CN113930074A - Toughened bismaleimide resin cured product and preparation method thereof - Google Patents
Toughened bismaleimide resin cured product and preparation method thereof Download PDFInfo
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- CN113930074A CN113930074A CN202111292540.8A CN202111292540A CN113930074A CN 113930074 A CN113930074 A CN 113930074A CN 202111292540 A CN202111292540 A CN 202111292540A CN 113930074 A CN113930074 A CN 113930074A
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention provides a toughened bismaleimide resin cured product and a preparation method thereof, which are applied to the technical field of high polymer polymerization, and the method comprises the following steps: adding polyaryletherketone containing epoxy groups into a solvent and stirring to obtain a mixed solution; adding bismaleimide and a curing agent into the mixed solution, stirring, and then carrying out curing treatment to obtain the toughened bismaleimide resin cured product. The toughened bismaleimide resin condensate prepared by the invention has excellent toughness and heat resistance.
Description
Technical Field
The invention relates to the technical field of high polymer polymerization, and particularly relates to a toughened bismaleimide resin cured product and a preparation method thereof.
Background
Bismaleimide resin (BMI) is a high-performance thermosetting matrix resin, which has excellent high-temperature resistance and good manufacturability, and also has very excellent matching property with other high-performance resins.
However, bismaleimides have a large number of polar carbonyl groups, which promote orderly stacking of polymer chains, are not favorable for energy dissipation, and have the defects of hard and brittle texture, easy cracking and poor impact resistance. Therefore, a high toughness bismaleimide resin is urgently needed.
Disclosure of Invention
The embodiment of the invention provides a toughened bismaleimide resin cured product and a preparation method thereof, and the toughened bismaleimide resin cured product has excellent toughness and heat resistance.
In a first aspect, the present invention provides a method for preparing a toughened bismaleimide resin cured product, comprising the steps of:
(1) adding polyaryletherketone containing epoxy groups into a solvent and stirring to obtain a mixed solution;
(2) adding bismaleimide and a curing agent into the mixed solution, stirring, and then carrying out curing treatment to obtain the toughened bismaleimide resin cured product.
Preferably, the toughened bismaleimide resin cured product is prepared from the following raw materials in parts by mass: 10-30 parts of epoxy-containing polyaryletherketone, 10-30 parts of solvent, 100 parts of bismaleimide and 5-20 parts of curing agent.
Preferably, in step (1), the preparation method of the epoxy group-containing polyaryletherketone comprises the following substeps:
(1.1) stirring polyaryletherketone, aluminum trichloride and a solvent for the first time to obtain a polyaryletherketone solution;
uniformly mixing bromoacetyl bromide and a diluent, then dropwise adding the mixture into the polyaryletherketone solution to obtain a first mixed solution, and then sequentially carrying out secondary stirring, quenching treatment and filtering and drying treatment on the first mixed solution to obtain the polyaryletherketone containing bromine;
(1.2) carrying out the first stirring on the bromine-containing polyaryletherketone, potassium carbonate and a solvent to obtain a bromine-containing polyaryletherketone solution;
uniformly mixing dihydric alcohol and a diluent, then dropwise adding the mixture into the bromine-containing polyaryletherketone solution to obtain a second mixed solution, and then sequentially carrying out third stirring, quenching treatment and filtering and drying treatment on the second mixed solution to obtain hydroxyl-containing polyaryletherketone;
(1.3) carrying out the first stirring on the hydroxyl-containing polyaryletherketone, potassium carbonate and a solvent to obtain a hydroxyl-containing polyaryletherketone solution;
and uniformly mixing epoxy chloropropane and a diluent, and then dropwise adding the mixture into the solution of the polyaryletherketone containing hydroxyl to obtain a solution of the polyaryletherketone containing epoxy, and then sequentially carrying out the third stirring, the quenching treatment and the filtering and drying treatment on the solution of the polyaryletherketone containing epoxy to obtain the polyaryletherketone containing epoxy.
Preferably, in the step (1.1), the mass parts of the components in the first mixed solution are as follows:
100 parts of polyaryletherketone, 45-55 parts of aluminum trichloride, 95-100 parts of solvent, 150-160 parts of bromoacetyl bromide and 95-100 parts of diluent.
