n (环状碳酸酯基团) :n (伯胺基团) =1:1, ensuring the complete ring-opening reaction, thereby improving the preparation efficiency and quality of the process.

[0010] Preferably, the monofunctional cyclic carbonate is added to the monoprimary amine compound containing Si-O, and the addition time of the monofunctional cyclic carbonate is controlled to be 0.5 to 1 hour. Since the cyclic carbonate and the primary amine have high reactivity, the reaction can be carried out in a relatively short time. If the addition time is too short, the two will react rapidly and violently, which will lead to side reactions; if the addition time is too long, the conversion rate of the reaction will not be greatly improved, and at the same time, the efficiency will be reduced. Therefore, the addition time of the monofunctional cyclic carbonate is controlled to be 0.5 to 1 hour.

[0011] Preferably, after the addition is completed, the ring-opening reaction time is controlled to be 1 to 2 hours; the ring-opening reaction temperature is controlled to be 70 to 100°C. The control of the reaction conditions reduces energy consumption while ensuring the conversion rate, but it is not obvious for improving the conversion rate, such as: the reaction time is short, resulting in insufficient reaction, residual cyclic carbonate and primary amine compounds in the modifier system, which will affect the performance of the product during subsequent use. Among them, the reaction temperature ensures sufficient reaction, avoids residual cyclic carbonate and primary amine compounds in the system, prevents the impact on subsequent products, and avoids side reactions.

[0012] The third purpose of the technical solution is to propose: applying a modifier containing a β-hydroxy-carbamate group to the preparation of an epoxy resin adhesive product to achieve toughening modification of the epoxy resin adhesive product, thereby obtaining a modified epoxy resin.

[0013] Preferably, in the epoxy resin adhesive product, the amount of the modifier containing the β-hydroxy-carbamate group is 5-20% of the mass of the epoxy resin component. The setting of the amount of addition ensures the modification effect. For example, if the amount of addition is too high, it will have an adverse effect on the temperature resistance of the subsequent product, for example, the glass transition temperature will be greatly affected.

[0014] In the technical solution, the modifier containing β-hydroxy-carbamate groups can be hydrolyzed during use to promote adhesion to the bonded substrate. In particular, since the modifier contains β-hydroxyl and carbamate groups, it can promote hydrogen bonding between the epoxy adhesive and the substrate, thereby further improving the bonding performance.

[0015] The beneficial technical effects brought about by adopting this technical solution are: 1. In the present invention, there is a hydroxyl group at the β position of the carbamate group in the improver structure, which can form hydrogen bonds with the polar groups in the resin matrix and the curing agent, effectively improving the intermolecular forces between the epoxy cured product system, thereby enhancing the interfacial bonding ability between the epoxy resin cured product and the substrate, and further increasing its toughness; Second, in the present invention, the preparation process of the modifier is simple, direct heating reaction, no catalyst is required, easy to operate, and high conversion rate; in addition, no organic solvent is involved, subsequent waste liquid treatment is avoided, and the environment is friendly; At the same time, the monofunctional primary amine compounds involved are widely available and cheap, and there are many types of monofunctional cyclic carbonates, such as propylene carbonate, glycerol carbonate, etc., which are by-products of bulk industrial synthesis and can be directly used in the preparation process; 3. During the use of epoxy resin adhesives, the modifier can react with the hydroxyl groups on the surface of the inorganic substrate and undergo "physical bonding" with the long molecular chains in the organic polymer, thereby coupling materials of different properties and achieving the purpose of improving the adhesion of the materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is the infrared spectrum of propylene carbonate and the corresponding modifier in Example 2; Figure 2 The GPC spectra of propylene carbonate, aminopropyltriethoxysilane and the corresponding modifier in Example 2; Figure 3 This is a cross-sectional SEM of the corresponding cured product after the modifier in Example 2 is applied to the epoxy resin adhesive; Figure 4 is the infrared spectrum of propylene oxide and the corresponding modifier in Comparative Example 1; Figure 5 This is the cross-sectional SEM of the corresponding cured product after the modifier in Comparative Example 1 is applied to the epoxy resin adhesive. DETAILED DESCRIPTION

[0017] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Example 1 This embodiment provides a modifier containing a β-hydroxy-carbamate group, the structural formula of which is shown in formula (I) or formula (II): ; Wherein, R1 is -CH3 or -CH2CH3; R2 is an alkane group containing -H, -OH or C2 to C6; R3 is an alkane group containing -H, -OH or C2-C6.

