CN115011298A - Rheological-stable single-component epoxy encapsulating adhesive and preparation method thereof - Google Patents
Rheological-stable single-component epoxy encapsulating adhesive and preparation method thereof Download PDFInfo
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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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Abstract
The invention discloses a single-component epoxy encapsulating adhesive with stable rheology and a preparation method thereof. The raw materials of the single-component epoxy encapsulating adhesive comprise the following components: the curing agent comprises, by weight, 30-40 parts of epoxy resin, 10-15 parts of a diluent, 16-18 parts of a compound curing agent, 2-3 parts of a thixotropic agent, 0.3-0.5 part of a curing accelerator and 0.2-0.3 part of a defoaming agent. The compound curing agent comprises an imidazole curing agent and a toughening curing agent in a mass ratio of 3 (1-1.5). In the technical scheme, the prepared toughening curing agent is compounded with an imidazole curing agent and phytic acid to obtain a compound curing agent which is used in single-component epoxy resin; the rheological stability of the single-component epoxy encapsulating adhesive is enhanced through the synergistic effect of the toughening curing agent and the phytic acid; the curing effect is enhanced by the auxiliary imidazole curing agent of the toughening curing agent, and simultaneously, the brittleness is inhibited, the cracking resistance is enhanced, and the adhesion is enhanced.
Description
Technical Field
The invention relates to the technical field of epoxy encapsulating glue, in particular to a single-component epoxy encapsulating glue with stable rheological property and a preparation method thereof.
Background
The epoxy encapsulating glue is divided into a single-component type and a double-component type; compared with the double-component epoxy encapsulating glue, the single-component epoxy encapsulating glue has better performance in the aspects of convenience, temperature resistance and adhesion, and is widely used in the packaging process of integrated circuits, electronic elements and the like. However, the preparation of the one-component epoxy encapsulating adhesive has technical difficulties; firstly, the problems of unstable rheological property and short shelf life exist in the existing single-component epoxy encapsulating glue due to the mixing with a curing agent, and the rheological property of the existing single-component epoxy encapsulating glue is easy to change in the storage or transportation process, so that the gluing process is difficult or the quality is reduced; secondly, the epoxy encapsulating adhesive has brittleness after being cured, so that the anti-stripping and anti-cracking performance of the epoxy encapsulating adhesive is poor. Therefore, there is a need to increase long-term storage properties while ensuring rheological properties.
In the prior art, in order to enhance the rheological stability of epoxy encapsulating glue, latent encapsulating glue is generally used, such as a capsule type curing agent in patent CN 202110528764.8; however, the capsule type curing agent generally has a complicated encapsulation technique, a general curing effect, and low adhesive strength. Therefore, it is necessary to prepare a latent curing agent which is simple and convenient to prepare and improve the curing performance; on the other hand, in order to enhance the mechanical properties of epoxy encapsulating adhesives, auxiliaries such as fillers and toughening agents are usually used, but the effect on the dispersibility and rheological properties is influenced.
In conclusion, the preparation of the single-component epoxy encapsulating adhesive with stable rheology is of great significance in solving the problems.
Disclosure of Invention
The invention aims to provide a single-component epoxy encapsulating adhesive with stable rheology and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a rheological stable single-component epoxy encapsulating adhesive comprises the following steps:
s1: sequentially adding epoxy resin, a diluent, a curing accelerator and a defoaming agent into a mixing tank, and stirring and homogenizing to obtain a mixed material A;
s2: and adding a compound curing agent and a thixotropic agent into the mixed material A, stirring, homogenizing and defoaming to obtain the single-component epoxy encapsulating adhesive.
Preferably, the single-component epoxy encapsulating adhesive comprises, by weight, 30-40 parts of epoxy resin, 10-15 parts of diluent, 16-18 parts of compound curing agent, 2-3 parts of thixotropic agent, 0.3-0.5 part of curing accelerator and 0.2-0.3 part of defoaming agent.
Preferably, the epoxy resin is one or a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin; the diluent is one or more of alkyl glycidyl ether, tertiary carbonic acid glycidyl ether and trimethylolpropane triglycidyl ether; the thixotropic agent is one or two of fumed silica and organic bentonite; the curing accelerator is 2,4, 6-tri (dimethylamine methyl phenol); the defoaming agent is a silane defoaming agent.
