CN112980372A - Adhesive and preparation method thereof - Google Patents
Adhesive and preparation method thereof Download PDFInfo
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- CN112980372A CN112980372A CN201911293527.7A CN201911293527A CN112980372A CN 112980372 A CN112980372 A CN 112980372A CN 201911293527 A CN201911293527 A CN 201911293527A CN 112980372 A CN112980372 A CN 112980372A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a binder, which comprises a first binder component and a second binder component, wherein the ratio of the addition mass of the first binder component to the addition mass of the second binder component is (1.0-1.8): 1, mixing when in use; wherein the first binder component comprises the following components: the epoxy resin-epoxy functional group-containing modified nano silicon dioxide is prepared from epoxy resin, epoxy group-containing modified nano silicon dioxide and epoxy modified silicone oil, wherein the ratio of the addition mass of the epoxy resin to the addition mass of the epoxy group-containing modified nano silicon dioxide to the addition mass of the epoxy modified silicone oil is 1: (0.05-0.1): (0.2 to 0.3); the second binder component comprises the following components: the curing agent comprises polyether amine, amino functional group-containing modified nano-silica and a curing accelerator, wherein the addition mass ratio of the polyether amine to the amino functional group-containing modified nano-silica to the curing accelerator is 1: (0.05-1): (0.05-0.1).
Description
Technical Field
The invention relates to the field of adhesives, in particular to an adhesive and a preparation method thereof.
Background
The epoxy resin means an organic compound having two or more epoxy groups in a molecule, and neither of them has a high relative molecular mass. The molecular structure of the epoxy resin is characterized in that a molecular chain contains active epoxy groups, and the epoxy groups can be positioned at the tail ends, in the middle or in a ring structure. Because the molecular structure contains active epoxy group, they can produce cross-linking reaction with several curing agents to form insoluble and infusible high polymer with three-dimensional network structure.
The epoxy resin is a thermosetting resin with strong adhesion, small shrinkage, good corrosion resistance and good processing performance, and the epoxy resin has the characteristics of excellent adhesive property, mechanical property and chemical stability resistance, so that the epoxy resin is widely applied to the fields of aviation, aerospace, automobiles, machinery, buildings, chemical engineering, light industry, electronics, electrical appliances, daily life sealant and the like.
However, after the epoxy resin is cured and opened, a dense three-dimensional network structure is formed, so that the cured product has the defects of high brittleness, easiness in cracking, high internal stress and the like, and the wider application of the epoxy resin is limited. In the prior art, the adhesive is prepared by compounding the nano material and the epoxy resin material, so that the epoxy resin does not weaken other advantages and can achieve an effective way of toughening effect. The nano silicon dioxide is one of the nano materials which are put into application at the earliest time, and has the advantages of high temperature resistance, no toxicity, no pollution and the like besides the specific surface effect, volume effect and quantum effect of the nano materials. However, the large surface energy makes it easy to agglomerate when blended with binder materials, so that the viscosity of the system increases sharply, and the fluidity of the binder is deteriorated, and the processability is deteriorated. And the compatibility of the nano silicon dioxide and the epoxy resin is poor, and the product after blending has poor toughness and fluidity and cannot be used well, so that the wide application of the adhesive is influenced.
Disclosure of Invention
The invention aims to provide an adhesive and a preparation method thereof, and aims to solve the problems that in the prior art, the compatibility of a nano material and an epoxy resin material is poor and the toughness of the adhesive is influenced in the process of preparing the adhesive by compounding the nano material and the epoxy resin material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a binder comprises a first binder component and a second binder component, wherein the ratio of the addition mass of the first binder component to the second binder component is (1.0-1.8): 1, mixing when in use;
wherein the first binder component comprises the following components: the epoxy resin-epoxy functional group-containing modified nano silicon dioxide is prepared from epoxy resin, epoxy group-containing modified nano silicon dioxide and epoxy modified silicone oil, wherein the ratio of the addition mass of the epoxy resin to the addition mass of the epoxy group-containing modified nano silicon dioxide to the addition mass of the epoxy modified silicone oil is 1: (0.05-0.1): (0.2 to 0.3); the second binder component comprises the following components: the curing agent comprises polyether amine, amino functional group-containing modified nano-silica and a curing accelerator, wherein the addition mass ratio of the polyether amine to the amino functional group-containing modified nano-silica to the curing accelerator is 1: (0.05-0.1): (0.05-0.1).
