CN113136089A - Rapid curing wave-transparent composite material and preparation method thereof - Google Patents
Rapid curing wave-transparent composite material and preparation method thereof Download PDFInfo
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- CN113136089A CN113136089A CN202110536612.2A CN202110536612A CN113136089A CN 113136089 A CN113136089 A CN 113136089A CN 202110536612 A CN202110536612 A CN 202110536612A CN 113136089 A CN113136089 A CN 113136089A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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Abstract
The invention discloses a fast curing wave-transparent composite material and a preparation method thereof. The preparation method comprises the following steps: the amino functional groups are quantitatively added into the liquid epoxy resin to enable the epoxy groups to be controlled and pre-polymerized, the molecular weight of part of the epoxy groups is increased after polymerization, the viscosity is increased, and the purpose of controlling the viscosity of the resin is further achieved. Infiltrating the prepreg resin with fibers with low dielectric loss to obtain a prepreg; curing the prepreg to obtain a wave-transparent composite material; the composite material has low dielectric constant and loss tangent under the condition of high frequency band, can be quickly cured under the condition of medium temperature, and can be widely applied to the field of high-performance wave-transparent composite materials.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to a composite material which can be rapidly cured and has low dielectric loss and excellent wave-transmitting performance and a preparation method thereof.
Background
With the rapid development of modern technologies such as satellite positioning and radar, the requirements on high-performance wave-transmitting materials are higher and higher, and in order to meet the requirements on long-distance, high-speed and high-fidelity transmission of high-frequency communication, the wave-transmitting materials are required to have good dielectric properties, high mechanical properties, low water absorption and good forming process properties, and have corresponding requirements on the strength, weight, corrosion resistance and the like of the materials, so that the direction is pointed to the development of the wave-transmitting composite materials.
The wave-transparent composite material prepared by the prepreg meets the requirements, and meanwhile, in order to improve the product manufacturing rate, the prepreg is also a key requirement of the prepreg, and the prepreg can be quickly cured.
SUMMARY OF THE PATENT FOR INVENTION
In view of the problems in the prior art, the invention aims to solve the problems of low curing speed of an epoxy resin prepreg, poor prepreg resin impregnation effect, non-uniform dispersion, poor wave permeability of a glass fiber product and the like, and provides a fast curing wave-transmitting composite material and a preparation method thereof.
In order to solve the problems, the technical scheme provided by the invention is as follows:
a fast curing wave-transparent composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) prepolymerizing a certain amount of addition type curing agent containing primary amine functional groups and liquid epoxy resin to regulate the viscosity, thereby obtaining modified resin;
(2) compounding glue solution obtained by mixing modified resin and a curing agent with low-dielectric-loss fiber cloth to obtain prepreg;
(3) and curing the prepreg to obtain the wave-transmitting composite material.
The liquid epoxy resin includes glycidyl ether epoxy resin, glycidyl ester epoxy resin and mixed resin thereof, the viscosity of which is before 1000-20000mPa.s at room temperature.
The rapid-curing addition type primary amino-containing curing agent is one or more of aliphatic polyamine, alicyclic polyamine, low molecular weight polyamide and modified aromatic amine which can be cured at 20-50 ℃;
the addition amount of the rapid curing addition type primary amino group-containing curing agent is 20-30% of the theoretical curing agent required for complete curing; the amount of the curing agent added at the time of precuring is preferably 22%.
The curing agent corresponding to the modified resin is added when the prepreg is prepared, the curing agent adopts superfine dicyandiamide, and the accelerant is modified urea, modified imidazole or a compound of the two.
The low dielectric loss fiber cloth is a quartz fiber fabric. Preferably, the thread count of the fabric is 16 x 16 threads/cm.
The preparation method of the wave-transmitting composite material comprises the step of placing a prepreg in a mould pressing die, wherein the thickness of a product is 0.1-10 mm. Preferably, the curing condition is 140 ℃, and the mold is released and taken out after 10 min.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that:
1. the resin system scheme provided by the invention uses the superfine dicyandiamide as the curing agent, so that the resin can be cured at a lower temperature, and the storage period of the resin at room temperature is not influenced.
2. According to the invention, the liquid epoxy resin is modified by using the addition type amine epoxy curing agent, the pre-polymerization degree of the resin is accurately controlled, the viscosity of the resin is regulated, the risk of implosion is reduced, the rapid curing is ensured, and the wettability of the resin to the fiber fabric is ensured.
3. According to the invention, by using the quartz fiber fabric with low dielectric loss, the composite material product obtained after the prepreg is cured has excellent mechanical property, low dielectric loss and good wave-transmitting performance.
