CN114752334B - Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof - Google Patents
Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof Download PDFInfo
- Publication number
- CN114752334B CN114752334B CN202210376595.5A CN202210376595A CN114752334B CN 114752334 B CN114752334 B CN 114752334B CN 202210376595 A CN202210376595 A CN 202210376595A CN 114752334 B CN114752334 B CN 114752334B
- Authority
- CN
- China
- Prior art keywords
- accelerator
- adhesive film
- epoxy
- epoxy resin
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/35—Applications of adhesives in processes or use of adhesives in the form of films or foils for aeronautic or naval applications
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/26—Presence of textile or fabric
- C09J2400/263—Presence of textile or fabric in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of adhesives, and particularly relates to a moisture-heat-resistant storage-stable medium-temperature cured epoxy structural adhesive film and a preparation method thereof. The epoxy structure adhesive film is prepared by hot melting and compounding a sizing material containing epoxy resin, a toughening agent, a curing agent and an accelerator @ graphene compound with a carrier. On the premise of not affecting other performances, the laminated structure of the graphene is utilized to prevent water molecules from invading the epoxy resin, so that the moisture and heat resistance of the epoxy structural adhesive film is obviously improved; the steric hindrance effect and ionic bond complexation of the graphene are utilized to reduce the reactivity of the substituted urea accelerator under the storage condition, so that the storage period of the epoxy structure adhesive film is longer, the problems of poor wet heat resistance of an epoxy resin system and short storage period of a dicyandiamide-substituted urea curing system are solved, the requirement of a large-scale aviation aircraft on the intermediate-temperature epoxy structure adhesive film is met, and the epoxy structure adhesive film is suitable for adhesive bonding of composite materials or bearing structures such as metals.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a moisture-heat-resistant storage-stable medium-temperature cured epoxy structural adhesive film and a preparation method thereof.
Background
The intermediate temperature cured epoxy structural adhesive film is mainly used for bonding a plate-plate and a plate-core of a metal material and a composite material of a bearing structure, is widely applied in the field of aerospace, and is the most main variety in the current aviation structural adhesive. The curing temperature of the intermediate temperature curing epoxy structural adhesive film is 120-130 ℃, and compared with the high temperature curing (170-180 ℃) adhesive film, the curing temperature is greatly reduced, so that the secondary molding buckling deformation of the composite material caused by high temperature curing can be reduced, and the requirements of the molding process of the composite material on the appearance precision and fatigue performance of structural members are met.
Most of the existing intermediate temperature cured epoxy structural adhesive films at home and abroad use dicyandiamide-substituted urea as a curing system and rubber as a toughening agent. Representative foreign products are "Redux312 film" from Hexcel corporation, "FM73 film" from Cytec corporation, "AF163 film" from 3M corporation, and "EA9628 film" from Henkel-Loctite corporation; representative products in China are J-95 adhesive films of the national academy of sciences of Heilongjiang province, SY-24 series adhesive films of the national academy of aviation materials of Beijing, of China, and the like. The intermediate temperature curing epoxy structural adhesive films have the main advantages of excellent adhesive bonding performance, high technical maturity and wide application. However, the storage period of the medium-temperature curing structural adhesive film taking the substituted urea as the accelerator is generally only about 30 days, and when large-area adhesive bonding is performed, the problem that the adhesive film is aged to cause obvious increase in viscosity and even gelation can occur, so that the adhesive strength of the adhesive film and the quality of corresponding parts are affected. Meanwhile, the epoxy resin system for the adhesive has strong internal polarity and contains a large amount of hydroxyl groups due to the requirement of adhesive performance, so that the epoxy resin system is easy to adsorb water molecules and is immersed by the water molecules, and the problem of poor wet heat resistance is caused.
Disclosure of Invention
The invention provides a moisture and heat resistant and storage stable intermediate temperature cured epoxy structural adhesive film and a preparation method thereof, which are designed aiming at the problems existing in the prior art.
