CN117487312A - Reactive flow controllable zero-glue-absorption epoxy resin-based prepreg - Google Patents

Reactive flow controllable zero-glue-absorption epoxy resin-based prepreg Download PDF

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CN117487312A
CN117487312A CN202311431982.5A CN202311431982A CN117487312A CN 117487312 A CN117487312 A CN 117487312A CN 202311431982 A CN202311431982 A CN 202311431982A CN 117487312 A CN117487312 A CN 117487312A
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epoxy resin
reactive
zero
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resin
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尚武林
郑庆磊
马晴
张森林
高常青
杨威
张先波
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Lianyungang Shenying Composite Material Technology Co ltd
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Abstract

The reactive flow-controllable zero-glue-absorption epoxy resin-based prepreg has lower viscosity at 60-70 ℃, is suitable for low-temperature coating and impregnation, has better manufacturability during preparation and has better operability during use; the method can trigger the quick chemical reaction of the reactive thickener at the temperature of 80-90 ℃ so as to slow down or prevent the quick reduction trend of the viscosity of the epoxy resin system along with the temperature rise, and the minimum viscosity of the resin at high temperature can be regulated and controlled by increasing or decreasing the proportion of the reactive thickener and the high molecular weight toughening agent, so that the addition amount of the high molecular weight toughening agent is obviously reduced. The method not only can meet the requirements of the advanced resin matrix composite on the zero-glue-absorption autoclave molding process, but also has better toughness and coordinated mechanical properties of the composite, is suitable for autoclave molding of products such as a high-performance composite transmitting cylinder, aviation components and the like, and has the characteristics of easily available raw materials, simple process method and strong popularization.

