CN113698593A - Composite material and preparation method thereof - Google Patents

Composite material and preparation method thereof Download PDF

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CN113698593A
CN113698593A CN202111172447.3A CN202111172447A CN113698593A CN 113698593 A CN113698593 A CN 113698593A CN 202111172447 A CN202111172447 A CN 202111172447A CN 113698593 A CN113698593 A CN 113698593A
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nitrile
composite material
benzoxazine
glass fiber
fiber cloth
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徐明珍
刘甜
徐小茜
李博
任登勋
刘孝波
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres

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  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a composite material and a preparation method thereof, the composite material is obtained by compounding toughened nitrile-based resin and benzoxazine-containing nitrile-based resin, the preparation process is simple, the steps are simple, the fracture toughness of the benzoxazine-containing nitrile-based resin matrix composite material is improved while the high mechanical strength, excellent thermal stability, outstanding self-flame retardance and corrosion resistance of the original benzoxazine-containing nitrile-based resin are maintained, and the application field of the benzoxazine-containing nitrile-based resin matrix composite material is widened.

Description

Composite material and preparation method thereof
Technical Field
The invention relates to the technical field of special polymer synthesis and polymer composite material preparation, in particular to a composite material and a preparation method thereof.
Background
In recent years, with the great development of high and new technology fields, resin-based composite materials with high temperature resistance and high structural strength are widely applied to the fields of aerospace, mechanical ships and rail traffic. Nitrile resin is widely concerned as a high-performance resin matrix which is halogen-free, phosphorus-free and self-flame-retardant. However, the conventional nitrile resin has the defects of high curing temperature, long curing time, poor toughness and the like, and the application range and depth of the resin matrix composite material are seriously limited (CN 113246564A; CN 104845349A).
The benzoxazine-containing nitrile-based resin is a high-performance nitrile-based resin modified through structural design, and obviously reduces the molding temperature of a resin matrix and shortens the molding time while maintaining the excellent performance of the conventional nitrile-based resin. However, as a thermosetting resin, the benzoxazine-containing nitrile-based resin has the characteristics of poor toughness and high brittleness of the traditional thermosetting resin. The benzoxazine-containing nitrile resin forms a three-dimensional space network structure with short distance between cross-linking points in the addition polymerization reaction process, so that the polymer has poor energy transmission and dissipation effects under the action of external load, and shows obvious brittleness and poor impact resistance toughness.
In order to improve the problem of high brittleness of the thermosetting resin after cross-linking polymerization, the following methods are generally adopted to toughen and modify the resin matrix: 1) introducing rubber particles for toughening; 2) introducing thermoplastic resin for toughening; 3) rigid nano particles are introduced for toughening; 4) introducing a core-shell structure for toughening; wherein the thermoplastic resin toughening thermosetting resin is prepared with low cost and strong operability.
However, the existing toughening modification system still has the following defects: 1) due to the constraint effect of the reinforced fiber, the resin performance is difficult to be completely reflected to the performance of the composite material, the toughness and strength of the composite material are improved by a limited range 2) the problems of poor solubility, large dissolving viscosity, poor compatibility with thermosetting resin and the like generally exist in the thermoplastic resin, so that the toughening modification process is complex in process and complicated in steps, and the modified resin system is difficult to process. 3) The glass transition temperature of the thermoplastic resin is generally below 200 ℃, which causes the heat resistance of the modified resin polymer to be reduced, and the material requirement of the application field with high temperature resistance requirement is difficult to meet.
Therefore, the technical problem to be solved by the technical personnel in the field is how to provide a composite material with high temperature resistance, high toughness, simple preparation process and convenient processing and a preparation method thereof.