The aim of the invention is realized by the following technical scheme:
the intermediate temperature cured epoxy structural adhesive film with stable moisture and heat resistance is prepared by hot melt compounding of a sizing material consisting of epoxy resin, a toughening agent, a curing agent and an accelerator @ graphene compound and a carrier, and can be cured at 120-130 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 60-80 parts of epoxy resin; 10-20 parts of toughening agent; 10-25 parts of curing agent; 4-12 parts of accelerator @ graphene compound.
The epoxy resin is prepared by mixing two or more of bisphenol A type epoxy resins with the marks of E-54, E-51, E-44, 0194, 0191 and 850S.
The toughening agent is one or more of epoxy nitrile rubber, carboxyl nitrile rubber, epoxy polybutadiene rubber, carboxyl polybutadiene rubber and core-shell rubber particles.
The curing agent is superfine dicyandiamide, and the grain diameter of the curing agent is less than or equal to 10 mu m.
The accelerator @ graphene compound is a compound formed by complexing a substituted urea accelerator and carboxyl groups on the surface of graphene oxide in an interaction manner to form a salt, so that the substituted urea accelerator is attached to the surface of a graphene sheet in an ionic bond manner.
The substituted urea accelerator is 2, 4-di (N, N-dimethyl) urea toluene, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea, 4-di (N, N-dimethyl) urea diphenylmethane or other urea derivatives.
The diameter of the graphene oxide sheet layer is 100nm-10 mu m.
The weight ratio of the substituted urea accelerator to the graphene oxide is (1-2): (3-5).
The carrier is one of nylon gauze, polyester gauze and non-woven fabric.
A preparation method of a moisture-heat resistant storage stable intermediate temperature cured epoxy structural adhesive film comprises the following steps:
(1) weighing an accelerator and graphene oxide according to the weight ratio; mixing graphene oxide with deionized water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide aqueous solution; dissolving the accelerator in ethanol or acetone as a solvent to prepare accelerator solution; mixing the graphene oxide aqueous solution and the accelerator solution together, and stirring for 30min at the temperature of 30-60 ℃; filtering the product, and drying in vacuum to obtain an accelerator @ graphene compound;
(2) weighing epoxy resin, adding the epoxy resin into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a uniformly mixed epoxy resin mixture;
(3) weighing an epoxy resin mixture, a curing agent, a toughening agent and an accelerator @ graphene compound according to parts by weight;
(4) uniformly mixing the accelerator @ graphene compound obtained in the step (1) and the epoxy resin mixture obtained in the step (2) with a curing agent and a toughening agent by adopting a mechanical blending method to obtain a sizing material;
(5) and (3) through a film coating machine, the sizing material prepared in the step (4) is coated into a film at the temperature of 50-80 ℃ and is compounded with a carrier in a hot melting way, so that the intermediate-temperature cured epoxy structural film is prepared.
The invention has the advantages and beneficial effects that:
according to the invention, the laminated structure of graphene is utilized to prevent water molecules from invading the epoxy resin, so that the moisture and heat resistance of the epoxy structure adhesive film is obviously improved; by utilizing the steric hindrance effect and ionic bond complexation of the graphene, on one hand, the reactivity of the substituted urea accelerator attached to the surface at the storage temperature can be obviously reduced, and the storage stability of the corresponding epoxy structure adhesive film is greatly improved. When large-area gluing is carried out, the phenomenon that the adhesive property of the epoxy structural adhesive film is reduced due to the fact that the adhesive film is remarkably increased or even gelled when the epoxy structural adhesive film is placed for a long time at normal temperature, and further the quality of a finished product is unqualified is avoided, and the urgent requirement of a large-scale aviation aircraft is met. On the other hand, in the middle temperature curing (120-130 ℃), weaker ionic bonds are broken, and the substituted urea accelerator can be separated from the graphene sheets, so that the reactivity is obviously improved, and the reactivity of the epoxy resin system is not affected basically in the middle temperature curing. The medium-temperature cured epoxy structural adhesive film has longer storage period, meets the requirement of a large-sized aviation aircraft on the medium-temperature epoxy structural adhesive film, and is suitable for cementing a composite material or a metal and other bearing structures.
