CN115678275A - Bismaleimide resin for autoclave zero-suction-rubber molding prepreg and preparation method thereof - Google Patents

Bismaleimide resin for autoclave zero-suction-rubber molding prepreg and preparation method thereof Download PDF

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Publication number
CN115678275A
CN115678275A CN202211398679.5A CN202211398679A CN115678275A CN 115678275 A CN115678275 A CN 115678275A CN 202211398679 A CN202211398679 A CN 202211398679A CN 115678275 A CN115678275 A CN 115678275A
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Prior art keywords
bismaleimide resin
bismaleimide
resin
autoclave
component
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CN202211398679.5A
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Inventor
董大为
胡静航
桂起林
郝杰
欧秋仁
张铁夫
唐中华
赵亮
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Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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Priority to CN202211398679.5A priority Critical patent/CN115678275A/en
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Abstract

The invention provides bismaleimide resin for autoclave zero-absorption molding prepreg and a preparation method thereof. The resin is prepared from a bismaleimide resin monomer component, a modifier component, a cyanate ester component and a toughening agent component by a slurry method, wherein the bismaleimide resin monomer component comprises 30-50 parts by mass, 10-25 parts by mass, 30-60 parts by mass and 15-30 parts by mass, the bismaleimide resin monomer component comprises at least one of a diphenylmethane diamine type bismaleimide monomer, a m-phenylenediamine type bismaleimide monomer or an aliphatic bismaleimide monomer, the modifier component comprises at least one of diallyl bisphenol A, diallyl bisphenol A ether or diallyl bisphenol S, the cyanate ester component comprises at least one of bisphenol A cyanate ester, bisphenol F cyanate ester or phenolic cyanate ester, and the toughening agent component comprises thermoplastic polyimide micron-sized particles. The prepreg prepared by the bismaleimide resin has good room-temperature spreadability and long storage life, can realize the control modes of can feeding pressurization and zero-glue-absorption process in the autoclave forming process, and greatly improves the product forming quality.

Description

Bismaleimide resin for autoclave zero-suction-rubber molding prepreg and preparation method thereof
Technical Field
The invention relates to bismaleimide resin for autoclave zero-absorption molding prepreg and a preparation method thereof, belonging to the field of preparation of raw materials in the field of composite materials.
Background
The bismaleimide resin is a highly crosslinked polymer with a three-dimensional network structure, and the network structure endows the bismaleimide resin with excellent characteristics of high temperature resistance, radiation resistance, humidity resistance, good mechanical property, dimensional stability and the like, so the bismaleimide resin is widely applied to main sections of aviation and aerospace and composite material structural members.
The autoclave molding process is the most common molding method for aerospace high-performance resin-based composite material structural members, and is used for manufacturing resin-based composite material structural members with complex structures and large overall sizes. When a traditional bismaleimide resin system adopts an autoclave molding process to prepare a resin matrix composite material, the heating rate, the heat preservation step, the pressurization point and the glue absorption process in the molding process need to be determined according to the rheological property of resin. The setting of the pressure point and the glue absorption process in the composite material forming process needs to be changed according to the size and the thickness of a composite material part and the structural form of a mould, so that the dependence on process experience is large, and the quality fluctuation of the composite material part is often large. The pressurizing point is an important parameter of the autoclave forming process, and the determination of the pressurizing point directly influences the performance of the composite material. If the pressing time is too late (after the gel point of the resin matrix), more voids and even large-area delamination of the composite material can be caused, and the resin matrix can be unevenly distributed in the composite material; for the resin matrix with low viscosity, if the pressing time is too early, the resin matrix can be greatly lost, and various performances of the composite material can be seriously influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a bismaleimide resin system capable of realizing a control mode of tank inlet pressurization and zero glue absorption process in an autoclave molding process engineering, and solves the problems of large quality fluctuation and low molding efficiency of composite material workpieces caused by pressurization point control and the glue absorption process.