Disclosure of Invention
In view of the above, the invention provides a high-temperature-resistant high-toughness benzoxazine-containing nitrile-based resin composite material and a preparation method thereof, the preparation process is simple, the steps are simple, the fracture toughness of the benzoxazine-containing nitrile-based resin composite material is improved while the high mechanical strength, excellent thermal stability, outstanding self-flame retardance and corrosion resistance of the original benzoxazine-containing nitrile-based resin are maintained, and the application field of the benzoxazine-containing nitrile-based resin composite material is widened.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite material is obtained by compounding toughened nitrile-based resin and benzoxazine-containing nitrile-based resin;
wherein, the toughened nitrile-based resin is phenolphthalein type polyaryl ether nitrile, and the structural formula is as follows:
Figure BDA0003293886270000021
wherein n is 22 to 86;
the structural formula of the benzoxazine-nitrile-group-containing resin is as follows:
Figure BDA0003293886270000031
the preparation method of the composite material comprises the following steps:
(1) adding phenolphthalein, dichlorotolunitrile, anhydrous potassium carbonate, toluene and N-methylpyrrolidone into a reaction container, heating to 130-145 ℃, dehydrating and refluxing for 2-2.5 hours, discharging generated byproducts and toluene, continuously heating to 160-180 ℃, keeping the temperature for continuous reaction for 2.5-3 hours, pouring the reaction liquid into water to separate out a copolymer, crushing the copolymer, soaking the copolymer in dilute hydrochloric acid, standing for 8-12 hours, washing, filtering, and drying in an oven to obtain phenolphthalein type polyaryl ether nitrile powder;
(2) sequentially adding the phenolphthalein type polyaryl ether nitrile powder and benzoxazine-containing nitrile resin solution into a reaction container, and stirring until the phenolphthalein type polyaryl ether nitrile powder is completely dissolved to obtain a mixed solution;
(3) uniformly dipping the mixed solution on 6-20 pieces of glass fiber cloth;
(4) and putting the glass fiber cloth into an oven for drying, then trimming, stacking and putting into a press for pressing to obtain the composite laminated board.
In the preparation method, the temperature is raised to 130-145 ℃ in the step (1) because the dehydration reaction is only carried out at the temperature, the dehydration reaction cannot be carried out below the temperature, and serious side reactions can occur above the temperature;
dehydrating and refluxing for 2-2.5 h, wherein the later-period molecular weight is too large, the viscosity of the reaction kettle is too large, the reaction is stopped, and the later-period molecular weight is too short, so that incomplete dehydration is caused, and the subsequent reaction cannot be carried out;
continuously heating to 160-180 ℃, wherein the molecular weight of the synthesized poly (arylene ether nitrile) is too high when the temperature is higher than the temperature, and the molecular weight of the synthesized poly (arylene ether nitrile) is too low when the temperature is lower than the temperature;
the temperature is kept for 2.5 to 3 hours, the molecular weight of the synthesized poly (arylene ether nitrile) is too large and the reaction efficiency is reduced if the time is longer, and the molecular weight of the synthesized poly (arylene ether nitrile) is too small and the poly (arylene ether nitrile) cannot play a toughening role if the time is shorter;
standing for 8-12h, wherein the reaction time is shorter than that, the reaction of potassium carbonate and hydrochloric acid is insufficient, and the efficiency of the purification process is too low when the reaction time is longer than that.
The 6-20 pieces of glass fiber cloth are selected because the number of the glass fiber cloth is less than 6, the thickness of the composite material is too small, and the polymerization process of the resin matrix is not easy to control, so that the interlayer bonding strength of the composite material is low, and the structural strength is reduced; the number of the sheets is more than 20, the thickness of the composite material is too large in the preparation process, the heat conductivity of the composite material is poor in the pressing process, the defect of resin micro-polymerization occurs in the composite material, and the structural performance of the composite material is seriously influenced.
Preferably, the reaction vessel in step (1) is a three-necked flask equipped with mechanical stirring, a thermometer, a water separator and a reflux condenser.
Preferably, in the step (1), the molar ratio of the phenolphthalein, dichlorotolunitrile and anhydrous potassium carbonate is (1.01-1.04): 1: 1; the poly (arylene ether nitrile) with the molecular weight higher than the above ratio is too low to play a role in toughening and modifying; the molecular weight of the synthesized poly (arylene ether nitrile) is too high and the solubility is too poor due to the lower proportion, so that the poly (arylene ether nitrile) cannot be well compatible with a corresponding thermosetting resin system;
the volume ratio of the toluene to the N-methylpyrrolidone is 1: (2.5-3); higher than this ratio can result in slower temperature rise of the reaction system and lower reaction efficiency; the temperature of the reaction system rises faster due to the fact that the proportion is lower than the proportion, and the reaction process is uncontrollable;
the mass volume ratio (g: ml) of the solid raw materials to the solvent system in the reaction vessel is 1: (1-1.5); above this ratio, the solid raw material is insufficiently dissolved and the synthesis reaction cannot be expected to occur; a ratio lower than this ratio results in excessively low concentration of the reaction solution, a decrease in reaction rate, an increase in reaction time, and a decrease in reaction efficiency.