And, a method for preparing a binder, the method comprising the steps of:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator according to the binder;
carrying out first mixing treatment on the epoxy resin, the modified nano silicon dioxide containing the epoxy functional group and the epoxy modified silicone oil to obtain a first binder component;
carrying out second mixing treatment on the polyether amine, the modified nano-silica containing the amino functional group and the curing accelerator to obtain a second binder component;
when the adhesive is used, the first adhesive component and the second adhesive component are mixed to obtain the adhesive.
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises epoxy resin, modified nano silicon dioxide containing epoxy functional groups and epoxy modified silicone oil, epoxy resin is taken as a matrix material, a certain amount of modified nano-silica containing epoxy functional groups is added to modify the surface of the epoxy resin, the modified nano-silica containing epoxy functional groups is interacted with the epoxy resin through epoxy groups on the surface, the inherent nano-performance of the nano-material is utilized, the wear resistance, tensile strength, folding resistance and aging resistance of the epoxy resin are improved, meanwhile, the surface energy and the reaction activity of the modified nano silicon dioxide containing the epoxy functional group are lower, the dispersibility of the silicon dioxide in epoxy resin can be improved, and the silicon dioxide is better fused with epoxy resin materials; secondly, a certain amount of epoxy modified silicone oil is added to provide flexible functional groups for epoxy resin modification, so that the epoxy resin, the modified nano silicon dioxide containing epoxy functional groups and the epoxy modified silicone oil have a synergistic effect, and the first adhesive component has good toughness and wear resistance while maintaining good adhesive force. The second adhesive component comprises polyether amine, amino-functional-group-containing modified nano-silica and a curing accelerator, and the dispersibility of the silica can be improved due to the addition of the amino-functional-group-containing modified nano-silica, so that the polyether amine, the amino-functional-group-containing modified nano-silica and the curing accelerator are in synergistic action, and the curing efficiency of the second adhesive component is improved.
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component and the second adhesive component are mixed when in use, and in the process of mixing the first adhesive component and the second adhesive component and then using the mixture, the modified nano-silica containing epoxy functional groups in the first adhesive component and the modified nano-silica containing amino functional groups in the second adhesive component can interact to form higher compactness, so that the toughness and the corrosion resistance of the adhesive are enhanced, a certain amount of water vapor can be blocked, and the prepared adhesive not only keeps better adhesive strength, but also has better toughness, wear resistance and corrosion resistance.
The preparation method of the adhesive only needs to prepare the first adhesive component and the second adhesive component respectively according to the proportion of the components, and when the adhesive is used, the first adhesive component and the second adhesive component are mixed to obtain the adhesive. The preparation method can uniformly disperse all substances, simultaneously prepares the two components respectively, and mixes the two components when in use, is beneficial to storing products, ensures the beneficial effects of the binder, and endows the binder with excellent stability. In addition, the preparation method has simple process, controllable conditions and low equipment requirement, and can be used for industrial production.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The invention provides a binder, which comprises a first binder component and a second binder component, and specifically, the first binder component comprises the following components: epoxy resin, modified nano-silica containing epoxy functional groups and epoxy modified silicone oil, wherein the first binder component comprises the epoxy resin, the modified nano-silica containing epoxy functional groups and the epoxy modified silicone oil, epoxy resin is taken as a matrix material, a certain amount of modified nano-silica containing epoxy functional groups is added to modify the surface of the epoxy resin, the modified nano-silica containing epoxy functional groups is interacted with the epoxy resin through epoxy groups on the surface, the inherent nano-performance of the nano-material is utilized, the wear resistance, tensile strength, folding resistance and aging resistance of the epoxy resin are improved, meanwhile, the surface energy and the reaction activity of the modified nano silicon dioxide containing the epoxy functional group are lower, the dispersibility of the silicon dioxide in epoxy resin can be improved, and the silicon dioxide is better fused with epoxy resin materials; secondly, a certain amount of epoxy modified silicone oil is added to provide flexible functional groups for epoxy resin modification, so that the epoxy resin, the modified nano silicon dioxide containing epoxy functional groups and the epoxy modified silicone oil have a synergistic effect, and the first adhesive component has good toughness and wear resistance while maintaining good adhesive force.
