CN114774041A

CN114774041A - Novel single-component adhesive and preparation method thereof

Info

Publication number: CN114774041A
Application number: CN202110569276.1A
Authority: CN
Inventors: 谢富平; 陆璐侃; 王雨亭
Original assignee: Zhenjiang Leader Composite Co ltd
Current assignee: Zhenjiang Leader Composite Co ltd
Priority date: 2021-05-25
Filing date: 2021-05-25
Publication date: 2022-07-22

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a novel single-component adhesive and a preparation method thereof. A novel single-component adhesive is prepared from at least epoxy resin and/or modified epoxy resin; also comprises 0.1 to 1.5 portions of fumed silica. The novel single-component adhesive and the preparation method thereof provided by the invention have high temperature resistance and impact resistance; the novel single-component adhesive provided by the invention solves the problem of 'wet inside and dry outside' in the gluing process, ensures the stability of the adhesive applied on the surface of materials such as metal and the like, and can ensure that the shear strength is not changed after the adhesive is placed for 1 month at 150 ℃.

Description

Novel single-component adhesive and preparation method thereof

Technical Field

The invention belongs to the technical field of adhesives, and particularly relates to a novel single-component adhesive and a preparation method thereof.

Background

The adhesive is a material which has good adhesive performance, can form a film between the surfaces of two objects and firmly adhere the two objects together, and is generally prepared from an adhesive substance, a curing agent, a toughening agent, a diluent, a modifier and the like. Most of Chinese adhesive enterprises are established in 80-90 years of the 20 th century and start late, but China companies have great development potential in the adhesive industry at the present stage, and under the background of the current economic transformation and upgrading of China, a lot of good development opportunities exist in the fields of high-speed development, such as automobiles, packaging, new energy, buildings and the like.

The single-component adhesive on the market at present has many varieties, but generally has poor high temperature resistance, oil resistance and cold and heat shock resistance, and further optimization and improvement on the formula and preparation process of the adhesive in the prior art are needed in order to solve the problems that the single-component adhesive in the prior art has high temperature resistance, oil resistance and the like in the fields of automobiles and the like, particularly when a metal material is bonded with the surface of a polymer material. Has important significance for improving the application range and the application value of the single-component adhesive.

Disclosure of Invention

In order to solve the technical problems, the invention provides a novel single-component adhesive, which is prepared from raw materials at least comprising epoxy resin and/or modified epoxy resin; also comprises 0.1 to 1.5 portions of fumed silica.

As a preferable technical scheme, the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.5-1.2).

As a preferable technical scheme, the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.9-1.1).

As a preferred technical scheme, the preparation raw material also comprises an auxiliary agent; the auxiliary agent is selected from one or more of defoaming agent, curing agent, coupling agent, filler and black paste.

As a preferred technical scheme, the filler is selected from one or more of calcium carbonate, mica powder, talcum powder and barium carbonate.

As a preferable technical scheme, the weight of the calcium carbonate is 10-60 wt% of the weight of the epoxy resin and/or the modified epoxy resin.

As a preferred technical solution, the curing agent is at least one selected from dicyandiamide, polyamine and benzoxazine.

In a preferred embodiment, the polyamine is selected from aromatic amines.

The second aspect of the invention provides a preparation method of a novel single-component adhesive, which comprises the following steps:

1) adding epoxy resin and/or modified epoxy resin and auxiliary agent into a stirring kettle, stirring and dispersing for 15-20min, controlling the temperature at 15-25 ℃, and discharging;

2) grinding the material obtained in the step 1) on a three-roller machine, and controlling the temperature to be below 25 ℃;

3) and (3) stirring the ground material again, controlling the temperature to be 15-25 ℃, defoaming in vacuum, controlling the vacuum degree, defoaming for 20-40min, and discharging to obtain the composite material.

As a preferable technical proposal, the vacuum degree in the step 3) is-0.098 to-0.1 MPa.

Has the advantages that: compared with the prior art, the adhesive prepared by the invention has the following advantages:

1. the novel single-component adhesive and the preparation method thereof provided by the invention have high temperature resistance and impact resistance;

2. the novel single-component adhesive and the preparation method thereof provided by the invention are simple to operate, strong in storage stability and high in economic benefit;

3. the novel single-component adhesive provided by the invention has higher shear strength in the using process, has better bonding performance on metal materials, and has huge application prospects in the fields of automobiles, packaging, new energy, buildings and the like;

4. the novel single-component adhesive provided by the invention solves the problem of 'inside wet and outside dry' in the gluing process, ensures the stability of the adhesive applied on the surface of materials such as metal and the like, and can ensure that the adhesive is placed at 150 ℃ for 1 month without changing the shear strength.

