CN114478971A - Nitrile-group functionalized benzoxazine resin and preparation method of polymer and composite material thereof - Google Patents
Nitrile-group functionalized benzoxazine resin and preparation method of polymer and composite material thereof Download PDFInfo
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Abstract
The invention provides a novel nitrile-group functionalized benzoxazine resin, a polymer thereof and a preparation method of a composite material, which are used for modifying a benzoxazine-containing nitrile resin matrix and improving the process in production of the prepolymer, can solve the problems of unmatched processing performance and product performance and the like of the existing benzoxazine-containing nitrile resin system, ensure the high efficiency of preparation of the nitrile resin composite material and have 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 polymer synthesis processes, in particular to a nitrile-based functionalized benzoxazine resin and a preparation method of a polymer and a composite material thereof.
Background
The nitrile resin polymer is an important high-performance thermosetting polymer, and under the condition of thermal initiation polymerization, 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, so that the resin polymer has excellent thermal stability, mechanical properties, 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 enable the nitrile-based resin polymer to have wide application in the fields of mechanical ships, aerospace and defense military industry.
With the continuous enhancement of the requirements of energy conservation and emission reduction, the processing application of the high-energy consumption resin-based composite material is greatly limited. For the traditional nitrile resin, because the reaction inertia of the nitrile group in the molecular structure of the bisphthalonitrile causes the polymerization reaction to be slow and the curing processing temperature is required to be high, under the condition of no catalyst or curing agent, the curing can be realized within a few days under the high-temperature condition, which greatly limits the wide application of the bisphthalonitrile and greatly increases the application cost. Therefore, in order to improve the curing process, curing agents such as organic amine, organic acid and amine salt thereof, transition metal and salt thereof and the like are used to reduce the curing temperature and curing time, and the improvement of the polymerization performance becomes a way for modifying the nitrile-based resin. Meanwhile, the molecular structure of the nitrile resin can be designed and constructed, and a novel functional group or branched chain is introduced, so that the purposes of nitrile functionalization and autocatalytic polymerization are achieved.
The traditional benzoxazine-containing nitrile-based resin mainly has the following problems: 1) the polymerization reaction rate of the benzoxazine-containing nitrile-based resin system is slow, the production efficiency of the benzoxazine-containing nitrile-based resin composite material is influenced, and the production cost is increased, so that the expansion of the application field of the benzoxazine-containing nitrile-based resin composite material is limited; 2) the curing agent or catalyst containing benzoxazine nitrile resin has the problems of dispersibility, volatilization and decomposition, so that the polymerization reaction cannot 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 influenced; 3) the main structure of the benzoxazine nitrile group-containing resin is not diversified enough, and the release of product performance is limited essentially. There is a need to eliminate these drawbacks and to improve the synthesis process of benzoxazine-containing nitrile resins.
Patent CN202110541508.2 discloses a benzoxazine-containing nitrile-based resin curing agent, a preparation method and applications thereof. The novel curing agent and the benzoxazine functional group are combined to realize synergistic effect, active hydrogen ions are released through amino groups, the oxazine ring is rapidly promoted to generate ring-opening reaction, and an active Mannich structure is formed, so that the rate of ring-forming polymerization of the nitrile group is accelerated, and the efficient curing molding of the nitrile resin is realized. However, the benzoxazine-containing nitrile-based resin composite material prepared by curing the curing agent has low mechanical property, and the outstanding advantages of nitrile-based resin cannot be exerted.
In order to further improve the polymerization efficiency of nitrile resin polymers and the service performance of composite materials thereof, the invention provides a preparation method of novel nitrile functionalized benzoxazine and a method for copolymerizing the nitrile functionalized benzoxazine with benzoxazine-containing nitrile resin to form polymers and obtain fiber reinforced composite materials thereof, so that the obtained resin has more ideal curing rate and excellent mechanical properties, and simultaneously maintains excellent thermal stability.