Specifically, the ratio of the added mass of the epoxy resin, the modified nano silicon dioxide containing epoxy functional groups and the epoxy modified silicone oil is 1: (0.05-0.1): (0.2-0.3). If the addition amount of the modified nano-silica containing the epoxy functional group is too much, the modified nano-silica containing the epoxy functional group is easy to agglomerate and aggregate and is not beneficial to dispersion, and the modified nano-silica containing the epoxy functional group cannot be well mixed with epoxy resin so as to modify the epoxy resin; if the amount of the modified nanosilica containing an epoxy functional group is too small, the effect of modifying the epoxy resin cannot be achieved, the modification effect is poor, and the abrasion resistance, tensile strength, folding resistance and aging resistance of the epoxy resin cannot be improved. Furthermore, the epoxy modified silicone oil is added for providing a flexible functional group, and the surface of the epoxy resin is subjected to flexible treatment, so that the obtained first adhesive component has good toughness and wear resistance while maintaining good adhesive force. If the addition amount of the epoxy modified silicone oil is too much, the strength of the prepared adhesive is not enough, and the adhesive is not beneficial to use; if the amount of the epoxy-modified silicone oil added is too small, the surface of the epoxy resin is not completely softened, and the toughness is affected.
Preferably, the epoxy resin is selected from at least one of bisphenol a epoxy resin E55, bisphenol a epoxy resin E51, and bisphenol a epoxy resin E44. Any one or more of the epoxy resins can be selected as a parent material and can be subjected to corresponding modification treatment.
Specifically, the second binder component comprises the following components: the polyether amine, the amino functional group-containing modified nano-silica and the curing accelerator are added, so that the dispersibility of the silica can be improved, the polyether amine, the amino functional group-containing modified nano-silica and the curing accelerator are subjected to a synergistic effect, and the curing efficiency of the second binder component is improved.
Specifically, the ratio of the added mass of the polyether amine, the modified nano silicon dioxide containing the amino functional group and the curing accelerator is 1: (0.05-0.1): (0.05-0.1). If the addition amount of the modified nano-silica containing the amino functional group is too much, the modified nano-silica containing the amino functional group is easy to agglomerate and aggregate and is not beneficial to dispersion, and the modified nano-silica containing the amino functional group cannot be well mixed with the first bonding component to exert the effect; if the amount of the modified nanosilica containing an amino functional group is too small, the effect of modifying the matrix material cannot be achieved, and the modification effect is poor. Furthermore, the purpose of adding the curing accelerator is to improve the curing rate of the binder in the using process, if the addition amount of the curing accelerator is too small, the curing speed is too slow, and the curing effect of the product is influenced; if the amount is too large, the curing rate becomes too fast, and the brittleness of the product becomes large, which affects the product performance.
Preferably, the polyetheramine is selected from a mixture of polyetheramines having a number average molecular weight of 400 and polyetheramines having a number average molecular weight of 2000. The polyether amine material is a mixture of polyether amine with the number average molecular weight of 400 and polyether amine with the number average molecular weight of 2000, interaction between the polyether amine and the modified nano silicon dioxide containing amino functional groups is facilitated, and the finally prepared adhesive is good in performance.
Preferably, the curing accelerator is any one selected from DMP-10, DMP-20 and DMP-30. Any one of the above curing accelerators may be selected to increase the curing rate of the binder during use.
Specifically, the ratio of the addition mass of the first binder component to the addition mass of the second binder component is (1.0-1.8): 1, mixing when in use; the adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component and the second adhesive component are mixed when in use, and in the process of mixing the first adhesive component and the second adhesive component and then using the mixture, the modified nano-silica containing epoxy functional groups in the first adhesive component and the modified nano-silica containing amino functional groups in the second adhesive component can interact to form higher compactness, so that the toughness and the corrosion resistance of the adhesive are enhanced, a certain amount of water vapor can be blocked, and the prepared adhesive not only keeps better adhesive strength, but also has better toughness, wear resistance and corrosion resistance. Controlling the ratio of the adding mass of the first binder component to the adding mass of the second binder component to be (1.0-1.8): if the addition amount of the first adhesive component is too small or too large, the interaction effect of the modified nano-silica containing epoxy functional groups in the first adhesive component and the modified nano-silica containing amino functional groups in the second adhesive component is poor, high compactness cannot be formed, and the adhesive strength and toughness are poor.