Preferably, the volume ratio of the reaction liquid to water in the step (1) is 1: (10-15); the product precipitation is incomplete when the proportion is lower than the above proportion, the impurity content is high, and the wastewater is greatly increased when the proportion is higher than the above proportion, so that the difficulty of sewage treatment is increased;
in the dilute hydrochloric acid: the volume ratio of the hydrochloric acid to the water is 1: (20-100); if the ratio is lower than the range, the hydrochloric acid and the reaction residue potassium carbonate can not completely react, if the ratio is higher than the range, the hydrochloric acid is excessive, and the steps for purifying the product at the later stage are complicated;
preferably, the washing in the step (1) is hot water washing at 80-100 ℃; the drying is carried out for 48 hours at the temperature of 80 ℃; the hot water is selected at 80-100 ℃ because the potassium chloride cannot be completely dissolved when the water temperature is too low, so that the impurity content in the product is high.
Preferably, the solvent in the benzoxazine nitrile group-containing resin solution in the step (2) is N, N-dimethylformamide, the solid content of the benzoxazine nitrile group-containing resin solution is 57%, and the content of the phenolphthalein type polyarylether nitrile powder is 10% of the benzoxazine nitrile group-containing resin.
Preferably, the drying procedure in step (4) is as follows: maintaining at 80 deg.C for 30min and at 180 deg.C for 25 min.
Preferably, the press procedure in step (4) is: the temperature is 200 ℃, and the pressure is 20MPa and maintained for 4 h.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1) the benzoxazine-containing nitrile-based resin is subjected to crosslinking reaction at high temperature, so that the nitrile-based resin and the poly (arylene ether nitrile) are subjected to phase separation and delamination, the toughness of the nitrile-based resin composite material is improved, and the fracture toughness is improved to 85KJ/m2The application field of benzoxazine-containing nitrile resin limited by high brittleness is widened;
2) due to the excellent thermal stability of the phenolphthalein type poly (arylene ether nitrile), the thermal stability of the benzoxazine nitrile-based resin matrix composite material provided by the invention is increased;
3) the processing temperature of the benzoxazine nitrile group resin-based glass fiber reinforced composite board is low and is not higher than 200 ℃;
the preparation process has simple steps, the synthesis process of the thermoplastic resin used by the invention is mature, the cost is low, and the processing continuity can be realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a bar graph of impact strength for various composite laminates;
Detailed Description
The technical solutions in the embodiments of the present invention will be 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
The preparation method of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board comprises the following steps:
step (1) phenolphthalein (PP, 39.72g), dichlorotolunitrile (DCBN, 20.64g), anhydrous potassium carbonate (K)2CO321.56g), toluene (MB, 23.3ml), N-methylpyrrolidone (NMP,70ml) were charged into a 500ml three-necked flask equipped with mechanical stirring, thermometer, water separator and reflux condenser, wherein phenolphthalein (PP) and Dichlorotolunitrile (DCBN), anhydrous potassium carbonate (K)2CO3) Gradually heating to 135 ℃ at a molar ratio of 1.04:1:1, dehydrating and refluxing for 2h, discharging a by-product generated in the water separator and toluene at the moment, continuously heating to 165 ℃ for 30min, maintaining at 170 ℃ for 1h, maintaining at 175 ℃ for 30min, maintaining at 180 ℃ for 30min, pouring the reaction solution into distilled water (1300ml), separating out white flexible thin strip-shaped copolymer, crushing and soaking in distilled water (1300ml) filled with 50ml of hydrochloric acid (HCl) by using a crusher, standing for 9h, repeatedly washing and filtering the product by hot water at 100 ℃, and drying in an oven at 80 ℃ for 48h to obtain the phenolphthalein type polyaryl ether nitrile with the number average molecular weight of 8422g/mol, wherein the dispersibility index is 2.13112.