Preferably, in the step (1.2), the mass parts of the components in the second mixed solution are as follows:
110 parts of bromine-containing polyaryletherketone, 35-45 parts of potassium carbonate, 95-100 parts of solvent, 13-18 parts of dihydric alcohol and 32-38 parts of diluent.
Preferably, in the step (1.3), the epoxy group-containing polyaryletherketone solution comprises the following components in parts by weight:
75 parts of hydroxyl-containing polyaryletherketone, 26-34 parts of potassium carbonate, 95-100 parts of solvent, 20-25 parts of epoxy chloropropane and 78-82 parts of diluent.
Preferably, the stirring temperature of the first stirring is 80-100 ℃, and the stirring time is 8-12 min;
the stirring temperature of the second stirring is 35-45 ℃, and the stirring time is 3.5-4.5 h.
Preferably, the stirring temperature of the third stirring is 35-45 ℃, and the stirring time is 23-25 h.
Preferably, the quenching treatment is quenching with deionized water;
the diluent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the filtering and drying treatment is suction filtration treatment under-0.085 MPa, washing with deionized water for 2-4 times, and finally drying for 7-9 hours under the conditions of vacuum degree of-0.085 MPa and temperature of 38-42 ℃.
Preferably, the polyaryletherketone is at least one of polyetheretherketone, polyetherketone, polyetherketoneketone and polyetheretherketoneketone;
the epoxy-containing polyaryletherketone is at least one of epoxy-containing polyetheretherketone, epoxy-containing polyetherketone, epoxy-containing polyetherketoneketone and epoxy-containing polyetheretherketoneketone.
Preferably, the bismaleimide resin is at least one of p-phenylenediamine bismaleimide resin, bisphenol A bismaleimide resin, alicyclic bismaleimide resin and diphenylmethane bismaleimide resin;
the solvent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the curing agent is at least one of an aromatic diamine and an aliphatic diamine.
Preferably, in the step (1), the stirring temperature of the stirring is 190-210 ℃, and the stirring time is 3-7 min;
in the step (2), the stirring temperature is 80-100 ℃, and the stirring time is 60-120 min.
Preferably, in the step (2), the curing treatment is performed at 110-130 ℃ for 1.5-2.5 h, and then at 210-230 ℃ for 1.5-2.5 h.
In a second aspect, the invention provides a toughened bismaleimide resin cured product prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
in the invention, the epoxy-containing polyaryletherketone, the bismaleimide and the curing agent are mixed in the solvent and then are subjected to curing treatment, so that the thermoplastic epoxy-containing polyaryletherketone and the bismaleimide are combined on the molecular layer, and the obtained toughened bismaleimide resin cured product has excellent toughness and heat resistance by virtue of the thermoplasticity of the chain epoxy-containing polyaryletherketone and the rigidity provided by the aromatic ring structure.
In the invention, the epoxy group in the epoxy-containing polyaryletherketone is positioned on the side chain of the polyaryletherketone, and the epoxy group enables the polyaryletherketone to be chemically crosslinked with bismaleimide and be combined on a molecular layer, so that the molecular layer has better combination chemical compatibility, a crosslinking network is more compact, and the improvement on the heat resistance and the bending property of the bismaleimide resin is more obvious.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a preparation method of a toughened bismaleimide resin cured product, which comprises the following steps:
(1) adding polyaryletherketone containing epoxy groups into a solvent and stirring to obtain a mixed solution;
(2) adding bismaleimide and a curing agent into the mixed solution, stirring, and then carrying out curing treatment to obtain the toughened bismaleimide resin cured product.
In the invention, the epoxy-containing polyaryletherketone, the bismaleimide and the curing agent are mixed in the solvent and then are subjected to curing treatment, so that the thermoplastic epoxy-containing polyaryletherketone and the bismaleimide are combined on the molecular layer, and the obtained toughened bismaleimide resin cured product has excellent toughness and heat resistance by virtue of the thermoplasticity of the chain epoxy-containing polyaryletherketone and the rigidity provided by the aromatic ring structure.
According to some preferred embodiments, in the step (1), the stirring temperature of the stirring is 190 to 210 ℃ (for example, 190 ℃, 200 ℃, 210 ℃ or 220 ℃), and the stirring time is 3 to 7min (for example, 3min, 4min, 5min, 6min or 7 min);
in the step (2), the stirring temperature is 80 to 100 ℃ (for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃), and the stirring time is 60 to 120min (for example, 60min, 70min, 80min, 90min, 100min, 110min or 120 min).