Disclosure of Invention
In view of the above, the invention provides a novel nitrile-group functionalized benzoxazine resin, a polymer thereof and a preparation method of a composite material, which are used for modification of a benzoxazine-containing nitrile-group resin matrix and process improvement in prepolymer production, can solve the problems of unmatched processability and product performance and the like of the existing benzoxazine-containing nitrile-group resin system, ensure high efficiency of preparation of the nitrile-group resin composite material, and have a certain promotion effect on improving the mechanical property and the thermal stability of the nitrile-group resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of nitrile-based 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 is finished, continuously heating to 70-85 ℃, reacting for 3-6 hours, then heating to 90-110 ℃, and removing the solvent to obtain a nitrile group functionalized benzoxazine-containing resin (MD-cn) monomer;
wherein, the synthetic route is as follows:
(2) preparing a benzoxazine-containing nitrile resin (BA-ph) monomer, wherein the raw materials of the BA-ph resin are 4-aminophenoxy phthalonitrile (4-APN), bisphenol A (BPA), paraformaldehyde, N-Dimethylformamide (DMF) and xylene;
wherein, the synthetic route is as follows:
(3) preparing a curing agent (BAB) for a benzoxazine-containing nitrile resin (BA-ph) monomer, wherein the BAB is synthesized from 2, 6-dichlorobenzonitrile, p-aminophenol, anhydrous potassium carbonate, toluene and N-methylpyrrolidone (NMP);
wherein, the synthetic route is as follows:
(4) mixing a nitrile-group functionalized benzoxazine-containing resin monomer, a benzoxazine-containing nitrile resin (BA-ph) monomer and a benzoxazine-containing nitrile resin (BA-ph) monomer with a curing agent (BAB) to obtain a mixture, dissolving the mixture in a solvent, and reacting at 130-150 ℃ for 1.5-2.5 h to obtain the nitrile-group functionalized benzoxazine-containing resin.
In the temperature setting, the reaction is carried out for 1.5-2.5 h at the temperature of 130-150 ℃, the copolymerization reaction is not controlled uniformly and is easy to generate gel, the copolymerization resin cannot be obtained, and the raw materials cannot be copolymerized fully below the temperature, so that a resin system for subsequent polymers and composite materials cannot be prepared. Longer than this time, the reaction efficiency is lowered, and resources are wasted, and the system cannot be sufficiently copolymerized shorter than this time.
Preferably, 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-to-liquid ratio of the reaction system is 1: 0.5 to 0.8.
The beneficial effects brought by the optimization are as follows: the proportion of the three raw materials is beyond the range of the proportion, and the resin monomer with a preset structure cannot be obtained; the proportion of the mixed solvent is higher than the proportion, the solubility of the paraformaldehyde raw material in the solvent is poor, the efficiency of the synthesis reaction is influenced, and the azeotropic point of the mixed solvent system is lower than the proportion, so that the temperature of the reaction system cannot 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 resin monomer in the step (2) is (0.05-0.2): 1; the molar ratio of the benzoxazine-nitrile-group-containing resin monomer to the curing agent for the benzoxazine-nitrile-group-containing resin monomer is 0.15: 1;
above this ratio, the polymerization reaction rapidly occurs, the desired resin cannot be obtained due to the easy occurrence of gel, and below this ratio, the copolymerization effect is not significant, and an effectively copolymerized resin system cannot be 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 high, the reaction takes place rapidly, it is not easy to control, below this ratio, the reaction efficiency is low, the copolymerization effect is poor.
The solvent is one or a mixture of DMF and NMP.
A preparation method of a nitrile-functionalized benzoxazine resin polymer comprises the following steps:
1) drying the nitrile-group functionalized benzoxazine resin prepared by the preparation method of the nitrile-group functionalized benzoxazine resin at 80-100 ℃ for 8-12 h to obtain nitrile-group functionalized benzoxazine-containing resin powder;
drying at the temperature of 80-100 ℃ for 8-12 h, wherein the time is shorter than the temperature, the solvent cannot be completely removed, and the time is longer than the temperature, so that the efficiency is low and energy is wasted;
2) and carrying out heat treatment on the nitrile-group functionalized benzoxazine-containing resin powder at the temperature of 180-200 ℃ for 2-4 h to obtain the nitrile-group functionalized benzoxazine-containing polymer.
The heat treatment is carried out at the temperature of 80-200 ℃ for 2-4 h, the time is shorter than the temperature, the polymer is not completely cured, the performance is not good, and the time is longer than the temperature, the polymer performance improvement effect is not obvious, and the energy consumption is high.