Step (2) adding 3.81g of the phenolphthalein type poly (arylene ether nitrile) powder obtained in the step (1) and 66.94g of benzoxazine-containing nitrile resin glue solution with the solid content of 57% into a three-necked bottle in sequence, and mechanically stirring until the powder is completely dissolved in the solution;
step (3) uniformly soaking the mixed solution of the poly (arylene ether nitrile) and the nitrile-based resin in the step (2) on ten pieces of 17cmx17cm glass fiber cloth, and weighing the glass fiber cloth to obtain 51.31g of the mixed solution;
and (4) hanging the glass fiber cloth in the step (3) in a blast oven for drying, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 80 ℃, maintaining for 30min, quickly taking out the glass fiber cloth, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 180 ℃, maintaining for 25min, and quickly taking out the glass fiber cloth.
And (5) simply trimming the ten pieces of glass fiber cloth dried by the solvent in the step (4), and stacking the glass fiber cloth together.
And (6) heating the press to 200 ℃ and stabilizing, putting the ten pieces of glass fiber cloth stacked in order in the step (5) into the press, and pressurizing to 20 Mpa.
The impact strength of the poly (arylene ether nitrile)/benzoxazine nitrile based resin glass fiber reinforced composite board prepared by the steps is 77KJ/m2The thermal decomposition temperature was 357.56 ℃ and the weight percentage of the residual carbon amount at 800 ℃ was 64.18%.
Example 2
The preparation method of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board comprises the following steps:
step (1) phenolphthalein (PP, 38.58g), dichlorotolunitrile (DCBN, 20.64g), anhydrous potassium carbonate (K)2CO321.56g), toluene (MB, 23.3ml), N-methylpyrrolidone (NMP,70ml) were charged into a 500ml three-necked flask equipped with mechanical stirring, thermometer, water separator and reflux condenser, wherein phenolphthalein (PP) and Dichlorotolunitrile (DCBN), anhydrous potassium carbonate (K)2CO3) Gradually heating to 135 deg.C at a molar ratio of 1.01:1:1, dehydrating and refluxing for 2 hr until the by-product generated by reaction in the water separator approaches theoretical value, discharging the by-product and toluene, continuously heating to 165 deg.C for 1 hr, maintaining at 170 deg.C for 1.5 hr, maintaining at 175 deg.C for 30min, maintaining at 180 deg.C for 10min, pouring the reaction solution into distilled water (1400ml), separating white flexible thin strip copolymer, crushing with a pulverizer, and soaking in 50ml hydrochloric acid(HCl) in distilled water (1350ml), after standing for 9h, the filtered product was washed repeatedly with hot water at 100 ℃ and dried in an oven at 80 ℃ for 48h to obtain phenolphthalein-type polyarylene ether nitrile having a number average molecular weight of 17965g/mol and a dispersibility index of 2.51022.
Step (2) sequentially adding 4.01g of the phenolphthalein type polyaryl ether nitrile powder obtained in the step (1) and 66.94g of benzoxazine-containing nitrile resin glue solution with solid content of 60% into a three-necked bottle, and mechanically stirring until the powder is completely dissolved in the solution;
step (3) uniformly soaking the mixed solution of the poly (arylene ether nitrile) and the nitrile-based resin in the step (2) on ten pieces of 17cmx17cm glass fiber cloth, and weighing the glass fiber cloth to obtain 51.31g of the mixed solution;
and (4) hanging the glass fiber cloth in the step (3) in a blast oven for drying, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 80 ℃, maintaining for 30min, quickly taking out the glass fiber cloth, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 180 ℃, maintaining for 25min, and quickly taking out the glass fiber cloth.
And (5) simply trimming the ten pieces of glass fiber cloth dried by the solvent in the step (4), and stacking the glass fiber cloth together.
And (6) heating the press to 200 ℃ and stabilizing, putting the ten pieces of glass fiber cloth stacked in order in the step (5) into the press, and pressurizing to 20 Mpa.