According to some preferred embodiments, in the step (2), the curing treatment is performed for 1.5 to 2.5 hours (e.g., 1.5 hours, 2 hours, or 2.5 hours) at 110 to 130 ℃ (e.g., 110 ℃, 115 ℃, 120 ℃, 125 ℃, or 130 ℃), and then for 1.5 to 2.5 hours (e.g., 1.5 hours, 2 hours, or 2.5 hours) at 210 to 230 ℃ (e.g., 210 ℃, 220 ℃, or 230 ℃).
In the step (1), the stirring temperature is higher than the boiling point of the solvent, and therefore the stirring is performed in a reflux apparatus.
It should be noted that, in the preparation method provided by the present invention, because the epoxy-containing polyaryletherketone is a high molecular polymer and is relatively insoluble compared to bismaleimide and a curing agent, it is necessary to dissolve the epoxy-containing polyaryletherketone at a high temperature, and then add bismaleimide and a curing agent, and if the epoxy-containing polyaryletherketone, the bismaleimide and the curing agent are added into a solvent at the same time, a situation that the epoxy-containing polyaryletherketone cannot be dissolved or is cured under a condition of insufficient dissolution due to an excessively high temperature may occur.
According to some preferred embodiments, the polyaryletherketone is at least one of polyetheretherketone, polyetherketone, polyetherketoneketone, and polyetheretherketoneketone;
the epoxy-containing polyaryletherketone is at least one of epoxy-containing polyetheretherketone, epoxy-containing polyetherketone, epoxy-containing polyetherketoneketone and epoxy-containing polyetheretherketoneketone.
In the invention, the molecular structure general formula of the epoxy-containing polyaryletherketone is as follows:
wherein m is a positive integer, n is 1, 2 or 3, n is 1 when the dihydric alcohol is ethylene glycol, n is 2 when the dihydric alcohol is butanediol, and n is 3 when the dihydric alcohol is hexanediol.
According to some preferred embodiments, the bismaleimide resin is at least one of a p-phenylenediamine type bismaleimide resin, a bisphenol a type bismaleimide resin, an alicyclic bismaleimide resin, a diphenylmethane bismaleimide resin;
the solvent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
The solvents are selected from aprotic solvents having similar cohesive energy density or solubility parameters.
According to some preferred embodiments, the curing agent is at least one of an aromatic diamine and an aliphatic diamine.
For example, the curing agent may be specifically diaminodiphenylmethane which is an aromatic diamine.
At least one of them is a mixture of any one or any several of them mixed in any ratio.
In the invention, the epoxy group in the epoxy-containing polyaryletherketone is positioned on the side chain of the polyaryletherketone, and the epoxy group enables the polyaryletherketone to be chemically crosslinked with bismaleimide and be combined on a molecular layer, so that the molecular layer has better combination chemical compatibility, a crosslinking network is more compact, and the improvement on the heat resistance and the bending property of the bismaleimide resin is more obvious.
It should be noted that, if the polyaryletherketone does not contain an epoxy group, the polyaryletherketone cannot be chemically cross-linked with bismaleimide, and only exists in the form of small particles in the gaps of the cross-linked network of the bismaleimide resin cured product, and cannot form chemical cross-linking on the molecular layer, so that the heat resistance and toughness of the bismaleimide resin cannot be significantly improved.
The epoxy group located in the side chain of the epoxy-containing polyaryletherketone enables the epoxy-containing polyaryletherketone to have a distorted non-coplanar structure, so that the regularity of the molecular structure is reduced, the crystallinity is reduced, and the solubility is more excellent.
According to some preferred embodiments, the mass parts of the raw materials in the process of preparing the toughened bismaleimide resin cured product are as follows: 10-30 parts (for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts) of epoxy group-containing polyaryletherketone, 10-30 parts (for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts) of solvent, 100 parts of bismaleimide and 5-20 parts (for example, 5 parts, 10 parts, 15 parts or 20 parts) of curing agent.
Experiments prove that when the mass parts of other raw materials are in the range, if the mass part of the epoxy-containing polyaryletherketone exceeds 30 parts, the epoxy-containing polyaryletherketone with overlarge fluid resistance can cause that the mixed solution is difficult to stir uniformly, and the epoxy-containing polyaryletherketone with small viscosity can reduce the manufacturability of a solidified product of the bismaleimide resin and has poor matching property with other resins; if the mass part of the epoxy polyaryletherketone is less than 10 parts, the prepared bismaleimide resin has poor toughness.
