CN113004518B - Phthalonitrile resin prepolymer and preparation method thereof - Google Patents
Phthalonitrile resin prepolymer and preparation method thereof Download PDFInfo
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- CN113004518B CN113004518B CN202110323224.6A CN202110323224A CN113004518B CN 113004518 B CN113004518 B CN 113004518B CN 202110323224 A CN202110323224 A CN 202110323224A CN 113004518 B CN113004518 B CN 113004518B
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- 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
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
Abstract
The invention discloses a high-temperature-resistant phthalonitrile resin prepolymer and a preparation method thereof. The technical characteristics are as follows: dissolving 100 parts (by mass) of phthalonitrile resin and 1-100 parts of 1, 7-bis-hydroxymethyl-m-carborane in an organic solvent, and carrying out prepolymerization reaction for 1-8 h at 100-250 ℃. After the pre-coalescence is finished, cooling the reaction liquid to room temperature, pouring the reaction liquid into water, carrying out suction filtration to obtain a precipitated precipitate, and drying the precipitate to obtain the phthalonitrile resin prepolymer. The phthalonitrile resin prepolymer prepared by the method has excellent thermal oxidation resistance, mechanical property and dielectric property, has good solubility in common organic solvents, reduces the curing temperature, and has wide application prospect in the fields of aerospace, national defense, communication and the like.
Description
Technical Field
The invention relates to preparation of a phthalonitrile resin prepolymer, namely 1, 7-dihydroxymethyl-m-carborane catalyzed prepolymerized phthalonitrile resin and a preparation method thereof.
Background
The phthalonitrile resin is widely applied to a plurality of important fields of aerospace, national defense and the like as an important high-temperature resistant matrix material. The material is characterized in that the molecule contains cyano, can react under the action of a curing agent to form various nitrogen-containing aromatic rings, and has excellent thermal oxidation resistance, dielectric property and mechanical property.
The phthalonitrile resin is successfully researched and developed by Keller team of American navy laboratory, has very high decomposition temperature after being cured, has almost the same decomposition temperature difference between air and nitrogen, shows very good thermal oxidation resistance, and has heat resistance superior to common thermosetting resins such as bismaleimide resin, benzoxazine resin, polyimide resin and the like.
Studies show that the curing process of the phthalonitrile resin monomer is very slow, and under the condition of 250 ℃ and no curing agent, the obvious gel phenomenon can be observed within 4 to 5 days. Therefore, phthalonitrile resin needs to be added with a curing agent to improve the processing performance, and the common curing agents at present are: organic amine, metal salt, organic phenol, etc. However, the common organic amine curing agent is easily decomposed at high temperature, thereby affecting the thermal property and the mechanical property of the polymer. Even with the addition of such curing agents, heating to 375 ℃ or even higher is required to fully cure the resin, greatly limiting the use of phthalonitrile resins. In addition, phthalonitrile resin has poor solubility, and has good solubility in high boiling point solvents such as N, N-dimethylformamide and N-methylpyrrolidone, but is insoluble in low boiling point solvents such as acetone, tetrahydrofuran, ethanol and ethyl acetate, which makes it difficult to prepare a composite material.
Carborane (C)2B10H12) The compound is a three-dimensional super-aromatic polyhedral compound consisting of three atoms of boron, carbon and hydrogen, and has extremely high heat resistance due to a cage structure and a large amount of boron atoms. And 1, 7-bis-hydroxymethyl-m-carborane (C)4H16B10O2) The hydroxymethyl is introduced while the excellent high-temperature resistance of the carborane is not influenced, so that the chemical reaction activity is improved. In addition, the polymer has high boron-carbon ratio, and can be used as a precursor of boron carbide and an atomic oxygen resistant coating for space technology.