Preferably, the compound curing agent comprises an imidazole curing agent and a toughening curing agent in a mass ratio of 3 (1-1.5).
Preferably, the compounding method of the compound curing agent comprises the following steps: ultrasonically dispersing an imidazole curing agent in deionized water; adding a toughening curing agent, and uniformly stirring; dripping phytic acid solution, and stirring and reacting for 1-1.5 hours; and (4) removing the solvent by rotary evaporation to obtain the compound curing agent.
Preferably, the mass ratio of the imidazole curing agent to the phytic acid is 1 (0.5-0.8).
Preferably, the preparation method of the toughening curing agent comprises the following steps: dispersing graphene oxide in deionized water under the nitrogen atmosphere, adding tannic acid and vinyl pyrrolidone, refluxing for 10-12 hours at the temperature of 95-105 ℃, washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 1-aminoundecanoic acid, and uniformly stirring; adding maleic anhydride, and reacting for 24-36 hours at the set temperature of 92-95 ℃; and washing and drying to obtain the toughening curing agent.
Preferably, the mass ratio of the graphene oxide to the tannic acid to the vinyl pyrrolidone is 1 (0.45-0.55) to 0.05; the mass ratio of the tannic acid to the 1-aminoundecanoic acid to the maleic anhydride is 1 (0.2-0.4): 1.
Preferably, the imidazole curing agent is alkyl imidazole, including one or more of 2-methyl imidazole, 2-ethyl-4-methyl imidazole and 2-undecyl imidazole.
Preferably, the single-component epoxy encapsulating adhesive prepared by the preparation method of the single-component epoxy encapsulating adhesive with stable rheology is characterized in that: the curing process of the single-component epoxy encapsulating adhesive comprises the following steps: curing at 120-125 ℃ for 20 minutes, and heating to 140-145 ℃ for 40 minutes.
According to the technical scheme, the toughening curing agent is prepared and compounded with the imidazole curing agent and the phytic acid to obtain a compound curing agent, and the rheological stability of the single-component epoxy encapsulating adhesive is enhanced through the synergistic effect of the toughening curing agent and the phytic acid; the curing effect is enhanced by the toughening curing agent and the imidazole curing agent, and meanwhile, the brittleness is inhibited, and the binding agent and the cracking resistance are increased.
In the scheme, in order to control the rheological stability, phytic acid, a toughening curing agent and an imidazole curing agent are compounded; the imidazole curing agent is passivated, and the low-temperature reactivity is inhibited, so that the rheological stability of the single-component epoxy resin is enhanced. The curing process of the prepared single-component epoxy encapsulating adhesive is carried out at two temperatures in sequence, the imidazole curing agent is deblocked and cured at 120 ℃, and then the toughening curing agent is cured at 140 ℃, so that the curing stress is effectively buffered, and the brittleness is reduced.
The imidazole curing agent has high curing activity, is very suitable for preparing the single-component epoxy encapsulating adhesive with medium and low curing temperature, but can be cured at normal temperature due to high activity, so that the rheological stability is low, and the normal-temperature storage property is poor. Therefore, in the scheme, phytic acid and the toughening curing agent are used for passivating the imidazole curing agent through an acid-base salt forming reaction, so that the rheological stability is improved. The active group of the prepared toughening curing agent is terminal carboxyl, the reaction speed is low at normal temperature, the reaction can be carried out only at medium temperature, and the prepared toughening curing agent has good stability at normal temperature. The oxygen-containing group in the toughening curing agent can increase the stability of the imidazole curing agent and ensure the rheological stability.
Wherein, the toughening curing agent is synthesized by a two-step method; the first step is as follows: placing graphene oxide in vinyl pyrrolidone and tannic acid, initiating polymerization of the vinyl pyrrolidone by using the graphene oxide, and grafting micromolecular polyvinylpyrrolidone on the surface of the vinyl pyrrolidone; hydrophobic and hydrogen bond actions between polyvinylpyrrolidone and tannic acid and hydrogen bond actions between graphene oxide and tannic acid are utilized, tannic acid is loaded on the surface, and the enhancement of graphene oxide lamella spacing is promoted; the grafting of the two substances is cooperated to ensure that the modified graphene has higher free volume after being added into the epoxy resin, so that the toughness of the epoxy encapsulating adhesive is obviously enhanced, and the bonding property is improved. And the roughness generated by surface grafting increases the compatibility and the bonding strength.