Detailed Description

The present invention will be more readily understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, 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 invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of …" appears in a clause of the claim body and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise numerical value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the above problems, a first aspect of the present invention provides a novel one-component adhesive, which is prepared from at least epoxy resin and/or modified epoxy resin; also comprises 0.1 to 1.5 portions of fumed silica.

In some preferred embodiments, the fumed silica is a hydrophobic fumed silica.

Hydrophobic fumed silica, purchased from Weifang Heng Ci scintillating nanomaterials Ltd.

In some preferred embodiments, the preparation raw material at least comprises epoxy resin and modified epoxy resin.

The epoxy resin described herein is not particularly limited, and includes, but is not limited to, at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol a type epoxy resin, p-phenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ether type epoxy resin, and glycidyl amine type epoxy resin.

In some preferred embodiments, the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.5-1.2).

In some preferred embodiments, the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.9-1.1).

In some preferred embodiments, the epoxy resin is selected from bisphenol a type epoxy resins.

In some preferred embodiments, the modified epoxy resin is a polyurethane modified epoxy resin.

The bisphenol A type epoxy resin is available from a commercial manufacturer without any particular limitation, and is available, for example, from Guangxi Zhejiang chemical Co., Ltd., model E51.

Polyurethane modified epoxy resin, model EPU-303, was purchased from Complex advanced materials (Shanghai) Inc.

In the experimental process, the applicant finds that the high-temperature resistance of the adhesive can be improved by adding the epoxy resin into the system to prepare the adhesive, but the applicant finds that when the epoxy resin is singly used, the brittleness of the adhesive is higher, and the adhesive cannot be used under special conditions such as high temperature and the like. In order to further improve the toughness and tensile shear strength of the adhesive, the applicant has been researched and obtained through a large number of creative experiments, the epoxy resin and the polyurethane modified epoxy resin are added into the system, so that the toughness of the adhesive can be further improved while the high-temperature stability of the adhesive is improved, and the applicant speculates that the possible reasons are as follows: under the premise of existence of epoxy resin, reactive active groups can be provided for a system, when the adhesive is compounded with polyurethane modified epoxy resin, further crosslinking action can be generated in the system to form a compact three-dimensional network structure, when the adhesive is subjected to external high-temperature action, high-frequency movement of a molecular chain is limited due to the constraint of the compact network structure, and the high-temperature stability and toughness of the adhesive are improved.

In addition, the applicant has surprisingly found that when the weight ratio of epoxy resin to urethane-modified epoxy resin is 1: (0.9-1.1), the tensile shear strength of the adhesive can be improved, and the applicant speculates that the possible reason is that: along with the change of the addition amount of the polyurethane modified epoxy resin, the strength of intermolecular interaction is greatly different, and the weight ratio of the epoxy resin to the polyurethane modified epoxy resin is 1: (0.9-1.1), free active groups in the system are increased along with the increase of the content of the polyurethane modified epoxy resin, more branch points can be introduced on a polyurethane chain segment by the epoxy resin in the system in a synergistic manner, and when the polyurethane modified epoxy resin is stretched by external force, the stress can be uniformly dispersed, so that the concentration of local stress is avoided, and the tensile shear strength is improved. However, the applicant found that when the content of the polyurethane added is larger than the range protected by the present application, the crosslinking density between molecules is too large, the rigidity of the molecules is enhanced, and the impact resistance is greatly reduced.

In some preferred embodiments, the preparation feedstock further comprises an auxiliary agent; the auxiliary agent is selected from one or more of defoaming agent, curing agent, coupling agent, filler and black paste.

In some preferred embodiments, the preparation raw materials further comprise a defoaming agent, a curing agent, a coupling agent, a filler and black slurry.

In the present application, the black slurry can be made and purchased by self; the purchasing manufacturer has no special limitation, and the preparation method can refer to the following steps:

mixing carbon black and 128 matrix resin according to a weight ratio of 1: 1.8, and grinding to obtain the product.

The carbon black is generally sold in the market, and the 128 matrix resin is purchased from Jiangsu Yangyang agricultural chemical industry Co.

In some preferred embodiments, the filler is selected from one or more of calcium carbonate, mica powder, talcum powder and barium carbonate.

In some preferred embodiments, the filler is selected from calcium carbonate and mica powder.