[0019] Example 2 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to aminopropyltriethoxysilane, the addition time is controlled within 1 h, and the temperature is controlled at 100° C. After the addition is completed, continue the reaction for 2 h to obtain modifier 1 with a yield of 99.8%.

[0020] Among them, the infrared spectra corresponding to propylene carbonate and modifier 1 are as follows Figure 1 As shown; The GPC spectra of propylene carbonate, aminopropyltriethoxysilane and modifier 1 are as follows: Figure 2 shown.

[0021] Example 3 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to aminopropyltrimethoxysilane, the addition time is controlled at 0.5 h, and the temperature is controlled at 70°C; after the addition is completed, continue the reaction for 1 h to obtain modifier 2 with a yield of 99.7%.

[0022] Example 4 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to ureidopropyltriethoxysilane, the addition time is controlled at 0.8 h, and the temperature is controlled at 85°C; after the addition is completed, continue the reaction for 1.5 h to obtain modifier 3 with a yield of 99.8%.

[0023] Example 5 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to 2-aminoethyl-aminopropyltrimethoxysilane, the addition time is controlled at 0.5 h, and the temperature is controlled at 70°C; after the addition is completed, continue the reaction for 1 h to obtain modifier 4 with a yield of 98.2%.

[0024] Example 6 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to 2-aminoethyl-aminopropyltrimethoxysilane, the addition time is controlled within 1 h, and the temperature is controlled at 80°C; after the addition is completed, continue the reaction for 2 h to obtain modifier 5 with a yield of 99.4%.

[0025] Example 7 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to diethylenetriaminopropyltrimethoxysilane, the addition time is controlled at 0.8 h, and the temperature is controlled at 90°C; after the addition is completed, the reaction is continued for 1.5 h to obtain modifier 6 with a yield of 99.7%.

[0026] Example 8 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to diethylenetriaminopropyltrimethoxysilane, the addition time is controlled at 0.5 h, and the temperature is controlled at 95°C; after the addition is completed, continue the reaction for 1.1 h to obtain modifier 7 with a yield of 99.6%.

[0027] Example 9 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to aminoethylaminopropyltrimethoxysilane, the addition time is controlled within 1 h, and the temperature is controlled at 75°C; after the addition is completed, continue the reaction for 2 h to obtain modifier 8 with a yield of 98.9%.

[0028] Example 10 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to aminoethylaminopropyltrimethoxysilane, the addition time is controlled at 0.9 h, and the temperature is controlled at 97°C; after the addition is completed, the reaction is continued for 1.8 h to obtain modifier 9 with a yield of 99.4%.

[0029] Embodiment 11 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to aminoethylaminopropylmethyldimethoxysilane, the addition time is controlled at 0.6 h, and the temperature is controlled at 90°C; after the addition is completed, the reaction is continued for 1.8 h to obtain modifier 10 with a yield of 98.7%.

[0030] Example 12 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add propylene carbonate in the same molar ratio to aminoethylaminopropylmethyldimethoxysilane, the addition time is controlled at 1 h, and the temperature is controlled at 78°C; after the addition is completed, continue the reaction for 1.4 h to obtain modifier 11 with a yield of 99.5%.

[0031] Example 13 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: Slowly add glycerol carbonate in the same molar ratio to ureidopropyltrimethoxysilane, the addition time is controlled within 1 h, and the temperature is controlled at 90°C; after the addition is completed, continue the reaction for 2 h to obtain modifier 12 with a yield of 99.4%.

[0032] Embodiment 14 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: 59 kg of glycerol carbonate was added to 110.5 kg of aminopropyltriethoxysilane. The addition was carried out at a uniform speed, and the addition time was controlled at 0.5 h and the temperature was controlled at 90° C. After the addition was completed, the reaction was continued for 1 h to obtain modifier 13 with a yield of 98.4%.

[0033] Embodiment 15 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: 51 kg of propylene carbonate was added to 111 kg of aminoethylaminopropyltrimethoxysilane, wherein the feeding was carried out at a uniform speed, and the feeding time was controlled at 1 hour and the temperature was controlled at 70°C. After the feeding was completed, the reaction was continued for 2 hours to obtain modifier 14 with a yield of 98.7%.

[0034] Example 16 This embodiment provides a method for preparing a modifier containing a β-hydroxy-carbamate group, comprising the following steps: 51 kg of propylene carbonate was added to 111 kg of ureidopropyltrimethoxysilane at a uniform speed, and the addition time was controlled at 1 h and the temperature was controlled at 100° C. After the addition was completed, the reaction was continued for 1.5 h to obtain modifier 15 with a yield of 98.2%.