Drawings
Fig. 1 shows the results of the dielectric loss test of the wave-transparent materials prepared by different methods.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few 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 of the present invention without any inventive step, are within the scope of the present invention.
The invention provides a fast curing wave-transparent composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparation of modified epoxy resin
The liquid epoxy resin used in the present invention includes glycidyl ether type epoxy resin, glycidyl ester type epoxy resin and mixed resin thereof having a viscosity of 1000-20000mPa.s at room temperature. And (2) gradually adding 70-100 parts of liquid epoxy resin, 0-20 parts of diluent, 5-30 parts of toughening agent and 0.5-2 parts of defoaming agent into the reaction kettle according to a proportion, mixing and defoaming.
And adding a proper amount of addition type amino curing agent into the epoxy mixed liquid at the temperature of lower than 50 ℃, and fully stirring for 10-30 min.
(2) Preparation of prepregs
Mixing the curing agent superfine dicyandiamide and the accelerator in proportion, and grinding and mixing for 2-3 times on a three-roller grinding machine; then adding the modified resin obtained in the step (1) into the mixture, and stirring the mixture for 10 to 30 min.
And preparing the mixed resin and curing agent and quartz fiber fabric into prepreg by using a melting method, and carrying out constant-temperature post-treatment.
(3) Cutting the prepreg obtained in the step into corresponding shapes according to the shapes of the products, selecting the number of corresponding layers according to the thickness of the products, placing the prepreg into a cavity of the product, setting the temperature of a mold at 110-160 ℃, setting the curing time at 10-30min, and taking out the product after curing.
Example 1
The epoxy resin system comprises the following components in percentage by mass: 100 parts of liquid epoxy resin, 10 parts of diluent, 10 parts of toughening agent and 0.5 part of defoaming agent are gradually added into a reaction kettle according to the proportion to be mixed and defoamed, and are stirred for 30 min.
Adding 2.5 parts of addition type amino curing agent (triethylene tetramine) into the epoxy mixed solution at the temperature of below 50 ℃, and fully stirring for 20 min.
Mixing 7 parts of curing agent superfine dicyandiamide and 3 parts of modified urea accelerant in proportion, and grinding and mixing for 2 times on a three-roller grinding machine; then adding the modified resin obtained in the step (1) and stirring for 10 min.
Mixing the mixed resin and curing agent with 400g/m by melting method2The quartz fiber fabric cloth with warp and weft density of 20 x 20 pieces/cm is prepared into prepreg and is treated after being kept at the constant temperature of 30 ℃ for 3 days.
(3) Cutting the prepreg obtained in the previous step into corresponding shapes according to the shapes of the products, selecting the number of corresponding layers according to the thickness of the products, placing the layers into a cavity of the product, setting the temperature of a mould at 120 ℃, setting the curing time at 20min, and taking out the product after curing. The dielectric loss of the product tested was 0.004 at a loss angle (tangent/10 GHz).
Example 2
The epoxy resin system comprises the following components in percentage by mass: and (3) gradually adding 90 parts of liquid epoxy resin, 10 parts of diluent, 5 parts of toughening agent and 0.5 part of defoaming agent into the reaction kettle according to the proportion, mixing and defoaming, and stirring for 30 min.
And adding 3 parts of addition type amino curing agent (triethylene tetramine) into the epoxy mixed solution at the temperature of below 50 ℃, and fully stirring for 30 min.
Mixing 7.5 parts of curing agent superfine dicyandiamide and 3 parts of modified urea accelerant in proportion, and grinding and mixing for 2 times on a three-roller grinding machine; then adding the modified resin obtained in the step (1) and stirring for 20 min.
Mixing the mixed resin and curing agent with 400g/m by melting method2The quartz fiber fabric cloth with warp and weft density of 16 x 16 pieces/cm is prepared into prepreg and is treated after being kept at the constant temperature of 30 ℃ for 3 days.
(3) Cutting the prepreg obtained in the previous step into corresponding shapes according to the shapes of the products, selecting the number of corresponding layers according to the thickness of the products, placing the layers into a cavity of the products, setting the temperature of a mould at 140 ℃, setting the curing time at 10min, and taking out the products after curing. Article test dielectric loss gave a loss angle (tangent/10 GHz) of 0.0025.
Example 3
The epoxy resin system comprises the following components in percentage by mass: 100 parts of liquid epoxy resin, 10 parts of diluent, 10 parts of toughening agent and 0.5 part of defoaming agent are gradually added into a reaction kettle according to the proportion to be mixed and defoamed, and are stirred for 30 min.
And adding 4 parts of addition type amino curing agent (triethylene tetramine) into the epoxy mixed solution at the temperature of below 50 ℃, and fully stirring for 20 min.
