CN113621219A - Fast-curing epoxy resin composite material and preparation method thereof - Google Patents

Fast-curing epoxy resin composite material and preparation method thereof Download PDF

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Publication number
CN113621219A
CN113621219A CN202111021297.6A CN202111021297A CN113621219A CN 113621219 A CN113621219 A CN 113621219A CN 202111021297 A CN202111021297 A CN 202111021297A CN 113621219 A CN113621219 A CN 113621219A
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epoxy resin
curing
parts
composite material
resin composite
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CN113621219B (en
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林文丹
李刚
黄必文
郑斯祥
邓辉尧
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Shanxi Yude New Materials Technology Co ltd
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Guangdong Huacai Composite Material Co ltd
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • 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
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    • 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
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    • 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
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    • 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
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract

According to the fast-curing epoxy resin composite material and the preparation method thereof, the epoxy resin composite material with excellent appearance and mechanical property is obtained by adjusting the formula of the composite material and optimizing the microwave curing process. Specifically, from the aspects of the type of epoxy resin and epoxy equivalent, bisphenol A or bisphenol F type epoxy resin, cardanol-based epoxy resin and multifunctional epoxy resin are selected as resin matrixes, and components such as nano-filler, curing agent, curing accelerator and the like are matched to prepare the epoxy resin composite material suitable for the microwave curing process; meanwhile, the microwave power, temperature and time in the microwave curing process are optimized, so that the epoxy resin composite material can be completely cured in a short time, compared with the traditional thermosetting process, the epoxy resin composite material is uniform in curing, good in appearance and greatly maintained in mechanical property, the energy consumption can be reduced, the production cost of the composite material is reduced, and the industrial application of the epoxy resin composite material is facilitated.

Description

Fast-curing epoxy resin composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to a fast-curing epoxy resin composite material and a preparation method thereof.
Background
The epoxy resin composite material has the advantages of high specific strength, high specific modulus, corrosion resistance, fatigue resistance, damping vibration attenuation, size stability, mechanical property and the like, and has wide application in the industrial fields of aerospace, transportation, wind power generation, sports goods, marine shipbuilding and the like.
At present, epoxy resin composite materials are mainly cured in a thermosetting mode, the defects of long curing time, high energy consumption and low curing efficiency exist, heat is transferred from the outside to the inside during curing, a certain temperature gradient exists in the materials, uneven curing and residual stress accumulation are easily caused, and the defects of the composite materials are further enlarged.
The microwave has the characteristics of uniform heat transfer, high heating efficiency, high curing speed, easy control and the like due to the unique characteristics of uniform heating in molecules, selective heating and the like, and has become a research hotspot in the aspect of replacing the traditional thermosetting. It is known that for different epoxy resin composite materials, due to the difference between the types of epoxy resins and curing agents, a specific curing process is required to achieve the best overall performance, and the change of the curing process has a significant influence on the performance of the final product. In the practical application process of microwave curing, the curing process cannot be adjusted according to a specific epoxy resin composite material, and an immature curing process often causes more pores in a final product, so that the appearance and the mechanical property of the material are poor.
Therefore, how to develop a proper microwave curing process according to the composition of the epoxy resin composite material to obtain the effect with good appearance and mechanical property is the key point that research and development personnel need to pay attention.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides the rapidly-cured epoxy resin composite material and the preparation method thereof, and the epoxy resin composite material with excellent appearance and mechanical property is obtained by adjusting the formula of the composite material and optimizing the microwave curing process.
In order to achieve the purpose, the invention adopts the following technical scheme that the rapidly-cured epoxy resin composite material comprises the following raw materials in parts by weight:
60-100 parts of bisphenol A or bisphenol F type epoxy resin with the epoxy equivalent of 400-600 g/eq; 20-40 parts of cardanol-based epoxy resin with the epoxy equivalent of 280-380 g/eq; 2-6 parts of polyfunctional epoxy resin with the epoxy equivalent of 150-250 g/eq; 2-5 parts of nano filler; 5-15 parts of a curing agent; 0-0.5 part of curing accelerator; 5-20 parts of reactive diluent.