[0035] Embodiment 17 This embodiment is based on Example 2, and the prepared modifier containing β-hydroxy-carbamate group is applied to prepare epoxy resin adhesive products. Among them, the epoxy resin adhesive product specifically includes: 100 parts of bisphenol A epoxy resin (E51), 5 parts of β-hydroxy-carbamate compound, 15 parts of propylene carbonate, 3 parts of dicyandiamide curing agent, 0.5 parts of imidazole accelerator, 3 parts of silane coupling agent and 50 parts of high-quality clay (100 mesh).

[0036] The performance indicators of the obtained epoxy resin adhesive product include: shear strength (aluminum-aluminum) 17.4MP, tensile strength 72.5MPa, elongation at break 1.3%, compression strength 93MPa, and peel strength 0.21KN / m.

[0037] Among them, after applying modifier 1 to epoxy resin adhesive, the corresponding cross-sectional SEM of the cured product is as follows: Figure 3 shown.

[0038] Embodiment 18 This embodiment is based on Example 2, and the prepared modifier containing β-hydroxy-carbamate group is applied to prepare epoxy resin adhesive products. Among them, the epoxy resin adhesive product specifically includes: 100 parts of phenolic epoxy resin (F51), 20 parts of β-hydroxy-urethane compound, 5 parts of polypropylene glycol diglycidyl ether, 3 parts of imidazole curing agent, 1 part of tertiary amine accelerator, 1 part of titanate coupling agent and 200 parts of barium sulfate (150 mesh).

[0039] The performance indicators of the obtained epoxy resin adhesive product include: shear strength (aluminum-aluminum) 18.4MP, tensile strength 65.7Mpa, elongation at break 2.2%, compression strength 78Mpa and peel strength 0.43KN / m.

[0040] Embodiment 19 This embodiment is based on Example 2, and the prepared modifier containing β-hydroxy-carbamate group is applied to prepare epoxy resin adhesive products. Among them, the epoxy resin adhesive product specifically includes: 100 parts of alicyclic epoxy resin, 10 parts of β-hydroxy-carbamate compound, 6 parts of ethylene glycol diglycidyl ether, 5 parts of aromatic diamine curing agent, 0.5 parts of organic urea accelerator, 1.5 parts of KH560 and 80 parts of a mixture of talc and white carbon black (1:1, 300 mesh).

[0041] The performance indicators of the obtained epoxy resin adhesive product include: shear strength (aluminum-aluminum) 18.4MP, tensile strength 75.9Mpa, elongation at break 0.7%, compression strength 83Mpa and peel strength 0.11KN / m.

[0042] Embodiment 20 This embodiment is based on Example 2, and the prepared modifier containing β-hydroxy-carbamate group is applied to prepare epoxy resin adhesive products. Among them, the epoxy resin adhesive product specifically includes: 100 parts of phenolic epoxy resin, 18 parts of β-hydroxy-carbamate compound, 11 parts of a mixture of 1,6-hexanediol diglycidyl ether and polyethylene glycol diglycidyl ether (1:2), 8 parts of dicyandiamide curing agent, 1 part of imidazole accelerator, 2 parts of titanate coupling agent and 188 parts of mica powder (200 mesh).

[0043] The performance indicators of the obtained epoxy resin adhesive product include: shear strength (aluminum-aluminum) 18.4MP, tensile strength 70.9Mpa, elongation at break 1.3%, compression strength 76Mpa and peel strength 0.21KN / m.

[0044] Comparative Example 1 On the basis of Example 2, in order to compare the performance test of the corresponding product, this control example replaces the raw material propylene carbonate with propylene oxide, and the rest is the same as Example 2, so as to further illustrate the technical solution.

[0045] The obtained product was recorded as comparative modifier 1.

[0046] Among them, the infrared spectra corresponding to propylene oxide and comparative modifier 1 are as follows Figure 4 shown.

[0047] In addition, after the comparative modifier 1 was applied to the epoxy resin adhesive (other things were the same as in Example 17), the cross-sectional SEM of the corresponding cured product was as follows: Figure 5 shown.

[0048] Comparative Example 2 On the basis of Example 2, in order to compare the performance test of the corresponding product, this control example controls the feeding time to 20 minutes, and the rest is the same as Example 2, so as to further illustrate the technical solution.

[0049] The obtained product was recorded as comparative modifier 2.

[0050] Comparative Example 3 On the basis of Example 2, in order to compare the performance test of the corresponding product, this control example controls the ring-opening reaction time to 0.5h, and the rest is the same as Example 2, so as to further illustrate the technical solution.