The purpose of the invention is mainly realized by the following technical scheme:
the bismaleimide resin for the autoclave zero-suction glue molding prepreg comprises the following components in parts by mass:
bismaleimide resin monomer component: 30-50 parts;
the modifier comprises the following components: 10-25 parts;
cyanate ester component: 30-60 parts;
the toughening agent comprises the following components: 15-30 parts;
the bismaleimide resin is prepared from the four components by a slurry method; when the prepreg of the bismaleimide resin is formed by an autoclave, the monomer component and the toughening agent component of the bismaleimide resin exert the function of regulating and controlling the viscosity of the resin in a powder form at a low temperature section, and the toughening agent component is gradually dissolved in the modifier component or the cyanate ester component at a high temperature section to exert the function of regulating and controlling the viscosity of the resin.
Preferably, the bismaleimide resin monomer component is at least one of a diphenylmethane diamine type bismaleimide monomer, a m-phenylenediamine type bismaleimide monomer or an aliphatic bismaleimide monomer.
Preferably, the modifier component is at least one of diallyl bisphenol A, diallyl bisphenol A ether or diallyl bisphenol S.
Preferably, the cyanate ester component is at least one of bisphenol a cyanate ester, bisphenol F cyanate ester or phenolic cyanate ester.
Preferably, the toughening agent component is thermoplastic polyimide micron-sized particles with an average particle size of 5-30um.
A preparation method of bismaleimide resin for autoclave zero-absorption molding prepreg is prepared by a slurry method and comprises the following steps:
the method comprises the following steps: adding the bismaleimide resin monomer component into the modifier component, and grinding into paste;
step two: adding the toughening agent component into the cyanate ester component, and uniformly stirring;
step three: and (3) mixing the components obtained in the first step and the second step, and uniformly dispersing to obtain the bismaleimide resin with good room-temperature spreadability for the autoclave zero-suction adhesive molding prepreg.
Preferably, step one is ground to the paste using a three-roll grinder.
A preparation method of a bismaleimide resin-based composite material comprises the following steps:
preparing the bismaleimide resin prepared by the invention into a hot-melt resin adhesive film, and then compounding the hot-melt resin adhesive film with fibers to obtain a prepreg;
and curing the prepreg by adopting an autoclave molding process to obtain the bismaleimide resin based composite material.
The bismaleimide resin-based composite material prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bismaleimide resin can realize tank feeding pressurization and a zero-glue-suction process, solves the problems of large quality fluctuation and low molding efficiency of composite material workpieces caused by pressurization point control and a glue-suction process, and greatly improves the product molding quality. Because the resin is prepared by a slurry method, the bismaleimide resin monomer and the toughening agent play a role in regulating and controlling the viscosity of the resin in a powder form at a low temperature section, and the no-flow adhesive is ensured, and the toughening agent is gradually dissolved in the modifier or cyanate at a high temperature section to play a role in regulating and controlling the viscosity, so that the no-flow adhesive is ensured. The bismaleimide resin system can realize the control modes of tank feeding pressurization and zero glue absorption process in the autoclave forming process engineering, wherein the tank feeding pressurization refers to that after the bismaleimide prepreg is placed into an autoclave, the pressure required by prepreg curing can be immediately filled for heating and curing (namely, the temperature is raised under pressure, so that the resin can flow out under pressure because the resin viscosity is reduced due to temperature rise is avoided), the temperature does not need to be raised firstly, the resin is reacted for a period of time, and then pressurization is carried out after the resin viscosity is increased. The control mode of the zero glue absorption process is that resin does not flow out along with the rise of temperature and the increase of pressure in the process of curing the resin prepreg by the autoclave, namely glue does not flow in the curing process.
(2) Because the resin is prepared by a slurry method, the bismaleimide resin monomer and the toughening agent are not dissolved in the modifier or cyanate in advance, and the system has better viscosity and room temperature spreadability; on the other hand, different from that the bismaleimide resin monomer and the toughening agent are pre-dissolved in each component of the modifier system to be dispersed in a molecular level, and each component of the system exists in a form of micro powder particles, so that the reaction rate of the bismaleimide monomer component, the modifier component and the cyanate component at room temperature is remarkably reduced, and the storage life is longer.
(3) The cyanate component is introduced into the system, the cyanate is a thermosetting resin with excellent humidity resistance and dielectric property, the glass transition temperature of the cyanate, particularly phenolic cyanate, can reach more than 380 ℃, and is far higher than that of the bismaleimide resin, and the bismaleimide resin is modified by the cyanate, so that the dielectric property and the heat resistance of the bismaleimide resin can be improved simultaneously on the premise of not reducing the toughness of the bismaleimide resin.
