CN114752314B - High-durability high-temperature cured epoxy structural adhesive film and preparation method thereof - Google Patents
High-durability high-temperature cured epoxy structural adhesive film and preparation method thereof Download PDFInfo
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- CN114752314B CN114752314B CN202210376676.5A CN202210376676A CN114752314B CN 114752314 B CN114752314 B CN 114752314B CN 202210376676 A CN202210376676 A CN 202210376676A CN 114752314 B CN114752314 B CN 114752314B
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 48
- 239000004593 Epoxy Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 83
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004513 sizing Methods 0.000 claims abstract description 19
- 239000012745 toughening agent Substances 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 18
- -1 bisphenol S modified bisphenol A Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000007888 film coating Substances 0.000 claims description 3
- 238000009501 film coating Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 7
- 125000001624 naphthyl group Chemical group 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 5
- 238000004026 adhesive bonding Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- 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
-
- 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
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
-
- 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
- C09J2463/00—Presence of epoxy resin
Abstract
The invention belongs to the technical field of adhesives, and particularly relates to a high-durability high-temperature cured epoxy structural adhesive film and a preparation method thereof. The invention is prepared by hot melting and compounding sizing material containing bisphenol A type epoxy resin, special epoxy resin, bisphenol S, toughening agent and curing agent with a carrier. On the premise of not affecting other performances, bisphenol S is utilized to modify bisphenol A type epoxy resin, so that the heat resistance of the epoxy resin is improved from the molecular structure; the special epoxy resin is utilized to improve the crosslinking density of an epoxy resin system and introduce naphthyl, so that the heat resistance and the damp-heat resistance of the epoxy structure adhesive film are obviously improved; the core-shell rubber particles are utilized to solve the problem that the heat resistance of an epoxy resin system is obviously reduced due to insufficient rubber phase separation, and the high-temperature-resistant adhesive film has higher high-temperature resistance, meets the requirement of a large-scale aviation aircraft on a high-temperature epoxy structure adhesive film, and is suitable for the 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 high-durability high-temperature cured epoxy structural adhesive film and a preparation method thereof.
Background
The high-temperature cured epoxy structural adhesive film is an adhesive product with the curing temperature of about 180 ℃, 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 aerospace field, and is the most main variety in the current aviation structural adhesive.
Most of the existing high-temperature cured epoxy structural adhesive films at home and abroad use bisphenol A type epoxy resin-dicyandiamide as a curing system and thermoplastic resin and rubber as toughening agents. Representative foreign products are "Redux319 adhesive film" by Hexcel corporation, "FM300 adhesive film" by Cytec corporation, etc.; representative products in China are J-116 adhesive films of the national academy of sciences of Heilongjiang province, SY-14 series adhesive films of the national academy of aviation materials of Beijing, of China, and the like. The high-temperature cured epoxy structural adhesive films have the main advantages of excellent adhesive bonding performance, high technical maturity and wide application. However, in the high-temperature cured structural adhesive film, thermoplastic resin and rubber are used as toughening agents, the traditional rubber toughening agents are not thoroughly separated from the epoxy resin system after curing, so that the high-temperature resistance of the epoxy structural adhesive film can be influenced, and the thermoplastic resin can improve the high-temperature resistance of the adhesive film, but meanwhile, the adhesive property of the adhesive film at normal temperature is poor, so that the adhesive film is not beneficial to paving. Meanwhile, the epoxy resin for the adhesive film has strong internal polarity and contains a large amount of hydroxyl groups due to the requirement of adhesive property, so that the epoxy resin is easy to adsorb water molecules and is immersed by the water molecules, and the problem of poor wet heat resistance and lack of durability is caused. In the field of modern aviation, requirements are made on the durability of an epoxy structural adhesive film, and good adhesive properties are expected to be achieved in various environments (high temperature, high humidity, damp heat and other environments), so that the problems existing in the high-temperature cured adhesive film are urgently needed to be solved.
Disclosure of Invention
The invention provides a high-durability high-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 high-durability high-temperature cured epoxy structural adhesive film is prepared by compounding a sizing material consisting of bisphenol A type epoxy resin, special epoxy resin, bisphenol S, a toughening agent and a curing agent with a carrier through hot melting, and is cured at 180 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 40-60 parts of bisphenol A epoxy resin; 15-25 parts of special epoxy resin; 10-20 parts of bisphenol S; 10-20 parts of toughening agent; 15-25 parts of curing agent.
The bisphenol A type 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 special epoxy resin comprises multifunctional epoxy resin and naphthalene-containing epoxy resin.
The multifunctional epoxy resin is one of AFG-90, AG-80, AG601 and AG-70, and the naphthalene group-containing epoxy resin is EBA-65 naphthalene group-containing epoxy resin.
The toughening agent is core-shell rubber particles containing carboxyl, hydroxyl or amino reactive functional groups.
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.