According to some preferred embodiments, in step (1), the method for preparing epoxy-containing polyaryletherketones comprises the following substeps:
(1.1) stirring polyaryletherketone, aluminum trichloride and a solvent for the first time to obtain a polyaryletherketone solution;
uniformly mixing bromoacetyl bromide and a diluent, then dropwise adding the mixture into the polyaryletherketone solution to obtain a first mixed solution, and then sequentially carrying out secondary stirring, quenching treatment and filtering and drying treatment on the first mixed solution to obtain the polyaryletherketone containing bromine;
(1.2) carrying out the first stirring on the bromine-containing polyaryletherketone, potassium carbonate and a solvent to obtain a bromine-containing polyaryletherketone solution;
uniformly mixing dihydric alcohol and a diluent, then dropwise adding the mixture into the bromine-containing polyaryletherketone solution to obtain a second mixed solution, and then sequentially carrying out third stirring, quenching treatment and filtering and drying treatment on the second mixed solution to obtain hydroxyl-containing polyaryletherketone;
(1.3) carrying out the first stirring on the hydroxyl-containing polyaryletherketone, potassium carbonate and a solvent to obtain a hydroxyl-containing polyaryletherketone solution;
and uniformly mixing epoxy chloropropane and a diluent, and then dropwise adding the mixture into the solution of the polyaryletherketone containing hydroxyl to obtain a solution of the polyaryletherketone containing epoxy, and then sequentially carrying out the third stirring, the quenching treatment and the filtering and drying treatment on the solution of the polyaryletherketone containing epoxy to obtain the polyaryletherketone containing epoxy.
In the step (1.1) of the present invention, bromoacetyl bromide and a diluent are diluted with stirring in an ice bath at 4 ℃, and are added dropwise to a polyaryletherketone solution at a rate of 10mL/min using a constant pressure dropping funnel.
In the step (1.2) of the present invention, a constant pressure dropping funnel is used to drop into the polyaryletherketone solution at a rate of 5 mL/min.
In the step (1.3) of the present invention, a constant pressure dropping funnel is used to drop into the polyaryletherketone solution at a rate of 10 mL/min.
In the invention, when the polyaryletherketone is polyetheretherketone, taking the preparation of polyether ether ketone containing epoxy group as an example, the glycol is selected from glycol, and the synthetic route is as follows:
wherein, PEEK is polyether-ether-ketone, PEEK-Br is polyether-ether-ketone containing bromine, PEEK-OH is polyether-ether-ketone containing hydroxyl, PEEK-EP is polyether-ether-ketone containing epoxy groups, and m is a positive integer; wherein, the step (a) is the step (1.1), the step (b) is the step (1.2), and the step (c) is the step (1.3).
According to some preferred embodiments, in step (1.1), the parts by mass of the components in the first mixed solution are as follows:
100 parts of polyaryletherketone, 45-55 parts (for example, 45 parts, 50 parts or 55 parts) of aluminum trichloride, 95-100 parts (for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts) of solvent, 150-160 parts (for example, 150 parts, 151 parts, 152 parts, 153 parts, 154 parts, 155 parts, 156 parts, 157 parts, 158 parts, 159 parts or 160 parts) of bromoacetyl bromide, and 95-100 parts (for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts) of diluent.
More specifically, for example, the first mixed solution includes the following components in parts by mass: 100 parts of polyaryletherketone, 55 parts of aluminum trichloride, 100 parts of solvent, 150 parts of bromoacetyl bromide and 95 parts of diluent; for example, the first mixed solution comprises the following components in parts by mass: 100 parts of polyaryletherketone, 45 parts of aluminum trichloride, 95 parts of solvent, 160 parts of bromoacetyl bromide and 100 parts of diluent; for example, the first mixed solution comprises the following components in parts by mass: 100 parts of polyaryletherketone, 45 parts of aluminum trichloride, 99 parts of solvent, 155 parts of bromoacetyl bromide and 99 parts of diluent.
