CN112375380B - Modified phthalonitrile resin and preparation method thereof - Google Patents
Modified phthalonitrile resin and preparation method thereof Download PDFInfo
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- CN112375380B CN112375380B CN202011324276.7A CN202011324276A CN112375380B CN 112375380 B CN112375380 B CN 112375380B CN 202011324276 A CN202011324276 A CN 202011324276A CN 112375380 B CN112375380 B CN 112375380B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Abstract
The invention relates to a modified phthalonitrile resin and a preparation method thereof, wherein the modified phthalonitrile resin consists of phthalonitrile resin, co-curable toughening agent and curing agent, wherein the mass fraction of the phthalonitrile resin is 70-100, the mass fraction of the co-curable toughening agent is 10-30, and the mass fraction of the curing agent is 0-10; the composite material is cured and molded at 170-375 ℃. The modified phthalonitrile resin system has a longer process window and proper melt viscosity, and is suitable for a molding process of a die-pressing composite material. The composite material has higher strength and interlaminar shear strength, and is suitable for composite material parts with high-temperature resistant structures.
Description
Technical Field
The invention relates to a modified phthalonitrile resin and a preparation method thereof, in particular to a modified phthalonitrile resin containing a co-curable toughening agent and a preparation method thereof, belonging to the technical field of phthalonitrile resin modification.
Background
The rapidly developed aviation and aerospace industries put higher requirements on the performance of materials in extreme environments, and the development trend is towards the integration of high strength, high modulus, high heat resistance, high toughness and structural functions. The phthalonitrile resin is widely applied in the fields of aerospace, ships, machinery, electronic materials and the like due to excellent high-temperature resistance, outstanding chemical corrosion resistance, flame retardance and moisture absorption resistance, and is one of the most high-temperature resistant resin systems with structure-function integrated application potential at present. But because of the higher crosslinking density and rigid structure, the cured resin has large internal stress and has the defects of brittle quality, poor impact toughness and the like.
The phthalonitrile resin generally has higher crosslinking density and rigid structure to ensure excellent heat resistance, but the excessively high cyano-group density increases the inherent brittleness of crosslinking networks, so that the impact toughness and the interlaminar shear performance of the cyano-group resin and the composite material thereof are poor, and further expansion of the application field of the cyano-group resin is severely limited.
The performance research of the phthalonitrile resin is limited to structural characteristics such as heat resistance and mechanics, the process research of the resin system is less, and the resin system is basically in the starting stage.
The prior method for toughening the phthalonitrile resin mainly comprises rigid nano ion filling, thermoplastic resin and other thermosetting resin blending. The filling phase comprises nano silicon carbide, silicon nitride, zinc oxide and ternary metal MAX phase Ti 3 SiC 2 Alumina, zirconia, two Polysilsesquioxanes (POSS), etc., but the mechanical properties are affected by the problem of poor compatibility. The thermoplastic resin includes polysulfone, polyethersulfone, polyarylethernitrile, etc., and has an influence on the heat resistance of the resin. Thermosetting resins include epoxy resins, bismaleimide resins, phenolic resins, and the like, and also affect the heat resistance of the resin.
Therefore, in view of the above disadvantages, it is desirable to provide a modified phthalonitrile resin and a method for preparing the same.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve the technical problems that the compatibility of the traditional toughening method for phthalonitrile resin is poor, the mechanical property of the phthalonitrile resin is influenced and the heat resistance of the resin is poor.
(II) technical scheme
In order to solve the above technical problems, the present invention provides, in a first aspect, a modified phthalonitrile resin, comprising, in parts by mass:
70-100 parts of phthalonitrile resin;
10-30 parts of co-curable toughening agent;
0-10 parts of curing agent.
The present invention provides, in a second aspect, a method for producing a modified phthalonitrile resin according to the first aspect of the present invention, comprising the steps of:
(1) Weighing phthalonitrile resin, a co-curable toughening agent and a curing agent;
(2) Melting phthalonitrile resin;
(3) Adding the co-curable toughening agent into the molten phthalonitrile resin and stirring to obtain a blend;
(4) And reducing the temperature of the blend, adding the curing agent, and stirring to obtain the modified phthalonitrile resin.
