CN114854313A - High-temperature-resistant epoxy structural adhesive for glass fiber reinforced material - Google Patents

High-temperature-resistant epoxy structural adhesive for glass fiber reinforced material Download PDF

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Publication number
CN114854313A
CN114854313A CN202210810145.2A CN202210810145A CN114854313A CN 114854313 A CN114854313 A CN 114854313A CN 202210810145 A CN202210810145 A CN 202210810145A CN 114854313 A CN114854313 A CN 114854313A
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temperature
xylylenediamine
bisphenol
component
parts
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周阳
江蕾
刘小磊
朱慧宁
李双
姚晓慧
夏小忠
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SUZHOU AITESI ENVIRONMENTAL PROTECTION EQUIPMENT CO Ltd
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SUZHOU AITESI ENVIRONMENTAL PROTECTION EQUIPMENT CO Ltd
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to the technical field of structural adhesives, in particular to a high-temperature-resistant epoxy structural adhesive for a glass fiber reinforced material, which comprises a component A and a component B, wherein the component A comprises: bisphenol F epoxy resin, bisphenol A epoxy resin, alumina, titanium dioxide, modified silica, antimony trioxide, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and a reactive diluent; the component B comprises: m-xylylenediamine, an epoxy addition product of m-xylylenediamine-bisphenol F, and benzyl alcohol. The epoxy structural adhesive disclosed by the invention is simple in processing process and easy to operate, has good fireproof and high-temperature resistant characteristics, can still keep high-efficiency bonding performance in an environment with the temperature of more than 200 ℃, has the bonding strength of more than 57MPa, can be used for bonding glass fiber reinforced plastics, can be compounded with fibers to form a fiber reinforced plastic material, can be applied to bonding and corrosion prevention of pipe joints, and has wide application prospects.

Description

High-temperature-resistant epoxy structural adhesive for glass fiber reinforced material
Technical Field
The invention relates to the technical field of structural adhesives, in particular to a high-temperature-resistant epoxy structural adhesive for a glass fiber reinforced material.
Background
Epoxy resin is a high molecular prepolymer which contains two or more epoxy groups and can finally form an insoluble and infusible three-dimensional network structure through the reaction of the epoxy groups and amine groups in a curing agent. The epoxy resin has excellent performances of strong adhesion, small shrinkage, excellent dielectric property and heat resistance, good chemical stability and the like, and is well developed in the field of structural adhesives.
The epoxy resin adhesive has excellent heat resistance, electrical insulation, adhesion, water resistance, mechanical property and chemical resistance, and is widely applied to water conservancy and traffic and the like; but also can be compounded with fiber to form fiber reinforced plastic material, thereby being applied to the pipe joint bonding and corrosion prevention, wherein the fiber reinforced glass material comprises: 1. epoxy resin and glass fiber reinforced material; 2. unsaturated polyester resin (vinyl and modified resin thereof) and glass fiber reinforcement; 3. phenolic glass fiber reinforced plastic; air pipes used in ventilation and exhaust systems of semiconductor factories are all glass fiber reinforced materials, and structural adhesive is needed during bonding, so that the structural adhesive needs to have the characteristics of high temperature resistance, flame retardance, high strength, corrosion resistance and the like.
For example, chinese patent application No. CN201010278347.4 discloses a high temperature resistant single-component epoxy structural adhesive, and a preparation method and a use method thereof, wherein the epoxy structural adhesive is prepared from the following raw materials in parts by weight: the epoxy structural adhesive has good bonding effect, but has general high temperature resistance and corrosion resistance, and can not be applied to pipe joint bonding and corrosion resistance when being compounded with fibers to form a fiber reinforced plastic material, so that the use of the epoxy structural adhesive has certain limitation, and the epoxy structural adhesive has no wide application prospect.
Disclosure of Invention
The invention aims to provide the high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material, which has the advantages of simple and easy operation in the processing process, good fireproof and high-temperature-resistant characteristics, high-efficiency bonding performance under the environment of more than 200 ℃, bonding strength of more than 57MPa, capability of being used for bonding glass fiber reinforced plastics, capability of being compounded with fibers to form a fiber reinforced plastic material, capability of being applied to bonding and corrosion prevention of a pipe joint and wide application prospect.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 42-50 parts of bisphenol F epoxy resin, 3-6 parts of bisphenol A epoxy resin, 22-28 parts of aluminum oxide, 5-10 parts of titanium dioxide, 5-8 parts of modified silicon dioxide, 2-5 parts of antimony trioxide, 3-6 parts of brominated epoxy resin, 1-2 parts of chlorinated paraffin, 1-5 parts of silane coupling agent and 1-5 parts of active diluent; the component B comprises: 5.5 to 7.5 portions of m-xylylenediamine, 1.5 to 2.5 portions of m-xylylenediamine-bisphenol F epoxy addition product and 1.0 to 1.5 portions of benzyl alcohol.
In a further preferred embodiment of the present invention, the reactive diluent is a (meth) acrylate reactive diluent, and may specifically be beta-hydroxyethyl methacrylate.