Description

Reactive flow controllable zero-glue-absorption epoxy resin-based prepreg
Technical Field
The invention relates to the technical field of new material application, in particular to a reactive flow-controllable zero-glue-absorption epoxy resin-based prepreg.
Background
The carbon fiber composite material has the characteristics of high specific strength, high specific modulus, light weight, good fatigue resistance, acid and alkali corrosion resistance, rust resistance, high X-ray transmission rate and the like, has the advantages of strong structural designability, simple forming process, capability of being integrally formed with various materials and the like, is a first choice of lightweight structural materials, and is widely applied to high-end fields such as aerospace, military industry and the like.
The autoclave molding process is a main method for molding an advanced resin matrix composite material, and can be divided into a glue absorption process, a pre-glue absorption process and a zero glue absorption process according to a glue absorption mode. The zero glue sucking process has the characteristics of saving raw materials, easily controlling the fiber content, being suitable for forming thick parts and the like, and becomes a main method for manufacturing structural parts such as airplane bearing and the like. The typical characteristic of the zero-suction process is that the flow is controllable, the minimum viscosity of the resin is high, the resin can be pressurized initially, and the resin basically does not flow out during molding, so that the elimination of air and volatile components in the paving layer mainly depends on the effects of vacuum exhaust and resin pressure. According to related researches, the temperature is low at the initial stage of forming, vacuum is favorable for removing air inclusion and the like, when the temperature is increased, the air passage is blocked after the resin is in a viscous state, and the residual air inclusion cannot be removed through vacuum action, but air bubbles can be crushed under the action of larger resin pressure, and the air inclusion can become dispersed and distributed of a plurality of small air bubbles, so that no obvious pores are observed in the composite material under the combined action of the vacuum and the resin pressure.
The typical characteristic of the zero-suction process is that the prepreg resin content is low, generally between 30 and 36 percent, and the high pressure is started at the initial stage of autoclave molding, but the whole process controls the resin to be low or not lost, and the key point is the control of the resin viscosity. The minimum viscosity of the traditional epoxy resin prepreg is generally hundreds to thousands of millipascals in seconds along with the temperature rise, if high pressure is added at the initial stage of molding, the resin can flow easily, so that the resin and the fiber of the composite material are unevenly distributed, and the appearance dimensional stability and the mechanical property of the composite material are seriously affected. Therefore, in order to meet the zero glue-absorbing process requirement of the epoxy resin-based prepreg, the minimum viscosity of the resin matrix in the curing process needs to be high enough to reach more than 2000-4000 cps, so that the epoxy resin is not easy to flow even under high pressure in the curing process, and the uniformity distribution between the fibers and the resin is ensured.
In order to achieve the above object, the flow-controllable epoxy resin matrix has been reported to achieve an increase in viscosity of the epoxy resin composition by adding a large proportion of a high molecular weight compound, and the prepared epoxy resin system has a high physical heating melt viscosity before preparing the prepreg. The epoxy resin matrix prepared by the method can realize the purpose of zero glue absorption of the prepreg, but has some obvious defects, such as the requirement of higher melting temperature to reduce the viscosity of the resin matrix when the prepreg is prepared by a two-step method, so that the uniform coating of the resin and the sufficient infiltration of the surface of the fiber can be ensured, the higher melting temperature of the resin can shorten the room temperature pot life of the prepreg, and the application of the prepreg on the prepreg cured at low temperature and the prepreg with large thickness is also not facilitated; the addition of a large amount of a high molecular weight compound also reduces the self-tackiness and flexibility of the prepreg, thereby affecting the handleability of the prepreg.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art, and provides a reactive flow-controllable zero-glue-absorption epoxy resin-based prepreg capable of ensuring better wettability between a prepreg resin matrix and fibers and a preparation method thereof.
The invention aims to solve the technical problems by the following technical scheme, and the reactive flow-controllable zero-glue-absorption epoxy resin-based prepreg is characterized in that:
comprises epoxy resin, a high molecular weight toughening agent, a reactive thickener, a curing agent and an accelerator, wherein the mass ratio of the components is 50-90: 1 to 10:0.1 to 5: 2-10: 1-5, firstly preparing a reactive type flow controllable zero-suction adhesive epoxy resin system, and then preparing the reactive type flow controllable zero-suction adhesive prepreg by a two-step dry process of gluing and impregnation, wherein the preparation method comprises the following steps:
7) Preparation of an epoxy resin composition: weighing liquid epoxy resin, solid epoxy resin, high molecular weight toughening agent and other components in proportion, adding the components into a double-planetary stirring kettle with a wall scraping effect, stirring the components for 60 to 240 minutes at the temperature of 80 to 200 ℃ to fully mix the components, and then reducing the temperature of materials in the kettle to 50 to 70 ℃ to control Wen Daiyong;
8) Preparation of the curing agent composition: weighing the components such as liquid epoxy resin, curing agent, accelerator and the like according to a proportion, stirring the components by using a high-speed dispersing machine until the components are uniform in visual state, and further grinding the components by using a three-roller grinder to fully mix the components;