Preferably, the fast-curing epoxy resin composite material comprises the following raw materials in parts by weight:
bisphenol A or bisphenol F type epoxy resin with the epoxy equivalent of 400-600g/eq, 80-90 parts; 30-35 parts of cardanol-based epoxy resin with the epoxy equivalent of 300-350 g/eq; 2-6 parts of polyfunctional epoxy resin with the epoxy equivalent of 180-220 g/eq; 2-5 parts of nano filler; 8-10 parts of a curing agent; 0.2-0.5 part of curing accelerator; 10-15 parts of reactive diluent.
The bisphenol A or bisphenol F type epoxy resin is an epoxy resin commonly used in the field, and the epoxy equivalent is preferably 450-550 g/eq; more preferably 480-500 g/eq.
The epoxy equivalent of the cardanol-based epoxy resin anacardic acid or cardanol modified epoxy resin is preferably 300-350 g/eq; has the following chemical structural formula:
Figure BDA0003242065860000021
the multifunctional epoxy resin is one of four-functional epoxy resin, and the epoxy equivalent is preferably 180-220 g/eq; has the following chemical structural formula:
Figure BDA0003242065860000022
the particle size of the nano filler is 100-200nm, and the nano filler is selected from at least one of alumina, silica, zirconia, titania and calcium carbonate; preferably, the nano filler is modified by a coupling agent, and the coupling agent is one of a silane coupling agent or a titanate coupling agent.
The curing agent is aliphatic, alicyclic or araliphatic polyamine containing two or three primary amines, selected from linear alkyl diamines of C8-C12, such as: octanediamine, nonanediamine, decanediamine, undecanediamine, or dodecanediamine; and at least one of 1, 4-diaminocyclohexane, bis (4-amino-3-ethylcyclohexyl) methane, isophoronediamine, 1, 4-bis (aminomethyl) benzene, 4-aminomethyl-1, 8-octanediamine, 1,3, 5-tris (aminomethyl) benzene, 1,3, 5-tris (aminomethyl) cyclohexane, tris (2-aminoethyl) amine, and tris (2-aminopropyl) amine.
The curing accelerator is metal organic acid salt or imidazole substance, and is at least one selected from zinc laurate, zinc stearate, tin octoate, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole and 2-phenylimidazole.
The reactive diluent is monoglycidyl ether and is selected from at least one of butyl glycidyl ether, C8-C13 alkyl glycidyl ether and benzyl glycidyl ether.
Another object of the present invention is to provide a method for preparing a fast-curing epoxy resin composite material, comprising the steps of:
(1) sequentially adding bisphenol A or bisphenol F epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 200-500r/min for 10-20 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 800-1000r/min, and stirring for 20-30 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.05-0.08MPa, and stirring at the rotating speed of 800 plus materials and 1000r/min for 20-30min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mould, placing the mould in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 50-70W, the temperature is 70-80 ℃, and the curing time is 5-10 min; the microwave power of the second stage is 100-; the microwave power of the third stage is 80-90W, the temperature is 120-125 ℃, and the curing time is 3-5 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the epoxy resin composite material with excellent appearance and mechanical property is obtained by adjusting the formula of the composite material and optimizing the microwave curing process. Specifically, from the aspects of the type of epoxy resin and epoxy equivalent, bisphenol A or bisphenol F type epoxy resin, cardanol-based epoxy resin and multifunctional epoxy resin are selected as resin matrixes, and components such as nano-filler, curing agent, curing accelerator and the like are matched to prepare the epoxy resin composite material suitable for the microwave curing process; meanwhile, the microwave power, temperature and time in the microwave curing process are optimized, so that the epoxy resin composite material can be completely cured in a short time.