Detailed Description
The present invention will be described in further detail below with reference to specific examples.
Example 1
Adding 40g of diphenylmethane diamine bismaleimide monomer into 20g of diallyl bisphenol A, primarily stirring uniformly, grinding into paste by using a three-roll grinder, adding 20g of thermoplastic polyimide microparticles into 50g of phenolic cyanate ester, uniformly stirring, and finally mixing and dispersing the two components uniformly to obtain bismaleimide resin for the autoclave zero-suction-rubber molding prepreg with good room-temperature spreadability.
The bismaleimide resin prepared by the invention is prepared into a hot melt resin adhesive film, and then is compounded with CCF800S carbon fiber to prepare the hot melt prepreg. The prepreg is cut and laid to be a board with the size of 320mm multiplied by 2mm, an autoclave molding process is adopted for curing, and two pressurizing modes of pressurizing at room temperature (25 ℃) and pressurizing after heat preservation for 1 hour at 130 ℃ are selected. The glue yield of the formed plate is counted, and shown in table 1, the glue yield of the plate under the two pressing points is changed very little, which shows that the resin pressing window is very wide, the glue yield is controllable, and the manufacturability is good.
TABLE 1 amount of gum formed from flat plate
Pressure point 25℃ Keeping the temperature at 130 ℃ for 1h
Amount of gum discharged/g 4.6 3.8
Example 2
Adding 30g of m-phenylenediamine bismaleimide monomer into 25g of diallyl bisphenol A ether, stirring uniformly primarily, grinding into paste by using a three-roll grinder, adding 30g of thermoplastic polyimide microparticles into 30g of bisphenol F cyanate, stirring uniformly, and finally mixing and dispersing uniformly the two components to obtain the bismaleimide resin for the autoclave zero-absorption molding prepreg with good room temperature spreadability.
The bismaleimide resin prepared by the invention is prepared into a hot melt resin adhesive film, and then is compounded with CCF800S carbon fiber to prepare the hot melt prepreg. The prepreg is cut and laid to be a board with the thickness of 320mm multiplied by 2mm, an autoclave molding process is adopted for curing, and two pressurization modes of pressurization at room temperature (25 ℃) and pressurization after heat preservation at 130 ℃ for 1 hour are selected. The glue yield of the formed plate is counted, and shown in table 2, the glue yield of the plate under the two pressing points is changed very little, which shows that the resin pressing window is very wide, the glue yield is controllable, and the manufacturability is good.
TABLE 2 amount of glue discharged from the plate forming
Pressure point 25℃ Keeping the temperature at 130 ℃ for 1h
Amount of gum discharged/g 4.3 3.7
Example 3
Adding 50g of aliphatic bismaleimide monomer into 20g of diallyl bisphenol S, primarily stirring uniformly, grinding into paste by using a three-roll grinder, adding 15g of thermoplastic polyimide microparticles into 60g of bisphenol A cyanate, uniformly stirring, mixing the two components, and uniformly dispersing to obtain the bismaleimide resin for the autoclave zero-absorption molding prepreg with good room temperature spreadability.
The bismaleimide resin prepared by the invention is prepared into a hot melt resin adhesive film, and then is compounded with CCF800S carbon fiber to prepare the hot melt prepreg. The prepreg is cut and laid to be a board with the thickness of 320mm multiplied by 2mm, an autoclave molding process is adopted for curing, and two pressurization modes of pressurization at room temperature (25 ℃) and pressurization after heat preservation at 130 ℃ for 1 hour are selected. The glue yield of the formed plate is counted, and shown in table 3, the glue yield of the plate under the two pressing points is changed very little, which shows that the resin pressing window is very wide, the glue yield is controllable, and the manufacturability is good.
TABLE 3 Flat plate Molding run-out
Pressure point 25℃ Keeping the temperature at 130 ℃ for 1h
Amount of gum discharged/g 4.9 4.1
Example 4
Adding 30g of aliphatic bismaleimide monomer into 10g of diallyl bisphenol A ether, primarily stirring uniformly, grinding into paste by using a three-roll grinder, adding 15g of thermoplastic polyimide microparticles into 40g of phenolic cyanate, uniformly stirring, mixing the two components, and uniformly dispersing to obtain the bismaleimide resin for the autoclave zero-absorption molding prepreg with good room temperature spreadability.