Although the cracking resistance and the bonding strength of the epoxy encapsulating adhesive can be remarkably improved, the modified graphene has relatively poor miscibility with an epoxy resin matrix, so that the curing is not uniform; the grafting of polyvinylpyrrolidone increases the miscibility, while the tannin grafting enhances the peeling strength, but the accumulation of aromatic groups of the tannin grafting is poor in miscibility with epoxy resin, so that a precipitation phenomenon exists; and the surface of the material has more hydroxyl groups and the curing temperature is higher. Therefore, in the scheme, the second step of reaction treatment is carried out: the modified graphene reacts with acid anhydride under the catalysis of pyridine, and the tannic acid loaded on the surface is subjected to end carboxylation, wherein the carboxyl has high activity, and can be quickly reacted and cured at 140 ℃ under the promotion of a curing accelerator and an imidazole curing agent, so that medium-temperature curing is realized. In addition, 1-aminoundecanoic acid is introduced during the carboxylation process, which also has a curing effect, but the amino group activity is weak, the curing temperature is high, and the curing speed is slow, so that, also in pyridine, the amino group is converted into a carboxyl end group, which promotes the curing effect. Improving the dispersibility of the toughening curing agent in the epoxy resin; and the presence of the terminal carboxyl groups increases the fluid stability.
Certainly, as the surface of the toughening agent is loaded with substances such as polyvinylpyrrolidone, tannic acid and the like, the addition of the toughening agent can increase the viscosity, reduce the mobility, reduce the curing activity and influence the curing effect; in the scheme, the toughness of the single-component epoxy encapsulating adhesive is obviously improved and the bonding performance and the stability are enhanced by controlling the end carboxylation process and the addition amount in the toughening curing agent amount under the condition of ensuring that the increase of the basic viscosity is not more than 2%.
Detailed Description
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 only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the graphene oxide was prepared by Hummers method. The preparation method comprises the following steps: sequentially adding 1g of graphite powder and 0.5g of sodium nitrate into 25mL of concentrated sulfuric acid, adding 2g of potassium perchlorate and 3g of potassium permanganate, setting the temperature to be 10 ℃, and stirring for reaction for 2 hours; setting the temperature to be 38 ℃, and stirring for reaction for 30 minutes; adding 100mL of deionized water, and setting the temperature to be 95 ℃ for reaction for 30 minutes; adding deionized water to terminate the reaction, adding 15mL of 20% hydrogen peroxide, and stirring for 30 minutes; adding 30mL of hydrochloric acid with the concentration of 10% and stirring for 1 hour; and washing and drying to obtain the graphene oxide.
Example 1:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.5g of tannic acid and 0.05g of vinyl pyrrolidone, refluxing for 12 hours at the temperature of 100 ℃, washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.3g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and reacting for 32 hours at the set temperature of 94 ℃; and washing and drying to obtain the toughening curing agent.
(2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Example 2:
s1: sequentially adding 30 parts of bisphenol A type epoxy resin, 10 parts of tertiary carbonic acid glycidyl ether, 0.3 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.45g of tannic acid and 0.05g of vinyl pyrrolidone, refluxing for 12 hours at the temperature of 95 ℃, washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.2g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and reacting for 36 hours at the set temperature of 92 ℃; and washing and drying to obtain the toughening curing agent.
(2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 2 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.5.
Example 3:
s1: sequentially adding 40 parts of bisphenol A type epoxy resin, 15 parts of tertiary carbonic acid glycidyl ether, 0.5 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.3 part of silane defoaming agent into a mixing tank, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the atmosphere of nitrogen, adding 0.55g of tannic acid and 0.05g of vinyl pyrrolidone, refluxing for 10 hours at the set temperature of 105 ℃, washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.4g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and setting the temperature to be 95 ℃ for reaction for 24 hours; and washing and drying to obtain the toughening curing agent.
(2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1.5 hours; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 18 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and performing vacuum defoaming to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of the 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1.5; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.8.
