CN114478971B - Preparation methods of nitrile functional benzoxazine resin, polymer and composite material thereof - Google Patents
Preparation methods of nitrile functional benzoxazine resin, polymer and composite material thereof Download PDFInfo
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Abstract
The invention provides a preparation method of novel nitrile functional benzoxazine resin, a polymer and a composite material thereof, which are used for modifying a matrix of the benzoxazine-containing nitrile resin and improving the process in the production of a prepolymer, can solve the problems of unmatched processing performance and product performance of the existing benzoxazine-containing nitrile resin system, ensures the high efficiency of the preparation of the nitrile resin composite material, and has a certain promotion effect on improving the mechanical property and the thermal stability of the nitrile resin.
Description
Technical Field
The invention relates to the technical field of high polymer synthesis processes, in particular to a preparation method of nitrile functional benzoxazine resin, and a polymer and composite material thereof.
Background
The nitrile resin polymer is an important high-performance thermosetting polymer, and nitrile groups in a molecular structure can be subjected to addition polymerization to form a large number of aromatic heterocyclic structures with outstanding thermal stability under the condition of thermal initiation polymerization, so that the resin polymer has excellent thermal stability, mechanical property, flame retardance and ablation resistance. Meanwhile, the thermal polymerization process is mainly addition polymerization, no small molecules are released in the forming process, and the processing process is safe and environment-friendly. The outstanding advantages lead the nitrile resin polymer to have wide application in the fields of mechanical ships, aerospace and national defense war industry.
Along with the continuous reinforcement of the energy-saving and emission-reducing requirements, the processing application of the high-energy-consumption resin matrix composite is greatly limited. For the traditional nitrile resin, the polymerization reaction is slow and the curing processing temperature is required to be high due to the reaction inertia of the nitrile group in the molecular structure of the bisphthalonitrile, and the curing can be realized under the high-temperature condition without the action of a catalyst or a curing agent, so that the wide application of the nitrile resin is greatly limited, and the application cost is greatly increased. Therefore, in order to improve the curing process, curing agents such as organic amines, organic acids and amine salts thereof, transition metals and salts thereof are used to reduce the curing temperature and curing time, and to improve the polymerization properties thereof, as a means of modifying nitrile resins. Meanwhile, the molecular structure of the nitrile resin can be designed and constructed, and a novel functional group or a branched chain can be introduced to achieve the purposes of nitrile functionalization and autocatalysis polymerization.
The conventional benzoxazine nitrile group-containing resin mainly has the following problems: 1) The polymerization reaction rate of the benzoxazine-containing nitrile resin system is slow, so that the production efficiency of the benzoxazine-containing nitrile resin composite material is affected, the production cost is increased, and the expansion of the application field of the benzoxazine-containing nitrile resin composite material is limited; 2) The curing agent or catalyst containing the benzoxazine nitrile resin has the problems of dispersibility, volatilization and decomposition, so that the polymerization reaction can not be thoroughly carried out, a polymer system with high polymerization degree is difficult to prepare, and the application performance of the resin and the composite material thereof is finally affected; 3) The main structure of the benzoxazine nitrile-based resin is not diversified enough, and the release of the product performance is essentially limited. It is desirable to eliminate these drawbacks and to improve the synthetic process of benzoxazine-containing nitrile-based resins.
Patent CN202110541508.2 discloses a benzoxazine nitrile-based resin curing agent, a preparation method and application thereof. The invention combines the synergistic effect of the novel curing agent and the benzoxazine functional group, releases active hydrogen ions through amino groups, and rapidly promotes the oxazine ring to generate ring-opening reaction to form an active Mannich structure, thereby accelerating the rate of ring-forming polymerization of nitrile groups and realizing the efficient curing and forming of the nitrile resin. However, the mechanical properties of the benzoxazine-containing nitrile resin composite material prepared by curing the curing agent are low, and the outstanding advantages of the nitrile resin cannot be exerted.