In a third aspect the present invention provides a method of testing tensile strength and interlaminar shear strength, said method comprising the steps of:
preparing a solution from the modified phthalonitrile resin prepared by the preparation method in the first aspect of the invention or the second aspect of the invention and acetone, uniformly stirring the solution to prepare a T700 unidirectional carbon fiber prepreg, then preparing a composite material laminated board, carrying out curing reaction on the composite material laminated board, then cooling to room temperature to obtain a T700/phthalonitrile resin composite material, cutting the composite material into a standard sample (refer to the standard GB/T3354-1999, JC/T773-2010), and carrying out tensile strength and interlaminar shear strength tests.
(III) advantageous effects
The technical scheme of the invention has the following advantages:
(1) The invention adopts the phthalonitrile resin modified by the co-curable toughening agent, improves the melt viscosity of the phthalonitrile resin by using the toughening agent, and the melt viscosity of the modified phthalonitrile resin is more than 1 Pa.s, thereby meeting the requirements of a molding process of a mold pressing composite material on the resin, effectively improving the interlaminar shear strength of the resin-based composite material and improving the toughness of the resin.
(2) The co-curable toughening agent used in the invention has higher melt viscosity and better compatibility with phthalonitrile resin, and the co-curing reaction is carried out between the phthalonitrile end group or side group and the phthalonitrile group, so that the compatibility with phthalonitrile resin is improved, the curing window of phthalonitrile resin is increased, the problem of extremely low melt viscosity of phthalonitrile resin is solved, and the process requirement of a mould pressing process on resin is met.
(3) The modified phthalonitrile resin prepared by the invention can be used for preparing high-temperature-resistant structural composite materials, and is used for aviation structural materials of commercial airplanes, unmanned planes, military warplanes and the like and civil fields of transportation, ships, naval vessels, electronics and electricians and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a modified phthalonitrile resin, which comprises the following components in parts by weight:
70-100 parts of phthalonitrile resin (for example, 75 parts, 80 parts, 90 parts and the like can be realized);
co-curable toughener 10-30 (e.g., 15 parts, 20 parts, 25 parts, etc.);
0 to 10 parts of curing agent (for example, 3 parts, 7 parts, 10 parts, etc.) is acceptable.
According to some preferred embodiments, the phthalonitrile resin is a monomeric phthalonitrile resin or an autocatalytic phthalonitrile resin;
the specific type of the phthalonitrile is not particularly limited, and may be bisphenol a type phthalonitrile resin, bisphenol F type phthalonitrile resin, resorcinol type phthalonitrile resin, or other types of phthalonitrile resin, and may be liquid or solid at room temperature.
According to some preferred embodiments, the co-curable toughening agent is a thermoplastic polymer containing pendant or terminal phthalonitrile groups;
preferably, the co-curable toughening agent comprises polyetheretherketone, polyphenylene oxide or polyethersulfone;
more preferably, the number of phthalonitrile groups available for reaction in each of the co-curable toughener molecules is not less than 2;
more preferably, the molecular weight of the co-curable toughening agent is 1000 to 5000, and the molar mass of the co-curable toughening agent is (1000 to 5000) g/mol.
According to some preferred embodiments, the curing agent is an organic curing agent containing active hydrogens;
preferably, the curing agent may be aromatic amine or aromatic alcohol;
more preferably, the curing agent is in a powder state at room temperature.
The present invention provides, in a second aspect, a method for producing a modified phthalonitrile resin according to the first aspect of the present invention, comprising the steps of:
(1) Weighing phthalonitrile resin, a co-curable toughening agent and a curing agent;
(2) Melting phthalonitrile resin;
(3) Adding the co-curable toughening agent into the molten phthalonitrile resin and stirring to obtain a blend;
(4) And reducing the temperature of the blend, adding the curing agent, and stirring to obtain the modified phthalonitrile resin.
According to some preferred embodiments, the temperature at which the phthalonitrile resin melts is from 100 ℃ to 160 ℃;
in step (2), the phthalonitrile is melted to a homogeneous liquid.
According to some preferred embodiments, in the step (3), the stirring time is 20 to 30min.