(2) The invention takes bisphenol A or bisphenol F type epoxy resin which is common in the field as a main matrix, adds the cardanol based epoxy resin and the multifunctional epoxy resin, improves the curing speed and the curing degree, powerfully improves the appearance defects of white spots, fog and the like of the composite material, reduces the porosity and warping degree of the composite material, and improves the mechanical property and the curing effect of the composite material.
(3) Compared with the traditional thermosetting process, the microwave curing process adopted by the invention has the advantages of uniform curing, good appearance, great maintenance of mechanical properties, capability of reducing energy consumption and production cost of the composite material, and contribution to industrial application of the epoxy resin composite material.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow. All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
Example 1
A fast-curing epoxy resin composite material comprises the following raw materials in parts by weight:
100 parts of bisphenol A epoxy resin with the epoxy equivalent of 400 g/eq; 40 parts of cardanol-based epoxy resin with the epoxy equivalent of 380 g/eq; 5 parts of polyfunctional epoxy resin with the epoxy equivalent of 150 g/eq; 5 parts of nano filler; 15 parts of a curing agent; 0.5 part of curing accelerator; 20 parts of a reactive diluent;
the cardanol-based epoxy resin is of a formula (I) structure, the polyfunctional epoxy resin is of a formula (V) structure, the nano filler is nano silicon oxide, the particle size is 120nm, the curing agent is a mixture of decamethylene diamine and tris (2-aminoethyl) amine according to a weight ratio of 2:1, the curing accelerator is zinc stearate, and the active diluent is butyl glycidyl ether;
the preparation method of the fast-curing epoxy resin composite material comprises the following steps:
(1) sequentially adding bisphenol A type epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 500r/min for 10 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 1000r/min, and stirring for 30 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.05MPa, and stirring at the rotating speed of 1000r/min for 20min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mold, placing the mold in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 70W, the temperature is 80 ℃, and the curing time is 5 min; the microwave power of the second stage is 110W, the temperature is 110 ℃, and the curing time is 15 min; the microwave power of the third stage is 80W, the temperature is 125 ℃, and the curing time is 4 min.
Example 2
A fast-curing epoxy resin composite material comprises the following raw materials in parts by weight:
80 parts of bisphenol F type epoxy resin with the epoxy equivalent of 600 g/eq; 30 parts of cardanol-based epoxy resin with the epoxy equivalent of 300 g/eq; 4 parts of polyfunctional epoxy resin with the epoxy equivalent of 150 g/eq; 4 parts of nano filler; 10 parts of a curing agent; 0.4 part of curing accelerator; 15 parts of a reactive diluent;
the cardanol-based epoxy resin is of a formula (II), the polyfunctional group epoxy resin is of a formula (V), the nano filler is nano titanium oxide, the particle size is 200nm, the curing agent is a mixture of dodecyl diamine and isophorone diamine according to a weight ratio of 1:1, the curing accelerator is 1-benzyl-2-phenylimidazole, and the reactive diluent is a mixture of dodecyl glycidyl ether and benzyl glycidyl ether according to a weight ratio of 1: 2;
the preparation method of the fast-curing epoxy resin composite material comprises the following steps:
(1) sequentially adding bisphenol F type epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 400r/min for 20 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 800r/min, and stirring for 30 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.08MPa, and stirring at the rotating speed of 1000r/min for 20min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mold, placing the mold in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 60W, the temperature is 70 ℃, and the curing time is 10 min; the microwave power of the second stage is 110W, the temperature is 100 ℃, and the curing time is 20 min; the microwave power of the third stage is 90W, the temperature is 120 ℃, and the curing time is 3 min.