The adhesive is prepared by the following preparation method of the adhesive.
Correspondingly, the embodiment of the invention also provides a preparation method of the adhesive. The method comprises the following steps:
s01, respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator according to the binder;
s02, carrying out first mixing treatment on the epoxy resin, the modified nano silicon dioxide containing the epoxy functional group and the epoxy modified silicone oil to obtain a first binder component;
s03, carrying out second mixing treatment on the polyether amine, the modified nano-silica containing the amino functional group and the curing accelerator to obtain a second binder component;
and S04, mixing the first binder component and the second binder component to obtain the binder.
Specifically, in the step S01, the preferred content and type of each component of the binder are as described above, and will not be described herein for brevity.
Specifically, in step S02, a first mixing treatment is performed on the epoxy resin, the modified nanosilicon dioxide containing an epoxy group functional group, and the epoxy-modified silicone oil to obtain a first binder component; preferably, in the step of performing the first mixing treatment on the epoxy resin, the modified nano-silica containing an epoxy group functional group and the epoxy modified silicone oil, the temperature of the first mixing treatment is 20 to 30 ℃, the rotating speed of the first mixing treatment is 300 to 500 revolutions per minute, and the time of the first mixing treatment is 30 to 90 minutes. The temperature of the mixing treatment is controlled to be 20-30 ℃, the first bonding component is guaranteed to be prepared at a lower temperature, and the first bonding component is guaranteed not to have a curing reaction in the preparation process.
Preferably, the preparation steps of the modified nano-silica containing epoxy functional groups are as follows: and (2) sufficiently mixing the nano-silica with a silane coupling agent containing an epoxy functional group, and carrying out a first heating reaction to obtain the modified nano-silica containing the epoxy functional group.
Preferably, the ratio of the added mass of the nano silica to the added mass of the epoxy group-containing silane coupling agent is 1: (4-8), if the addition amount of the silane coupling agent containing epoxy functional groups is too large, waste is caused, and the cost is increased; if the addition amount of the silane coupling agent containing an epoxy functional group is too small, the modification treatment effect on the surface of the nano-silica is poor, and the performance of the binder is affected.
Preferably, the epoxy-containing silane coupling agent is selected from KH560, KH560 is an epoxy-containing coupling agent, and KH560 is selected to react with the nano-silica to obtain the modified nano-silica containing epoxy functional groups.
Preferably, the particle size of the nano-silica is 40-100nm, and the nano-silica with the particle size is adopted to react with KH560 to obtain the modified nano-silica containing the epoxy functional group with moderate particle size, so that the performance of the modified nano-silica containing the epoxy functional group is not influenced by overlarge particle size of the modified nano-silica containing the epoxy functional group; the particle size of the modified nano silicon dioxide containing epoxy functional groups is not too small, so that agglomeration is easily caused to influence the modification effect of the epoxy resin. In a preferred embodiment of the invention, the nano-silica is dried and then fully mixed with a silane coupling agent containing an epoxy functional group to prepare the modified nano-silica containing the epoxy functional group.
Preferably, in the step of performing the first heating reaction to obtain the modified nano-silica containing the epoxy functional group, the first heating temperature is 220 to 230 ℃, and the first heating time is 15 to 16 hours. In a preferred embodiment of the present invention, the temperature of the first heating is 220 ℃ and the time of the first heating is 16 hours. And reacting under the temperature condition to obtain the modified nano-silica containing the epoxy functional group with better modification effect.
Specifically, in step S03, a second mixing treatment is performed on the polyether amine, the modified nano-silica containing amino functional groups, and the curing accelerator to obtain a second binder component; preferably, the temperature of the second mixing treatment is 20-30 ℃, the rotating speed of the second mixing treatment is 300-500 r/min, and the time of the second mixing treatment is 30-90 min. The temperature of the mixing treatment is controlled to be 20-30 ℃, the second bonding component is guaranteed to be prepared at a lower temperature, and the second bonding component is guaranteed not to have a curing reaction in the preparation process.