9) Preparation of the reactive thickener composition: weighing liquid epoxy resin and reactive thickener in proportion, and stirring uniformly at 30-50 ℃ under vacuum to obtain the reactive thickener;
10 Preparation of reactive flow-controllable zero-suction epoxy resin system: rapidly adding the curing agent composition and the reactive thickener into a double-planetary stirring kettle filled with the epoxy resin composition at one time, controlling the temperature of materials in the kettle to be 50-70 ℃, stirring for 10-60 min, and stirring at a speed of 3-2000 RPM, thereby obtaining the epoxy resin matrix;
11 Preparation of a resin adhesive film: slowly pouring the freshly prepared epoxy resin matrix into a pair roller of a gumming machine while the epoxy resin matrix is hot, controlling the temperature of the pair roller of the gumming machine to be 50-70 ℃, adjusting the gap between the pair roller to uniformly coat the epoxy resin matrix on release paper, rapidly cooling, covering a PE film, and rolling to obtain a resin adhesive film;
12 Preparation of prepregs: fully attaching the resin adhesive film/high-performance fiber or fabric/resin adhesive film thereof according to a sandwich structure, hot-pressing by a pair roller with an impregnating machine to enable the resin adhesive film to be melted and permeate into fiber tows in the vertical thickness direction, cooling again to cover the PE film, and winding to obtain the reactive flow controllable zero-glue-absorption epoxy resin-based prepreg.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the viscosity of the reactive type flow-controllable zero-suction epoxy resin system is not higher than 100000cps at 70 ℃, and the controllable chemical reaction of the reactive thickener can be triggered at 80-90 ℃ or more to prevent or slow down the reduction of the viscosity of the epoxy resin system, so that the minimum viscosity of the epoxy resin system is always between 2000-4000 cps at high temperature.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the toughening agent is one or a combination of more than two of polyurethane modified epoxy, rubber modified epoxy, ultra-high molecular weight epoxy, core-shell epoxy and thermoplastic resin micro powder, and the technical problem to be solved by the invention can be further solved by the following technical scheme that the liquid epoxy resin and the solid epoxy resin are one or a combination of more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, phenolic epoxy resin and polyfunctional epoxy resin.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the curing agent composition is a premix of one or two of dicyandiamide and organic urea accelerator micropowder combination, 4' -diaminophenylsulfone and boron trifluoride ethylamine micropowder combination and liquid bisphenol A type epoxy resin.
The technical problem to be solved by the invention can be further solved by the following technical scheme that the reactive thickener composition is one or more of imidazole compounds, alicyclic amine compounds, aliphatic amine compounds, polyether amine compounds, aromatic amine compounds and polyamide compounds, and is combined with liquid epoxy, and the reactive thickener composition and the epoxy resin composition can slowly react at low temperature or be heated to 80-90 ℃ to quickly react, and the corresponding ratio of the consumable epoxy groups is 0.1-10% of the total epoxy resin.
The technical problem to be solved by the invention can be further solved by the following technical scheme, wherein the high-performance fiber is one or the combination of more than two of carbon fiber, glass fiber, quartz fiber, basalt fiber, aramid fiber, ultra-high molecular weight polyethylene fiber and PBO fiber.
Compared with the prior art, the reactive flow controllable zero-suction epoxy resin-based prepreg has lower viscosity at 60-70 ℃, has viscosity not higher than 10000cps, is suitable for low-temperature coating and impregnation, has better manufacturability during preparation and has better operability during use; the method can trigger the quick chemical reaction of the reactive thickener at the temperature of 80-90 ℃ so as to slow down or prevent the quick reduction trend of the viscosity of the epoxy resin system along with the temperature rise, and the minimum viscosity of the resin at the high temperature can be regulated and controlled by increasing or decreasing the proportion of the reactive thickener and the high molecular weight toughening agent, so that the addition amount of the high molecular weight toughening agent is obviously reduced, and some problems of the traditional flow-controllable epoxy resin system are solved. The reactive flow controllable zero-suction epoxy resin-based prepreg can meet the autoclave molding process requirements of an advanced resin-based composite material on zero suction, has better toughness and coordinated mechanical properties of the composite material, is suitable for autoclave molding of products such as a high-performance composite material transmitting cylinder, aviation components and the like, and has the characteristics of easily available raw materials, simple process method and strong popularization.
Detailed Description
The following further describes the specific technical solutions of the present invention, so that the purpose, technical solutions and advantages of the embodiments of the present invention will be more apparent to those skilled in the art to further understand the present invention, and the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments, but not limitations on the claims thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A reactive flow-controllable zero-glue-absorption epoxy resin-based prepreg consists of epoxy resin, a high molecular weight toughening agent, a reactive thickener, a curing agent and an accelerator, wherein the mass ratio of the components is 50-90: 1 to 10:0.1 to 5: 2-10: 1-5, firstly preparing a reactive type flow controllable zero-suction adhesive epoxy resin system, preparing the reactive type flow controllable zero-suction adhesive prepreg through a two-step dry process of adhesive coating and impregnation,
the preparation method comprises the following steps:
1) Preparation of an epoxy resin composition: weighing liquid epoxy resin, solid epoxy resin, high molecular weight toughening agent and other components in proportion, adding the components into a double-planetary stirring kettle with a wall scraping effect, stirring the components for 60 to 240 minutes at the temperature of 80 to 200 ℃ to fully mix the components, and then reducing the temperature of materials in the kettle to 50 to 70 ℃ to control Wen Daiyong;
2) Preparation of the curing agent composition: weighing the components such as liquid epoxy resin, curing agent, accelerator and the like according to a proportion, stirring the components by using a high-speed dispersing machine until the components are uniform in visual state, and further grinding the components by using a three-roller grinder to fully mix the components;
3) Preparation of the reactive thickener composition: weighing liquid epoxy resin and reactive thickener in proportion, and stirring uniformly at 30-50 ℃ under vacuum to obtain the reactive thickener;
4) Preparation of a reactive flow-controllable zero-glue-absorption epoxy resin system: rapidly adding the curing agent composition and the reactive thickener into a double-planetary stirring kettle filled with the epoxy resin composition at one time, controlling the temperature of materials in the kettle to be 50-70 ℃, stirring for 10-60 min, and stirring at a speed of 3-2000 RPM, thereby obtaining the epoxy resin matrix;
5) Preparation of a resin adhesive film: slowly pouring the freshly prepared epoxy resin matrix into a pair roller of a gumming machine while the epoxy resin matrix is hot, controlling the temperature of the pair roller of the gumming machine to be 50-70 ℃, adjusting the gap between the pair roller to uniformly coat the epoxy resin matrix on release paper, rapidly cooling, covering a PE film, and rolling to obtain a resin adhesive film;
6) Preparation of the prepreg: fully attaching the resin adhesive film/high-performance fiber or fabric/resin adhesive film thereof according to a sandwich structure, hot-pressing by a pair roller with an impregnating machine to enable the resin adhesive film to be melted and permeate into fiber tows in the vertical thickness direction, cooling again to cover the PE film, and winding to obtain the reactive flow controllable zero-glue-absorption epoxy resin-based prepreg.
The viscosity of the reactive flow controllable zero-glue-absorption epoxy resin system is not higher than 100000cps at 70 ℃, and the controllable chemical reaction of the reactive thickener can be triggered at 80-90 ℃ to prevent or slow down the reduction of the viscosity of the epoxy resin system, so that the minimum viscosity of the epoxy resin system is kept between 2000-4000 cps all the time at high temperature.
The toughening agent is one or more of polyurethane modified epoxy, rubber modified epoxy, ultra-high molecular weight epoxy, core-shell epoxy and thermoplastic resin micropowder, and the solid epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, phenolic epoxy resin and polyfunctional epoxy resin.
The curing agent composition is one or the combination of dicyandiamide and organic urea accelerator micropowder combination, 4' diaminophenylsulfone and boron trifluoride ethylamine micropowder combination, and is a premix of the curing agent composition and liquid bisphenol A type epoxy resin.
The reactive thickener composition is one or more of imidazole compounds, alicyclic amine compounds, aliphatic amine compounds, polyether amine compounds, aromatic amine compounds and polyamide compounds, and is combined with liquid epoxy, and the reactive thickener composition and the epoxy resin composition can slowly react at low temperature or be heated to 80-90 ℃ to quickly react, and the corresponding consumable epoxy group proportion is 0.1-10% of the total epoxy resin.
The high-performance fiber is one or the combination of more than two of carbon fiber, glass fiber, quartz fiber, basalt fiber, aramid fiber, ultra-high molecular weight polyethylene fiber and PBO fiber.
The ratio of the liquid epoxy resin to the solid epoxy resin in the step 1) is 1 to 1.5:1 to 2. The total mass of the epoxy resin used in the steps 1), 2) and 3) is 50 to 90 parts (including liquid epoxy resin and solid epoxy resin) which are consistent with the total mass proportion.
The invention and the realization method of the reactive flow controllable zero-glue-absorption epoxy resin ensure that the epoxy resin matrix has higher minimum melt viscosity in the whole curing process, meets the process requirement of 'initial pressurization' of an autoclave, ensures that the resin matrix has better manufacturability when the prepreg is prepared, is suitable for low-temperature glue coating and impregnation, has better operability when the prepreg is used for preparing medium-low temperature curing prepreg and prepreg with large thickness, and can ensure that the prepreg resin matrix and fiber have better wettability.
The principle of reactive flow-controllable zero-suction glue is that the viscosity of a resin matrix is regulated and controlled by adding a certain amount of reactive thickener, so that the content of a high molecular weight toughening agent can be obviously reduced, the resin matrix is ensured to have proper viscosity when the prepreg is prepared, the coating and impregnation are convenient, the prepreg is good in self-viscosity and flexibility, the resin system is ensured to have high viscosity along with the rising of temperature when the prepreg is molded, the reactive toughening agent is triggered to react quickly after the temperature reaches a certain temperature, the further reduction of the viscosity of the resin system is prevented, and the process requirement of zero-suction glue of the composite material is realized. The specific characteristics are that the viscosity is lower at 60-70 ℃, the viscosity is not higher than 100000cps, the preparation method is suitable for low-temperature coating and impregnation, the prepreg has better manufacturability in preparation and better operability in use, and the preparation method is suitable for low-temperature curing prepreg and large-thickness prepreg; when the temperature reaches 80-90 ℃, the reactive thickener can be triggered to perform quick chemical reaction so as to improve the viscosity of the resin matrix, prevent the viscosity of the resin system from further reducing along with the temperature rise, and enable the minimum viscosity of the resin system to be always kept above 2000-4000 cps during molding; meanwhile, the fluidity of the resin system can be designed at will by adjusting the proportion of the reactive thickener and the high molecular weight toughening agent, so that the preparation of the reactive flow-controllable zero-glue-absorption epoxy resin matrix is realized.