As a further preferred embodiment of the present invention, the formulation method of the a component is as follows:
sequentially adding bisphenol F epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and an active diluent into a container according to the parts by weight, mechanically stirring the mixture until the mixture is uniform, then adding the mixture into the container after ball milling and mixing alumina, titanium dioxide, modified silicon dioxide and antimony trioxide, and continuously stirring the mixture for 1 to 5 hours to obtain a component A;
the preparation method of the component B comprises the following steps:
sequentially adding m-xylylenediamine, m-xylylenediamine-bisphenol F epoxy addition products and benzyl alcohol into a container according to the parts by weight, and mechanically stirring the mixture until the mixture is uniform to obtain the component B.
As a further preferable scheme of the invention, deionized water is used as a medium for ball milling, the rotating speed is 300-400rpm, and the ball milling time is 10-30 min.
As a further preferred embodiment of the present invention, the modified silica is prepared by the following method:
(1) adding sodium dodecyl sulfate and doped silicon dioxide into the mixed solution, stirring for 1-3h, then carrying out ultrasonic treatment for 30-50min, then heating to 70-80 ℃, adding a silane coupling agent KH-570, controlling the adding time to be 4-6h, reacting at constant temperature for 3-5h, then taking out, repeatedly washing with ethanol, then adding into an ethanol solution, dropwise adding hydroxyl silicone oil and dibutyltin dilaurate, stirring for 5-8h at room temperature, centrifugally washing the product, and drying to obtain pretreated silicon dioxide;
(2) under the condition of room temperature, adding 1-5g of pretreated silicon dioxide into 150mL of 100-mL ethanol solution, dispersing at high speed for 20-40min to obtain dispersion liquid, then using ethanol as a solvent to prepare 0.5-0.8g/mL 8-hydroxyquinoline solution 100-150mL, slowly adding 8-hydroxyquinoline solution into the dispersion liquid, carrying out high-speed dispersion for 30-50min, then vacuumizing, keeping the vacuum for 5-8h, then taking out a product, repeatedly washing with ethanol, centrifuging and drying to obtain the modified silicon dioxide.
In a further preferred embodiment of the present invention, in the step (1) of the method for producing a modified silica, the sodium lauryl sulfate, the doped silica, the mixed solution, the silane coupling agent KH-570, the ethanol solution, the hydroxy silicone oil, and the dibutyltin dilaurate are used in a ratio of (0.8 to 1.5) g: (20-30) g: (600-800) mL: (3-5) g: (300-500) mL: (2-4) g: (0.3-0.8) g;
in the step (1) of the preparation method of the modified silicon dioxide, the mixed solution is prepared by mixing ethanol and deionized water according to a volume ratio of 1: 1.
As a further preferred embodiment of the present invention, the preparation method of the doped silica is as follows:
under the condition of room temperature, adding 1, 2-bis (triethoxysilyl) ethane and boric acid into absolute ethyl alcohol, mixing uniformly, continuously stirring for 10-15h at 800r/min of 600-: 0.05-0.5: 0.3-0.35: 43-46.
As a further preferred embodiment of the present invention, the m-xylylenediamine-bisphenol F epoxy adduct is prepared by the following method:
(1) adding ethanol, m-xylylenediamine and trimethylolpropane triacrylate into a container, stirring and reacting at 30-35 ℃ for 5-8h, repeatedly washing a reaction product with methanol, and drying to obtain an intermediate for later use;
(2) adding methanol, m-xylylenediamine and the intermediate into a container, uniformly mixing, stirring at 30-35 ℃ for reaction for 23-28h, carrying out reduced pressure distillation, repeatedly washing the product with methanol, and drying to obtain a viscous liquid product;
(3) adding the viscous liquid product and adipic acid into a container, stirring and heating to 150-160 ℃ under the protection of nitrogen, reacting for 1-2h at the temperature, heating to 230-240 ℃ and continuing to react for 3-5h, and after the reaction is finished, carrying out reduced pressure distillation, dissolving the obtained product in dimethyl sulfoxide to obtain a mixed solution for later use;
(4) and (3) respectively adding epoxy chloropropane and bisphenol F into the mixed solution obtained in the step (3) in a dropwise manner at a constant temperature of 80-85 ℃, reacting for 3-5h, adding m-xylylenediamine and a sodium hydroxide aqueous solution, reacting for 4-6h at a constant temperature of 50-55 ℃, after the reaction is finished, distilling under normal pressure, filtering, and distilling under reduced pressure to obtain an m-xylylenediamine-bisphenol F epoxy addition product.
In a further preferred embodiment of the present invention, in the step (1) of the method for producing an m-xylylenediamine-bisphenol F epoxy adduct, the ratio of the amount of ethanol, m-xylylenediamine, and trimethylolpropane triacrylate used is (15 to 20) mL: (1.2-1.8) g: (29-32) g;
in the above method for producing an m-xylylenediamine-bisphenol F epoxy adduct, in step (2), the ratio of the amount of methanol, m-xylylenediamine, and the amount of the intermediate is (7.5 to 9.5) mL: (103-120) g: (6.0-7.8) g;
in the step (3) of the preparation method of the m-xylylenediamine-bisphenol F epoxy addition product, the dosage ratio of the viscous liquid product, adipic acid and dimethyl sulfoxide is (10-15) g: (1-3) g: (80-100) mL.