A preparation method of a nitrile-functionalized benzoxazine resin composite material comprises the following steps: and (2) impregnating the nitrile functional benzoxazine resin prepared by the preparation method of the nitrile functional benzoxazine resin with glass fiber to obtain prepreg cloth, and then preparing the nitrile functional benzoxazine resin composite material by adopting a laminated hot pressing method.
Preferably, the glue content of the prepreg is 45%.
Preferably, the lamination hot press method is: 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.
Wherein, the heat treatment is carried out for 30min at the temperature of 80 ℃, partial solvent is removed, the self-adhesiveness of the prepreg is ensured, and the polymerization degree of the resin is not influenced;
carrying out heat treatment at 155-185 ℃ for 30-60 min, wherein the time is shorter than the temperature, the solvent is not completely removed, and internal air hole defects are caused in the pressing forming process; above this temperature for this period of time, the degree of crosslinking of the resin system increases, resulting in loss of tack in the prepreg, delamination of the composite during pressing, and significant loss of structural strength of the composite.
Through the technical scheme, 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, can improve the reaction rate of the benzoxazine-containing nitrile resin, does not generate phase separation, and has good curing effect;
2) the active chain introduced into the benzoxazine-containing nitrile group resin precursor is another benzoxazine-containing mononitrile resin with simple structure and strong autocatalysis capability, and can reduce steric hindrance in the polymerization process, thereby being beneficial to ring formation polymerization of nitrile groups and forming a more compact spatial network structure, and further realizing the preparation of high-performance polymers;
3) the introduced active chain can realize the synergistic catalysis effect with the curing agent, further accelerate the curing reaction of the system and improve the curing performance. In conclusion, the novel nitrile-based functionalized 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 technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the 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 given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Step (1), 59.7975g (0.5025mol) of p-hydroxybenzonitrile and 30.075g (1.0025mol) of paraformaldehyde are sequentially added into 46.5mL of dimethylbenzene and 23.2mL of absolute ethyl alcohol mixed solvent (volume ratio is 1: 0.5) (solid-to-liquid ratio is 1: 0.5), the temperature is slowly increased to 40 ℃, 49.5g (0.25mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) is added for a small amount of times, a yellow reaction solution is obtained after the addition is finished, the temperature is slowly increased to about 85 ℃, after reaction is carried out for 6 hours, the solvent is removed at the temperature of 90-110 ℃, and the nitrile group functionalized benzoxazine-containing resin (MD-cn) monomer is obtained;
step (2), mixing 1.356g (0.0043mol) of BAB, 1.2908g (0.0022mol) of MD-cn resin monomer and 33.766g (0.0285mol) of BA-ph resin monomer in a three-necked bottle, dissolving in 9mL of DMF solvent, and reacting at 150 ℃ for 2.5h to obtain BA-ph/MD-cn/BAB resin glue solution;
step (3) processing 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) in a high-temperature drying oven, and performing heat treatment at the temperature of 180 ℃ for 4 hours to prepare a nitrile-group functionalized benzoxazine-containing polymer;
and (5) dipping the nitrile-group functionalized benzoxazine-containing resin obtained in the step (2) into Glass Fiber (GF) to obtain prepreg cloth, 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 and hot pressing are as follows: heat treatment is carried out at 80 ℃ for 30min, then at 185 ℃ for 60min, and finally hot pressing is carried out in a press at 200 ℃ and 20MPa for 4 h.
The nitrile group functionalized benzoxazine-containing resin powder prepared by the steps has the gelation time (180 ℃) of 930 s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has the thermal decomposition temperature of 404.5 ℃ and the weight percentage of the residual carbon at 800 ℃ of 66.81%; 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 24.35 GPa.