In order to further improve the polymerization efficiency of the nitrile resin polymer and the service performance of the composite material, the invention provides a preparation method of novel nitrile functional benzoxazine and a method for copolymerizing the novel nitrile functional benzoxazine with the benzoxazine-containing nitrile resin to form the polymer and obtain the fiber reinforced composite material, so that the obtained resin has more ideal curing rate and excellent mechanical property, and simultaneously has excellent thermal stability.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a novel nitrile functional benzoxazine resin, a polymer and a composite material thereof, which are used for modifying a benzoxazine-containing nitrile resin matrix and improving the process in the production of a prepolymer, can solve the problems of unmatched processability and product performance of the existing benzoxazine-containing nitrile resin system, ensures the high efficiency of the preparation of the nitrile resin composite material, and has a certain promotion effect on improving the mechanical property and the thermal stability of the nitrile resin.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of nitrile group functionalized benzoxazine resin comprises the following steps:
(1) Sequentially adding p-hydroxybenzonitrile and paraformaldehyde into a mixed solvent of dimethylbenzene and absolute ethyl alcohol, heating to 40 ℃, then adding 4,4' -diaminodiphenylmethane, obtaining a yellow reaction solution after the addition, continuously heating to 70-85 ℃, reacting for 3-6 hours, heating to 90-110 ℃ and removing the solvent to obtain a nitrile functional benzoxazine-containing resin (MD-cn) monomer;
the synthetic route is as follows:
(2) Preparing a benzoxazine nitrile group-containing resin (BA-ph) monomer, wherein the BA-ph resin is prepared from 4-aminophenoxy phthalonitrile (4-APN), bisphenol A (BPA), paraformaldehyde, N-Dimethylformamide (DMF) and dimethylbenzene;
the synthetic route is as follows:
(3) Preparing a curing agent (BAB) for a benzoxazine nitrile-containing resin (BA-ph) monomer, wherein the synthetic raw materials of the BAB are 2, 6-dichlorobenzonitrile, p-aminophenol, anhydrous potassium carbonate, toluene and N-methylpyrrolidone (NMP);
the synthetic route is as follows:
(4) Mixing a nitrile functional benzoxazine-containing resin monomer with a benzoxazine-containing nitrile resin (BA-ph) monomer and a curing agent (BAB) for the benzoxazine-containing nitrile resin (BA-ph) monomer to obtain a mixture, dissolving the mixture in a solvent, and reacting for 1.5-2.5 h at 130-150 ℃ to obtain the nitrile functional benzoxazine-containing resin.
In the setting of the temperature, the reaction is carried out for 1.5 to 2.5 hours at the temperature of 130 to 150 ℃, the copolymerization is not controlled at the temperature, the gel is easy to appear, the copolymerization resin can not be obtained, the raw materials can not be fully copolymerized at the temperature, and the resin system for the subsequent polymer and the composite material can not be prepared. Longer than this time, the reaction efficiency is lowered, the resource waste is shorter than this time, and the system cannot be fully copolymerized.
Preferably, the molar ratio of 4,4' -diaminodiphenylmethane, paraformaldehyde and p-hydroxybenzonitrile in step (1) is 1:4.01 to 4.1:2.01 to 2.1; the volume ratio of the dimethylbenzene to the absolute ethyl alcohol is 1:0.5 to 0.8, the solid-liquid ratio of the reaction system is 1:0.5 to 0.8.
The beneficial effects brought by the optimization are as follows: the resin monomer with a preset structure cannot be obtained when the proportion of the three raw materials exceeds the proportion range; the proportion of the mixed solvent is higher than that, the solubility of the paraformaldehyde raw material in the solvent is poor, the efficiency of the synthesis reaction is affected, and the azeotropic point of the blend solvent system is lower than that, so that the temperature of the reaction system can not be flexibly regulated. The solid-liquid ratio of the reaction system is higher than the ratio, the raw materials cannot be fully dissolved in the solvent system, the synthesis reaction cannot be controlled to be carried out according to the preset ratio, and the concentration of the raw materials in the solvent system is too low below the ratio, so that the synthesis reaction efficiency is reduced.