A preparation method of a high-durability high-temperature cured epoxy structural adhesive film comprises the following steps:
(1) weighing bisphenol A type epoxy resin, special epoxy resin and bisphenol S according to a proportion, adding the bisphenol A type epoxy resin, the special epoxy resin and the bisphenol S into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture;
(2) weighing bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture, curing agent and toughening agent according to parts by weight, and uniformly mixing the bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture obtained in the step (1) with the curing agent and the toughening agent by adopting a mechanical blending method to obtain sizing material;
(3) and (3) through a film coating machine, the sizing material prepared in the step (2) 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 high-temperature cured epoxy structural film is prepared.
The invention has the advantages and beneficial effects that:
the invention takes bisphenol A type epoxy resin modified by bisphenol S/special epoxy resin-dicyandiamide as a curing system and takes core-shell rubber particles as a toughening system. On the premise of not affecting other performances, bisphenol S is utilized to modify bisphenol A type epoxy resin, so that the heat resistance of the epoxy resin is improved from the molecular structure; the special epoxy resin is utilized to improve the crosslinking density of an epoxy resin system and introduce naphthyl, so that the heat resistance and the damp-heat resistance of the epoxy structure adhesive film are obviously improved; the core-shell rubber particles are utilized to solve the problem that the heat resistance of an epoxy resin system is obviously reduced due to insufficient rubber phase separation, the problems of poor wet heat resistance and poor adhesive film adhesion of a high-temperature cured epoxy resin system are solved by the means, and the high-temperature-resistant adhesive film has higher high-temperature resistance, meets the requirement of a large-scale aviation aircraft on a high-temperature epoxy structure adhesive film, and is suitable for the adhesive bonding of composite materials or bearing structures such as metals.
Detailed Description
The following will be described in further detail with reference to examples:
the high-durability high-temperature cured epoxy structural adhesive film is prepared by compounding a sizing material consisting of bisphenol A type epoxy resin, special epoxy resin, bisphenol S, a toughening agent and a curing agent with a carrier through hot melting, and is cured at 180 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 40-60 parts of bisphenol A epoxy resin; 15-25 parts of special epoxy resin; 10-20 parts of bisphenol S; 10-20 parts of toughening agent; 15-25 parts of curing agent.
The bisphenol A type 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 special epoxy resin comprises multifunctional epoxy resin and naphthyl-containing epoxy resin; the multifunctional epoxy resin is one of AFG-90, AG-80, AG601 and AG-70, and is mainly used for providing the crosslinking density of an epoxy resin system so as to provide the high temperature resistance of the epoxy resin system; the naphthyl-containing epoxy resin is EBA-65 naphthyl epoxy resin; the toughening agent is core-shell rubber particles containing carboxyl, hydroxyl or amino reactive functional groups; 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.
A preparation method of a high-durability high-temperature cured epoxy structural adhesive film comprises the following steps:
(1) weighing bisphenol A type epoxy resin, special epoxy resin and bisphenol S according to a proportion, adding the bisphenol A type epoxy resin, the special epoxy resin and the bisphenol S into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture;
(2) weighing bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture, curing agent and toughening agent according to parts by weight, and uniformly mixing the bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture obtained in the step (1) with the curing agent and the toughening agent by adopting a mechanical blending method to obtain sizing material;
(3) and (3) through a film coating machine, the sizing material prepared in the step (2) 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 high-temperature cured epoxy structural film is prepared.
Embodiment one:
(1) according to 35:10:20:10 weight portions of E-54, 0194, AFG-90 and bisphenol S are weighed and added into a reaction kettle, and the mixture is continuously stirred, heated to 130 ℃ and kept for 30 minutes to prepare a bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture which is uniformly mixed;
(2) according to 75:12:18 weight portions of bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture, hydroxyl core-shell rubber particles and dicyandiamide curing agent are weighed, and the three are uniformly mixed by adopting a mechanical blending method to prepare sizing material;
(3) and (3) through a film machine, the sizing material prepared in the step (2) is coated into a film at the temperature of 65 ℃ and is subjected to hot melting compounding with a non-woven fabric carrier, so that the high-temperature cured epoxy structural film is prepared.
Embodiment two:
(1) the weight ratio is 40:15:15:15 weight portions of E-44, 850S, AG-80 and bisphenol S are weighed and added into a reaction kettle, and the mixture is continuously stirred, heated to 140 ℃ and kept for 30 minutes to prepare a bisphenol A type epoxy resin/special epoxy resin mixture modified by bisphenol S which is uniformly mixed;
(2) according to the weight ratio of 85:12:18 weight portions of bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture, carboxyl core-shell rubber particles and dicyandiamide curing agent are weighed, and the three are uniformly mixed by adopting a mechanical blending method to prepare sizing material;
(3) and (3) through a film machine, the sizing material prepared in the step (2) is coated into a film at the temperature of 60 ℃ and is subjected to hot melting compounding with a non-woven fabric carrier, so that the high-temperature cured epoxy structural film is prepared.