Preferably, the preparation steps of the modified nano-silica containing amino functional groups are as follows: and (3) sufficiently mixing the nano silicon dioxide and the silane coupling agent containing the amino functional group, and carrying out a second heating reaction to obtain the modified nano silicon dioxide containing the epoxy functional group.
Preferably, the ratio of the added mass of the nano silicon dioxide to the added mass of the silane coupling agent containing amino functional groups is 1: (6-10), if the addition amount of the silane coupling agent containing an amino functional group is too large, waste is caused, and the cost is increased; if the addition amount of the silane coupling agent containing an amino functional group is too small, the modification treatment effect on the surface of the nano silicon dioxide is poor, and the performance of the binder is affected.
Preferably, the amino-functional silane coupling agent is any one of KH550, KH602, KH791 and KH792, and the epoxy-functional modified nano silica can be obtained by reacting nano silica with any one of the amino-functional silane coupling agents.
Preferably, the particle size of the nano-silica is 40-100nm, and the nano-silica with the particle size is adopted to react with KH560 to obtain the modified nano-silica containing the epoxy functional group with moderate particle size, so that the performance of the modified nano-silica containing the epoxy functional group is not influenced by overlarge particle size of the modified nano-silica containing the epoxy functional group; the particle size of the modified nano silicon dioxide containing epoxy functional groups is not too small, so that agglomeration is easily caused to influence the modification effect of the epoxy resin. In a preferred embodiment of the invention, the nano-silica is dried and then fully mixed with a silane coupling agent containing an amino functional group to prepare the modified nano-silica containing an amino functional group.
Preferably, in the step of performing the second heating reaction to obtain the modified nano-silica containing the epoxy functional group, the second heating temperature is 240-250 ℃, and the second heating time is 20-22 hours. In a preferred embodiment of the present invention, the temperature of the second heating is 240 ℃ and the time of the second heating is 20 hours. And reacting under the temperature condition to obtain the modified nano-silica containing the amino functional group with better modification effect.
Specifically, in the step S04, the first binder component and the second binder component are mixed to obtain the binder. Preferably, the ratio of the addition mass of the first binder component to the second binder component is (1.0-1.8): 1. if the addition amount of the first adhesive component is too small or too large, the interaction effect between the modified nano-silica containing epoxy functional groups in the first adhesive component and the modified nano-silica containing amino functional groups in the second adhesive component is poor, and the high compactness cannot be formed, so that the adhesive strength and the toughness are poor.
The preparation method of the adhesive only needs to prepare the first adhesive component and the second adhesive component respectively according to the proportion of the components, and when the adhesive is used, the first adhesive component and the second adhesive component are mixed to obtain the adhesive. The preparation method can uniformly disperse all substances, simultaneously prepares the two components respectively, and mixes the two components when in use, is beneficial to storing products, ensures the beneficial effects of the binder, and endows the binder with excellent stability. In addition, the preparation method has simple process, controllable conditions and low equipment requirement, and can be used for industrial production.
The present invention will now be described in further detail by taking binder component content and preparation method as examples.
Example 1
Modified nano silicon dioxide containing epoxy functional group and preparation method thereof
The preparation method comprises the following steps:
providing 20g of nano silicon dioxide powder with the particle size of 60nm, and drying the nano silicon dioxide powder for 24 hours at 160 ℃;
120g of a silane coupling agent KH560 (. gamma. - (2, 3-glycidoxy) propyltrimethoxysilane) was provided,
mixing the nano silicon dioxide powder obtained by drying with the silane coupling agent KH560, heating in a reaction bottle with a condensation reflux device at 220 ℃ for 16 hours, and obtaining a crude product after the reaction is finished.
And naturally cooling the crude product, and performing centrifugal separation to obtain the modified nano silicon dioxide containing the epoxy functional group.
Example 2
Modified nano silicon dioxide containing amino functional group and preparation method thereof
The preparation method comprises the following steps:
providing 20g of nano silicon dioxide powder with the particle size of 60nm, and drying the nano silicon dioxide powder for 24 hours at 160 ℃;
120g of a silane coupling agent KH792(N- (. beta. -aminoethyl) - γ -aminopropyl-trimethoxysilane) was provided,
mixing the nano silicon dioxide powder obtained by drying with the silane coupling agent KH792, and heating in a reaction bottle with a condensation reflux device at 240 ℃ for 20 hours to obtain a crude product after the reaction is finished.