In a more preferred embodiment of the present invention, in the step (4) of the method for producing an epoxy adduct of m-xylylenediamine and bisphenol F, the epichlorohydrin, bisphenol F, the mixed solution, m-xylylenediamine, and the aqueous sodium hydroxide solution are used in an amount of (10 to 15) g of (1.2 to 1.8) g of (50 to 80) mL: (3-7) g: (5-10) mL;
the concentration of the sodium hydroxide aqueous solution is 40-50 wt%.
A high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials is used by the following method:
after the component A is oscillated and stirred, the component A and the component B are mixed evenly and coated between two bonding surfaces evenly, and then the mixture is solidified for 20 to 50min at the temperature of 120-160 ℃ and is cooled naturally.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, hydroxyl silicone oil and a silane coupling agent KH-570 are selected as modifiers and are grafted to the surface of doped silica, the outer part formed by the modifiers is coated to enable the outer contour of the doped silica to present non-spherical irregular edges, so that the dispersing performance of the doped silica is improved, the phenomenon of agglomeration and precipitation of the doped silica in the component A can be effectively avoided, the stability of the component A is improved, and meanwhile, the silane coupling agent KH-570 can enable the number of cross-links formed between the double-modifier modified doped silica and epoxy resin to be larger, so that a high-density cross-linking network is formed, the interaction between the double-modifier modified doped silica and the epoxy resin is enhanced, so that the formed epoxy structural adhesive has more excellent bonding performance, and the bonding strength of the material can be obviously improved; moreover, the pretreated silicon dioxide obtained after the treatment of the modifier can easily form an unstable active intermediate in a compound type proton solvent consisting of ethanol and 8-hydroxyquinoline, and then the unstable active intermediate is condensed into a Si-O-Si chain mutually, and the Si-O-Si chain is polymerized to form a film with a net structure, so that the bonding property of the pretreated silicon dioxide can be further improved, and the formed film can play a role in blocking and isolating external corrosive substances such as acid, alkali, salt and the like, so that the corrosion resistance of the epoxy structural adhesive can be improved.
In addition, in the invention, the silicon dioxide is doped, boron is doped into the silicon dioxide by adopting a sol-gel method, so that the doped silicon dioxide is obtained, and the Si-O-B bond generated by the reaction of boric acid and 1, 2-bis (triethoxysilyl) ethane has better thermal stability than the Si-O-Si bond, so that the thermal stability of the network structure film formed by polymerization is improved, the structure can be kept complete in a high-temperature environment, the effects of isolating external heat and increasing heat transfer loss can be achieved, the epoxy structure adhesive has good thermal stability, and the epoxy structure adhesive still has good bonding performance at high temperature.
In the invention, trimethylolpropane triacrylate and m-xylylenediamine are used as raw materials to synthesize dendritic macromolecules with a plurality of acrylate double bonds on the periphery, then the dendritic macromolecules react with the m-xylylenediamine to synthesize modified polyamine with a polyamino dendritic macromolecule structure on the periphery, then adipic acid is used for amidation treatment, epichlorohydrin is used as a chain extender to react with the amidated modified polyamine and bisphenol F, and ring opening reaction is carried out to carry out chain extension, thus obtaining the m-xylylenediamine-bisphenol F epoxy addition product curing agent, the molecular motion of the curing agent is accelerated at high temperature (120-150 ℃), a plurality of active hydrogens are arranged on the periphery of the dendritic macromolecule of the modified polyamine, the reaction is easy to occur, the curing speed is greatly accelerated, compared with the common curing agent, the curing speed is improved by more than 15 times, thereby being beneficial to realizing the rapid curing of the epoxy structural adhesive.
The epoxy structural adhesive disclosed by the invention is simple in processing process and easy to operate, has good fireproof and high-temperature resistant characteristics, can still keep high-efficiency bonding performance in an environment with the temperature of more than 200 ℃, has the bonding strength of more than 57MPa, can be used for bonding glass fiber reinforced plastics, can be compounded with fibers to form a fiber reinforced plastic material, can be applied to bonding and corrosion prevention of pipe joints, and has wide application prospects.
Drawings
FIG. 1 is an infrared spectrum of doped silica prepared in example 2 (maximum absorption 1047 cm) -1 This is caused by Si — O stretching vibration);
FIG. 2 is an infrared spectrum (at 3372 cm) of the modified silica prepared in example 2 -1 And 1621 cm -1 The Si-OH absorption peak appears, and the Si-O stretching vibration moves to the low frequency and moves to 1031cm -1 At (c);
FIG. 3 is an infrared spectrum (3358 cm) of an epoxy adduct of m-xylylenediamine-bisphenol F prepared in example 2 -1 Is at 1608 cm when the amino group is out of peak -1 、1508 cm -1 、701 cm -1 The peak is shown by a benzene ring, no obvious epoxy structure is found in the infrared image, and the epoxy structure is judged to have undergone addition reaction and disappear);
FIG. 4 shows the production of an epoxy adduct of m-xylylenediamine-bisphenol F prepared in example 2 1 H NMR chart (in CDCl) 3 The solvent is a solvent, wherein two peaks of 7.27ppm and 7.20ppm are assigned to the peak of hydrogen protons in a benzene ring and m-xylylenediamine on bisphenol F epoxy, and the peak of 3.91ppm is assigned to the peak of methylene connected with two benzene rings in a bisphenol F structure).