Detailed Description
The following will be described in further detail with reference to examples:
the intermediate temperature cured epoxy structural adhesive film with stable moisture and heat resistance is prepared by hot melt compounding of a sizing material consisting of epoxy resin, a toughening agent, a curing agent and an accelerator @ graphene compound and a carrier, and can be cured at 120-130 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 60-80 parts of epoxy resin; 10-20 parts of toughening agent; 10-25 parts of curing agent; 4-12 parts of accelerator @ graphene compound. The epoxy resin is prepared by mixing two or more of bisphenol A type epoxy resins with the marks of E-54, E-51, E-44, 0194, 0191 and 850S; the toughening agent is one or more of epoxy nitrile rubber, carboxyl nitrile rubber, epoxy polybutadiene rubber, carboxyl polybutadiene rubber and core-shell rubber particles; the curing agent is superfine dicyandiamide, and the grain diameter of the curing agent is less than or equal to 10 mu m; the carrier is one of nylon gauze, polyester gauze and non-woven fabric.
The accelerator @ graphene compound is a compound formed by complexing a substituted urea accelerator and carboxyl groups on the surface of graphene oxide in an interactive manner to form a salt, so that the substituted urea accelerator is attached to the surface of a graphene sheet in an ionic bond mode; the substituted urea accelerator is 2, 4-di (N, N-dimethyl) urea toluene, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea, 4-di (N, N-dimethyl) urea diphenylmethane or other urea derivatives; the diameter of the graphene oxide sheet is 100nm-10 mu m; the weight ratio of the substituted urea accelerator to the graphene oxide is (1-2): (3-5).
A preparation method of a moisture-heat resistant storage stable intermediate temperature cured epoxy structural adhesive film comprises the following steps:
(1) weighing an accelerator and graphene oxide according to the weight ratio; mixing graphene oxide with deionized water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide aqueous solution; dissolving the accelerator in ethanol or acetone as a solvent to prepare accelerator solution; mixing the graphene oxide aqueous solution and the accelerator solution together, and stirring for 30min at the temperature of 30-60 ℃; filtering the product, and drying in vacuum to obtain an accelerator @ graphene compound;
(2) weighing epoxy resin, adding the epoxy resin into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a uniformly mixed epoxy resin mixture;
(3) weighing an epoxy resin mixture, a curing agent, a toughening agent and an accelerator @ graphene compound according to parts by weight;
(4) uniformly mixing the accelerator @ graphene compound obtained in the step (1) and the epoxy resin mixture obtained in the step (2) with a curing agent and a toughening agent by adopting a mechanical blending method to obtain a sizing material;
(5) and (3) through a film coating machine, the sizing material prepared in the step (4) is coated into a film at the temperature of 50-80 ℃ and is compounded with a carrier in a hot melting way, so that the intermediate-temperature cured epoxy structural film is prepared.
Embodiment one:
(1) according to the following steps: 4, weighing N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea accelerator and graphene oxide according to the weight ratio; mixing graphene oxide with deionized water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide aqueous solution; the N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea accelerator was dissolved in an ethanol solvent to prepare a solution. Mixing the N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea accelerator solution and the graphene oxide aqueous solution together, and stirring for 30min at 40 ℃; filtering and vacuum drying the product to obtain an N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea accelerator @ graphene compound;
(2) the following steps are carried out according to 55:20 weight ratio of E-54 and 0194, adding into a reaction kettle, continuously stirring, heating to 130 ℃, and preserving heat for 30min to obtain a uniformly mixed epoxy resin mixture;
(3) weighing 75 parts of epoxy resin mixture, 15 parts of dicyandiamide curing agent, 15 parts of carboxyl-terminated nitrile rubber toughening agent and 8 parts of N- (3, 4-dichlorophenyl) -N, N' -diphenylurea@graphene compound according to parts by weight;
(4) uniformly mixing the N- (3, 4-dichlorophenyl) -N, N' -diphenyl urea accelerator @ graphene compound obtained in the step (1) and the epoxy resin mixture obtained in the step (2) with a dicyandiamide curing agent and a carboxyl-terminated nitrile rubber toughening agent by adopting a mechanical blending method to obtain a sizing material;
(5) and (3) through a film machine, the sizing material prepared in the step (4) is scraped into a film at the temperature of 65 ℃ and is subjected to hot melting compounding with a non-woven fabric carrier, so that the intermediate-temperature cured epoxy structural film is prepared.