According to some preferred embodiments, in step (1.2), the parts by mass of the components in the second mixed solution are as follows:
110 parts of the bromine-containing polyaryletherketone, 35-45 parts (for example, 35 parts, 40 parts or 45 parts) of potassium carbonate, 95-100 parts (for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts) of a solvent, 13-18 parts (for example, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts or 18 parts) of a glycol, and 32-38 parts (for example, 32 parts, 34 parts, 36 parts or 38 parts) of a diluent.
More specifically, for example, the second mixed solution includes the following components in parts by mass: 110 parts of bromine-containing polyaryletherketone, 35 parts of potassium carbonate, 100 parts of solvent, 13 parts of dihydric alcohol and 38 parts of diluent; for example, the second mixed solution comprises the following components in parts by mass: 110 parts of bromine-containing polyaryletherketone, 45 parts of potassium carbonate, 95 parts of solvent, 18 parts of dihydric alcohol and 32 parts of diluent; for example, the second mixed solution comprises the following components in parts by mass: 110 parts of bromine-containing polyaryletherketone, 40 parts of potassium carbonate, 99 parts of solvent, 16 parts of dihydric alcohol and 36 parts of diluent.
According to some preferred embodiments, in step (1.3), the mass parts of the components in the solution of epoxy-containing polyaryletherketone are as follows:
75 parts of hydroxyl-containing polyaryletherketone, 26-34 parts (for example, 26 parts, 28 parts, 30 parts, 32 parts or 34 parts) of potassium carbonate, 95-100 parts (for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts) of solvent, 20-25 parts (for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts) of epichlorohydrin and 78-82 parts (for example, 78 parts, 79 parts, 80 parts, 81 parts or 82 parts) of diluent.
More specifically, for example, the epoxy group-containing polyaryletherketone solution comprises the following components in parts by weight: 26 parts of potassium carbonate, 100 parts of solvent, 20 parts of epoxy chloropropane and 82 parts of diluent; for example, the epoxy group-containing polyaryletherketone solution comprises the following components in parts by weight: 34 parts of potassium carbonate, 95 parts of solvent, 25 parts of epoxy chloropropane and 78 parts of diluent; for example, the epoxy group-containing polyaryletherketone solution comprises the following components in parts by weight: 30 parts of potassium carbonate, 99 parts of solvent, 23 parts of epoxy chloropropane and 80 parts of diluent.
In the present invention, aluminum trichloride and potassium carbonate are used as catalysts to increase the rate of the reaction.
According to some preferred embodiments, the first stirring is performed at a stirring temperature of 80 to 100 ℃ (for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃) and for a stirring time of 8 to 12min (for example, 8min, 9min, 10min, 11min or 12 min);
the stirring temperature of the second stirring is 35-45 ℃ (for example, 35 ℃, 40 ℃ or 45 ℃), and the stirring time is 3.5-4.5 h (for example, 3.5h, 4h or 4.5 h).
According to some preferred embodiments, the stirring temperature of the third stirring is 35 to 45 ℃ (for example, 35 ℃, 40 ℃ or 45 ℃) and the stirring time is 23 to 25 hours (for example, 23 hours, 24 hours or 25 hours).
According to some preferred embodiments, the quenching treatment is quenching with deionized water;
the diluent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
According to some preferred embodiments, the filtering and drying process is a suction filtration process at-0.085 MPa, followed by washing with deionized water 2-4 times (for example, 2, 3 or 4 times), and finally drying for 7-9 h (for example, 7h, 8h or 9h) under a vacuum degree of-0.085 MPa and a temperature of 38-42 ℃ (for example, 38 ℃, 39 ℃, 40 ℃, 41 ℃ or 42 ℃).
In the invention, the reaction solution is quenched by dripping into deionized water, and is filtered by a Buchner funnel and dried by a vacuum drying oven.
The invention also provides a toughened bismaleimide resin cured product prepared by the preparation method.
In order to more clearly illustrate the technical scheme and advantages of the present invention, a toughened bismaleimide and a preparation method thereof are described in detail through several examples.