Comparative example 1:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) under the nitrogen atmosphere, 1g of graphene oxide is ultrasonically dispersed in 50mL of deionized water, 0.5g of tannic acid and 0.05g of vinyl pyrrolidone are added, reflux is carried out at the temperature of 100 ℃ for 12 hours, and washing and drying are carried out, so as to obtain the modified graphene. (2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to modified graphene is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Comparative example 2:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.5g of tannic acid and 0.05g of vinyl pyrrolidone, refluxing for 12 hours at the temperature of 100 ℃, washing and drying to obtain modified graphene; placing the modified graphene in 20mL of pyridine solution under the nitrogen atmosphere, adding 1g of maleic anhydride, and reacting at the temperature of 94 ℃ for 32 hours; and washing and drying to obtain the toughening curing agent. (2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Comparative example 3:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.055g of vinyl pyrrolidone, refluxing for 12 hours at the set temperature of 100 ℃, and washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.3g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and reacting for 32 hours at the set temperature of 94 ℃; and washing and drying to obtain the toughening curing agent. (2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Comparative example 4:
a preparation method of a rheological stable single-component epoxy encapsulating adhesive comprises the following steps:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.55g of tannic acid, refluxing for 12 hours at the temperature of 100 ℃, and washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.3g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and reacting for 32 hours at the set temperature of 94 ℃; and washing and drying to obtain the toughening curing agent. (2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 3: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Comparative example 5:
a preparation method of a rheological stable single-component epoxy encapsulating adhesive comprises the following steps:
s1: adding 35 parts of bisphenol A epoxy resin, 12 parts of tertiary carbonic acid glycidyl ether, 0.4 part of 2,4, 6-tri (dimethylamine methyl phenol) and 0.2 part of silane defoaming agent into a mixing tank in sequence, and homogenizing at 1000rpm under stirring to obtain a mixed material A;
s2: (1) ultrasonically dispersing 1g of graphene oxide in 50mL of deionized water under the nitrogen atmosphere, adding 0.5g of tannic acid and 0.05g of vinyl pyrrolidone, refluxing for 12 hours at the temperature of 100 ℃, washing and drying to obtain modified graphene; under the atmosphere of nitrogen, placing the modified graphene in 20mL of pyridine solution, adding 0.3g of 1-aminoundecanoic acid, and uniformly stirring; adding 1g of maleic anhydride, and reacting for 32 hours at the set temperature of 94 ℃; and washing and drying to obtain the toughening curing agent.
(2) Ultrasonically dispersing 2-ethyl-4-methylimidazole in deionized water; adding a toughening curing agent, and uniformly stirring; dripping 10 wt% phytic acid solution, and stirring for reaction for 1 hour; and (4) performing rotary evaporation to obtain the compound curing agent.
(3) And adding 16 parts of compound curing agent and 3 parts of fumed silica into the mixed material A, stirring and homogenizing at 600rpm, and defoaming in vacuum to obtain the single-component epoxy encapsulating adhesive.
In the technical scheme, in the compound curing agent, the mass ratio of 2-ethyl-4-methylimidazole to the toughening curing agent is 1: 1; the mass ratio of the 2-ethyl-4-methylimidazole to the phytic acid is 1: 0.6.