The impact strength of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board prepared by the steps is 87KJ/m2The thermal decomposition temperature was 382.12 ℃ and the weight percentage of the residual carbon amount at 800 ℃ was 77.14%.
Example 3
The preparation method of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board comprises the following steps:
step (1) phenolphthalein (PP, 38.58g), dichlorotolunitrile (DCBN, 20.64g), anhydrous potassium carbonate (K)2CO321.56g), toluene (MB, 23.3ml), N-methylpyrrolidone (NMP,70ml) were charged into a 500ml three-necked flask equipped with mechanical stirring, thermometer, water separator and reflux condenser, wherein phenolphthalein (PP) and Dichlorotolunitrile (DCBN),anhydrous potassium carbonate (K)2CO3) Gradually heating to 140 ℃ at a molar ratio of 1.01:1:1, dehydrating and refluxing for 2h, discharging a by-product generated in the water separator and toluene when the by-product is close to a theoretical value, continuously heating to 165 ℃ for 1h, maintaining at 170 ℃ for 1h, maintaining at 175 ℃ for 30min, maintaining at 180 ℃ for 30min, pouring the reaction solution into distilled water (1450ml), separating out white flexible thin strip copolymer, crushing and soaking in distilled water (1300ml) filled with 50ml of hydrochloric acid (HCl) by using a crusher, repeatedly washing and filtering the product by hot water at 100 ℃ after standing for 9h, and drying in an oven at 80 ℃ for 48h to obtain the phenolphthalein type polyaryl ether nitrile with the number average molecular weight of 33566g/mol, wherein the dispersibility index is 2.06967.
Step (2) sequentially adding 4.07g of the phenolphthalein type polyaryl ether nitrile powder obtained in the step (1) and 66.94g of benzoxazine-containing nitrile resin glue solution with the solid content of 61% into a three-necked bottle, and mechanically stirring until the powder is completely dissolved in the solution;
step (3) uniformly soaking the mixed solution of the poly (arylene ether nitrile) and the nitrile-based resin in the step (2) on ten pieces of 17cmx17cm glass fiber cloth, and weighing the glass fiber cloth to obtain 51.31g of the mixed solution;
and (4) hanging the glass fiber cloth in the step (3) in a blast oven for drying, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 80 ℃, maintaining for 30min, quickly taking out the glass fiber cloth, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 180 ℃, maintaining for 25min, and quickly taking out the glass fiber cloth.
And (5) simply trimming the ten pieces of glass fiber cloth dried by the solvent in the step (4), and stacking the glass fiber cloth together.
And (6) heating the press to 200 ℃ and stabilizing, putting the ten pieces of glass fiber cloth stacked in order in the step (5) into the press, and pressurizing to 20 Mpa.
The impact strength of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board prepared by the steps is 71KJ/m2The thermal decomposition temperature was 374.98 ℃ and the weight percentage of the residual carbon amount at 800 ℃ was 66.65%.
FIG. 1 shows the mixture of poly (arylene ether nitriles) with different molecular weightsThe column diagram of the impact strength of the benzoxazine-containing nitrile-based resin-based glass fiber reinforced composite board shows that the fracture toughness of one composite material reaches 85KJ/m2Above, the toughening effect is very good
Comparative example 1
The preparation method of the benzoxazine nitrile group resin-based glass fiber reinforced composite board comprises the following steps:
evenly impregnating 73.63g of nitrile resin solution on ten pieces of glass fiber cloth with the mass of 51.31g and the mass of 17cmx17 cm;
and (2) hanging the glass fiber cloth in the step (1) in a blast oven for drying, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 80 ℃, maintaining for 30min, quickly taking out the glass fiber cloth, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 180 ℃, maintaining for 25min, and quickly taking out the glass fiber cloth.
And (3) simply trimming the ten pieces of glass fiber cloth dried by the solvent in the step (2), and stacking the glass fiber cloth together.
And (4) heating the press to 200 ℃ for stabilization, putting the ten pieces of glass fiber cloth stacked in order in the step (3) into the press, and pressurizing by 20 Mpa.
The impact strength of the benzoxazine nitrile-based resin glass fiber reinforced composite board prepared by the steps is 76KJ/m2The thermal decomposition temperature was 379.42 ℃ and the weight percentage of the residual carbon amount at 800 ℃ was 72.61%.