Embodiment two:
(1) according to 1.5:3.5 weight ratio of 2, 4-di (N, N-dimethyl) urea toluene accelerator and graphene oxide; mixing graphene oxide with deionized water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide aqueous solution; 2, 4-bis (N, N-dimethyl) urea toluene accelerator was dissolved in an acetone solvent to prepare a solution. Mixing the 2, 4-di (N, N-dimethyl) urea toluene accelerator solution and the graphene oxide aqueous solution together, and stirring for 30min at 60 ℃; filtering and vacuum drying the product to obtain a 2, 4-di (N, N-dimethyl) urea toluene accelerator @ graphene compound;
(2) the following steps are carried out according to 55:15 weight ratio of the two epoxy resins E-44 and 850S are weighed, added into a reaction kettle, continuously stirred, heated to 140 ℃, and kept at the temperature for 30 minutes to prepare an epoxy resin mixture which is uniformly mixed;
(3) weighing 70 parts of epoxy resin mixture, 18 parts of dicyandiamide curing agent, 12 parts of carboxyl-terminated nitrile rubber toughening agent and 10 parts of 2, 4-di (N, N-dimethyl) urea toluene accelerator @ graphene compound according to parts by weight;
(4) uniformly mixing the 2, 4-di (N, N-dimethyl) urea toluene accelerator @ graphene compound obtained in the step (1) and the epoxy resin mixture obtained in the step (2) with a dicyandiamide curing agent and a carboxyl-terminated nitrile rubber toughening agent by adopting a mechanical blending method to obtain a sizing material;
(5) and (3) through a film machine, the sizing material prepared in the step (4) is scraped into a film at the temperature of 60 ℃, and is subjected to hot melting compounding with a non-woven fabric carrier, so that the intermediate-temperature cured epoxy structural film is prepared.
Comparative example one:
(1) the following steps are carried out according to 55:15 weight ratio of the two epoxy resins E-44 and 850S are weighed, added into a reaction kettle, continuously stirred, heated to 140 ℃, and kept at the temperature for 30 minutes to prepare an epoxy resin mixture which is uniformly mixed;
(2) weighing 70 parts of epoxy resin mixture, 30 parts of dicyandiamide curing agent, 15 parts of carboxyl-terminated nitrile rubber toughening agent and 3 parts of 2, 4-di (N, N-dimethyl) urea toluene accelerator according to parts by weight;
(3) uniformly mixing the epoxy resin mixture prepared in the step (1) with a dicyandiamide curing agent, a carboxyl-terminated nitrile rubber toughening agent and a 2, 4-di (N, N-dimethyl) urea toluene accelerator by adopting a mechanical blending method to prepare a sizing material;
(4) and (3) through a film machine, the sizing material prepared in the step (3) is scraped into a film at the temperature of 60 ℃, and is subjected to hot melting compounding with a non-woven fabric carrier, so that the epoxy structural film is prepared.
The wet heat resistance and storage stability data for example one, example two and comparative example one are shown in the following table:
TABLE 1 moisture and thermal resistance of the adhesive films prepared in examples one, two and comparative example one
Note that: all samples were tested at (24.+ -. 3). Degree.C.
TABLE 2 mechanical Properties of the adhesive films prepared in examples one, two and comparative example one before and after storage
TABLE 3 viscosity changes with time at 80℃when the adhesive films prepared in examples one, two and comparative example one were stored at ordinary temperature (24.+ -. 3 ℃ C.)