Example 1:
(1) preparing epoxy group-containing polyaryletherketone: adding 100g of polyetheretherketone and 50g of aluminum trichloride into 100g N, N-dimethylformamide, and stirring at 90 ℃ for 10min to obtain a polyetheretherketone solution;
stirring and diluting 155g of bromoacetyl bromide and 100g N, N-dimethylformamide at 4 ℃, uniformly mixing, pouring into a constant-pressure dropping funnel, dropwise adding into a polyetheretherketone solution at the speed of 10mL/min, then raising the temperature of the obtained solution to 40 ℃, stirring for 4 hours to obtain a reaction solution, dropwise adding the reaction solution into 1L of deionized water for quenching reaction, transferring the solution into a Buchner funnel for suction filtration (the vacuum degree is-0.0852 MPa) to obtain a filter cake, washing the obtained filter cake with deionized water for 3 times, and then placing in a vacuum drying oven for drying for 8 hours (the vacuum degree is-0.085 MPa, 40 ℃) to obtain polyether-ether-ketone powder containing bromine;
adding 110g of bromine-containing polyetheretherketone powder and 40g of potassium carbonate into 100g N, N-dimethylformamide, and stirring at 90 ℃ for 10min to obtain a bromine-containing polyetheretherketone solution;
stirring and diluting 16g of ethylene glycol and 35g N, N-dimethylformamide at 25 ℃, pouring the mixture into a constant-pressure dropping funnel after uniformly mixing, dropwise adding the mixture into a bromine-containing polyether-ether-ketone solution at the speed of 5mL/min, then raising the temperature of the obtained solution to 40 ℃, stirring for 24 hours to obtain a reaction solution, dropwise adding the reaction solution into 1L of deionized water for quenching reaction, transferring the solution into a Buchner funnel after quenching for suction filtration (the vacuum degree is-0.0852 MPa) to obtain a filter cake, washing the obtained filter cake with the deionized water for 3 times, and then placing the filter cake into a vacuum drying oven for drying for 8 hours (the vacuum degree is-0.085 MPa, 40 ℃) to obtain hydroxyl-containing polyether-ether-ketone powder;
adding bromine-containing polyetheretherketone powder and hydroxyl-containing polyetheretherketone powder into 100g N, N-dimethylformamide, and stirring at 90 deg.C for 10min to obtain hydroxyl-containing polyetheretherketone solution;
stirring and diluting 22g of epichlorohydrin and 80g N, N-dimethylformamide at 25 ℃, pouring the mixture into a constant-pressure dropping funnel after uniformly mixing, dropwise adding the mixture into a hydroxyl-containing polyether-ether-ketone solution at the speed of 10mL/min, then raising the temperature of the obtained solution to 40 ℃, stirring for 24 hours to obtain a reaction solution, dropwise adding the reaction solution into 1L of deionized water for quenching reaction, transferring the solution into a Buchner funnel after quenching for suction filtration (the vacuum degree is-0.0852 MPa) to obtain a filter cake, washing the obtained filter cake with the deionized water for 3 times, and then placing the filter cake into a vacuum drying oven for drying for 8 hours (the vacuum degree is-0.085 MPa, 40 ℃) to obtain the epoxy-containing polyether-ether-ketone powder.
(2) Preparing a toughened bismaleimide resin cured product: adding 20g of polyether ether ketone powder containing epoxy groups into 20g N-methyl pyrrolidone, placing the mixture in a reflux device, heating the mixture to 205 ℃, stirring the mixture for 5min, then adding 100g of diphenylmethane bismaleimide and 10g of diaminodiphenylmethane, stirring the mixture for 80min at 90 ℃ to obtain a uniform transparent solution, curing the solution for 2h at 120 ℃, and then curing the solution for 2h at 220 ℃ to obtain a toughened bismaleimide resin cured product.
Example 2:
example 2 is essentially the same as example 1, except that:
in the step (1), polyether-ether-ketone is replaced by polyether-ketone to obtain polyether-ketone containing epoxy groups; and using the polyether ketone containing epoxy groups obtained in the step (1) in the step (2).
Example 3:
example 3 is essentially the same as example 1, except that:
in the step (1), polyether-ether-ketone is replaced by polyether-ketone to obtain polyether-ketone containing epoxy groups; and using the polyether ketone containing epoxy groups obtained in the step (1) in the step (2).
Example 4:
example 4 is essentially the same as example 1, except that:
in the step (1), polyether-ether-ketone is replaced by polyether-ether-ketone to obtain polyether-ether-ketone containing epoxy groups; and (2) using the polyether ether ketone containing epoxy groups obtained in the step (1) in the step (2).