Preferably, the mass ratio of the nitrile group functionalized benzoxazine-containing resin monomer to the benzoxazine-containing nitrile group-containing resin monomer in the step (2) is (0.05-0.2): 1, a step of; the molar ratio of the benzoxazine-containing nitrile resin monomer to the curing agent for the benzoxazine-containing nitrile resin monomer is 0.15:1;
above this ratio, polymerization rapidly occurs, gel is liable to occur, and the desired resin is not obtained, below this ratio, the copolymerization effect is not obvious, and an effectively copolymerized resin system is not obtained
The mass volume ratio of the mixture to the solvent is 1 (0.9-1.3);
above this ratio, the system concentration is too large, the reaction rapidly occurs, the control is difficult, and below this ratio, the reaction efficiency is low, and the copolymerization effect is poor.
The solvent is any one or two of DMF and NMP.
A method for preparing a nitrile functional benzoxazine resin polymer, which comprises the following steps:
1) Drying the nitrile functional benzoxazine resin prepared in the preparation method of the nitrile functional benzoxazine resin for 8-12 hours at the temperature of 80-100 ℃ to obtain nitrile functional benzoxazine resin-containing powder;
drying at 80-100 deg.c for 8-12 hr to lower the temperature for short period to eliminate solvent completely and to raise the efficiency and waste energy;
2) And (3) performing heat treatment on the nitrile functional benzoxazine-containing resin powder at 180-200 ℃ for 2-4 hours to obtain the nitrile functional benzoxazine-containing polymer.
The heat treatment is carried out for 2-4 hours at the temperature of 80-200 ℃, the temperature is lower than the temperature, the curing of the polymer is incomplete, the performance is poor, the temperature is higher than the temperature, the improvement effect of the polymer performance is not obvious, and the energy consumption is high.
A preparation method of a nitrile functional benzoxazine resin composite material comprises the following steps: the preparation method of the nitrile functional benzoxazine resin comprises the steps of impregnating glass fibers with the nitrile functional benzoxazine resin to obtain prepreg, and preparing the nitrile functional benzoxazine resin composite material by adopting a lamination hot-pressing method.
Preferably, the glue content of the prepreg cloth is 45%.
Preferably, the laminated hot pressing method is characterized in that: heat-treating at 80 deg.c for 30min, then at 155-185 deg.c for 30-60 min, and finally hot-pressing in a press at 200 deg.c and 20MPa for 2-4 hr.
Wherein, heat treatment is carried out for 30min at 80 ℃, partial solvent is removed, the self-adhesion of the prepreg is ensured, and the polymerization degree of the resin is not influenced;
heat treatment is carried out for 30-60 min at 155-185 ℃, the temperature is lower than the temperature, the solvent is not thoroughly removed, and internal air hole defects are caused in the compression molding process; above this temperature, the degree of crosslinking of the resin system increases, resulting in the prepreg losing its cohesiveness, delamination of the composite during pressing, and significant damage to the structural strength of the composite.
Compared with the prior art, the invention has the following beneficial effects:
1) The curing agent used in the system is a mononitrile compound with an aniline structure, so that the reaction rate of benzoxazine-containing nitrile resin can be improved, phase separation is not generated, and the curing agent has a good curing effect;
2) The active chain introduced in the benzoxazine-containing nitrile resin precursor is another benzoxazine-containing Shan Jingji resin with a simple structure and strong self-catalytic capability, so that the steric hindrance can be reduced in the polymerization process, the loop polymerization of nitrile groups is facilitated, a more compact space network structure is formed, and the preparation of a high-performance polymer is realized;
3) The introduced active chain can realize synergistic catalysis with the curing agent, so that the curing reaction of the system is further accelerated, and the curing performance is improved. In conclusion, the novel nitrile functional benzoxazine resin polymer provided by the invention has the advantages of high curing efficiency, strong functionality, simple preparation method, universality and easiness in popularization.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Example 1