As can be seen from table 1, the mechanical properties of the samples prepared by the examples of the present invention are not significantly reduced after the wet heat treatment, which indicates that the adhesive film of the present invention has excellent wet heat resistance; as can be seen from tables 2 and 3, after 60day (d is day in the table) of the (24.+ -. 3 ℃) place, the mechanical properties of the test sample are not significantly affected, and the viscosity increase with time at 80 ℃ is not large, which indicates that the adhesive film of the present invention has good storage stability. In contrast, the samples prepared from the comparative examples were significantly reduced in mechanical properties after the wet heat treatment and after 60day at 26℃and rapidly increased in viscosity after 30day at 80℃with an increase in viscosity within the accepted range. The intermediate temperature cured epoxy adhesive film is resistant to damp and heat and stable in storage, is suitable for large-area gluing of composite materials or metal and other bearing structures, and meets the requirements of the aviation field.
Claims (7)
1. The moisture-heat resistant storage stable medium temperature curing epoxy structure adhesive film is characterized in that the epoxy structure adhesive film is prepared by compounding a sizing material consisting of epoxy resin, a toughening agent, a curing agent and an accelerator @ graphene compound with a carrier through hot melting, and can be cured at 120-130 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 60-80 parts of epoxy resin; 10-20 parts of toughening agent; 10-25 parts of curing agent; 4-12 parts of accelerator @ graphene compound;
the accelerator @ graphene compound is a compound formed by complexing a substituted urea accelerator and carboxyl groups on the surface of graphene oxide in an interactive manner to form a salt, so that the substituted urea accelerator is attached to the surface of a graphene sheet in an ionic bond mode;
the substituted urea accelerator is 2, 4-di (N, N-dimethyl) urea toluene, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, N- (3, 4-dichlorophenyl) -N, N' -diphenylurea, 4-di (N, N-dimethyl) urea diphenylmethane;
the weight ratio of the substituted urea accelerator to the graphene oxide is (1-2): (3-5).
2. The moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film according to claim 1, wherein the epoxy resin is a mixture of two or more of the epoxy resins with the designations of E-54, E-51, E-44, 0194, 0191 and 850S bisphenol A.
3. The moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film according to claim 1, wherein the toughening agent is one or more of epoxy nitrile rubber, carboxyl nitrile rubber, epoxy polybutadiene rubber, carboxyl polybutadiene rubber and core-shell rubber particles.
4. The moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film according to claim 1, wherein the curing agent is superfine dicyandiamide with a particle size less than or equal to 10 μm.
5. The moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film of claim 1, wherein the graphene oxide sheets have a diameter of 100nm-10 μm.
6. The moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film according to claim 1, wherein the carrier is one of nylon gauze, polyester gauze and nonwoven fabric.
7. The method for preparing the moisture and heat resistant storage stable intermediate temperature cured epoxy structural adhesive film according to any one of claims 1 to 6, comprising the following steps:
(1) weighing an accelerator and graphene oxide according to the weight ratio; mixing graphene oxide with deionized water, and performing ultrasonic treatment for 30min to obtain a uniformly dispersed graphene oxide aqueous solution; dissolving the accelerator in ethanol or acetone as a solvent to prepare accelerator solution; mixing the graphene oxide aqueous solution and the accelerator solution together, and stirring for 30min at the temperature of 30-60 ℃; filtering the product, and drying in vacuum to obtain an accelerator @ graphene compound;
(2) weighing epoxy resin, adding the epoxy resin into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a uniformly mixed epoxy resin mixture;
(3) weighing an epoxy resin mixture, a curing agent, a toughening agent and an accelerator @ graphene compound according to parts by weight;
(4) uniformly mixing the accelerator @ graphene compound obtained in the step (1) and the epoxy resin mixture obtained in the step (2) with a curing agent and a toughening agent by adopting a mechanical blending method to obtain a sizing material;