In some preferred embodiments, the weight ratio of calcium carbonate to mica powder is 26: (2-3).

In the experimental process, the applicant finds that although the stability of the adhesive is improved by selecting the latent curing agent, the applicant finds that the addition of the latent curing agent may cause the adhesive to be in a condition of 'wet inside and dry outside' in the using process, and in order to solve the problems, the applicant conducts a great deal of creative research, and the problem can be solved by adding calcium carbonate and mica powder, particularly when the weight ratio of the calcium carbonate to the mica powder is 26: (2-3), the adhesive will not be "wet inside and dry outside", and the shear strength of the adhesive will be improved, and the applicant speculates that the reason for this phenomenon may be: with the addition of the calcium carbonate and the mica powder into the adhesive, the rheological property of the adhesive is properly adjusted, and the stability of the calcium carbonate and the mica powder in the system is promoted under the synergistic action of a silane coupling agent and the like in the system, because the weight ratio of the added mica powder is 26: (2-3), the calcium carbonate, the epoxy resin and the curing agent can be promoted to form ordered dispersion among mica powder lamellar structures, the transferability among cured substances is promoted in the curing process, the curing effect is enhanced, and the condition of 'wet inside and dry outside' is avoided; thereby improving the shearing strength of the adhesive,

in addition, the applicant finds that when the proportion of the added calcium carbonate is larger than the range of the application, the calcium carbonate particles are agglomerated in the preparation process of the adhesive, so that defects occur in the adhesive, the shear strength is reduced, and the use conditions and the use range of the adhesive are limited.

In some preferred embodiments, the calcium carbonate is present in an amount of 10 to 60 weight percent based on the weight of the epoxy resin and/or modified epoxy resin.

In some preferred embodiments, the calcium carbonate is present in an amount of 10 to 60 weight percent based on the weight of the epoxy resin and the urethane-modified epoxy resin.

In the experimental process, when the weight of the calcium carbonate is 10-60 wt% of the total weight of the epoxy resin and the polyurethane modified epoxy resin, the dispersion stability of the calcium carbonate in a system can be promoted on the premise of cooperating with the mica powder, so that the use stability of the adhesive under special conditions is improved. Can ensure that the tensile shear strength of the alloy is not changed after the alloy is placed in lubricating oil for 24 hours.

In some preferred embodiments, the curing agent is selected from at least one of dicyandiamide, polyamine, benzoxazine.

In some preferred embodiments, the polyamine is selected from aromatic amines.

In some preferred embodiments, the aromatic amine is selected from diaminodiphenyl sulfone (CAS: 80-08-0).

In some preferred embodiments, the weight ratio of the polycyanamide, the diaminodiphenyl sulfone, and the benzoxazine is 1: (4-5): 1.

in the experimental process, the applicant finds that the type of the selected curing agent has an important influence on the stability of the single-component adhesive in the preparation process of the single-component adhesive, the curing temperature of the single-component curing agent can be reduced by adding dicyandiamide, an aromatic amine curing agent and a benzoxazine curing agent into the system, and the stability of the adhesive is improved, and the applicant finds that when the aromatic amine curing agent selects diaminodiphenyl sulfone, the weight ratio of dicyandiamide to diaminodiphenyl sulfone to benzoxazine is 1: (4-5): 1 hour, the storage stability of the adhesive can be ensured, and the adhesive can be kept at 150 ℃ for 1 month without changing the tensile shear strength. The applicant speculates that possible reasons are: the sulfone group in the diamine diphenyl sulfone structure tends to attract electrons on a benzene ring, so that the benzene ring lacks electrons, and can be more easily combined with electron-donating groups in a system to form a stable structure when dicyandiamide and benzoxazine in the system act synergistically, so that the storage stability of the adhesive is improved, and the adhesive can be ensured to be placed for 1 month at the temperature of 150 ℃ in an epoxy resin and modified epoxy resin system, and the tensile shear strength is not changed.

In addition, the applicant found that if the weight ratio of the diamine curing agent added in the system exceeds the range of the present application, the water resistance of the adhesive is reduced.

In some preferred embodiments, the raw materials for preparing the novel one-component adhesive comprise, by weight: 20-35 parts of epoxy resin, 25-40 parts of modified epoxy resin, 0.1-1 part of fumed silica, 1-5 parts of black paste, 0.001-0.005 part of defoaming agent, 0.05-0.5 part of coupling agent, 5-20 parts of curing agent and 25-50 parts of filler.