Example 3
A fast-curing epoxy resin composite material comprises the following raw materials in parts by weight:
60 parts of bisphenol A epoxy resin with the epoxy equivalent of 500 g/eq; 20 parts of cardanol-based epoxy resin with the epoxy equivalent of 280 g/eq; 2 parts of polyfunctional epoxy resin with the epoxy equivalent of 200 g/eq; 2 parts of nano filler; 8 parts of a curing agent; 0.2 part of curing accelerator; 10 parts of a reactive diluent;
the cardanol-based epoxy resin is of a formula (III) structure, the polyfunctional epoxy resin is of a formula (VI) structure, the nano filler is nano zirconia, the particle size is 150nm, the curing agent is a mixture of nonanediamine and 1,3, 5-tris (aminomethyl) benzene according to a weight ratio of 1:1, the curing accelerator is 2-phenylimidazole, and the reactive diluent is a mixture of nonyl glycidyl ether and butyl glycidyl ether according to a weight ratio of 1: 1;
the preparation method of the fast-curing epoxy resin composite material comprises the following steps:
(1) sequentially adding bisphenol A type epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 200r/min for 20 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 900r/min, and stirring for 25 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.05MPa, and stirring at the rotating speed of 1000r/min for 30min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mold, placing the mold in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 50W, the temperature is 75 ℃, and the curing time is 6 min; the microwave power of the second stage is 110W, the temperature is 100 ℃, and the curing time is 20 min; the microwave power of the third stage is 85W, the temperature is 120 ℃, and the curing time is 5 min.
Example 4
A fast-curing epoxy resin composite material comprises the following raw materials in parts by weight:
70 parts of bisphenol F type epoxy resin with the epoxy equivalent of 520 g/eq; 30 parts of cardanol-based epoxy resin with the epoxy equivalent of 300 g/eq; 6 parts of polyfunctional epoxy resin with the epoxy equivalent of 180 g/eq; 5 parts of nano filler; 12 parts of a curing agent; 0.3 part of curing accelerator; 15 parts of a reactive diluent;
the cardanol-based epoxy resin is of a formula (IV) structure, the polyfunctional epoxy resin is of a formula (VI) structure, the nano filler is nano aluminum oxide with the particle size of 100nm, the curing agent is a mixture of 1, 4-diaminocyclohexane and tris (2-aminopropyl) amine according to a weight ratio of 1:1, the curing accelerator is 2-ethyl-4-methylimidazole, and the active diluent is a mixture of undecyl glycidyl ether and butyl glycidyl ether according to a weight ratio of 1: 1;
the preparation method of the fast-curing epoxy resin composite material comprises the following steps:
(1) sequentially adding bisphenol F type epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 400r/min for 15 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 1000r/min, and stirring for 20 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.08MPa, and stirring at the rotating speed of 1000r/min for 30min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mold, placing the mold in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 70W, the temperature is 80 ℃, and the curing time is 5 min; the microwave power of the second stage is 100W, the temperature is 110 ℃, and the curing time is 13 min; the microwave power of the third stage is 90W, the temperature is 125 ℃, and the curing time is 3 min.
Comparative example 1
The cardanol-based epoxy resin is not added, and the rest components, the proportion and the preparation method are completely consistent with those of the embodiment 1.
Comparative example 2
The multifunctional epoxy resin is not added, and the rest components, the proportion and the preparation method are completely consistent with those of the embodiment 1.
Comparative example 3
The method is characterized by adopting a thermocuring process for curing, and specifically comprises the following steps: the temperature is 80 ℃, and the curing time is 5 min; the temperature is 110 ℃, and the curing time is 15 min; the temperature is 125 ℃, the curing time is 4min, and the rest components, the proportion and the preparation method are completely consistent with those of the example 1.
The epoxy resin composites obtained in examples 1 to 4 and comparative examples 1 to 3 were tested to observe the appearance quality, whether they were flat, smooth, and free from defects such as pinholes, and at the same time, the porosity, curing degree, tensile strength, and warpage, and the test results are shown in table 1.