[0051] The obtained product was recorded as comparative modifier 3.

[0052] Comparative Example 4 On the basis of Example 2, in order to compare the performance test of the corresponding product, this control example sets the ring-opening reaction temperature to 65°C, and the rest is the same as Example 2, to further illustrate the technical solution.

[0053] The obtained product was recorded as comparative modifier 4.

[0054] Comparative Example 5 On the basis of Example 2, in order to compare the performance test of the corresponding product, this control example sets the ring-opening reaction temperature to 105°C, and the rest is the same as Example 2, to further illustrate the technical solution.

[0055] The obtained product was recorded as comparative modifier 5.

[0056] The modifier products prepared by Examples 2-16 and Comparative Examples 1-5 were respectively applied to the modification of epoxy resin E51, and D230 was selected as the curing agent to test the performance of the epoxy cured products.

[0057] The specific test standards are as follows: Compression strength: in accordance with GB / T 2567-2021 standard; Shear strength: in accordance with GB / T 7124-2008 standard, the test tensile rate is 2 mm / min; Tensile strength and elongation at break: in accordance with GB / T 2567-2008 standard, the test tensile rate is 10 mm / min; Peel strength: According to GB / T2791-1995 standard, the test tensile rate is 100 mm / min. The properties of the products prepared by applying the modifiers of various embodiments to epoxy resin E51 and curing with D230 are shown in Table 1.

[0058] From Table 1 above, it can be seen that under appropriate preparation process conditions, the monofunctional cyclic carbonate is reacted with the primary amine compound containing Si-O to obtain a modifier having excellent functional properties, which can give the subsequent cured product excellent bonding properties and meet the high strength requirements. In contrast, for the comparative modifier 1, the epoxy group is used to replace the cyclic carbonate group to prepare the modifier, and the bonding properties and flexibility of the subsequent cured product are not well improved. This further confirms that the modifier prepared by the present invention can improve the performance of the product well.

[0059] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification or equivalent change made to the above embodiment based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A modifier containing a β-hydroxy-carbamate group, characterized in that The structural formula of the modifier is shown in the following formula (I) or (II): ； Wherein, R1 is -CH3 or -CH2CH3; R2 is an alkane group containing -H, -OH or C2 to C6; R3 is an alkane group containing -H, -OH or C2-C6.

2. A method for preparing a modifier containing a β-hydroxy-carbamate group, characterized in that: The method comprises the following steps: subjecting a monofunctional cyclic carbonate to a ring-opening reaction with a primary amine compound containing Si-O to obtain a compound represented by formula (I) or formula (II), that is, a modifier containing a β-hydroxy-carbamate group; The structural formulas of the compounds represented by formula (I) and formula (II) are as follows: ； The structural formula of the monofunctional cyclic carbonate is as follows: ； The structural formula of the primary amine compound containing Si-O is as follows: ； R1 is -CH3 or -CH2CH3; R2 is an alkane group containing -H, -OH or C2 to C6; R3 is an alkane group containing -H, -OH or C2-C6.

3. The method for preparing a modifier containing a β-hydroxy-carbamate group according to claim 2, characterized in that: The Si-O-containing primary amino compound is aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, ureidopropyltrimethoxysilane or ureidopropyltriethoxysilane.

4. The method for preparing a modifier containing a β-hydroxy-carbamate group according to claim 3, characterized in that: The molar ratio of the monofunctional cyclic carbonate to the Si-O-containing primary amine compound is 1:

1.

5. The method for preparing a modifier containing a β-hydroxy-carbamate group according to claim 4, characterized in that: The monofunctional cyclic carbonate is added to the monoprimary amine compound containing Si-O, and the adding time of the monofunctional cyclic carbonate is controlled to be 0.5-1h.

6. The method for preparing a modifier containing a β-hydroxy-carbamate group according to claim 5, characterized in that: After the addition is completed, the ring-opening reaction time is controlled to be 1 to 2 hours; the ring-opening reaction temperature is controlled to be 70 to 100°C.

7. A β-hydroxy-carbamate group-containing modifier is used in the preparation of an epoxy resin adhesive product, wherein the β-hydroxy-carbamate group-containing modifier is the β-hydroxy-carbamate group-containing modifier according to claim 1, or a β-hydroxy-carbamate group-containing modifier obtained by the preparation method described in any one of claims 2 to 6.

8. The use according to claim 7, characterized in that: In the epoxy resin adhesive product, the added amount of the modifier containing β-hydroxy-urethane group is 5 to 20% of the mass of the epoxy resin component.

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