Step (1) adding 59.7975g (0.5025 mol) of p-hydroxybenzonitrile and 30.075g (1.0025 mol) of paraformaldehyde into a mixed solvent (volume ratio of 1:0.5) of 46.5mL of xylene and 23.2mL of absolute ethyl alcohol (solid-liquid ratio of 1:0.5) in sequence, slowly heating to 40 ℃, starting to add 49.5g (0.25 mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) for a small number of times, obtaining a yellow reaction solution after the addition is finished, slowly heating to a temperature of about 85 ℃, reacting for 6 hours, and removing the solvent at a temperature of 90-110 ℃ to obtain the nitrile group functional benzoxazine-containing resin (MD-cn) monomer;
step (2) mixing 1.356g (0.0043 mol) BAB, 1.2908g (0.0022 mol) MD-cn resin monomer and 33.766g (0.0285 mol) BA-ph resin monomer in a three-necked flask, dissolving in 9mL DMF solvent, and reacting at 150 ℃ for 2.5h to obtain BA-ph/MD-cn/BAB resin glue solution;
step (3), treating the resin glue solution obtained in the step (2) at the temperature of 80 ℃ for 10 hours, and drying the flux to obtain nitrile group functionalized benzoxazine-containing resin powder;
step (4), placing the nitrile group functionalized benzoxazine-containing resin powder prepared in the step (3) into a high-temperature drying oven, and performing heat treatment at 180 ℃ for 4 hours to prepare a nitrile group functionalized benzoxazine-containing polymer;
and (5) impregnating the Glass Fiber (GF) with the nitrile group functionalized benzoxazine-containing resin obtained in the step (2) to obtain prepreg, and preparing the BA-ph/MD-cn/BAB/GF composite material by adopting a laminated hot pressing method. Wherein, the glue content of the prepreg cloth is 45%, and the specific conditions of lamination hot pressing are as follows: the heat treatment is carried out at 80 ℃ for 30min, then at 185 ℃ for 60min, and finally the hot pressing is carried out in a press at 200 ℃ and 20MPa for 4h.
The nitrile group functionalized benzoxazine-containing resin powder prepared by the steps has a gelation time (180 ℃) of 930s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has a thermal decomposition temperature of 404.5 ℃ and a carbon residue weight percentage of 66.81% at 800 ℃; the BA-ph/MD-cn/BAB/GF composite material prepared by the steps has the bending strength of 462.14MPa and the bending modulus of 24.35GPa.
Example 2
Step (1) adding 59.7975g (0.5025 mol) of p-hydroxybenzonitrile and 30.75g (1.025 mol) of paraformaldehyde into a mixed solvent (volume ratio of 1:0.6) of 52.5mL of xylene and 31.5mL of absolute ethyl alcohol in sequence (solid-liquid ratio of 1:0.6), slowly heating to 40 ℃, starting to add 49.5g (0.25 mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) for a small number of times, obtaining a yellow reaction solution after the addition is finished, slowly heating to a temperature of about 80 ℃, reacting for 5 hours, and removing the solvent at a temperature of 90-110 ℃ to obtain the nitrile group functional benzoxazine-containing resin (MD-cn) monomer;
step (2) mixing 1.2997g (0.0041 mol) of BAB, 2.464g (0.0042 mol) of MD-cn resin monomer and 32.231g (0.0272 mol) of BA-ph resin monomer in a three-necked flask, dissolving in 12.5mL of DMF solvent, and reacting at 150 ℃ for 2 hours to obtain BA-ph/MD-cn/BAB resin glue solution;
step (3), treating the resin glue solution obtained in the step (2) at the temperature of 80 ℃ for 11 hours, and drying the flux to obtain nitrile group functionalized benzoxazine-containing resin powder;
step (4), placing the nitrile group functionalized benzoxazine-containing resin powder prepared in the step (3) into a high-temperature drying oven, and performing heat treatment at the temperature of 190 ℃ for 3 hours to prepare a nitrile group functionalized benzoxazine-containing polymer;
and (5) impregnating the Glass Fiber (GF) with the nitrile group functionalized benzoxazine-containing resin obtained in the step (2) to obtain prepreg, and preparing the BA-ph/MD-cn/BAB/GF composite material by adopting a laminated hot pressing method. Wherein, the glue content of the prepreg cloth is 45%, and the specific conditions of lamination hot pressing are as follows: the heat treatment is carried out at 80 ℃ for 30min, then at 170 ℃ for 60min, and finally the hot pressing is carried out in a press at 200 ℃ and 20MPa for 3h.