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 present invention, the bisphenol A type epoxy resin used was provided with a brand number of jER 828 (epoxy equivalent 184-194 g/eq) (supplied by Shanghai Zhongsi industries, Ltd.); the bisphenol F epoxy resin used was designated jER 807 (epoxy equivalent 160-175 g/eq) (supplied by Shanghai Zhongsi industries, Ltd.); the brominated epoxy resin (68928-70-1) (available from Nantong Runfeng petrochemical Co., Ltd.).
Example 1
The high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 42 parts of bisphenol F epoxy resin, 3 parts of bisphenol A epoxy resin, 22 parts of alumina, 5 parts of titanium dioxide, 5 parts of modified silica, 2 parts of antimony trioxide, 3 parts of brominated epoxy resin, 1 part of chlorinated paraffin, 1 part of silane coupling agent and 1 part of methacrylic acid-beta-hydroxyethyl ester; the component B comprises: 5.5 parts of m-xylylenediamine, 1.5 parts of m-xylylenediamine-bisphenol F epoxy addition product and 1.0 part of benzyl alcohol;
the preparation method of the component A comprises the following steps:
sequentially adding bisphenol F epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and beta-hydroxyethyl methacrylate into a container according to the parts by weight, mechanically stirring the mixture to be uniform, then adding alumina, titanium dioxide, modified silicon dioxide and antimony trioxide into the container after ball-milling and mixing the mixture, and continuously stirring the mixture for 1h to obtain a component A, wherein deionized water is used as a medium for ball milling, the rotating speed is 300rpm, and the ball-milling time is 10 min;
the preparation method of the component B comprises the following steps:
sequentially adding m-xylylenediamine, m-xylylenediamine-bisphenol F epoxy addition products and benzyl alcohol into a container according to the parts by weight, and mechanically stirring the mixture until the mixture is uniform to obtain the component B.
The preparation method of the modified silicon dioxide comprises the following steps:
(1) 0.8g of sodium dodecyl sulfate, 20g of doped silica are added to 600mL of a solution prepared from ethanol and deionized water in a volume ratio of 1: 1, stirring at 300r/min for 1h, then performing ultrasonic treatment at 200W for 30min, heating to 70 ℃, adding 3g of silane coupling agent KH-570, controlling the adding time to be 4h, reacting at constant temperature for 3h, taking out, repeatedly washing with ethanol, then adding into 300mL of ethanol solution, dropwise adding 2g of hydroxy silicone oil and 0.3g of dibutyltin dilaurate, stirring at room temperature at 300r/min for 5h, centrifugally washing a product, and drying to obtain pretreated silicon dioxide;
(2) under the condition of room temperature, 1g of pretreated silicon dioxide is added into 100mL of ethanol solution, the mixture is dispersed at a high speed of 1500r/min for 20min to obtain dispersion liquid, then 100mL of 8-hydroxyquinoline solution is prepared by taking ethanol as a solvent, 8-hydroxyquinoline solution is slowly added into the dispersion liquid, the mixture is dispersed at a high speed of 1500r/min for 30min and then vacuumized, the product is taken out after the vacuum is maintained for 5h, and the product is repeatedly washed by ethanol, centrifuged and dried to obtain the modified silicon dioxide.
The preparation method of the doped silica comprises the following steps:
adding 1, 2-bis (triethoxysilyl) ethane and boric acid into absolute ethyl alcohol at room temperature, stirring uniformly for 10 hours at 600r/min, then dropwise adding aqueous solution of nitric acid, stirring continuously for 12 hours at 800r/min, drying the obtained sol in an oven at 60 ℃ for 6 hours, grinding, and roasting in an air atmosphere at 300 ℃ for 3 hours to obtain doped silicon dioxide, wherein the absolute ethyl alcohol maintains the concentration of the 1, 2-bis (triethoxysilyl) ethane in the whole sol to be 5wt%, and the molar ratio of the 1, 2-bis (triethoxysilyl) ethane, the boric acid, the nitric acid and the water is controlled to be 1: 0.05: 0.3: 43.