Comparative example 2 (increasing the proportion of the polyarylene ether nitrile starting Material)
The preparation method of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board comprises the following steps:
step (1) phenolphthalein (PP, 38.58g), dichlorotolunitrile (DCBN, 20.64g), anhydrous potassium carbonate (K)2CO321.56g), toluene (MB, 23.3ml), N-methylpyrrolidone (NMP,70ml) were charged into a 500ml three-necked flask equipped with mechanical stirring, thermometer, water separator and reflux condenser, wherein phenolphthalein (PP) and Dichlorotolunitrile (DCBN), anhydrous potassium carbonate (K)2CO3) The mol ratio is 1.01:1:1, the temperature is gradually increased to 135 ℃, and dehydration reflux is carried outAnd 2h, discharging the byproduct generated by the reaction in the water separator and toluene, continuously heating to 165 ℃ for 1h, maintaining at 170 ℃ for 1.5h, maintaining at 175 ℃ for 30min, maintaining at 180 ℃ for 10min, pouring the reaction solution into distilled water, separating out white flexible thin strip-shaped copolymer, crushing and soaking in 50ml of distilled water containing hydrochloric acid (HCl) by using a crusher, standing for 9h, repeatedly washing and filtering the product by using 100 ℃ hot water, and drying in an oven at 80 ℃ for 48h to obtain the phenolphthalein type polyaryl ether nitrile with the number average molecular weight of 17965g/mol, wherein the dispersibility index is 2.51022.
Step (2) sequentially adding 8.02g of the phenolphthalein type polyaryl ether nitrile powder obtained in the step (1) and 66.94g of benzoxazine-containing nitrile resin glue solution with solid content of 60% into a three-necked bottle, and mechanically stirring until the powder is completely dissolved in the solution;
and (3) uniformly coating the mixed solution of the poly (arylene ether nitrile) and the nitrile-based resin in the step (2) on ten pieces of 17cmx17cm glass fiber cloth, wherein the apparent viscosity of a glue solution is too high, the glue solution is pasted on the surface of the fiber cloth, uniform impregnation cannot be realized, and the subsequent processing and preparation of the composite material cannot be carried out.
Comparative example 3 (reduction of the proportion of the polyarylene ether nitrile starting Material)
The preparation method of the polyaryl ether nitrile/benzoxazine nitrile resin based glass fiber reinforced composite board comprises the following steps:
step (1) phenolphthalein (PP, 38.58g), dichlorotolunitrile (DCBN, 20.64g), anhydrous potassium carbonate (K)2CO321.56g), toluene (MB, 23.3ml), N-methylpyrrolidone (NMP,70ml) were charged into a 500ml three-necked flask equipped with mechanical stirring, thermometer, water separator and reflux condenser, wherein phenolphthalein (PP) and Dichlorotolunitrile (DCBN), anhydrous potassium carbonate (K)2CO3) Gradually heating to 135 deg.C at a molar ratio of 1.01:1:1, dehydrating and refluxing for 2 hr, discharging byproduct generated by reaction in water separator and toluene, heating to 165 deg.C for 1 hr, maintaining 170 deg.C for 1.5 hr, maintaining 175 deg.C for 30min, maintaining 180 deg.C for 10min, pouring the reaction solution into distilled water (1450ml), separating white flexible thin strip copolymer, crushing with pulverizer, and soaking in distilled water (1300ml) containing 50ml hydrochloric acid (HCl)Standing for 9h, repeatedly washing the filtered product with hot water at 100 ℃, and drying in an oven at 80 ℃ for 48h to obtain the phenolphthalein type polyarylether nitrile with the number average molecular weight of 17965g/mol and the dispersity index of 2.51022.
Step (2) sequentially adding 2.005g of the phenolphthalein type polyaryl ether nitrile powder obtained in the step (1) and 66.94g of benzoxazine-containing nitrile resin glue solution with solid content of 60% into a three-necked bottle, and mechanically stirring until the powder is completely dissolved in the solution;
step (3) uniformly soaking the mixed solution of the poly (arylene ether nitrile) and the nitrile-based resin in the step (2) on ten pieces of 17cmx17cm glass fiber cloth, and weighing the glass fiber cloth to obtain 51.31g of the mixed solution;
and (4) hanging the glass fiber cloth in the step (3) in a blast oven for drying, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 80 ℃, maintaining for 30min, quickly taking out the glass fiber cloth, quickly hanging the glass fiber cloth in the oven after the temperature is increased to 180 ℃, maintaining for 25min, and quickly taking out the glass fiber cloth.