In some preferred embodiments, the vacuum degree in step 3) is-0.098 to-0.1 MPa.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Examples

Example 1

A novel single-component adhesive comprises the following preparation raw materials in parts by weight: 20 parts of epoxy resin, 25 parts of modified epoxy resin, 0.1 part of fumed silica, 1 part of black paste, 0.001 part of defoaming agent, 0.05 part of coupling agent, 5 parts of curing agent and 25 parts of filler.

The epoxy resin is bisphenol A type epoxy resin, model E51, and is purchased from Guangxi Zhejiang chemical industry Co., Ltd;

the modified epoxy resin is polyurethane modified epoxy resin, model EPU-303, and is purchased from complex advanced materials (Shanghai) Co., Ltd;

the fumed silica is hydrophobic silica and is purchased from Weifang Heng Cing nanometer material limited company;

the black paste is prepared by experimental experiments, and the preparation method comprises the following steps: mixing carbon black and 128 matrix resin according to a weight ratio of 1: 1.8, mixing and grinding to obtain the product.

The 128 matrix resin is purchased from Jiangsu Yangyang agricultural chemical industry Co., Ltd;

the defoamer, model BYK-016, is purchased from Shanghai Kaiyn chemical Co., Ltd;

the coupling agent is selected from KH-560;

the curing agent is selected from polycylamine, diamino diphenyl sulfone and benzoxazine, and the weight ratio of the curing agent to the curing agent is 1: 4: 1.

the filler is selected from calcium carbonate and mica powder, and the weight ratio of the filler to the mica powder is 26: 2.3.

a preparation method of the novel single-component adhesive comprises the following steps:

1) adding epoxy resin, modified epoxy resin, a defoaming agent and a coupling agent into a stirring kettle, stirring and dispersing for 20min, then adding calcium carbonate and mica powder, dispersing for 20min, then adding fumed silica, dispersing for 45min, controlling the temperature at 20 ℃, adding a curing agent, dispersing for 30min, controlling the temperature at 20 ℃, and discharging;

2) grinding the material obtained in the step 1) on a three-roller machine, and controlling the temperature at 20 ℃;

3) and (3) stirring the ground material again, controlling the temperature to be 22 ℃, defoaming in vacuum, controlling the vacuum degree to be-0.099 MPa, defoaming for 30min, and discharging to obtain the composite material.

Example 2

A novel single-component adhesive comprises the following preparation raw materials in parts by weight: 35 parts of epoxy resin, 40 parts of modified epoxy resin, 1 part of fumed silica, 5 parts of black paste, 0.005 part of defoaming agent, 0.5 part of coupling agent, 20 parts of curing agent and 50 parts of filler.

the modified epoxy resin is polyurethane modified epoxy resin, the model is EPU-303, and the modified epoxy resin is purchased from complex advanced materials (Shanghai) Co., Ltd;

the fumed silica is hydrophobic silica and is purchased from Weifang Heng Ci scintillating nanometer material Limited company;

the defoaming agent is BYK-016 available from Shanghai Kaiyin chemical Co., Ltd;

the coupling agent is selected from KH-560;

the curing agent is selected from polycyanamine, diamino diphenyl sulfone and benzoxazine, and the weight ratio is 1: 5: 1.

the filler is selected from calcium carbonate and mica powder, and the weight ratio of the filler to the mica powder is 26: 3.

3) and stirring the ground material again, controlling the temperature to be 22 ℃, defoaming in vacuum, controlling the vacuum degree to be-0.099 MPa, defoaming for 30min, and discharging to obtain the composite material.

Example 3

A novel single-component adhesive comprises the following preparation raw materials in parts by weight: 27 parts of epoxy resin, 29 parts of modified epoxy resin, 0.6 part of fumed silica, 2.3 parts of black paste, 0.003 part of defoaming agent, 0.2 part of coupling agent, 12 parts of curing agent and 28.9 parts of filler.

the black paste is prepared by experimental experiments, and the preparation method comprises the following steps: mixing carbon black and 128 matrix resin according to a weight ratio of 1: 1.8, and grinding to obtain the product.

the coupling agent is selected from KH-560;

the curing agent is selected from polycylamine, diamino diphenyl sulfone and benzoxazine, and the weight ratio of the curing agent to the curing agent is 1: 4.6: 1.

the filler is selected from calcium carbonate and mica powder, and the weight ratio of the filler to the mica powder is 26: 2.9.