And naturally cooling the crude product, and performing centrifugal separation to obtain the modified nano-silica containing the amino functional group.
Example 3
Binder and preparation method thereof
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises 60g E51 epoxy resin, 40g E44 epoxy resin, 20g of epoxy modified silicone oil, and 5g of epoxy functional group-containing modified nano-silica prepared in example 1; the second binder component included 70g of polyetheramine D400, 30g of polyetheramine D2000, 5g of curing accelerator DMP-30, 5g of the amino-functional group-containing modified nanosilica prepared in example 2.
The preparation method of the adhesive comprises the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator;
60g of E51 epoxy resin, 40g of E44 epoxy resin and 30g of epoxy modified silicone oil are mechanically stirred and dispersed for 30 minutes at the speed of 300 revolutions per minute; then 10g of the modified nano-silica containing epoxy functional groups prepared in example 1 was added, and the mixture was mechanically stirred and dispersed at a speed of 400 rpm for 90 minutes to obtain a first binder component;
70g of polyetheramine D400, 30g of polyetheramine D2000 and 10g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 10g of amino-functional group-containing modified nano-silica prepared in example 2 is added, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes to obtain a second binder component;
when the adhesive is used, the ratio of the adding mass of the first adhesive component to the adding mass of the second adhesive component is selected to be 1.4: 1, mixing the first binder component and the second binder component, and heating at 80 ℃ for 1 hour for curing to obtain the binder.
Example 4
Binder and preparation method thereof
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises 60g E51 epoxy resin, 40g E44 epoxy resin, 20g of epoxy modified silicone oil, and 5g of epoxy functional group-containing modified nano-silica prepared in example 1; the second binder component included 70g of polyetheramine D400, 30g of polyetheramine D2000, 5g of curing accelerator DMP-30, 5g of the amino-functional group-containing modified nanosilica prepared in example 2.
The preparation method of the adhesive comprises the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator;
60g of E51 epoxy resin, 40g of E44 epoxy resin and 30g of epoxy modified silicone oil are mechanically stirred and dispersed for 30 minutes at the speed of 300 revolutions per minute; then 10g of the modified nano-silica containing epoxy functional groups prepared in example 1 was added, and the mixture was mechanically stirred and dispersed at a speed of 400 rpm for 90 minutes to obtain a first binder component;
70g of polyetheramine D400, 30g of polyetheramine D2000 and 10g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 10g of amino-functional group-containing modified nano-silica prepared in example 2 is added, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes to obtain a second binder component;
when the adhesive is used, the ratio of the adding mass of the first adhesive component to the adding mass of the second adhesive component is selected to be 1.3: 1, mixing the first binder component and the second binder component, and heating at 80 ℃ for 1 hour for curing to obtain the binder.
Example 5
Binder and preparation method thereof
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises 50g E51 epoxy resin, 50g E44 epoxy resin, 25g epoxy modified silicone oil, 8g epoxy functional group-containing modified nano-silica prepared in example 1; the second binder component included 80g of polyetheramine D400, 20g of polyetheramine D2000, 8g of curing accelerator DMP-30, 8g of the amino-functional group-containing modified nanosilica prepared in example 2.
The preparation method of the adhesive comprises the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator;
mechanically stirring and dispersing 50g E51 epoxy resin, 50g E44 epoxy resin and 25g of epoxy modified silicone oil for 30 minutes at the speed of 300 revolutions per minute; then 8g of the modified nano-silica containing epoxy functional groups prepared in example 1 was added, and the mixture was mechanically stirred and dispersed at a speed of 400 rpm for 90 minutes to obtain a first binder component;
80g of polyetheramine D400, 20g of polyetheramine D2000 and 8g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 8g of amino-functional group-containing modified nano-silica prepared in example 2 is added, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes to obtain a second binder component;
when the adhesive is used, the ratio of the adding mass of the first adhesive component to the adding mass of the second adhesive component is selected to be 1.5: 1, mixing the first binder component and the second binder component, and heating at 80 ℃ for 1 hour for curing to obtain the binder.