TABLE 1
Numbering Appearance of the product Porosity/%) Degree of curing/%) Tensile strength/MPa Degree of warp/%)
Example 1 No white point and pinhole 0.61 96 107 0.63
Example 2 No white point and pinhole 0.69 97 109 0.62
Example 3 No white point and pinhole 0.83 95 109 0.59
Example 4 No white point and pinhole 0.85 96 108 0.65
Comparative example 1 Has white point and no pinhole 2.13 90 95 1.06
Comparative example 2 Has white point and no pinhole 2.52 92 90 1.23
Comparative example 3 No white point and pinhole 2.35 95 115 0.96
The test data in table 1 show that the epoxy resin composite material prepared by the method has good appearance, low porosity, high curing degree and low warping degree, and greatly maintains the tensile property of the material; it can also be found that the addition of cardanol-based epoxy resin and polyfunctional epoxy resin improves the porosity, curing degree, appearance, tensile strength and warping degree of the epoxy resin composite material to some extent.
Based on example 1, epoxy resin composites with different structures are prepared by selecting different types of cardanol-based epoxy resins, and the appearance, porosity, curing degree, tensile strength, warping degree and the like of the epoxy resin composites are tested, and the details are shown in table 2.
TABLE 2
Figure BDA0003242065860000071
Figure BDA0003242065860000081
From the experimental data of table 2, it can be found that the cardanol-based epoxy resin used in nos. S1-S2 has lower porosity and warpage and high tensile strength than the cardanol-based epoxy resin used in S5-S8, and is more suitable for the microwave curing process of the present invention.
Based on example 1, cardanol-based epoxy resins with different epoxy equivalent weights are selected to prepare epoxy resin composite materials with different structures, and the appearance, porosity, curing degree, tensile strength, warping degree and the like of the epoxy resin composite materials are tested, and the details are shown in table 3.
TABLE 3
Numbering Epoxy equivalent Appearance of the product Porosity/%) Degree of curing/%) Tensile strength/MPa Degree of warp/%)
L1 380 No white point and pinhole 0.61 96 107 0.63
L2 280 No white point and pinhole 0.84 96 105 0.73
L3 200 With a pinhole 1.56 93 100 1.35
L4 500 With white spots 1.23 90 98 1.06
From the test data in table 3, it can be found that the epoxy resin composite material with good appearance, low porosity, high curing degree and low warping degree is obtained by adjusting the epoxy equivalent of the cardanol-based epoxy resin.
Comparative example 4
The curing process specifically comprises the following steps: the microwave power of the first stage is 70W, the temperature is 80 ℃, and the curing time is 5 min; the microwave power of the second stage is 120W, the temperature is 120 ℃, and the curing time is 15 min; the microwave power of the third stage is 80W, the temperature is 125 ℃, the curing time is 4min, and the rest components, the proportion and the preparation method are completely consistent with those of the embodiment 1.
Comparative example 5
The curing process specifically comprises the following steps: the microwave power of the first stage is 70W, the temperature is 80 ℃, and the curing time is 5 min; the microwave power of the second stage is 110W, the temperature is 110 ℃, and the curing time is 15 min; the microwave power of the third stage is 120W, the temperature is 125 ℃, the curing time is 4min, and the rest components, the proportion and the preparation method are completely consistent with those of the embodiment 1.
Comparative example 6
The curing process specifically comprises the following steps: the microwave power of the first stage is 100W, the temperature is 80 ℃, and the curing time is 5 min; the microwave power of the second stage is 120W, the temperature is 120 ℃, and the curing time is 15 min; the microwave power of the third stage is 80W, the temperature is 125 ℃, the curing time is 4min, and the rest components, the proportion and the preparation method are completely consistent with those of the embodiment 1.
The appearance, porosity, degree of cure, tensile strength, warpage and the like of example 1 and comparative examples 4 to 6 were tested and are detailed in table 4.