Example 4

The specific implementation mode of the novel one-component adhesive is the same as that in example 3, and the difference from the example 3 is that the weight ratio of the epoxy resin to the polyurethane modified resin is 1: 2.

example 5

A novel one-component adhesive is disclosed, which is prepared in the same manner as in example 3, except that the urethane-modified epoxy resin is replaced with a bisphenol A epoxy resin, which is the same as in example 3.

Example 6

The specific implementation mode of the novel single-component adhesive is the same as that in example 3, and the weight ratio of the dicyandiamide to the diaminodiphenyl sulfone to the benzoxazine is 1: 1: 1.

example 7

The specific implementation mode of the novel one-component adhesive is the same as that in example 3, and the weight ratio of the polycycloamine to the diaminodiphenyl sulfone to the benzoxazine is 1: 6: 1.

example 8

The specific implementation mode of the novel one-component adhesive is the same as that in example 3, and the weight ratio of the polycycloamine to the diaminodiphenyl sulfone to the benzoxazine is 1: 1: 4.

example 9

The specific implementation mode of the novel one-component adhesive is the same as that in example 3, and the difference from example 3 is that mica powder is not contained in the filler.

Example 10

The specific implementation mode of the novel one-component adhesive is the same as that in example 3, and the difference from example 3 is that the weight ratio of calcium carbonate to mica powder is 1: 1.

and (4) performance testing:

bonding is carried out before testing, the bonding part is cleaned and dried before bonding, the adhesive is uniformly coated on the bonding surface, then an object is bonded, the bonded product and the bonding part are horizontally placed, and the bonded product and the bonding part are placed in a baking oven, wherein the curing condition is 120 ℃/15 min. And performing performance test after the operation is completed.

1. Tensile shear strength test: the adhesives prepared in examples 1 to 10 were used for tensile shear strength testing, according to GB/T7124-1986, for tensile test specimens No. 45 steel was selected, and the results are tabulated in the table below.

Tensile shear strength test at 2.150 ℃: and (3) standing at 150 ℃ for 1 month, then testing by referring to the test method of the test 1, judging the data change condition of the test 1, and counting the results in the following table.

3. High temperature resistance: the adhesives prepared in examples 1-10 were left at 200 ℃ for 30 minutes and then tested for tensile shear strength, which was determined according to the method of test 1 and was reduced from the data of test 1, and the results are shown in the following table.

4. And (3) testing the impact resistance: the test standards were referenced to GB/T1732-93 and the test results were tabulated below.

5. Oil resistance: the adhesives prepared in examples 1 to 3 were used for the tensile shear strength test, according to GB/T7124-1986, ten articles of which were placed in a lubricating oil for 24 hours after the test and were taken out and again subjected to the tensile shear strength test, the changes in tensile shear strength being recorded in the table below.

Experiment of the invention	Example 1	Example 2	Example 3
				Oil resistance	Is not changed	Is not changed	Is not changed

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A novel single-component adhesive is characterized in that the preparation raw materials at least comprise epoxy resin and/or modified epoxy resin; also comprises 0.1 to 1.5 portions of fumed silica.

2. The novel single-component adhesive as claimed in claim 1, wherein the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.5-1.2).

3. The novel single-component adhesive according to claim 1, wherein the weight ratio of the epoxy resin to the modified epoxy resin is 1: (0.9-1.1).

4. The novel one-component adhesive as claimed in claim 1, wherein the raw materials for preparation further comprise an auxiliary agent; the auxiliary agent is selected from one or more of defoaming agent, curing agent, coupling agent, filler and black paste.

5. The novel one-component adhesive according to claim 4, wherein the filler is one or more selected from calcium carbonate, mica powder, talcum powder and barium carbonate.

6. A novel one-component adhesive according to claim 5, wherein the weight of the calcium carbonate is 10-60 wt% of the weight of the epoxy resin and/or the modified epoxy resin.

7. The novel one-component adhesive according to claim 4, wherein the curing agent is at least one selected from dicyandiamide, polyamine and benzoxazine.

8. The novel one-component adhesive of claim 7, wherein the polyamine is selected from aromatic amines.

9. A method for preparing a new one-component adhesive according to any one of claims 4 to 8, characterized in that it comprises the following steps:

3) and stirring the ground material again, controlling the temperature to be 15-25 ℃, defoaming in vacuum, controlling the vacuum degree, defoaming for 20-40min, and discharging to obtain the composite material.

10. The method for preparing a new single-component adhesive according to claim 9, wherein the vacuum degree in step 3) is-0.098 to-0.1 MPa.