Example 6
Binder and preparation method thereof
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises 80g E51 epoxy resin, 20g E44 epoxy resin, 25g epoxy modified silicone oil, 8g epoxy functional group-containing modified nano-silica prepared in example 1; the second binder component included 50g of polyetheramine D400, 50g of polyetheramine D2000, 8g of curing accelerator DMP-30, 8g of the amino-functional group-containing modified nanosilica prepared in example 2.
The preparation method of the adhesive comprises the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator;
mechanically stirring and dispersing 80g E51 epoxy resin, 20g E44 epoxy resin and 25g of epoxy modified silicone oil for 30 minutes at the speed of 300 revolutions per minute; then 8g of the modified nano-silica containing epoxy functional groups prepared in example 1 was added, and the mixture was mechanically stirred and dispersed at a speed of 400 rpm for 90 minutes to obtain a first binder component;
50g of polyetheramine D400, 50g of polyetheramine D2000 and 8g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 8g of amino-functional group-containing modified nano-silica prepared in example 2 is added, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes to obtain a second binder component;
when the adhesive is used, the ratio of the adding mass of the first adhesive component to the adding mass of the second adhesive component is selected to be 1: 1, mixing the first binder component and the second binder component, and heating at 80 ℃ for 1 hour for curing to obtain the binder.
Example 7
Binder and preparation method thereof
The adhesive comprises a first adhesive component and a second adhesive component, wherein the first adhesive component comprises 40g E51 epoxy resin, 60g E44 epoxy resin, 25g epoxy modified silicone oil, 8g epoxy functional group-containing modified nano-silica prepared in example 1; the second binder component included 80g of polyetheramine D400, 20g of polyetheramine D2000, 8g of curing accelerator DMP-30, 8g of the amino-functional group-containing modified nanosilica prepared in example 2.
The preparation method of the adhesive comprises the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator;
mechanically stirring and dispersing 40g E51 epoxy resin, 60g E44 epoxy resin and 25g of epoxy modified silicone oil for 30 minutes at the speed of 300 revolutions per minute; then 8g of the modified nano-silica containing epoxy functional groups prepared in example 1 was added, and the mixture was mechanically stirred and dispersed at a speed of 400 rpm for 90 minutes to obtain a first binder component;
80g of polyetheramine D400, 20g of polyetheramine D2000 and 8g of curing accelerator DMP-30 are mechanically stirred and dispersed for 60 minutes at the speed of 300 revolutions per minute, 8g of amino-functional group-containing modified nano-silica prepared in example 2 is added, and mechanical stirring and dispersion are carried out at the speed of 400 revolutions per minute for 90 minutes to obtain a second binder component;
when the adhesive is used, the ratio of the adding mass of the first adhesive component to the adding mass of the second adhesive component is selected to be 1.8: 1, mixing the first binder component and the second binder component, and heating at 80 ℃ for 1 hour for curing to obtain the binder.
And (4) analyzing results:
the binders prepared in examples 3 to 7 were subjected to property measurement and analysis, and elongation at break, shear strength and water permeability were measured, respectively, and the results of the property measurements are shown in table 1, which is shown in table 1, and the elongation at break of the binders prepared in examples 3 to 7 were 19.88%, 23.16%, 25%, respectively19%, 24.32%, 27.58%; the shear strength is 23.91MPa, 24.66MPa, 25.73MPa, 28.12MPa and 26.36MPa respectively; the water permeability is 1.63g/m2、1.59g/m2、1.35g/m2、1.47g/m2、1.28g/m2。
The prepared adhesive not only maintains better adhesive strength, but also has better toughness and corrosion resistance, can block a certain amount of water vapor, has excellent water resistance, and is an epoxy adhesive with excellent performance.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The adhesive is characterized by comprising a first adhesive component and a second adhesive component, wherein the adding mass ratio of the first adhesive component to the second adhesive component is (1.0-1.8): 1, mixing when in use;
wherein the first binder component comprises the following components: the epoxy resin-epoxy functional group-containing modified nano silicon dioxide is prepared from epoxy resin, epoxy group-containing modified nano silicon dioxide and epoxy modified silicone oil, wherein the ratio of the addition mass of the epoxy resin to the addition mass of the epoxy group-containing modified nano silicon dioxide to the addition mass of the epoxy modified silicone oil is 1: (0.05-0.1): (0.2 to 0.3); the second binder component comprises the following components: the curing agent comprises polyether amine, amino functional group-containing modified nano-silica and a curing accelerator, wherein the addition mass ratio of the polyether amine to the amino functional group-containing modified nano-silica to the curing accelerator is 1: (0.05-1): (0.05-0.1).