According to some preferred embodiments, in step (4), the temperature of the blend is reduced to 110 to 140 ℃;
preferably, the temperature of the blend is reduced to 110-130 ℃;
the stirring time is 10-20 min.
In a third aspect the present invention provides a method of testing tensile strength and interlaminar shear strength, said method comprising the steps of:
preparing a solution from the modified phthalonitrile resin prepared by the method in the first aspect or the modified phthalonitrile resin prepared by the method in the second aspect of the invention and acetone, uniformly stirring the solution to prepare a T700 unidirectional fiber prepreg, then preparing a composite material laminated board, carrying out curing reaction on the composite material laminated board, then cooling to room temperature to obtain a T700/phthalonitrile resin composite material, cutting the composite material into a standard sample (refer to standard GB/T3354-1999, JC/T773-2010), and carrying out tensile strength and interlaminar shear strength tests.
According to some preferred embodiments, the concentration of the modified phthalonitrile resin in the solution of the modified phthalonitrile resin in acetone is 50% by weight;
the prepreg is prepared from T700-grade carbon fiber unidirectional fabric;
the composite material laminated board is prepared by adopting a compression molding process;
the temperature of the curing reaction is 170-375 ℃, and preferably, the temperature of the curing reaction is 320 ℃;
the curing reaction time is 3-5h.
Example 1
The formula is as follows (mass portions):
phthalonitrile resin (resorcinol type phthalonitrile) 85
Co-curable toughener (containing phthalonitrile capped polyethersulfone) 10
Curing agent (diamino diphenyl sulfone) 5
Wherein the molar mass of the polyether sulfone containing phthalonitrile end capping is 2000g/mol, and the number of phthalonitrile containing functional groups is 2;
the preparation method comprises the following steps:
(1) According to the following steps of 85:10:5, weighing resorcinol type phthalonitrile, polyether sulfone containing phthalonitrile end capping and diamino diphenyl sulfone in parts by weight;
(2) Melting resorcinol type phthalonitrile to uniform liquid at 150 ℃;
(3) Adding polyether sulfone containing phthalonitrile end capping into the molten phthalonitrile resin, and stirring for 30 minutes by using stirring equipment;
(4) Cooling the blend obtained in the third step to 130 ℃, adding weighed diamino diphenyl sulfone, and stirring for 10 minutes to obtain modified phthalonitrile resin, wherein the detected minimum melt viscosity of the resin is shown in table 1;
(5) Preparing a solution with the concentration of 50 weight percent by using modified phthalonitrile resin and acetone, uniformly stirring the solution, preparing a prepreg by using a T700-grade carbon fiber unidirectional fabric, preparing a composite material laminated board by adopting a compression molding process, curing the composite material to 320 ℃, cooling the composite material to room temperature, cutting the prepared composite material into standard samples according to the specification, and testing the tensile strength and the interlaminar shear strength, wherein the performance data are shown in table 1.
Example 2
The formula is as follows (mass portions):
phthalonitrile resin (bisphenol A type phthalonitrile) 85
Co-curable toughener (containing phthalonitrile-capped polyethersulfone) 10
Curing agent (diamino diphenyl sulfone) 5
Wherein the molar mass of the polyether sulfone containing phthalonitrile end capping is 2000g/mol, and the number of functional groups containing phthalonitrile is 2;
the preparation method comprises the following steps:
(1) According to the following steps of 85:10:5, weighing a certain amount of bisphenol A type dicyandiamide resin, polyether sulfone containing phthalonitrile end capping and diamino diphenyl sulfone;
(2) Melting bisphenol A phthalonitrile to uniform liquid at 160 ℃;
(3) Adding polyether sulfone containing phthalonitrile end capping into the molten phthalonitrile resin, and stirring for 30 minutes by using stirring equipment;
(4) Cooling the blend obtained in the third step to 130 ℃, adding weighed diamino diphenyl sulfone, and stirring for 20 minutes to obtain modified phthalonitrile resin, wherein the detected minimum melt viscosity of the resin is shown in table 1;
(5) Preparing a solution with the concentration of 50 wt% by using modified phthalonitrile resin and acetone, uniformly stirring the solution, preparing a prepreg by using a T700-grade carbon fiber unidirectional fabric, preparing a composite material laminated board by using a compression molding process, solidifying to 320 ℃, cooling to room temperature, cutting the prepared composite material into standard samples according to the specification, and testing the tensile strength and the interlaminar shear strength, wherein the performance data are shown in table 1.