Example 5:
example 5 is substantially the same as example 1 except that in step (2), the components are as follows:
10g of polyether ether ketone powder containing epoxy groups, 30g N-methyl pyrrolidone, 100g of diphenylmethane bismaleimide and 5g of diaminodiphenylmethane.
Example 6:
example 6 is substantially the same as example 1 except that in step (2), the components are as follows:
30g of polyether-ether-ketone powder containing epoxy groups, 10g N-methyl pyrrolidone, 100g of diphenylmethane bismaleimide and 20g of diaminodiphenylmethane.
Comparative example 1:
heating 100g of diphenylmethane bismaleimide to a molten state, adding 10g of diaminodiphenylmethane, stirring for 80min at 90 ℃ to obtain uniform transparent liquid, curing the transparent liquid at 120 ℃ for 2h, and curing at 220 ℃ for 2h to obtain a bismaleimide resin condensate.
Comparative example 2:
adding 20g of polybutylene terephthalate into 20g N-methyl pyrrolidone, placing the mixture in a reflux device, heating the mixture to 205 ℃ and stirring the mixture for 5min, then adding 100g of diphenylmethane bismaleimide and 10g of diaminodiphenylmethane, stirring the mixture for 80min at 90 ℃ to obtain a uniform transparent solution, curing the solution for 2h at 120 ℃, and then curing the solution for 2h at 220 ℃ to obtain a toughened bismaleimide resin cured product.
Comparative example 3:
adding 20g of polyetheretherketon into 20g N-methylpyrrolidone, placing in a reflux device, heating to 205 ℃, stirring for 5min, then adding 100g of diphenylmethane bismaleimide and 10g of diaminodiphenylmethane, stirring for 80min at 90 ℃ to obtain a uniform transparent solution, curing the solution for 2h at 120 ℃, and then curing for 2h at 220 ℃ to obtain the toughened bismaleimide resin cured product.
Comparative example 4:
comparative example 4 is substantially the same as example 1 except that:
in the step (2), the mass of the polyether-ether-ketone containing epoxy groups is changed from 20g to 5 g.
Comparative example 5:
comparative example 5 is substantially the same as example 1 except that:
in the step (2), the mass of the polyether-ether-ketone containing epoxy groups is changed from 20g to 50 g.
The bismaleimide resin cured products prepared in examples 1 to 4 and comparative examples 1 to 5 were tested for heat resistance and toughness, and the test results are shown in table 1:
TABLE 1
As can be seen from examples 1 to 6 and comparative example 1 in Table 1, the introduction of the epoxy group-containing polyaryletherketone enables the resulting bismaleimide resin cured product to have more excellent heat resistance, bending resistance and impact resistance.
As can be seen from examples 1 to 6 and comparative example 2 in Table 1, the polyaryletherketone has an aromatic ring structure and stronger molecular rigidity compared with other thermoplastic resins, and the introduction of the polyaryletherketone enables the obtained bismaleimide resin cured product to have more excellent heat resistance, flexibility and impact resistance.
As can be seen from examples 1 to 6 and comparative example 3 in Table 1, the epoxy group is introduced into the side chain of the polyaryletherketone, so that the polyaryletherketone containing the epoxy group and the bismaleimide are chemically crosslinked, and the heat resistance, the bending property and the impact resistance of a bismaleimide resin cured product are remarkably improved.
As can be seen from examples 1 to 6 and comparative example 4 in Table 1, when the amount of the epoxy group-containing polyaryletherketone is small, the resulting bismaleimide resin cured product is poor in heat resistance, flexibility and impact resistance.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the toughened bismaleimide resin cured product is characterized by comprising the following steps:
(1) adding polyaryletherketone containing epoxy groups into a solvent and stirring to obtain a mixed solution;
(2) adding bismaleimide and a curing agent into the mixed solution, stirring, and then carrying out curing treatment to obtain the toughened bismaleimide resin cured product.
2. The method of claim 1, wherein:
the toughened bismaleimide resin cured product is prepared from the following raw materials in parts by weight: 10-30 parts of epoxy-containing polyaryletherketone, 10-30 parts of solvent, 100 parts of bismaleimide and 5-20 parts of curing agent.