TABLE 4
Numbering Appearance of the product Porosity/%) Degree of curing/%) Tensile strength/MPa Degree of warp/%)
Example 1 No white point and pinhole 0.61 96 107 0.63
Comparative example 4 No white point and pinhole 0.95 95 105 0.68
Comparative example 5 No white point and pinhole 0.65 94 106 0.65
Comparative example 6 With white spots 1.23 90 103 0.86
From the test data in table 4, it can be found that the epoxy resin composite material with good appearance, low porosity, high curing degree and low warping degree is obtained by adjusting the microwave curing process, and the microwave power has significant influence on the porosity, curing degree and warping degree of the composite material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A fast curing epoxy resin composite characterized by: comprises the following raw materials in parts by weight,
60-100 parts of bisphenol A or bisphenol F type epoxy resin with the epoxy equivalent of 400-600 g/eq; 20-40 parts of cardanol-based epoxy resin with the epoxy equivalent of 280-380 g/eq; 2-6 parts of polyfunctional epoxy resin with the epoxy equivalent of 150-250 g/eq; 2-5 parts of nano filler; 5-15 parts of a curing agent; 0-0.5 part of curing accelerator; 5-20 parts of reactive diluent.
2. A fast curing epoxy resin composite according to claim 1, characterized in that: comprises the following raw materials in parts by weight,
bisphenol A or bisphenol F type epoxy resin with the epoxy equivalent of 400-600g/eq, 80-90 parts; 30-35 parts of cardanol-based epoxy resin with the epoxy equivalent of 300-350 g/eq; 2-6 parts of polyfunctional epoxy resin with the epoxy equivalent of 180-220 g/eq; 2-5 parts of nano filler; 8-10 parts of a curing agent; 0.2-0.5 part of curing accelerator; 10-15 parts of reactive diluent.
3. A fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the bisphenol A or bisphenol F type epoxy resin is an epoxy resin commonly used in the field, and the epoxy equivalent is preferably 450-550 g/eq.
4. A fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the epoxy equivalent of the cardanol-based epoxy resin anacardic acid or cardanol modified epoxy resin is preferably 300-350 g/eq; has the following chemical structural formula:
Figure FDA0003242065850000011
5. a fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the multifunctional epoxy resin is one of four-functional epoxy resin, and the epoxy equivalent is preferably 180-220 g/eq; has the following chemical structural formula:
Figure FDA0003242065850000012
6. a fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the particle size of the nano filler is 100-200nm, and the nano filler is selected from at least one of alumina, silica, zirconia, titania and calcium carbonate.
7. A fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the curing agent is an aliphatic, cycloaliphatic, or araliphatic polyamine containing two or three primary amines.
8. A fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the curing accelerator is metal organic acid salt or imidazole substance.
9. A fast curing epoxy resin composite according to any one of claims 1-2, characterized in that: the reactive diluent is monoglycidyl ether and is selected from at least one of butyl glycidyl ether, C8-C13 alkyl glycidyl ether and benzyl glycidyl ether.
10. A method of making a fast curing epoxy composite as claimed in claims 1 to 9 comprising the steps of:
(1) sequentially adding bisphenol A or bisphenol F epoxy resin, an active diluent and a nano filler into a dispersion kettle, and stirring at the rotating speed of 200-500r/min for 10-20 min;
(2) continuously adding cardanol-based epoxy resin and multifunctional epoxy resin, increasing the rotating speed to 800-1000r/min, and stirring for 20-30 min;
(3) finally, adding a curing agent and a curing accelerator, controlling the vacuum degree of the dispersion kettle to be 0.05-0.08MPa, and stirring at the rotating speed of 800 plus materials and 1000r/min for 20-30min to prepare a mixed glue solution;
(4) pouring the mixed glue solution into a mould, placing the mould in a microwave reactor, and curing under the microwave action with the frequency of 2.45GHZ to prepare the epoxy resin composite material, wherein the curing process is divided into a first stage, a second stage and a third stage, the microwave power of the first stage is 50-70W, the temperature is 70-80 ℃, and the curing time is 5-10 min; the microwave power of the second stage is 100-; the microwave power of the third stage is 80-90W, the temperature is 120-125 ℃, and the curing time is 3-5 min.
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CN116375727A (en) * 2023-03-31 2023-07-04 苏州大学 Bio-based epoxy monomer, medium-temperature curing epoxy resin system and preparation method

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CN106633649A (en) * 2016-12-09 2017-05-10 北京化工大学 Resin matrix applicable to microwave curing and preparation method of resin matrix
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