Example 2
Step (1), 59.7975g (0.5025mol) of p-hydroxybenzonitrile and 30.75g (1.025mol) of paraformaldehyde are sequentially added into a mixed solvent (volume ratio is 1: 0.6) of 52.5mL of dimethylbenzene and 31.5mL of absolute ethyl alcohol (volume ratio is 1: 0.6), the temperature is slowly increased to 40 ℃, 49.5g (0.25mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) is added for a few times, after the addition is finished, a yellow reaction solution is obtained, the temperature is slowly increased to about 80 ℃, after the reaction is carried out for 5 hours, the solvent is removed at the temperature of 90-110 ℃, and the nitrile group functionalized benzoxazine-containing resin (MD-cn) monomer is obtained;
step (2), 1.2997g (0.0041mol) of BAB, 2.464g (0.0042mol) of MD-cn resin monomer and 32.231g (0.0272mol) of BA-ph resin monomer are mixed in a three-necked flask, dissolved in 12.5mL of DMF solvent and reacted for 2h at the temperature of 150 ℃ to obtain BA-ph/MD-cn/BAB resin glue solution;
step (3) processing 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) dipping the nitrile-group functionalized benzoxazine-containing resin obtained in the step (2) into Glass Fiber (GF) to obtain prepreg cloth, 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 and hot pressing are as follows: heat treatment is carried out at 80 ℃ for 30min, then at 170 ℃ for 60min, and finally hot pressing is carried out in a press at 200 ℃ and 20MPa for 3 h.
The nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer solid powder prepared by the steps has the gelation time (180 ℃) of 520 s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has the thermal decomposition temperature of 405.4 ℃ and the weight percentage of residual carbon at 800 ℃ of 67.23%; 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 23.51 GPa.
Example 3
Step (1), 62.475g (0.525mol) of p-hydroxybenzonitrile and 30.75g (1.025mol) of paraformaldehyde are sequentially added into 58.8mL of dimethylbenzene and 41.1mL of absolute ethyl alcohol mixed solvent (volume ratio is 1: 0.7) (solid-to-liquid ratio is 1: 0.7), the temperature is slowly increased to 40 ℃, 49.5g (0.25mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) is added for a small amount of times, a yellow reaction solution is obtained after the addition is finished, the temperature is slowly increased to about 75 ℃, after 4 hours of reaction, the solvent is removed at 90-110 ℃, and the nitrile group functionalized benzoxazine-containing resin (MD-cn) monomer is obtained;
step (2), mixing 1.260g (0.0040mol) of BAB, 3.5357g (0.0060mol) of MD-cn resin monomer and 30.830g (0.0265mol) of BA-ph resin monomer in a three-necked bottle, dissolving in 15.8mL of DMF solvent, and reacting at 140 ℃ for 2h to obtain BA-ph/MD-cn/BAB resin prepolymer glue solution;
step (3) processing the resin glue solution obtained in the step (2) at the temperature of 80 ℃ for 12 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) in a high-temperature drying oven, and performing heat treatment at the temperature of 200 ℃ for 2 hours to prepare a nitrile-group functionalized benzoxazine-containing polymer;
and (5) impregnating the nitrile-group-functionalized benzoxazine-containing resin obtained in the step (2) into Glass Fiber (GF) to obtain prepreg cloth, 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 and hot pressing are as follows: heat treatment is carried out for 30min at 80 ℃, then for 30min at 185 ℃, and finally hot pressing is carried out for 2h at 200 ℃ and 20MPa in a press.
The nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer solid powder prepared by the steps has the gelation time (180 ℃) of 390 s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has the thermal decomposition temperature of 404.7 ℃ and the weight percentage of residual carbon at 800 ℃ of 67.51%; 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 26.12 GPa.
Example 4
Step (1), 62.475g (0.525mol) of p-hydroxybenzonitrile and 30.075g (1.0025mol) of paraformaldehyde are sequentially added into a mixed solvent (volume ratio is 1: 0.8) of 63.1mL of dimethylbenzene and 50.5mL of absolute ethyl alcohol (volume ratio is 1: 0.8) (solid-to-liquid ratio is 1: 0.8), the temperature is slowly increased to 40 ℃, 49.5g (0.25mol) of 4,4 '-diaminodiphenylmethane (4, 4' -MDA) is added for a few times, after the addition is finished, a yellow reaction solution is obtained, the temperature is slowly increased to about 70 ℃, after the reaction is carried out for 3 hours, the solvent is removed at the temperature of 90-110 ℃, and the nitrile group functionalized benzoxazine-containing resin (MD-cn) monomer is obtained;
mixing 1.2046g (0.0038mol) BAB, 4.518g (0.0077mol) MD-cn resin monomer and 29.544g (0.0253mol) BA-ph resin monomer in a three-necked flask, dissolving in 19.5mL DMF solvent, and reacting at 130 ℃ for 1.5h to obtain BA-ph/MD-cn/BAB resin prepolymer glue solution;
step (3) processing the resin glue solution obtained in the step (2) at the temperature of 80 ℃ for 12 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) in a high-temperature drying oven, and performing heat treatment at the temperature of 200 ℃ for 2 hours to prepare a nitrile-group functionalized benzoxazine-containing polymer;
and (5) dipping the nitrile-group functionalized benzoxazine-containing resin obtained in the step (2) into Glass Fiber (GF) to obtain prepreg cloth, 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 and hot pressing are as follows: heat treatment is carried out for 30min at 80 ℃, then for 60min at 155 ℃, and finally hot pressing is carried out for 2h at 200 ℃ and 20MPa in a press.