The solid powder of the nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer prepared by the steps has the gelation time (180 ℃) of 520s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has a thermal decomposition temperature of 405.4 ℃ and a carbon residue weight percentage of 67.23% at 800 ℃; the BA-ph/MD-cn/BAB/GF composite material prepared by the steps has the bending strength of 479.41MPa and the bending modulus of 23.51GPa.
Example 3
Step (1) adding 62.475g (0.525 mol) of p-hydroxybenzonitrile and 30.75g (1.025 mol) of paraformaldehyde into 58.8mL of xylene and 41.1mL of absolute ethyl alcohol mixed solvent (volume ratio is 1:0.7) in sequence (solid-liquid ratio is 1:0.7), slowly heating to 40 ℃, adding 49.5g (0.25 mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) for a small number of times, obtaining yellow reaction solution after the addition is finished, slowly heating to about 75 ℃, reacting for 4 hours, and removing the solvent at 90-110 ℃ to obtain the nitrile group functional benzoxazine-containing resin (MD-cn) monomer;
step (2) mixing 1.260g (0.0040 mol) of BAB, 3.5357g (0.0060 mol) of MD-cn resin monomer and 30.830g (0.0265 mol) of BA-ph resin monomer in a three-necked flask, dissolving in 15.8mL of DMF solvent, and reacting at 140 ℃ for 2 hours to obtain BA-ph/MD-cn/BAB resin prepolymer glue solution;
step (3), treating the resin glue solution obtained in the step (2) for 12 hours at the temperature of 80 ℃, and drying the flux to obtain nitrile group functionalized benzoxazine-containing resin powder;
step (4), placing the nitrile group functionalized benzoxazine-containing resin powder prepared in the step (3) into a high-temperature drying oven, and performing heat treatment at 200 ℃ for 2 hours to prepare a nitrile group functionalized benzoxazine-containing polymer;
and (5) impregnating the Glass Fiber (GF) with the nitrile group functionalized benzoxazine-containing resin obtained in the step (2) to obtain prepreg, and preparing the BA-ph/MD-cn/BAB/GF composite material by adopting a laminated hot pressing method. Wherein, the glue content of the prepreg cloth is 45%, and the specific conditions of lamination hot pressing are as follows: the heat treatment is carried out at 80 ℃ for 30min, then at 185 ℃ for 30min, and finally the hot pressing is carried out in a press at 200 ℃ and 20MPa for 2h.
The solid powder of the nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer prepared by the steps has the gelation time (180 ℃) of 390s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has a thermal decomposition temperature of 404.7 ℃ and a carbon residue weight percentage of 67.51% at 800 ℃; the BA-ph/MD-cn/BAB/GF composite material prepared by the steps has the bending strength of 493.95MPa and the bending modulus of 26.12GPa.
Example 4
Step (1) adding 62.475g (0.525 mol) of p-hydroxybenzonitrile and 30.075g (1.0025 mol) of paraformaldehyde into 63.1mL of xylene and 50.5mL of absolute ethyl alcohol mixed solvent (volume ratio is 1:0.8) in sequence (solid-liquid ratio is 1:0.8), slowly heating to 40 ℃, adding 49.5g (0.25 mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) for a small number of times, obtaining yellow reaction solution after the addition is finished, slowly heating to about 70 ℃, reacting for 3 hours, and removing the solvent at 90-110 ℃ to obtain the nitrile group functional benzoxazine-containing resin (MD-cn) monomer;
step (2) mixing 1.2046g (0.0038 mol) of BAB, 4.518g (0.0077 mol) of MD-cn resin monomer and 29.544g (0.0253 mol) of BA-ph resin monomer in a three-necked flask, dissolving in 19.5mL of DMF solvent, and reacting at 130 ℃ for 1.5h to obtain BA-ph/MD-cn/BAB resin prepolymer glue solution;
step (3), treating the resin glue solution obtained in the step (2) for 12 hours at the temperature of 80 ℃, and drying the flux to obtain nitrile group functionalized benzoxazine-containing resin powder;
step (4), placing the nitrile group functionalized benzoxazine-containing resin powder prepared in the step (3) into a high-temperature drying oven, and performing heat treatment at 200 ℃ for 2 hours to prepare a nitrile group functionalized benzoxazine-containing polymer;
and (5) impregnating the Glass Fiber (GF) with the nitrile group functionalized benzoxazine-containing resin obtained in the step (2) to obtain prepreg, and preparing the BA-ph/MD-cn/BAB/GF composite material by adopting a laminated hot pressing method. Wherein, the glue content of the prepreg cloth is 45%, and the specific conditions of lamination hot pressing are as follows: the heat treatment is carried out at 80 ℃ for 30min, then at 155 ℃ for 60min, and finally the hot pressing is carried out in a press at 200 ℃ and 20MPa for 2h.