Mixing 6 parts of curing agent superfine dicyandiamide and 2.5 parts of modified urea accelerant in proportion, and grinding and mixing for 2 times on a three-roller grinding machine; then adding the modified resin obtained in the step (1) and stirring for 10 min.
Mixing the mixed resin and curing agent with 400g/m by melting method2The quartz fiber fabric cloth with warp and weft density of 16 x 16 pieces/cm is prepared into prepreg and is treated after being kept at the constant temperature of 30 ℃ for 3 days.
(3) Cutting the prepreg obtained in the previous step into corresponding shapes according to the shapes of the products, selecting the number of corresponding layers according to the thickness of the products, placing the layers into a cavity of the product, setting the temperature of a mould at 160 ℃, setting the curing time at 10min, and taking out the product after curing. The dielectric loss of the article was measured to be 0.003 in terms of loss tangent (tangent/10 GHz).
Claims (7)
1. A fast curing wave-transparent composite material and a preparation method thereof are characterized in that: the preparation method comprises the following steps:
(1) prepolymerizing a certain amount of addition type curing agent containing primary amine functional groups and liquid epoxy resin to regulate the viscosity, thereby obtaining modified resin;
(2) compounding glue solution obtained by mixing modified resin and a curing agent with low-dielectric-loss fiber cloth to obtain prepreg;
(3) and curing the prepreg to obtain the wave-transmitting composite material.
2. The method according to claim 1, wherein the liquid epoxy resin comprises glycidyl ether-based epoxy resin, glycidyl ester-based epoxy resin, and mixed resin thereof having a viscosity of 1000-.
3. The method of claim 1, wherein the fast curing addition type primary amino group-containing curing agent is one or more of a combination of aliphatic polyamine, cycloaliphatic polyamine, low molecular weight polyamide and modified aromatic amine curable at 20-50 degrees celsius.
4. The method of claim 1, wherein the fast curing addition type primary amino group-containing curing agent is added in an amount of 20 to 30% of the theoretical curing agent required for complete curing.
5. The preparation method of claim 1, wherein the curing agent corresponding to the modified resin is added during the preparation of the prepreg, and the curing agent is ultra-fine dicyandiamide, accelerator unmodified urea and modified.
6. The method of claim 1, wherein the low dielectric loss fiber cloth is a quartz fiber fabric.
7. The preparation method according to claim 1, wherein the prepreg is placed in a mould pressing mold for the preparation of the composite material, the product thickness is 0.1-10mm, the curing condition is 110-160 ℃, the curing time is 10-30min, and then the prepreg is taken out after demoulding.
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| CN202110536612.2A CN113136089A (en) | 2021-05-17 | 2021-05-17 | Rapid curing wave-transparent composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789034A (en) * | 2021-10-13 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Low-heat-release epoxy resin composition and preparation method thereof |
| CN115027073A (en) * | 2022-04-20 | 2022-09-09 | 佛山铂瑞天辰医疗器械科技有限公司 | Fiber reinforced resin composite material capable of being digitally cut and preparation method and application thereof |
Citations (3)
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| CN104164053A (en) * | 2014-07-21 | 2014-11-26 | 航天材料及工艺研究所 | Flow controllable epoxy resin prepreg and preparation method thereof |
| CN107141717A (en) * | 2017-04-19 | 2017-09-08 | 中国航空工业集团公司基础技术研究院 | A kind of preparation method of transparent self toughening dicyandiamide/epoxy resin-base composite material |
| CN109535660A (en) * | 2018-12-18 | 2019-03-29 | 深圳航天科技创新研究院 | A kind of fire-retardant prepreg resin of the rapid curing that viscosity is controllable and preparation method thereof |
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2021
- 2021-05-17 CN CN202110536612.2A patent/CN113136089A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104164053A (en) * | 2014-07-21 | 2014-11-26 | 航天材料及工艺研究所 | Flow controllable epoxy resin prepreg and preparation method thereof |
| CN107141717A (en) * | 2017-04-19 | 2017-09-08 | 中国航空工业集团公司基础技术研究院 | A kind of preparation method of transparent self toughening dicyandiamide/epoxy resin-base composite material |
| CN109535660A (en) * | 2018-12-18 | 2019-03-29 | 深圳航天科技创新研究院 | A kind of fire-retardant prepreg resin of the rapid curing that viscosity is controllable and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789034A (en) * | 2021-10-13 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Low-heat-release epoxy resin composition and preparation method thereof |
| CN115027073A (en) * | 2022-04-20 | 2022-09-09 | 佛山铂瑞天辰医疗器械科技有限公司 | Fiber reinforced resin composite material capable of being digitally cut and preparation method and application thereof |
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