(5) and (3) through a film coating machine, the sizing material prepared in the step (4) is coated into a film at the temperature of 50-80 ℃ and is compounded with a carrier in a hot melting way, so that the intermediate-temperature cured epoxy structural film is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210376595.5A CN114752334B (en) | 2022-04-11 | 2022-04-11 | Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210376595.5A CN114752334B (en) | 2022-04-11 | 2022-04-11 | Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114752334A CN114752334A (en) | 2022-07-15 |
| CN114752334B true CN114752334B (en) | 2023-10-20 |
Family
ID=82328619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210376595.5A Active CN114752334B (en) | 2022-04-11 | 2022-04-11 | Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114752334B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262588A (en) * | 2014-09-12 | 2015-01-07 | 湖南大学 | Graphene oxide-based curing agent as well as preparation and use thereof |
| CN113004830A (en) * | 2021-03-05 | 2021-06-22 | 常州烯奇新材料有限公司 | Weather-resistant high-thermal-conductivity graphene-based epoxy resin adhesive and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120129980A1 (en) * | 2010-11-19 | 2012-05-24 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
-
2022
- 2022-04-11 CN CN202210376595.5A patent/CN114752334B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262588A (en) * | 2014-09-12 | 2015-01-07 | 湖南大学 | Graphene oxide-based curing agent as well as preparation and use thereof |
| CN113004830A (en) * | 2021-03-05 | 2021-06-22 | 常州烯奇新材料有限公司 | Weather-resistant high-thermal-conductivity graphene-based epoxy resin adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114752334A (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112322254B (en) | Biomass aldehyde-free adhesive and preparation and application methods thereof | |
| CN107779147B (en) | High-strength epoxy honeycomb adhesive and preparation method thereof | |
| CN102942892B (en) | Epoxy phenolic resin adhesive and epoxy phenolic adhesive tape and laminated board manufactured by adhesive | |
| CN111154442B (en) | Environment-friendly high-temperature-resistant modified epoxy resin adhesive and preparation method thereof | |
| CN113322024B (en) | Composite water-based crosslinking modifier and preparation method and application thereof | |
| CN110272715B (en) | High-temperature peanut meal-based formaldehyde-free adhesive and preparation method and application thereof | |
| CN113715422A (en) | High-wear-resistance epoxy glass fiber cloth laminated board and preparation method thereof | |
| CN112375539A (en) | High-mildew-proof water-resistant soybean meal protein adhesive and preparation method thereof | |
| CN114752314B (en) | High-durability high-temperature cured epoxy structural adhesive film and preparation method thereof | |
| CN114752334B (en) | Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof | |
| CN110804281A (en) | Preparation method of graphene-reinforced carbon fiber epoxy prepreg | |
| CN103881307A (en) | Ultralow-density composite material and resin combination prepreg as well as preparation method and applications thereof | |
| CN102504742A (en) | Bonding glue quickly solidified at room temperature | |
| CN114774043B (en) | Corrosion-inhibiting primer for structural adhesive bonding and preparation method thereof | |
| CN111635721B (en) | Modified urea-formaldehyde resin adhesive and preparation method thereof | |
| CN110746854B (en) | Room temperature fast curing coating with high infrared radiation coating as cured product and preparation method thereof | |
| CN113429890A (en) | Composite curing agent, adhesive, conductive adhesive, and preparation method and application thereof | |
| CN104448240A (en) | Blending method of epoxy resin moderate temperature curing for carbon fiber prepreg | |
| CN111495325A (en) | Method for producing zeolite cross-linking agent | |
| CN111673876A (en) | Preparation method of high-strength wood composite inorganic particle board | |
| CN105038662B (en) | A kind of method preparing composite solid gum | |
| CN117925162A (en) | Moisture-heat-resistant high-temperature-resistant middle-temperature-curing single-component epoxy adhesive and preparation method thereof | |
| CN114874748B (en) | Plant protein adhesive and preparation method and application thereof | |
| CN104231965B (en) | Homeotropic orientation conductive adhesive film and preparation method thereof | |
| CN113930199B (en) | Toughening phenolic adhesive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |