CN114773844A - Polyimide toughened phthalonitrile resin composition, composite material and preparation method thereof - Google Patents
Polyimide toughened phthalonitrile resin composition, composite material and preparation method thereof Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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Abstract
The invention relates to a polyimide toughened phthalonitrile resin composition, a composite material and a preparation method thereof; comprises phthalonitrile and polyimide resin containing cyano functional group; the technical problem that the compatibility of common thermoplastic resin and phthalonitrile resin is poor and the mechanical properties of a blended resin matrix and a composite material are influenced in the prior art is solved by toughening the phthalonitrile resin composition through polyimide.
Description
Technical Field
The invention relates to the technical field of high-temperature-resistant thermosetting resin-based composite materials, in particular to a polyimide toughened phthalonitrile resin composition, a composite material and a preparation method thereof.
Background
The matrix resin plays a role in binding and transferring load stress in the composite material, and the mechanical property, the heat resistance, the fatigue resistance and the like of the matrix resin are key factors for determining the performance of the composite material. The phthalonitrile resin is a high-performance thermosetting resin, and a condensate of the phthalonitrile resin has excellent thermal oxidation stability, chemical stability, low flammability, low water absorption and good processability, so that the phthalonitrile resin has wide application prospect in the field of aerospace. Although the high-temperature mechanical property of the phthalonitrile resin is obviously superior to that of the traditional thermosetting resin, the phthalonitrile resin has the defects of brittle quality, poor impact resistance and the like, so that the phthalonitrile resin is limited to be used in certain high and new technical fields.
Currently, the most common method of modifying thermosetting resins is to increase the toughness of the cured product by adding a toughening agent (e.g., a thermoplastic resin) to the resin system. However, the temperature resistance of the conventional thermoplastic resin is generally low, so that the blending modification affects the heat resistance of the phthalonitrile resin body. Meanwhile, the compatibility of the general thermoplastic resin and the phthalonitrile resin is poor, and the mechanical properties of the blended resin matrix and the composite material are influenced.
Therefore, in view of the above problems, the present invention is urgently needed to provide a polyimide toughened phthalonitrile resin composition, a composite material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a polyimide toughened phthalonitrile resin composition, a composite material and a preparation method thereof, and solves the technical problems that the compatibility of common thermoplastic resin and phthalonitrile resin is poor, and the mechanical properties of a blended resin matrix and the composite material are influenced in the prior art by the polyimide toughened phthalonitrile resin composition.
The invention provides a polyimide toughened phthalonitrile resin composition, which comprises phthalonitrile and cyano functional group-containing polyimide resin:
the structural formula of the polyimide resin containing the cyano functional group is shown as the specification.
In the cyano-containing functional polyimide resin, the value ranges of m and n are 0-30, and m and n are not 0 at the same time.
Preferably, the molar percentage of phthalonitrile and cyano-functional polyimidebesin resin is (80% -90%): (10% -20%).
Preferably, the phthalonitrile structure is
Preferably, the preparation process of the cyano-functional polyimide-containing resin comprises the following steps:
adding a mixture containing cyano diamine and m-phenylenediamine in a certain proportion into an organic solvent to obtain a mixed solution, adding 3,3 ', 4, 4' -biphenyl dicarboxylic anhydride (s-BPDA) into the mixed solution after the mixed solution is dissolved, and stirring at room temperature to obtain a polyimide resin glue solution containing a cyano functional group.
Preferably, the glue solution of the cyano-functional polyimide-containing resin has a solid content of (20 +/-2) wt%.
Preferably, the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone.
The invention also provides a composite material, which comprises fibers and the polyimide toughened phthalonitrile resin composition.
Preferably, the mass percentage of the fiber and polyimide toughened phthalonitrile resin composition is (40% -50%): (50% -60%).
Preferably, the fibers comprise one of carbon fibers and quartz fibers.
The invention also provides a preparation method based on the composite material, which comprises the following preparation steps:
coating the polyimide toughened phthalonitrile resin composition on fibers, and airing to obtain a prepreg;
and (3) putting the prepreg into a mould, carrying out hot press molding by a hot press molding process, and demoulding to obtain the composite material.
The molding temperature of the composite material is 260 ℃ to 380 ℃, and the molding pressure is 3-10 MPa.
Compared with the prior art, the polyimide toughened phthalonitrile resin composition, the composite material and the preparation method thereof provided by the invention have the following advantages:
1. according to the polyimide toughened phthalonitrile resin composition provided by the invention, cyano in the side group of the polyimide resin can participate in the curing with phthalonitrile resin under a high-temperature condition, the compatibility of the high-temperature-resistant thermoplastic resin heating agent and the phthalonitrile resin is improved, the curing crosslinking degree can be regulated and controlled through the cyano content in the side group, and the mechanical property of the resin-based composite material is further regulated and controlled.
2. According to the composite material provided by the invention, the polyimide toughened phthalonitrile resin composition is coated on the fibers, so that the temperature resistance of the composite material is improved.
3. The composite material obtained by the invention can be widely applied to high-tech fields such as aviation, aerospace and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. 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.
The invention provides a polyimide toughened phthalonitrile resin composition, which comprises phthalonitrile and polyimide resin containing cyano functional groups:
the structural formula of the polyimide resin containing cyano functional groups is shown as
In the cyano-containing functional polyimide resin, the value of m and n ranges from 0 to 30, and m and n are not 0 at the same time.
Specifically, the molar percentage of the phthalonitrile and the cyano-functional polyimide-containing resin is (80% -90%): (10% -20%).
Specifically, the phthalonitrile structure is
Specifically, the preparation process of the polyimide resin containing the cyano functional group comprises the following steps:
adding a mixture containing cyano diamine and m-phenylenediamine in a certain proportion into an organic solvent to obtain a mixed solution, adding 3,3 ', 4, 4' -biphenyl dicarboxylic anhydride (s-BPDA) into the mixed solution after the mixed solution is dissolved, and stirring at room temperature to obtain a polyimide resin glue solution containing a cyano functional group.
Specifically, the solid content in the glue solution of the polyimide resin containing the cyano functional group is (20 +/-2) wt%.
Specifically, the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone.
The invention also provides a composite material, which comprises fibers and the polyimide toughened phthalonitrile resin composition.
Specifically, the mass percentage of the fiber and polyimide toughened phthalonitrile resin composition is (40% -50%): (50% -60%).
Specifically, the fiber includes one of a carbon fiber and a quartz fiber.
The invention also provides a preparation method based on the composite material, which comprises the following preparation steps:
coating the polyimide toughened phthalonitrile resin composition solution on fibers, and airing to obtain a prepreg;
and (3) putting the prepreg into a mould, carrying out hot press molding by a hot press molding process, and demoulding to obtain the composite material.
The molding temperature of the composite material is 260-380 ℃, and the molding pressure is 3-10 MPa.
Example one
The preparation process of the polyimide toughened phthalonitrile resin composition comprises the following steps:
s101) adding diamine containing cyano groups (30.1 g,0.1 mol) and m-phenylenediamine (10.8, 0.1 mol) into N-methylpyrrolidine copper, after completely dissolving, adding 3,3 ', 4, 4' -biphenyldicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution, and stirring for 24 hours at room temperature to obtain polyimide resin glue solution containing cyano-functional groups and with the solid content of (20 +/-2) wt%;
s102) adding a phthalonitrile compound (326.8 g,0.9 mol) into a glue solution of a cyano-functional polyimide resin with a solid content of (20 +/-2) wt% (0.2 mol of the cyano-functional polyimide resin obtained in the step S101); and uniformly stirring until the solution is clear to obtain a polyimide toughening phthalonitrile resin composition solution, wherein the molar ratio of phthalonitrile to the cyano-functional group-containing polyimide resin is 9: 2, the mol percentage is 81.8 percent to 18.2 percent.
The preparation process of the composite material comprises the following steps:
s103) brushing the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and the cyano functional group-containing polyimide resin is 419.3 g) onto 419.3g of carbon fiber cloth, and airing for 12-48h to obtain a prepreg;
s104) placing the prepreg into a mold, placing the mold into a hot press, closing the mold, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing pressure and demolding to obtain a composite material;
among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin containing cyano functional groups in this example is:
the properties of the composite obtained are shown in table 1.
The organic solvent in this embodiment is not limited to N-methylpyrrolidone, and may be one of N, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide, in order to dissolve the cyano-containing diamine and m-phenylenediamine.
Example two
Adding cyano-containing diamine (30.1 g,0.1 mol) and m-phenylenediamine (10.8 g,0.1 mol) into N-methylpyrrolidone, adding 3,3 ', 4, 4' -biphenyldicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution after completely dissolving, and stirring at room temperature for 24h to obtain cyano-containing functional polyimide resin glue solution with solid content of (20 +/-2) wt%;
adding phthalonitrile compound (432.5 g,0.9 mol) into cyano-containing functional group imide resin glue solution with solid content of (20 +/-2) weight percent, and uniformly stirring until the solution is clear to obtain polyimide toughening phthalonitrile resin composition;
brushing the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and cyano functional group-containing polyimide resin is 525.0 g) onto 525.0g of carbon fiber cloth to prepare a prepreg with a certain gel content, and airing at room temperature for 12-48h to prepare the prepreg.
Cutting a prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin containing cyano functional groups in this example is:
the properties of the composite obtained are shown in table 1.
EXAMPLE III
Adding cyano-containing diamine (30.1 g,0.1 mol) and m-phenylenediamine (10.8 g,0.1 mol) into N-methylpyrrolidone, adding 3,3 ', 4, 4' -biphenyldicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution after completely dissolving, and stirring at room temperature for 24h to obtain cyano-containing functional polyimide resin glue solution with solid content of (20 +/-2) wt%;
adding phthalonitrile compound (394.6 g,0.9 mol) into (20 +/-2) wt% of cyano-containing functional polyimide resin glue solution, and uniformly stirring until the solution is clear to obtain the polyimide toughened phthalonitrile resin composition;
brushing the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and cyano functional group-containing polyimide resin is 487.1 g) onto 487.1g of carbon fiber cloth to prepare a prepreg with a certain gel content, and airing at room temperature for 12-48h to prepare the prepreg.
Cutting a prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin containing cyano functional groups in this example is:
the properties of the composite obtained are shown in table 1.
Example four
Adding diamine containing cyano groups (30.1 g,0.1 mol) and m-phenylenediamine (10.8 g,0.1 mol) into N-methylpyrrolidone, after completely dissolving, adding 3,3 ', 4, 4' -biphenyldicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution, stirring for 24 hours at room temperature to obtain a glue solution of the polyimideside resin containing cyano-functional groups and with the solid content of (20 +/-2) weight percent;
adding a phthalonitrile compound (529.2 g,0.9 mol) into a cyano-functional polyimide-containing resin glue solution with the solid content of (20 +/-2) wt%, and uniformly stirring until the solution is clear to obtain a polyimide toughened phthalonitrile resin composition;
brushing the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and cyano functional group-containing polyimide resin is 621.7 g) onto 621.7g of carbon fiber cloth to prepare a prepreg with a certain gel content, and airing at room temperature for 12-48h to prepare the prepreg.
Cutting the prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin containing cyano functional groups in this example is:
the properties of the composite obtained are shown in table 1.
EXAMPLE five
Adding diamine containing cyano (60.2 g, 0.2 mol) into N-methylpyrrolidone, after completely dissolving, adding 3,3 ', 4, 4' -biphenyl dicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution, and stirring for 24 hours at room temperature to obtain a glue solution of the polyimideside resin containing cyano and with solid content of (20 +/-2) weight percent;
adding phthalonitrile compound (529.2 g,0.9 mol) into cyano-containing functional group imide resin glue solution with solid content of (20 +/-2) weight percent, and uniformly stirring until the solution is clear to obtain polyimide toughening phthalonitrile resin composition;
brushing the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and cyano functional group-containing polyimide resin is 641 g) to 641g of carbon fiber cloth to prepare a prepreg with a certain gel content, and airing at room temperature for 12-48h to prepare the prepreg.
Cutting the prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin containing cyano functional groups in this example is:
the properties of the composite obtained are shown in table 1.
EXAMPLE six
Adding m-phenylenediamine (21.6 g, 0.2 mol) into N-methylpyrrolidone, adding 3,3 ', 4, 4' -biphenyl dicarboxylic anhydride (58.8 g, 0.2 mol) into the clear solution after completely dissolving, and stirring at room temperature for 24 hours to obtain cyano-functional polyimide resin glue solution with solid content of (20 +/-2) wt%;
adding phthalonitrile compound (529.2 g,0.9 mol) into cyano-containing functional group imide resin glue solution with solid content of (20 +/-2) weight percent, and uniformly stirring until the solution is clear to obtain polyimide toughening phthalonitrile resin composition;
the polyimide toughened phthalonitrile resin composition (the total content of phthalonitrile and the polyimide resin containing cyano functional groups is 602.4 g) is brushed onto 602.4g of carbon fiber cloth to prepare a prepreg with a certain gel content, and the prepreg is prepared after the prepreg is aired at room temperature for 12-48 h.
Cutting the prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the structure of the polyimide resin in this example is:
the properties of the composite material obtained are shown in Table 1
Comparative example
Adding a phthalonitrile compound (529.2 g,0.9 mol) into N-methylpyrrolidone, and uniformly stirring until the solution is clear to obtain a phthalonitrile resin solution;
brushing the phthalonitrile resin solution (with the phthalonitrile resin content of 529.2 g) onto 529.2g of carbon fiber cloth to prepare a prepreg with a certain gel content, and airing at room temperature for 12-48h to prepare the prepreg.
Cutting the prepreg according to the size of a mould, placing the cut prepreg in the mould, placing the mould in a hot press, closing the mould, carrying out temperature programming of 160 ℃/1h +240 ℃/2h +320 ℃/1h +380 ℃/2h for molding, cooling to below 50 ℃ after curing, releasing the pressure and demoulding to obtain the composite material.
Among them, the structure of the phthalonitrile compound in this example is:
the properties of the composite obtained are shown in table 1.
TABLE 1 composite Properties
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A polyimide toughening phthalonitrile resin composition is characterized in that: including phthalonitrile and cyano-containing functional group polyimide resins:
the structural formula of the polyimide resin containing cyano functional groups is shown as
In the cyano-containing functional polyimide resin, the value of m and n ranges from 0 to 30, and m and n are not 0 at the same time.
2. The polyimide toughened phthalonitrile resin composition according to claim 1, wherein: the mol percentage of the phthalonitrile and the cyano-functional polyimide resin is (80-90%): (10% -20%).
3. The polyimide toughened phthalonitrile resin composition as claimed in claim 2, wherein: the phthalonitrile structure is
4. The polyimide toughened phthalonitrile resin composition according to claim 3, wherein: the preparation process of the cyano-containing functional polyimide resin comprises the following steps:
adding a mixture containing cyano diamine and m-phenylenediamine in a certain proportion into an organic solvent to obtain a mixed solution, adding 3,3 ', 4, 4' -biphenyl dicarboxylic anhydride (s-BPDA) into the mixed solution after the mixed solution is dissolved, and stirring at room temperature to obtain a polyimide resin glue solution containing cyano functional groups.
5. The polyimide toughened phthalonitrile resin composition according to claim 4, wherein: the solid content in the glue solution of the polyimide resin containing the cyano functional group is (20 +/-2) wt%.
6. The polyimide toughened phthalonitrile resin composition according to claim 5, wherein: the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
7. A composite material characterized by: comprising fibers, and the polyimide toughened phthalonitrile resin composition as claimed in any of claims 1 to 6.
8. The composite material of claim 7, wherein: the mass percentage of the fiber and polyimide toughened phthalonitrile resin composition is (40-50%): (50% -60%).
9. The composite material according to claim 8, characterized in that: the fiber includes one of a carbon fiber and a quartz fiber.
10. A method for preparing a composite material according to claim 7, characterized in that: the preparation method comprises the following preparation steps:
coating the polyimide toughened phthalonitrile resin composition on fibers, and airing to obtain a prepreg;
and (3) putting the prepreg into a mould, carrying out hot press molding by a hot press molding process, and demoulding to obtain the composite material.
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Citations (6)
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| CN109096753A (en) * | 2017-06-21 | 2018-12-28 | 中国人民解放军国防科学技术大学 | Nitrile resin composite material and preparation method thereof |
| CN113246564A (en) * | 2020-02-13 | 2021-08-13 | 中国科学院化学研究所 | High-strength high-toughness phthalonitrile-based composite material and preparation method and application thereof |
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2022
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