Claims (7)

1. A reactive flow controllable zero-glue-absorption epoxy resin-based prepreg is characterized in that:
comprises epoxy resin, a high molecular weight toughening agent, a reactive thickener, a curing agent and an accelerator, wherein the mass ratio of the components is 50-90: 1 to 10:0.1 to 5: 2-10: 1-5, firstly preparing a reactive type flow controllable zero-suction adhesive epoxy resin system, preparing the reactive type flow controllable zero-suction adhesive prepreg through a two-step dry process of adhesive coating and impregnation,
the preparation method comprises the following steps:
1) Preparation of an epoxy resin composition: weighing liquid epoxy resin, solid epoxy resin, high molecular weight toughening agent and other components in proportion, adding the components into a double-planetary stirring kettle with a wall scraping effect, stirring the components for 60 to 240 minutes at the temperature of 80 to 200 ℃ to fully mix the components, and then reducing the temperature of materials in the kettle to 50 to 70 ℃ to control Wen Daiyong;
2) Preparation of the curing agent composition: weighing the components such as liquid epoxy resin, curing agent, accelerator and the like according to a proportion, stirring the components by using a high-speed dispersing machine until the components are uniform in visual state, and further grinding the components by using a three-roller grinder to fully mix the components;
3) Preparation of the reactive thickener composition: weighing liquid epoxy resin and reactive thickener in proportion, and stirring uniformly at 30-50 ℃ under vacuum to obtain the reactive thickener;
4) Preparation of a reactive flow-controllable zero-glue-absorption epoxy resin system: rapidly adding the curing agent composition and the reactive thickener into a double-planetary stirring kettle filled with the epoxy resin composition at one time, controlling the temperature of materials in the kettle to be 50-70 ℃, stirring for 10-60 min, and stirring at a speed of 3-2000 RPM, thereby obtaining the epoxy resin matrix;
5) Preparation of a resin adhesive film: slowly pouring the freshly prepared epoxy resin matrix into a pair roller of a gumming machine while the epoxy resin matrix is hot, controlling the temperature of the pair roller of the gumming machine to be 50-70 ℃, adjusting the gap between the pair roller to uniformly coat the epoxy resin matrix on release paper, rapidly cooling, covering a PE film, and rolling to obtain a resin adhesive film;
6) Preparation of the prepreg: fully attaching the resin adhesive film/high-performance fiber or fabric/resin adhesive film thereof according to a sandwich structure, hot-pressing by a pair roller with an impregnating machine to enable the resin adhesive film to be melted and permeate into fiber tows in the vertical thickness direction, cooling again to cover the PE film, and winding to obtain the reactive flow controllable zero-glue-absorption epoxy resin-based prepreg.
2. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the viscosity of the reactive flow controllable zero-glue-absorption epoxy resin system is not higher than 100000cps at 70 ℃, and the controllable chemical reaction of the reactive thickener can be triggered at 80-90 ℃ to prevent or slow down the reduction of the viscosity of the epoxy resin system, so that the minimum viscosity of the epoxy resin system is kept between 2000-4000 cps all the time at high temperature.
3. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the toughening agent is one or the combination of more than two of polyurethane modified epoxy, rubber modified epoxy, ultra-high molecular weight epoxy, core-shell epoxy and thermoplastic resin micropowder.
4. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the liquid epoxy resin or the solid epoxy resin is one or a combination of a plurality of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, phenolic epoxy resin and polyfunctional epoxy resin.
5. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the curing agent composition is one or the combination of dicyandiamide and organic urea accelerator micropowder combination, 4' diaminophenylsulfone and boron trifluoride ethylamine micropowder combination, and is a premix of the curing agent composition and liquid bisphenol A type epoxy resin.
6. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the reactive thickener composition is one or more of imidazole compounds, alicyclic amine compounds, aliphatic amine compounds, polyether amine compounds, aromatic amine compounds and polyamide compounds, and is combined with liquid epoxy resin, and the reactive thickener composition and the epoxy resin composition can slowly react at low temperature or be heated to 80-90 ℃ to quickly react, and the proportion of corresponding consumable epoxy groups is 0.1-10% of the total epoxy resin.
7. The reactive flow-controllable zero-suction epoxy resin-based prepreg of claim 1, wherein: the high-performance fiber is one or the combination of more than two of carbon fiber, glass fiber, quartz fiber, basalt fiber, aramid fiber, ultra-high molecular weight polyethylene fiber and PBO fiber.
CN202311431982.5A 2023-10-31 2023-10-31 Reactive flow controllable zero-glue-absorption epoxy resin-based prepreg Pending CN117487312A (en)

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Inventor after: Shang Wulin

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Inventor after: Gao Changqing

Inventor after: Yang Wei

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