the preparation method of the m-xylylenediamine-bisphenol F epoxy addition product comprises the following steps:
(1) adding 15mL of ethanol, 1.2g of m-xylylenediamine and 29g of trimethylolpropane triacrylate into a container, stirring and reacting for 5 hours at 30 ℃, repeatedly washing a reaction product with methanol, and drying to obtain an intermediate for later use;
(2) adding 7.5mL of methanol, 103g of m-xylylenediamine and 6.0g of intermediate into a container, uniformly mixing, stirring at 30 ℃ for reaction for 23 hours, carrying out reduced pressure distillation, repeatedly washing the product with methanol, and drying to obtain a viscous liquid product;
(3) adding 10g of the viscous liquid product and 1g of adipic acid into a container, stirring and heating to 150 ℃ under the protection of nitrogen, reacting for 1h at the temperature, heating to 230 ℃, continuing to react for 3h, after the reaction is finished, carrying out reduced pressure distillation, and dissolving the obtained product in 80mL of dimethyl sulfoxide to obtain a mixed solution for later use;
(4) at the constant temperature of 80 ℃, 10g of epichlorohydrin and 1.2g of bisphenol F are respectively added into 50mL of mixed solution in a dropwise manner, the mixture reacts for 3h, then 3g of m-xylylenediamine and 5mL of sodium hydroxide aqueous solution with the concentration of 40wt% are added, the mixture reacts for 4h at the constant temperature of 50 ℃, after the reaction is finished, the mixture is distilled under normal pressure, filtered, and then distilled under reduced pressure, and the m-xylylenediamine-bisphenol F epoxy addition product is obtained.
A high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials is used by the following method:
and oscillating and stirring the component A, then uniformly mixing the component A with the component B, uniformly coating the mixture between two bonding surfaces, curing the mixture for 20min at 120 ℃, and naturally cooling the mixture.
Example 2
The high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 48 parts of bisphenol F epoxy resin, 5 parts of bisphenol A epoxy resin, 25 parts of aluminum oxide, 7 parts of titanium dioxide, 6 parts of modified silicon dioxide, 3 parts of antimony trioxide, 5 parts of brominated epoxy resin, 1.5 parts of chlorinated paraffin, 3 parts of silane coupling agent and 3 parts of methacrylic acid-beta-hydroxyethyl ester; the component B comprises: 6.5 parts of m-xylylenediamine, 1.8 parts of m-xylylenediamine-bisphenol F epoxy addition product and 1.2 parts of benzyl alcohol;
the preparation method of the component A comprises the following steps:
sequentially adding bisphenol F epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and methacrylic acid-beta-hydroxyethyl into a container according to parts by weight, mechanically stirring until the mixture is uniform, then adding alumina, titanium dioxide, modified silica and antimony trioxide into the container after ball-milling and mixing, and continuously stirring for 3 hours to obtain a component A, wherein deionized water is used as a medium for ball milling, the rotating speed is 400rpm, and the ball milling time is 20 min;
the preparation method of the component B comprises the following steps:
sequentially adding m-xylylenediamine, m-xylylenediamine-bisphenol F epoxy addition products and benzyl alcohol into a container according to the parts by weight, and mechanically stirring the mixture until the mixture is uniform to obtain the component B.
The preparation method of the modified silicon dioxide comprises the following steps:
(1) 1.2g of sodium dodecyl sulfate, 25g of doped silica are added to 700mL of a solution prepared from ethanol and deionized water in a volume ratio of 1: 1, stirring at 400r/min for 2h, then carrying out ultrasonic treatment at 300W for 40min, heating to 75 ℃, adding 4g of silane coupling agent KH-570, controlling the adding time to be 5h, reacting at constant temperature for 4h, taking out, repeatedly washing with ethanol, then adding into 400mL of ethanol solution, dropwise adding 3g of hydroxy silicone oil and 0.5g of dibutyltin dilaurate, stirring at 400r/min for 7h at room temperature, centrifuging, washing and drying the product, thus obtaining pretreated silicon dioxide;
(2) under the condition of room temperature, 3g of pretreated silicon dioxide is added into 120mL of ethanol solution, the mixture is dispersed for 30min at a high speed of 2000r/min to obtain dispersion liquid, then ethanol is used as a solvent to prepare 130mL of 8-hydroxyquinoline solution, 8-hydroxyquinoline solution is slowly added into the dispersion liquid, the mixture is dispersed for 40min at a high speed of 2000r/min and then vacuumized, the product is taken out after the vacuum is kept for 6h, and the product is repeatedly washed by ethanol, centrifuged and dried to obtain the modified silicon dioxide.
The preparation method of the doped silica comprises the following steps:
adding 1, 2-bis (triethoxysilyl) ethane and boric acid into absolute ethyl alcohol at room temperature, uniformly mixing, continuously stirring for 12h at 700r/min, then dropwise adding aqueous solution of nitric acid, continuously stirring for 15h at 900r/min, drying the obtained sol in an oven at 70 ℃ for 8h, grinding, and roasting for 4h in an air atmosphere at 320 ℃ to obtain doped silicon dioxide, wherein the absolute ethyl alcohol maintains the concentration of the 1, 2-bis (triethoxysilyl) ethane in the whole sol to be 7wt%, and the molar ratio of the 1, 2-bis (triethoxysilyl) ethane, the boric acid, the nitric acid and the water is controlled to be 1: 0.3: 0.32: 45.