The nitrile group functionalized benzoxazine-containing bisphthalonitrile resin prepolymer solid powder prepared by the steps has the gelation time (180 ℃) of 212 s; the nitrile group functionalized benzoxazine-containing resin polymer prepared by the steps has the thermal decomposition temperature of 405.5 ℃ and the weight percentage of residual carbon at 800 ℃ of 66.25%; 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 20.16 GPa.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
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 (8)
1. A preparation method of nitrile-based functionalized benzoxazine resin is characterized by comprising 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 is finished, continuously heating to 70-85 ℃, reacting for 3-6 hours, then heating to 90-110 ℃, and removing the solvent to obtain a nitrile group functionalized benzoxazine-containing resin monomer;
(2) mixing the nitrile-group-functionalized benzoxazine-containing resin monomer obtained in the step (1) with a benzoxazine-containing nitrile-group-containing resin monomer and a curing agent for the benzoxazine-containing nitrile-group-containing resin monomer to obtain a mixture, dissolving the mixture in a solvent, and reacting for 1.5-2.5 hours at 130-150 ℃ to obtain the nitrile-group-functionalized benzoxazine-containing resin.
2. The method for preparing nitrile-based functionalized benzoxazine resin according to claim 1, wherein 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-to-liquid ratio of the reaction system is 1: 0.5 to 0.8.
3. The method for preparing nitrile-based functionalized benzoxazine resin according to claim 1, wherein the structures of the benzoxazine nitrile-based resin monomer and the curing agent for the benzoxazine nitrile-based resin monomer in step (2) are respectively as shown in formula 1 and formula 2:
4. the method for preparing nitrile-based functionalized benzoxazine resin according to claim 1, wherein the mass ratio of the nitrile-based functionalized benzoxazine-containing resin monomer to the benzoxazine-containing nitrile-based resin monomer in step (2) is (0.05-0.2): 1; the molar ratio of the benzoxazine-nitrile-group-containing resin monomer to the curing agent for the benzoxazine-nitrile-group-containing 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 one or a mixture of DMF and NMP.
5. A preparation method of a nitrile-functionalized benzoxazine resin polymer is characterized by comprising the following steps:
1) drying the nitrile-functional benzoxazine resin prepared by the method of any one of claims 1 to 4 at 80-100 ℃ for 8-12 hours to obtain nitrile-functional benzoxazine-containing resin powder;
2) and carrying out heat treatment on the nitrile-group functionalized benzoxazine-containing resin powder at the temperature of 180-200 ℃ for 2-4 h to obtain the nitrile-group functionalized benzoxazine-containing polymer.
6. A preparation method of a nitrile-based functionalized benzoxazine resin composite material is characterized by comprising the following steps: the nitrile-based functionalized benzoxazine resin prepared by the method of any one of claims 1-4, impregnating glass fiber with the nitrile-based functionalized benzoxazine resin to obtain prepreg, and then preparing the nitrile-based functionalized benzoxazine resin composite material by a lamination hot-pressing method.
7. The method for preparing a nitrile-based functionalized benzoxazine resin composite material according to claim 6, wherein the glue content of the prepreg cloth is 45%.
8. The preparation method of the nitrile-based functionalized benzoxazine resin composite material according to claim 6, wherein the lamination hot pressing method comprises the following steps: 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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