The bismaleimide resin prepared by the invention is prepared into a hot melt resin adhesive film, and then is compounded with CCF800S carbon fiber to prepare the hot melt prepreg. The prepreg is cut and laid to be a board with the thickness of 320mm multiplied by 2mm, an autoclave molding process is adopted for curing, and two pressurization modes of pressurization at room temperature (25 ℃) and pressurization after heat preservation at 130 ℃ for 1 hour are selected. The glue yield of the formed plate is counted, and shown in table 4, the glue yield of the plate under the two pressing points is changed very little, which shows that the resin pressing window is very wide, the glue yield is controllable, and the manufacturability is good.
TABLE 4 Flat plate Molding run-out
Applying pressureDot 25℃ Keeping the temperature at 130 ℃ for 1h
Amount of gum discharged/g 4.7 3.9
Comparative example 1
Adding 40g of diphenylmethane diamine type bismaleimide monomer into 20g of diallyl bisphenol A, heating to 130 ℃, keeping the temperature for 30min to enable the system to become uniform tan liquid, adding 20g of thermoplastic polyimide microparticles into 50g of phenolic cyanate, uniformly stirring, and finally mixing and uniformly dispersing the two components to obtain the modified bismaleimide resin.
The bismaleimide resin prepared by the invention is prepared into a hot melt resin adhesive film, and then is compounded with CCF800S carbon fiber to prepare the hot melt prepreg. The prepreg was cut and laid to a sheet material of 320mm × 320mm × 2mm, followed by curing, and two pressing methods of pressing at room temperature (25 ℃) and holding at 130 ℃ for 1 hour and then pressing were selected. The glue yield statistics of the molded sheet materials are shown in table 5, and the glue yield of the sheet materials under two pressing points is greatly changed, which indicates that the resin needs to accurately select the pressing points.
TABLE 5 Flat plate Molding run-out
Pressure point 25℃ Keeping the temperature at 130 ℃ for 1h
Amount of gum discharged/g 20.6 3.8
The particular embodiments of the present invention disclosed above are illustrative only and are not intended to be limiting, since various alternatives, modifications, and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The invention should not be limited to the disclosure of the embodiments in the present specification, but the scope of the invention is defined by the appended claims.

Claims (10)

1. The utility model provides an autoclave is zero inhales gluey shaping bimaleimide for preimpregnation material which characterized in that: the paint comprises the following components in parts by mass:
bismaleimide resin monomer component: 30-50 parts;
the modifier comprises the following components: 10-25 parts;
cyanate ester component: 30-60 parts;
the toughening agent comprises the following components: 15-30 parts;
the bismaleimide resin is prepared from the four components by a slurry method; when the prepreg of the bismaleimide resin is formed by an autoclave, the monomer component and the toughening agent component of the bismaleimide resin exert the function of regulating and controlling the viscosity of the resin in a powder form at a low temperature section, and the toughening agent component is gradually dissolved in the modifier component or the cyanate ester component at a high temperature section to exert the function of regulating and controlling the viscosity of the resin.
2. The bismaleimide resin for the autoclave zero-suction-glue molding prepreg according to claim 1, which is characterized in that: the bismaleimide resin monomer component is at least one of diphenylmethane diamine type bismaleimide monomer, m-phenylenediamine type bismaleimide monomer or aliphatic bismaleimide monomer.
3. The bismaleimide resin for the autoclave zero-suction-glue molding prepreg according to claim 1, which is characterized in that: the modifier component is at least one of diallyl bisphenol A, diallyl bisphenol A ether or diallyl bisphenol S.
4. The bismaleimide resin for the autoclave zero-suction-glue molding prepreg according to claim 1, which is characterized in that: the cyanate component is at least one of bisphenol A cyanate, bisphenol F cyanate or phenolic cyanate.
5. The bismaleimide resin for the autoclave zero-suction-glue molding prepreg according to claim 1, which is characterized in that: the toughening agent component is thermoplastic polyimide micron-sized particles.
6. The bismaleimide resin for the autoclave zero-suction-glue molding prepreg according to claim 5, wherein: the thermoplastic polyimide micron-sized particles have an average particle size of 5-30um.