Comparative example one:
(1) the weight ratio is as follows: 22 weight portions of E-44 and 850S are weighed and added into a reaction kettle, and the mixture is continuously stirred, heated to 140 ℃ and kept for 30 minutes to prepare an epoxy resin mixture which is uniformly mixed;
(2) according to 82:8:4:18 weight portions of epoxy resin mixture, polysulfone resin, carboxyl-terminated nitrile rubber and dicyandiamide curing agent are weighed and uniformly mixed by adopting a mechanical blending method to prepare sizing material;
(3) and (3) through a film machine, the sizing material prepared in the step (2) is coated into a film at the temperature of 60 ℃ and is subjected to hot melting compounding with a non-woven fabric carrier, so that the high-temperature cured epoxy structural film is prepared.
The bonding performance data and the adhesion under different temperatures and humid and hot environments of the first example, the second example and the first comparative example are shown in the following table:
TABLE 1 adhesive films prepared in examples one, two and comparative example one were adhesive and adhesive properties under different temperatures and damp-heat conditions
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; with the increase of the test temperature, the mechanical property of the sample gradually decreases, but the amplitude is slower; when the adhesive film is actually paved, the adhesiveness of the adhesive film meets the technological requirements. In contrast, the mechanical properties of the samples prepared in the comparative examples were greatly reduced after the wet heat treatment or when tested at high temperature; when the adhesive film is actually paved, the adhesiveness of the adhesive film is poor, and the process requirement is not met. Meanwhile, the adhesive property and the adhesiveness of the FM300 film were also evaluated, and the adhesiveness of the FM300 film also satisfied the requirements, but the adhesive property was inferior to those of the first and second examples. For example, the composite honeycomb tensile strengths at-55 ℃, 24 ℃ and 71 ℃ are only 4.50MPa, 4.87MPa and 4.69MPa, respectively. The composite/composite double lap shear strengths at-55 ℃, 24 ℃, 71 ℃ and 135 ℃ were only 21.2, 25.2MPa, 20.8MPa and 13.4MPa, respectively. The high-temperature cured epoxy adhesive film has good moisture and heat resistance and high temperature resistance, the adhesiveness meets the requirements of a paving process, and the high-temperature cured epoxy adhesive film is suitable for cementing bearing structures such as composite materials or metals and meets the requirements of the aviation field.
Claims (5)
1. The high-durability high-temperature cured epoxy structural adhesive film is characterized in that the epoxy structural adhesive film is prepared by compounding a sizing material consisting of bisphenol A type epoxy resin, special epoxy resin, bisphenol S, a toughening agent and a curing agent with a carrier through hot melting, and is cured at 180 ℃; the sizing material in the epoxy structural adhesive film is prepared from the following components in parts by weight: 40-60 parts of bisphenol A epoxy resin; 15-25 parts of special epoxy resin; 10-20 parts of bisphenol S; 10-20 parts of toughening agent; 15-25 parts of curing agent; the special epoxy resin comprises multifunctional epoxy resin, wherein the multifunctional epoxy resin is one of AFG-90, AG-80, AG601 and AG-70;
the bisphenol A type 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.
2. The high-durability high-temperature-curable epoxy structural adhesive film according to claim 1, wherein the toughening agent is a core-shell rubber particle containing carboxyl, hydroxyl or amino reactive functional groups.
3. The high-durability high-temperature cured epoxy structural adhesive film according to claim 1, wherein the curing agent is superfine dicyandiamide with the particle size less than or equal to 10 μm.
4. The high-durability high-temperature cured epoxy structural adhesive film according to claim 1, wherein the carrier is one of nylon gauze, polyester gauze and non-woven fabric.
5. The method for preparing a high-durability high-temperature cured epoxy structural adhesive film according to any one of claims 1 to 4, comprising the steps of:
(1) weighing bisphenol A type epoxy resin, special epoxy resin and bisphenol S according to a proportion, adding the bisphenol A type epoxy resin, the special epoxy resin and the bisphenol S into a reaction kettle, continuously stirring, heating to 120-140 ℃, and preserving heat for 30min to obtain a bisphenol S modified bisphenol A type epoxy resin/special epoxy resin mixture;
(2) weighing bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture, curing agent and toughening agent according to parts by weight, and uniformly mixing the bisphenol S modified bisphenol A epoxy resin/special epoxy resin mixture obtained in the step (1) with the curing agent and the toughening agent by adopting a mechanical blending method to obtain sizing material;
(3) and (3) through a film coating machine, the sizing material prepared in the step (2) 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 high-temperature cured epoxy structural film is prepared.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675478A (en) * | 2016-11-23 | 2017-05-17 | 江苏恒神股份有限公司 | Resin composition and intermediate temperature structure glue film |
| CN108395860A (en) * | 2018-04-12 | 2018-08-14 | 江苏恒神股份有限公司 | The preparation method of low-temperature setting structural film adhesive |
| CN109575237A (en) * | 2018-11-30 | 2019-04-05 | 陕西科技大学 | A kind of bisphenol S modified bisphenol A formaldehyde novolac epoxy and its synthetic method |
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