3. The method of claim 1, wherein:
in the step (1), the preparation method of the epoxy-containing polyaryletherketone comprises the following substeps:
(1.1) stirring polyaryletherketone, aluminum trichloride and a solvent for the first time to obtain a polyaryletherketone solution;
uniformly mixing bromoacetyl bromide and a diluent, then dropwise adding the mixture into the polyaryletherketone solution to obtain a first mixed solution, and then sequentially carrying out secondary stirring, quenching treatment and filtering and drying treatment on the first mixed solution to obtain the polyaryletherketone containing bromine;
(1.2) carrying out the first stirring on the bromine-containing polyaryletherketone, potassium carbonate and a solvent to obtain a bromine-containing polyaryletherketone solution;
uniformly mixing dihydric alcohol and a diluent, then dropwise adding the mixture into the bromine-containing polyaryletherketone solution to obtain a second mixed solution, and then sequentially carrying out third stirring, quenching treatment and filtering and drying treatment on the second mixed solution to obtain hydroxyl-containing polyaryletherketone;
(1.3) carrying out the first stirring on the hydroxyl-containing polyaryletherketone, potassium carbonate and a solvent to obtain a hydroxyl-containing polyaryletherketone solution;
and uniformly mixing epoxy chloropropane and a diluent, and then dropwise adding the mixture into the solution of the polyaryletherketone containing hydroxyl to obtain a solution of the polyaryletherketone containing epoxy, and then sequentially carrying out the third stirring, the quenching treatment and the filtering and drying treatment on the solution of the polyaryletherketone containing epoxy to obtain the polyaryletherketone containing epoxy.
4. The production method according to claim 3, characterized in that:
in the step (1.1), the mass parts of the components in the first mixed solution are as follows:
100 parts of polyaryletherketone, 45-55 parts of aluminum trichloride, 95-100 parts of solvent, 150-160 parts of bromoacetyl bromide and 95-100 parts of diluent;
in the step (1.2), the second mixed solution comprises the following components in parts by mass:
110 parts of bromine-containing polyaryletherketone, 35-45 parts of potassium carbonate, 95-100 parts of solvent, 13-18 parts of dihydric alcohol and 32-38 parts of diluent; and/or
In the step (1.3), the epoxy group-containing polyaryletherketone solution comprises the following components in parts by mass:
75 parts of hydroxyl-containing polyaryletherketone, 26-34 parts of potassium carbonate, 95-100 parts of solvent, 20-25 parts of epoxy chloropropane and 78-82 parts of diluent.
5. The production method according to claim 3, characterized in that:
the stirring temperature of the first stirring is 80-100 ℃, and the stirring time is 8-12 min;
the stirring temperature of the second stirring is 35-45 ℃, and the stirring time is 3.5-4.5 h; and/or
The stirring temperature of the third stirring is 35-45 ℃, and the stirring time is 23-25 h.
6. The production method according to claim 3, characterized in that:
the quenching treatment is quenching by using deionized water;
the diluent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; and/or
The filtering and drying treatment is carried out by carrying out suction filtration treatment under-0.085 MPa, washing for 2-4 times by using deionized water, and finally drying for 7-9 h under the conditions of vacuum degree of-0.085 MPa and temperature of 38-42 ℃.
7. The production method according to claim 1 or 3, characterized in that:
the polyaryletherketone is at least one of polyetheretherketone, polyetherketone, polyetherketoneketone and polyetheretherketoneketone;
the epoxy-containing polyaryletherketone is at least one of epoxy-containing polyetheretherketone, epoxy-containing polyetherketone, epoxy-containing polyetherketoneketone and epoxy-containing polyetheretherketoneketone.
8. The production method according to claim 1 or 3, characterized in that:
the bismaleimide resin is at least one of p-phenylenediamine bismaleimide resin, bisphenol A bismaleimide resin, alicyclic bismaleimide resin and diphenylmethane bismaleimide resin;
the solvent is at least one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; and/or
The curing agent is at least one of aromatic diamine and aliphatic diamine.
9. The production method according to any one of claims 1 to 8, characterized in that:
in the step (1), the stirring temperature of the stirring is 190-210 ℃, and the stirring time is 3-7 min;
in the step (2), the stirring temperature is 80-100 ℃, and the stirring time is 60-120 min; and/or
In the step (2), the curing treatment is to cure at 110-130 ℃ for 1.5-2.5 h, and then cure at 210-230 ℃ for 1.5-2.5 h.
10. A toughened bismaleimide resin cured product characterized by being produced by the production method according to any one of claims 1 to 9.
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