7. The method for preparing bismaleimide resin for autoclave zero-absorption molding prepreg according to claim 1, wherein the bismaleimide resin comprises: the method comprises the following steps:
the method comprises the following steps: adding the bismaleimide resin monomer component into the modifier component, and grinding into paste;
step two: adding the toughening agent component into the cyanate ester component, and uniformly stirring;
step three: and (3) mixing the components obtained in the first step and the second step, and uniformly dispersing to obtain the bismaleimide resin with good room-temperature spreadability for the autoclave zero-suction adhesive molding prepreg.
8. The preparation method of bismaleimide resin for autoclave zero-suction-rubber molding prepreg according to claim 7, wherein the bismaleimide resin comprises the following components: and step one, grinding the paste by using a three-roll grinder.
9. The preparation method of the bismaleimide resin-based composite material is characterized by comprising the following steps:
preparing the bismaleimide resin as claimed in any one of claims 1 to 6 into a hot-melt resin adhesive film, and then compounding the hot-melt resin adhesive film with fibers to obtain a prepreg;
and curing the prepreg by adopting an autoclave molding process to obtain the bismaleimide resin based composite material.
10. A bismaleimide resin based composite prepared according to the method of claim 9.
CN202211398679.5A 2022-11-09 2022-11-09 Bismaleimide resin for autoclave zero-suction-rubber molding prepreg and preparation method thereof Pending CN115678275A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008011765A1 (en) * 2006-07-19 2008-01-31 Beijing Institute of Aeronautical Materials, AVIC I A toughened composite material laminate and a process of preparation thereof
CN106832925A (en) * 2017-01-20 2017-06-13 航天材料及工艺研究所 It is a kind of to flow controllable bismaleimide resin system, preparation method and sweat connecting material
CN107459820A (en) * 2017-09-01 2017-12-12 江苏欧亚铂瑞碳复合材料有限公司 A kind of preparation method of micro-and nano-particles collaboration interlayer toughened span/carbon fibre composite
CN107955372A (en) * 2017-12-14 2018-04-24 威海光威复合材料股份有限公司 The preparation method of bimaleimide resin cyanate ester resin composite material
CN111320871A (en) * 2020-04-13 2020-06-23 上海蒂姆新材料科技有限公司 Bismaleimide resin prepreg composite material and preparation method thereof
CN113580711A (en) * 2021-06-15 2021-11-02 航天特种材料及工艺技术研究所 Ablation-resistant light bearing cover plate and preparation method thereof
CN113911401A (en) * 2021-09-30 2022-01-11 北京元蛋复合材料有限公司 Light/high-temperature-resistant integrated composite material satellite lens hood and preparation method thereof
CN114349994A (en) * 2022-01-10 2022-04-15 长春长光宇航复合材料有限公司 Modified bismaleimide carbon fiber prepreg, composite material and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008011765A1 (en) * 2006-07-19 2008-01-31 Beijing Institute of Aeronautical Materials, AVIC I A toughened composite material laminate and a process of preparation thereof
CN106832925A (en) * 2017-01-20 2017-06-13 航天材料及工艺研究所 It is a kind of to flow controllable bismaleimide resin system, preparation method and sweat connecting material
CN107459820A (en) * 2017-09-01 2017-12-12 江苏欧亚铂瑞碳复合材料有限公司 A kind of preparation method of micro-and nano-particles collaboration interlayer toughened span/carbon fibre composite
CN107955372A (en) * 2017-12-14 2018-04-24 威海光威复合材料股份有限公司 The preparation method of bimaleimide resin cyanate ester resin composite material
CN111320871A (en) * 2020-04-13 2020-06-23 上海蒂姆新材料科技有限公司 Bismaleimide resin prepreg composite material and preparation method thereof
CN113580711A (en) * 2021-06-15 2021-11-02 航天特种材料及工艺技术研究所 Ablation-resistant light bearing cover plate and preparation method thereof
CN113911401A (en) * 2021-09-30 2022-01-11 北京元蛋复合材料有限公司 Light/high-temperature-resistant integrated composite material satellite lens hood and preparation method thereof
CN114349994A (en) * 2022-01-10 2022-04-15 长春长光宇航复合材料有限公司 Modified bismaleimide carbon fiber prepreg, composite material and preparation method thereof

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