Experiment: carrying out viscosity detection and shear strength tests on the single-component epoxy encapsulating glue prepared in the examples 1-3 and the comparative examples 1-5; and its viscosity was checked again in the presence of the oil at 25 ℃ for 60 days, by comparing the viscosity change on day 1 and 60, the rate of viscosity change was obtained (| day 1 viscosity-day 60 viscosity | ÷ day 1 viscosity) × 100%; the data obtained are shown in the following table:
| examples | Viscosity rate of change/%) | Shear strength/MPa |
| Example 1 | ＜2 | 27.6 |
| Example 2 | ＜2 | 27.3 |
| Example 3 | ＜2 | 27.5 |
| Comparative example 1 | 6.4 | 24.3 |
| Comparative example 2 | 2.6 | 26.1 |
| Comparative example 3 | 3.8 | 21.2 |
| Comparative example 4 | 5.4 | 23.2 |
| Comparative example 5 | 7.3 | 28.1 |
And (4) conclusion: from the above data, it can be seen that: the single-component epoxy encapsulating adhesive prepared in the embodiments 1 to 3 has excellent rheological stability and better cohesiveness. Comparing example 1 with comparative examples 1-5, it is shown that: comparative example 1 does not undergo terminal carboxylation modification, so that rheological stability and cohesiveness are reduced; in comparative example 2, the adhesive property was lowered because 1-aminoundecanoic acid was not introduced; in comparative example 3, tannic acid was not introduced, so that toughness was decreased and shear strength was significantly decreased; also, in comparative example 4, since no vinylpyrrolidone was introduced, the shear strength was decreased; comparative example 3 and comparative example 4 data in combination with comparative example 1, show that tannic acid and vinyl pyrrolidone have a synergistic effect. In comparative example 5, the rheological properties were significantly reduced due to the increased content of the toughening curing agent.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of single-component epoxy encapsulating adhesive with stable rheology is characterized by comprising the following steps: the method comprises the following steps:
s1: sequentially adding epoxy resin, a diluent, a curing accelerator and a defoaming agent into a mixing tank, and stirring and homogenizing to obtain a mixed material A;
s2: and adding a compound curing agent and a thixotropic agent into the mixed material A, stirring, homogenizing and defoaming to obtain the single-component epoxy encapsulating adhesive.
2. The method of claim 1, wherein the method comprises the steps of: the single-component epoxy encapsulating adhesive comprises, by weight, 30-40 parts of epoxy resin, 10-15 parts of diluent, 16-18 parts of compound curing agent, 2-3 parts of thixotropic agent, 0.3-0.5 part of curing accelerator and 0.2-0.3 part of defoaming agent.
3. The method of claim 1, wherein the method comprises the steps of: the epoxy resin is one or a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin; the diluent is one or more of alkyl glycidyl ether, tertiary carbonic acid glycidyl ether and trimethylolpropane triglycidyl ether; the thixotropic agent is one or two of fumed silica and organic bentonite; the curing accelerator is 2,4, 6-tri (dimethylamine methyl phenol); the defoaming agent is a silane defoaming agent.
4. The method of claim 1, wherein the method comprises the steps of: the compound curing agent comprises an imidazole curing agent and a toughening curing agent in a mass ratio of 3 (1-1.5).
5. The method of claim 4, wherein the method comprises the steps of: the compounding method of the compound curing agent comprises the following steps: ultrasonically dispersing an imidazole curing agent in deionized water; adding a toughening curing agent, and uniformly stirring; dripping phytic acid solution, and stirring and reacting for 1-1.5 hours; and (4) performing rotary evaporation to obtain the compound curing agent.
6. The method of claim 5, wherein the method comprises the steps of: the mass ratio of the imidazole curing agent to the phytic acid is 1 (0.5-0.8).
7. The method of claim 4, wherein the method comprises the steps of: the preparation method of the toughening curing agent comprises the following steps: dispersing graphene oxide in deionized water under the nitrogen atmosphere, adding tannic acid and vinyl pyrrolidone, refluxing for 10-12 hours at the temperature of 95-105 ℃, washing and drying to obtain modified graphene; placing the modified graphene in a pyridine solution under the nitrogen atmosphere, adding 1-aminoundecanoic acid, and uniformly stirring; adding maleic anhydride, and reacting for 24-36 hours at the set temperature of 92-95 ℃; and washing and drying to obtain the toughening curing agent.
8. The method of claim 7, wherein the method comprises the steps of: the mass ratio of the graphene oxide to the tannic acid to the vinyl pyrrolidone is 1 (0.45-0.55) to 0.05; the mass ratio of the tannic acid to the 1-aminoundecanoic acid to the maleic anhydride is 1 (0.2-0.4): 1.
9. The method of claim 4, wherein the method comprises the steps of: the imidazole curing agent is alkyl imidazole and comprises one or a mixture of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-undecylimidazole.
10. The single-component epoxy encapsulating adhesive prepared by the preparation method of the rheology-stable single-component epoxy encapsulating adhesive according to any one of claims 1 to 9, characterized in that: the curing process of the single-component epoxy encapsulating adhesive comprises the following steps: curing at 120-125 ℃ for 20 minutes, and heating to 140-145 ℃ for 40 minutes.
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