2. The adhesive according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of bisphenol A epoxy resin E55, bisphenol A epoxy resin E51, and bisphenol A epoxy resin E44.
3. The binder of claim 1 or 2 wherein the polyetheramine is selected from the group consisting of polyetheramines having a number average molecular weight of 400 and polyetheramines having a number average molecular weight of 2000.
4. The bonding agent according to claim 1 or 2, wherein the curing accelerator is any one selected from the group consisting of DMP-10, DMP-20, and DMP-30.
5. A preparation method of the adhesive is characterized by comprising the following steps:
respectively weighing epoxy resin, modified nano-silica containing epoxy functional groups, epoxy modified silicone oil, polyether amine, modified nano-silica containing amino functional groups and a curing accelerator according to the binder of any one of claims 1 to 4;
carrying out first mixing treatment on the epoxy resin, the modified nano silicon dioxide containing the epoxy functional group and the epoxy modified silicone oil to obtain a first binder component;
carrying out second mixing treatment on the polyether amine, the modified nano-silica containing the amino functional group and the curing accelerator to obtain a second binder component;
when the adhesive is used, the first adhesive component and the second adhesive component are mixed to obtain the adhesive.
6. The method for preparing the binder according to claim 5, wherein in the step of performing the first mixing treatment on the epoxy resin, the modified nanosilica containing an epoxy functional group and the epoxy-modified silicone oil, the temperature of the first mixing treatment is 20 to 30 ℃, the rotation speed of the first mixing treatment is 300 to 500 revolutions per minute, and the time of the first mixing treatment is 30 to 90 minutes.
7. The method for preparing the adhesive according to claim 5, wherein in the step of performing the second mixing treatment on the polyetheramine, the modified nanosilicon dioxide containing an amino functional group and the curing accelerator, the temperature of the second mixing treatment is 20 to 30 ℃, the rotation speed of the second mixing treatment is 300 to 500 revolutions per minute, and the time of the second mixing treatment is 30 to 90 minutes.
8. The method for producing a binder according to any one of claims 5 to 7,
the preparation steps of the modified nano silicon dioxide containing the epoxy functional group are as follows: providing nano-silica and fully mixing a silane coupling agent containing an epoxy functional group, and carrying out a first heating reaction to obtain the modified nano-silica containing the epoxy functional group; and/or the presence of a gas in the gas,
the preparation method of the modified nano-silica containing the amino functional group comprises the following steps: and (3) sufficiently mixing the nano silicon dioxide and the silane coupling agent containing the amino functional group, and carrying out a second heating reaction to obtain the modified nano silicon dioxide containing the epoxy functional group.
9. The method for producing an adhesive according to claim 8,
in the step of providing sufficient mixing of the nano-silica and the silane coupling agent containing the epoxy functional group, the ratio of the added mass of the nano-silica to the added mass of the silane coupling agent containing the epoxy functional group is 1: (4-8); and/or the presence of a gas in the gas,
providing and fully mixing nano silicon dioxide and a silane coupling agent containing an amino functional group, wherein the ratio of the added mass of the nano silicon dioxide to the added mass of the silane coupling agent containing the amino functional group is 1: (6-10).
10. The method for producing an adhesive according to claim 8,
in the step of carrying out a first heating reaction to obtain the modified nano-silica containing the epoxy functional group, the first heating temperature is 220-230 ℃, and the first heating time is 15-16 hours; and/or the presence of a gas in the gas,
and in the step of carrying out a second heating reaction to obtain the modified nano-silica containing the epoxy functional group, the second heating temperature is 240-250 ℃, and the second heating time is 20-22 hours.
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| CN114262528A (en) * | 2021-12-07 | 2022-04-01 | 中国科学院深圳先进技术研究院 | Surface modification method and application of silicon dioxide |
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| CN116042151A (en) * | 2023-02-14 | 2023-05-02 | 东莞市鼎泰鑫电子有限公司 | Double-component thermosetting resin and preparation method and application thereof |
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