And (5) simply trimming the ten pieces of glass fiber cloth dried by the solvent in the step (4), and stacking the glass fiber cloth together.
And (6) heating the press to 200 ℃ and stabilizing, putting the ten pieces of glass fiber cloth stacked in order in the step (5) into the press, and pressurizing to 20 Mpa.
The impact strength of the poly (arylene ether nitrile)/benzoxazine nitrile based resin glass fiber reinforced composite board prepared by the steps is 65KJ/m2The thermal decomposition temperature was 385.34 ℃ and the weight percentage of the residual carbon amount at 800 ℃ was 75.41%.
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. The composite material is characterized by being obtained by compounding toughened nitrile-based resin and benzoxazine-containing nitrile-based resin;
wherein, the toughened nitrile-based resin is phenolphthalein type polyaryl ether nitrile, and the structural formula is as follows:
Figure FDA0003293886260000011
wherein n is 22 to 86;
the structural formula of the benzoxazine-nitrile-group-containing resin is as follows:
Figure FDA0003293886260000012
2. a method of preparing a composite material according to claim 1, comprising the steps of:
(1) adding phenolphthalein, dichlorotolunitrile, anhydrous potassium carbonate, toluene and N-methylpyrrolidone into a reaction container, heating to 130-145 ℃, dehydrating and refluxing for 2-2.5 hours, discharging generated byproducts and toluene, continuously heating to 160-180 ℃, keeping the temperature for continuous reaction for 2.5-3 hours, pouring the reaction liquid into water to separate out a copolymer, crushing the copolymer, soaking the copolymer in dilute hydrochloric acid, standing for 8-12 hours, washing, filtering, and drying in an oven to obtain phenolphthalein type polyaryl ether nitrile powder;
(2) sequentially adding the phenolphthalein type polyaryl ether nitrile powder and benzoxazine-containing nitrile resin solution into a reaction container, and stirring until the phenolphthalein type polyaryl ether nitrile powder is completely dissolved to obtain a mixed solution;
(3) uniformly dipping the mixed solution on 6-20 pieces of glass fiber cloth;
(4) and putting the glass fiber cloth into an oven for drying, then trimming, stacking and putting into a press for pressing to obtain the composite laminated board.
3. The method for preparing the composite material according to claim 2, wherein the molar ratio of the phenolphthalein, the dichlorotolunitrile and the anhydrous potassium carbonate in the step (1) is (1.01-1.04): 1: 1; the volume ratio of the toluene to the N-methylpyrrolidone is 1: (2.5-3); the mass volume ratio (g: ml) of the solid raw materials to the solvent system in the reaction vessel is 1: (1-1.5).
4. The method for preparing a composite material according to claim 2, wherein the volume ratio of the reaction solution to water in the step (1) is 1: (10-15); in the dilute hydrochloric acid: the volume ratio of the hydrochloric acid to the water is 1: (20-100).
5. The method for preparing the composite material according to claim 2, wherein the washing in the step (1) is hot water washing at 80-100 ℃; the drying is carried out at 80 ℃ for 48 h.
6. The method for preparing a composite material according to claim 2, wherein the solvent in the benzoxazine nitrile group-containing resin solution in step (2) is N, N-dimethylformamide, the solid content of the benzoxazine nitrile group-containing resin solution is 57-61%, and the content of the phenolphthalein type polyarylethernitrile powder is 10% of the benzoxazine nitrile group-containing resin.
7. The method for preparing a composite material according to claim 2, wherein the drying procedure in step (4) is as follows: maintaining at 80 deg.C for 30min and at 180 deg.C for 25 min.
8. The method for preparing a composite material according to claim 2, wherein the press procedure in step (4) is as follows: the temperature is 200 ℃, and the pressure is 20MPa and maintained for 4 h.
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