The solid powder of the nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer prepared by the steps has the gelation time (180 ℃) of 212s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has a thermal decomposition temperature of 405.5 ℃ and a carbon residue weight percentage of 66.25% at 800 ℃; the BA-ph/MD-cn/BAB/GF composite material prepared by the steps has the bending strength of 449.28MPa and the bending modulus of 20.16GPa.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. The preparation method of the nitrile group functionalized benzoxazine resin is characterized by comprising the following steps of:
(1) Sequentially adding p-hydroxybenzonitrile and paraformaldehyde into a mixed solvent of dimethylbenzene and absolute ethyl alcohol, heating to 40 ℃, then adding 4,4' -diaminodiphenylmethane, obtaining a yellow reaction solution after the addition, continuously heating to 70-85 ℃, reacting for 3-6 hours, heating to 90-110 ℃ and removing the solvent to obtain a nitrile functional benzoxazine-containing resin monomer;
(2) Mixing the nitrile functional benzoxazine-containing resin monomer obtained in the step (1) with the benzoxazine-containing nitrile resin monomer and a curing agent for the benzoxazine-containing nitrile resin monomer to obtain a mixture, dissolving the mixture in a solvent, and reacting for 1.5-2.5 h at 130-150 ℃ to obtain the nitrile functional benzoxazine-containing resin; the structures of the benzoxazine-containing nitrile resin monomer and the curing agent for the benzoxazine-containing nitrile resin monomer are shown in the formula 1 and the formula 2 respectively:
the molar ratio of 4,4' -diaminodiphenylmethane, paraformaldehyde and p-hydroxybenzonitrile in step (1) is 1: 4.01-4.1: 2.01-2.1; the volume ratio of the dimethylbenzene to the absolute ethyl alcohol is 1: 0.5-0.8, wherein the solid-liquid ratio of the reaction system is 1:0.5 to 0.8;
the mass ratio of the nitrile group functionalized benzoxazine-containing resin monomer to the benzoxazine-containing nitrile group-containing resin monomer in the step (2) is (0.05-0.2): 1, a step of; the molar ratio of the benzoxazine-containing nitrile resin monomer to the curing agent for the benzoxazine-containing nitrile resin monomer is 0.15:1; the mass volume ratio of the mixture to the solvent is 1 (0.9-1.3); the solvent is any one or two of DMF and NMP.
2. The preparation method of the nitrile group functionalized benzoxazine resin composite material is characterized by comprising the following steps of: the method for preparing the nitrile functional benzoxazine resin comprises the steps of impregnating glass fibers with the nitrile functional benzoxazine resin prepared in the preparation method of the nitrile functional benzoxazine resin to obtain prepreg, and preparing the nitrile functional benzoxazine resin composite material by adopting a lamination hot-pressing method.
3. The method for preparing the nitrile functional benzoxazine resin composite material according to claim 2, wherein the glue content of the prepreg is 45%.
4. The method for preparing the nitrile functional benzoxazine resin composite according to claim 2, wherein the lamination hot pressing method is as follows: heat treatment is carried out for 30min at 80 ℃, then heat treatment is carried out for 30-60 min at 155-185 ℃, and finally hot pressing is carried out for 2-4 h at 200 ℃ and 20MPa in a press.
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| CN100554246C (en) * | 2006-09-14 | 2009-10-28 | 电子科技大学 | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, cured article and its production and use |
| CN102976972A (en) * | 2012-12-03 | 2013-03-20 | 电子科技大学 | Nitrile resin monomer, nitrile resin polymer and preparation method of nitrile resin monomer and nitrile resin polymer |
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