the preparation method of the m-xylylenediamine-bisphenol F epoxy addition product comprises the following steps:
(1) adding 18mL of ethanol, 1.5g of m-xylylenediamine and 30g of trimethylolpropane triacrylate into a container, stirring and reacting for 6 hours at 32 ℃, repeatedly washing a reaction product with methanol, and drying to obtain an intermediate for later use;
(2) adding 8.5mL of methanol, 110g of m-xylylenediamine and 7.2g of intermediate into a container, uniformly mixing, stirring at 32 ℃ for reaction for 25h, carrying out reduced pressure distillation, repeatedly washing the product with methanol, and drying to obtain a viscous liquid product;
(3) adding 13g of the viscous liquid product and 2g of adipic acid into a container, stirring and heating to 155 ℃ under the protection of nitrogen, reacting for 1.5h at the temperature, heating to 235 ℃, continuing to react for 4h, after the reaction is finished, distilling under reduced pressure, and dissolving the obtained product in 90mL of dimethyl sulfoxide to obtain a mixed solution for later use;
(4) at a constant temperature of 82 ℃, 12g of epichlorohydrin and 1.5g of bisphenol F are respectively added into 60mL of mixed solution in a dropwise manner to react for 4h, then 5g of m-xylylenediamine and 8mL of sodium hydroxide aqueous solution with the concentration of 45wt% are added to react for 5h at a constant temperature of 52 ℃, after the reaction is finished, the mixture is distilled under normal pressure, filtered and distilled under reduced pressure to obtain the m-xylylenediamine-bisphenol F epoxy addition product.
A high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials is used by the following method:
and oscillating and stirring the component A, then uniformly mixing the component A with the component B, uniformly coating the mixture between two bonding surfaces, curing the mixture for 30min at 140 ℃, and naturally cooling the mixture.
Example 3
The high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 50 parts of bisphenol F epoxy resin, 6 parts of bisphenol A epoxy resin, 28 parts of alumina, 10 parts of titanium dioxide, 8 parts of modified silica, 5 parts of antimony trioxide, 6 parts of brominated epoxy resin, 2 parts of chlorinated paraffin, 5 parts of a silane coupling agent and 5 parts of methacrylic acid-beta-hydroxyethyl ester; the component B comprises: 7.5 parts of m-xylylenediamine, 2.5 parts of m-xylylenediamine-bisphenol F epoxy addition product and 1.5 parts of benzyl alcohol;
the preparation method of the component A comprises the following steps:
sequentially adding bisphenol F epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and beta-hydroxyethyl methacrylate into a container according to the parts by weight, mechanically stirring the mixture to be uniform, then adding alumina, titanium dioxide, modified silicon dioxide and antimony trioxide into the container after ball-milling and mixing the mixture, and continuously stirring the mixture for 5 hours to obtain a component A, wherein deionized water is used as a medium for ball milling, the rotating speed is 400rpm, and the ball-milling time is 30 min;
the preparation method of the component B comprises the following steps:
sequentially adding m-xylylenediamine, m-xylylenediamine-bisphenol F epoxy addition products and benzyl alcohol into a container according to the parts by weight, and mechanically stirring the mixture until the mixture is uniform to obtain the component B.
The preparation method of the modified silicon dioxide comprises the following steps:
(1) 1.5g of sodium dodecyl sulfate, 30g of doped silica are added to 800mL of a solution prepared from ethanol and deionized water in a volume ratio of 1: 1, stirring for 3 hours at a speed of 500r/min, then carrying out ultrasonic treatment for 50 minutes at a speed of 300W, then heating to 80 ℃, adding 5g of silane coupling agent KH-570, controlling the adding time to be 6 hours, reacting at a constant temperature for 5 hours, taking out, repeatedly washing with ethanol, then adding into 500mL of ethanol solution, dropwise adding 4g of hydroxy silicone oil and 0.8g of dibutyltin dilaurate, stirring for 8 hours at a speed of 500r/min at room temperature, centrifugally washing and drying a product to obtain pretreated silicon dioxide;
(2) under the condition of room temperature, 5g of pretreated silicon dioxide is added into 150mL of ethanol solution, the mixture is dispersed for 40min at a high speed of 3000r/min to obtain dispersion liquid, then ethanol is used as a solvent to prepare 150mL of 8-hydroxyquinoline solution, the 8-hydroxyquinoline solution is slowly added into the dispersion liquid, the mixture is dispersed for 50min at a high speed of 3000r/min and then vacuumized, the product is taken out after the vacuum is maintained for 8h, and the product is repeatedly washed by ethanol, centrifuged and dried to obtain the modified silicon dioxide.
The preparation method of the doped silica comprises the following steps:
adding 1, 2-bis (triethoxysilyl) ethane and boric acid into absolute ethyl alcohol at room temperature, stirring uniformly for 15h at 800r/min, then adding dropwise nitric acid aqueous solution, stirring continuously for 18h at 1000r/min, drying the obtained sol in an oven at 80 ℃ for 10h, grinding, and roasting in an air atmosphere at 360 ℃ for 5h to obtain doped silicon dioxide, wherein the absolute ethyl alcohol maintains the concentration of the 1, 2-bis (triethoxysilyl) ethane in the whole sol to be 8wt%, and the molar ratio of the 1, 2-bis (triethoxysilyl) ethane, the boric acid, the nitric acid and the water is controlled to be 1: 0.5: 0.35: 46.