Example 3
The formula is as follows (mass portions):
phthalonitrile resin (resorcinol type phthalonitrile) 85
Co-curable toughener (containing phthalonitrile-terminated polyetherketone) 10
Curing agent (diamino diphenyl sulfone) 5
The molar mass of the phthalonitrile-terminated polyether ketone is 2000g/mol, and the number of phthalonitrile-terminated functional groups is 2;
the preparation method comprises the following steps:
(1) According to the following steps of 85:10:5, weighing a certain amount of resorcinol type phthalonitrile, polyether ketone containing end capping phthalonitrile and diamino diphenyl sulfone;
(2) Melting resorcinol type phthalonitrile to uniform liquid at 150 ℃;
(3) Adding polyether ketone containing phthalonitrile end capping into molten phthalonitrile resin, and stirring for 30 minutes by using stirring equipment;
(4) Cooling the temperature of the blend obtained in the third step to 130 ℃, adding weighed diamino diphenyl sulfone, and stirring for 15 minutes to obtain modified phthalonitrile resin, wherein the detected minimum melt viscosity of the resin is shown in table 1;
(5) Preparing a solution with the concentration of 50 wt% by using modified phthalonitrile resin and acetone, uniformly stirring the solution, preparing a prepreg by using a T700-grade carbon fiber unidirectional fabric, preparing a composite material laminated board by using a compression molding process, solidifying to 320 ℃, cooling to room temperature, cutting the prepared composite material into standard samples according to the specification, and testing the tensile strength and the interlaminar shear strength, wherein the performance data are shown in table 1.
Example 4
Phthalonitrile resin (bisphenol A type phthalonitrile) 85
Co-curable toughener (containing phthalonitrile-terminated polyetherketone) 10
Curing agent (diamino diphenyl sulfone) 5
The molar mass of the phthalonitrile-terminated polyether ketone is 2000g/mol, and the number of phthalonitrile-terminated functional groups is 2;
the preparation method comprises the following steps:
(1) According to the following steps of 85:10:5, weighing a certain amount of phthalonitrile resin, polyether ketone containing phthalonitrile end capping and diamino diphenyl sulfone;
(2) Melting bisphenol A phthalonitrile to uniform liquid at 160 ℃;
(3) Adding polyether ketone containing phthalonitrile end capping into the molten phthalonitrile resin, and stirring for 30 minutes by using stirring equipment;
(4) Cooling the blend obtained in the third step to 130 ℃, adding weighed diamino diphenyl sulfone, and stirring for 10-20 minutes to obtain modified phthalonitrile resin, wherein the detected minimum melt viscosity of the resin is shown in table 1;
(5) Preparing a solution with the concentration of 50 weight percent by using modified phthalonitrile resin and acetone, uniformly stirring the solution, preparing a prepreg by using a T700-grade carbon fiber unidirectional fabric, preparing a composite material laminated board by adopting a compression molding process, curing the composite material to 320 ℃, cooling the composite material to room temperature, cutting the prepared composite material into standard samples according to the specification, and testing the tensile strength and the interlaminar shear strength, wherein the performance data are shown in table 1.
TABLE 1 modified phthalonitrile resins and their composite Properties
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 should 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 (12)
1. A modified phthalonitrile resin is characterized in that: the modified phthalonitrile resin comprises the following components in parts by weight:
70-100 parts of phthalonitrile resin;
10-30 parts of a co-curable toughening agent;
0-10 parts of curing agent;
the phthalonitrile resin is selected from the group consisting of bisphenol a type phthalonitrile resin, bisphenol F type phthalonitrile resin and resorcinol type phthalonitrile resin;
the co-curable toughening agent is selected from one of the group consisting of phthalonitrile capped polyether ether ketone, polyphenylene oxide or polyether sulfone; the number of phthalonitrile groups which can participate in the reaction in each molecule of the co-curable toughening agent is not less than 2; the molar mass of the co-curable toughening agent is (1000-5000) g/mol;
the curing agent is diamino diphenyl sulfone; the mass portion of the curing agent is not 0;
the modified phthalonitrile resin is obtained by reacting the molten phthalonitrile resin, the co-curable toughening agent and the curing agent; the melting temperature of the phthalonitrile resin is 100-160 ℃.
2. The modified phthalonitrile resin according to claim 1, characterized in that:
the purity of the phthalonitrile resin is more than 99%.
3. The modified phthalonitrile resin of claim 2, characterized in that:
the phthalonitrile resin is liquid or solid at room temperature.
4. The modified phthalonitrile resin according to claim 1, characterized in that:
the state of the curing agent at room temperature is powder.
5. A production method of a modified phthalonitrile resin according to any one of claims 1 to 4, characterized in that it comprises the steps of:
(1) Weighing phthalonitrile resin, a co-curable toughening agent and a curing agent;
(2) Melting phthalonitrile resin;
(3) Adding the co-curable toughening agent into the molten phthalonitrile resin and stirring to obtain a blend;
(4) And reducing the temperature of the blend, adding the curing agent, and stirring to obtain the modified phthalonitrile resin.
6. The production method according to claim 5, characterized in that:
in step (2), the phthalonitrile is melted to a homogeneous liquid.
7. The method of claim 5, wherein:
in the step (3), the stirring time is 20 to 30min.
8. The method of claim 5, wherein:
in step (4), the temperature of the blend is reduced to 110-140 ℃;
the stirring time is 10 to 20min.
9. The method of claim 8, wherein:
in step (4), the blend temperature is reduced to 110-130 ℃.
10. The preparation method of the T700/phthalonitrile resin composite material is characterized by comprising the following steps:
preparing a solution of the modified phthalonitrile resin according to any one of claims 1 to 4 or prepared by the method according to any one of claims 5 to 9 and acetone, uniformly stirring the solution to prepare a T700 unidirectional fiber prepreg, preparing a composite material laminated board, carrying out a curing reaction on the composite material laminated board, and cooling to room temperature to obtain the T700/phthalonitrile resin composite material.
11. The method of manufacturing according to claim 10, wherein:
in the solution prepared by the modified phthalonitrile resin and acetone, the concentration of the modified phthalonitrile resin is 50 weight percent;
the prepreg is prepared from T700-grade carbon fiber unidirectional fabric;
the composite material laminated board is prepared by adopting a compression molding process;
the temperature of the curing reaction is 170 to 375 ℃, and the time of the curing reaction is 3 to 5 hours.
12. The method for producing according to claim 11, characterized in that:
the temperature of the curing reaction was 320 ℃.
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| CN113201302B (en) * | 2021-05-06 | 2023-03-03 | 黑龙江省科学院石油化学研究院 | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof |
| CN114085524B (en) * | 2021-11-18 | 2023-09-29 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin prepreg, composite material and preparation method thereof |
| CN113913013B (en) * | 2021-11-18 | 2023-09-29 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin and preparation method and application thereof |
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| CN103834008B (en) * | 2014-03-10 | 2016-09-28 | 中国科学院化学研究所 | A kind of o-phthalonitrile resin and preparation method thereof |
| CN104845349B (en) * | 2015-05-25 | 2017-03-08 | 吉林大学 | Toughness reinforcing bi-phthalonitrile resin material of polyether sulfone and preparation method thereof |
| WO2018175025A1 (en) * | 2017-03-23 | 2018-09-27 | 3M Innovative Properties Company | Resin blends containing a phthalonitrile reactive diluent and a diphthalonitrile resin, prepregs, and articles |
| CN108454135B (en) * | 2018-01-31 | 2020-07-14 | 航天材料及工艺研究所 | Phthalonitrile resin prepreg, composite material and preparation method thereof |
| CN111875793A (en) * | 2020-07-31 | 2020-11-03 | 湖南恒缘新材科技股份有限公司 | Phthalonitrile resin for composite material and preparation method thereof |
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