the preparation method of the m-xylylenediamine-bisphenol F epoxy addition product comprises the following steps:
(1) adding 20mL of ethanol, 1.8g of m-xylylenediamine and 32g of trimethylolpropane triacrylate into a container, stirring and reacting for 8 hours at 35 ℃, repeatedly washing a reaction product with methanol, and drying to obtain an intermediate for later use;
(2) adding 9.5mL of methanol, 120g of m-xylylenediamine and 7.8g of intermediate into a container, uniformly mixing, stirring at 35 ℃ for reaction for 28 hours, carrying out reduced pressure distillation, repeatedly washing the product with methanol, and drying to obtain a viscous liquid product;
(3) adding 15g of the viscous liquid product and 3g of adipic acid into a container, stirring and heating to 160 ℃ under the protection of nitrogen, reacting for 2 hours at the temperature, heating to 240 ℃ and continuing to react for 5 hours, after the reaction is finished, carrying out reduced pressure distillation, and dissolving the obtained product in 100mL of dimethyl sulfoxide to obtain a mixed solution for later use;
(4) at the constant temperature of 85 ℃, 15g of epichlorohydrin and 1.8g of bisphenol F are respectively added into 80mL of mixed solution in a dropwise manner, the mixture reacts for 5 hours, 7g of m-xylylenediamine and 10mL of sodium hydroxide aqueous solution with the concentration of 50wt% are added, the mixture reacts for 6 hours at the constant temperature of 55 ℃, after the reaction is finished, the mixture is distilled under normal pressure, filtered, and then distilled under reduced pressure, and the m-xylylenediamine-bisphenol F epoxy addition product is obtained.
A high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials is used by the following method:
and oscillating and stirring the component A, then uniformly mixing the component A with the component B, uniformly coating the mixture between two bonding surfaces, curing the mixture for 50min at 160 ℃, and naturally cooling the mixture.
Comparative example 1: this comparative example is substantially the same as example 1 except that in the A component, ordinary silica is used instead of modified silica.
Comparative example 2: this comparative example is essentially the same as example 1 except that the modified silica was prepared using ordinary silica instead of doped silica.
Comparative example 3: this comparative example is essentially the same as example 1 except that the B component does not contain m-xylylenediamine-bisphenol F epoxy adduct.
Test experiments:
the epoxy structural adhesives of examples 1-3 and comparative examples 1-3 were subjected to performance tests, and the test results are shown in Table 1
TABLE 1 results of performance test of high temperature epoxy structural adhesives for glass fiber reinforced materials of examples and comparative examples
Figure DEST_PATH_IMAGE001
Note: testing the detection condition of the temperature resistance test immediately after keeping the temperature for 5 hours; the tensile shear strength is measured according to the GB/T7124-2008 standard, a phenolic glass fiber reinforced plastic sample is adopted, and a testing machine tests the speed: 5 mm/min; the tensile strength was determined according to the standard ISO 527-2:2012, using phenolic glass steel test specimens, testing machine test speed: when the strain is more than 0.25%, the strain is 10mm/min, and the tensile strength is in the range; testing the retention rate of tensile shear strength after the alkali resistance is 10 percent NaOH144 h; the retention rate of tensile shear strength after soaking in acid-resistant 5% sulfuric acid for 120h is tested.
According to the test results, the epoxy structural adhesive disclosed by the invention has good high-temperature resistance, excellent strength and corrosion resistance, can be well used in glass fiber reinforced materials, and is beneficial to improving the comprehensive performance of glass fiber reinforced plastics.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. The high-temperature-resistant epoxy structural adhesive for the glass fiber reinforced material comprises a component A and a component B, and is characterized in that the component A comprises the following components in parts by weight: 42-50 parts of bisphenol F epoxy resin, 3-6 parts of bisphenol A epoxy resin, 22-28 parts of aluminum oxide, 5-10 parts of titanium dioxide, 5-8 parts of modified silicon dioxide, 2-5 parts of antimony trioxide, 3-6 parts of brominated epoxy resin, 1-2 parts of chlorinated paraffin, 1-5 parts of silane coupling agent and 1-5 parts of active diluent; the component B comprises: 5.5 to 7.5 portions of m-xylylenediamine, 1.5 to 2.5 portions of m-xylylenediamine-bisphenol F epoxy addition product and 1.0 to 1.5 portions of benzyl alcohol.
2. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 1, wherein the component A is prepared by the following method:
sequentially adding bisphenol F epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, chlorinated paraffin, a silane coupling agent and an active diluent into a container according to the parts by weight, mechanically stirring the mixture until the mixture is uniform, then adding the mixture into the container after ball milling and mixing alumina, titanium dioxide, modified silicon dioxide and antimony trioxide, and continuously stirring the mixture for 1 to 5 hours to obtain a component A;
the preparation method of the component B comprises the following steps:
sequentially adding m-xylylenediamine, m-xylylenediamine-bisphenol F epoxy addition products and benzyl alcohol into a container according to the parts by weight, and mechanically stirring the mixture until the mixture is uniform to obtain the component B.
3. The high temperature resistant epoxy structural adhesive for glass fiber reinforced materials as claimed in claim 2, wherein deionized water is used as a medium for ball milling, the rotation speed is 300-400rpm, and the ball milling time is 10-30 min.
4. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 1, wherein the preparation method of the modified silica comprises the following steps:
(1) adding sodium dodecyl sulfate and doped silicon dioxide into the mixed solution, stirring for 1-3h, then carrying out ultrasonic treatment for 30-50min, then heating to 70-80 ℃, adding a silane coupling agent KH-570, controlling the adding time to be 4-6h, reacting at constant temperature for 3-5h, then taking out, repeatedly washing with ethanol, then adding into an ethanol solution, dropwise adding hydroxyl silicone oil and dibutyltin dilaurate, stirring for 5-8h at room temperature, centrifugally washing the product, and drying to obtain pretreated silicon dioxide;
(2) under the condition of room temperature, adding 1-5g of pretreated silicon dioxide into 150mL of 100-mL ethanol solution, dispersing at high speed for 20-40min to obtain dispersion liquid, then using ethanol as a solvent to prepare 0.5-0.8g/mL 8-hydroxyquinoline solution 100-150mL, slowly adding 8-hydroxyquinoline solution into the dispersion liquid, carrying out high-speed dispersion for 30-50min, then vacuumizing, keeping the vacuum for 5-8h, then taking out a product, repeatedly washing with ethanol, centrifuging and drying to obtain the modified silicon dioxide.
5. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 4, wherein in the step (1), the ratio of the sodium dodecyl sulfate, the doped silicon dioxide, the mixed solution, the silane coupling agent KH-570, the ethanol solution, the hydroxyl silicone oil and the dibutyltin dilaurate is (0.8-1.5) g: (20-30) g: (600-800) mL: (3-5) g: (300- & lt 500) mL: (2-4) g: (0.3-0.8) g;
in the step (1), the mixed solution is prepared from ethanol and deionized water according to a volume ratio of 1: 1.
6. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 4, wherein the doped silica is prepared by the following method:
under the condition of room temperature, adding 1, 2-bis (triethoxysilyl) ethane and boric acid into absolute ethyl alcohol, mixing uniformly, continuously stirring for 10-15h at 800r/min of 600-: 0.05-0.5: 0.3-0.35: 43-46.
7. The high temperature resistant epoxy structural adhesive for glass fiber reinforced material of claim 1, wherein the m-xylylenediamine-bisphenol F epoxy adduct is prepared by the following steps:
(1) adding ethanol, m-xylylenediamine and trimethylolpropane triacrylate into a container, stirring and reacting at 30-35 ℃ for 5-8h, repeatedly washing a reaction product with methanol, and drying to obtain an intermediate for later use;
(2) adding methanol, m-xylylenediamine and the intermediate into a container, uniformly mixing, stirring at 30-35 ℃ for reaction for 23-28h, carrying out reduced pressure distillation, repeatedly washing the product with methanol, and drying to obtain a viscous liquid product;
(3) adding the viscous liquid product and adipic acid into a container, stirring and heating to 150-160 ℃ under the protection of nitrogen, reacting for 1-2h at the temperature, heating to 230-240 ℃ and continuing to react for 3-5h, and after the reaction is finished, carrying out reduced pressure distillation, dissolving the obtained product in dimethyl sulfoxide to obtain a mixed solution for later use;
(4) and (3) respectively adding epoxy chloropropane and bisphenol F into the mixed solution obtained in the step (3) in a dropwise manner at a constant temperature of 80-85 ℃, reacting for 3-5h, adding m-xylylenediamine and a sodium hydroxide aqueous solution, reacting for 4-6h at a constant temperature of 50-55 ℃, after the reaction is finished, distilling under normal pressure, filtering, and distilling under reduced pressure to obtain an m-xylylenediamine-bisphenol F epoxy addition product.
8. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 7, wherein in the step (1), the ratio of the ethanol, the m-xylylenediamine and the trimethylolpropane triacrylate is (15-20) mL: (1.2-1.8) g: (29-32) g;
in the step (2), the dosage ratio of the methanol, the m-xylylenediamine and the intermediate is (7.5-9.5) mL: (103-120) g: (6.0-7.8) g;
in the step (3), the dosage proportion of the viscous liquid product, adipic acid and dimethyl sulfoxide is (10-15) g: (1-3) g: (80-100) mL.
9. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 7, wherein in the step (4), the usage ratio of the epichlorohydrin, the bisphenol F, the mixed solution, the m-xylylenediamine and the sodium hydroxide aqueous solution is (10-15) g, (1.2-1.8) g, (50-80) mL: (3-7) g: (5-10) mL;
the concentration of the sodium hydroxide aqueous solution is 40-50 wt%.
10. The high-temperature-resistant epoxy structural adhesive for glass fiber reinforced materials according to claim 1, which is used in the following way:
after the component A is oscillated and stirred, the component A and the component B are mixed evenly and coated between two bonding surfaces evenly, and then the mixture is solidified for 20 to 50min at the temperature of 120-160 ℃ and is cooled naturally.
CN202210810145.2A 2022-07-11 2022-07-11 High-temperature-resistant epoxy structural adhesive for glass fiber reinforced material Pending CN114854313A (en)

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