The method adopts 1, 7-bis-hydroxymethyl-m-carborane to catalyze and pre-polymerize phthalonitrile resin to form an organic-inorganic hybrid system, improves the solubility of the polymer, reduces the curing temperature of the resin, solves the problem of difficult processing, simultaneously improves the high temperature resistance and mechanical property of a cured product, and meets the requirements of a new generation of high-performance wave-transmitting material and a high-performance resin matrix for aerospace. The system is characterized in that: (1) the introduction of 1, 7-bis-hydroxymethyl-m-carborane improves the solubility of phthalonitrile resin. (2) The introduction of 1, 7-bis-hydroxymethyl-m-carborane lowers the curing temperature of the phthalonitrile resin. (3) The temperature resistance and the mechanical property of the system can be regulated and controlled by changing the adding amount of the 1, 7-bis-hydroxymethyl-m-carborane, and the thermal oxidation property and the mechanical property of the phthalonitrile resin at high temperature are improved. At present, relevant reports at home and abroad are not found.
Disclosure of Invention
The invention aims to provide a preparation method of a phthalonitrile resin prepolymer aiming at the defects in the prior art. The phthalonitrile-carborane hybrid prepolymer is prepared by reacting 1, 7-bis-hydroxymethyl-m-carborane with phthalonitrile resin, meets various advanced composite material forming processes, and can be applied to the fields of aerospace, communication and the like.
Technical scheme
A preparation method of a phthalonitrile resin prepolymer comprises the following steps:
(1) a preparation method of high-temperature-resistant phthalonitrile resin prepolymer is characterized by comprising the following steps:
dissolving 100 parts (by mass) of phthalonitrile resin and 1-100 parts of 1, 7-bis-hydroxymethyl-m-carborane in an organic solvent, stirring for 1-8 hours at 100-250 ℃, and carrying out prepolymerization reaction.
And pouring the prepolymer obtained by the reaction into water, stirring for 1-60 min to completely separate out the precipitate, performing suction filtration to obtain the precipitate, and drying the precipitate at 80-150 ℃ for 1-50 h to obtain the phthalonitrile resin prepolymer.
(2) The preparation method of the high-temperature-resistant phthalonitrile resin prepolymer in the step (1) is characterized by comprising the following steps: the phthalonitrile resin is: bisphenol a-type phthalonitrile resin, bisphenol S-type phthalonitrile resin, bisphenol F-type phthalonitrile resin, biphenyl-type phthalonitrile resin, benzoxazine-type phthalonitrile resin, phenol-aldehyde-type phthalonitrile resin, nitrile ether-type phthalonitrile resin.
(3) The method described in step (2), characterized in that: the organic solvent is one or more of 1, 4-dioxane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
(4) The prepolymerization temperature in the step (2) is 100-250 ℃, and preferably 160-220 ℃.
(5) The prepolymerization reaction time in the step (2) is 1-8 h, preferably 1-4 h.
Drawings
FIG. 1 is a DSC spectrum of a phthalonitrile resin prepolymer in example 1.
FIG. 2 is a TGA spectrum of a cured product of a phthalonitrile resin prepolymer in example 1.
FIG. 3 is a TGA spectrum of a cured product of the phthalonitrile resin prepolymer in example 2.
FIG. 4 is a TGA spectrum of a cured product of a phthalonitrile resin prepolymer in example 3.
Detailed Description
The invention is further described below:
the invention utilizes 1, 7-bis-hydroxymethyl-m-carborane to react with phthalonitrile resin to prepare phthalonitrile-carborane hybrid prepolymer. Firstly, mixing phthalonitrile resin and 1, 7-bis-hydroxymethyl-m-carborane in a solvent, wherein the raw material formula comprises 100 parts of phthalonitrile resin and 1-100 parts of 1, 7-bis-hydroxymethyl-m-carborane in a mass ratio. After the materials are completely dissolved, stirring the materials for 1 to 8 hours at the temperature of between 100 and 250 ℃ to perform prepolymerization reaction. And after the reaction is finished, pouring the prepolymer obtained by the reaction into water, stirring for 1-60 min to completely separate out the precipitate, performing suction filtration to obtain the precipitate, and drying the precipitate at 80-150 ℃ for 1-50 h to obtain the phthalonitrile resin prepolymer. The phthalonitrile resin can be bisphenol A phthalonitrile resin, bisphenol S phthalonitrile resin, bisphenol F phthalonitrile resin, biphenyl phthalonitrile resin, benzoxazine phthalonitrile resin, phenolic phthalonitrile resin and nitrile ether phthalonitrile resin.
Example 1
Pre-polymerization of phthalonitrile resin:
10g (22.83mmol) of biphenyl phthalonitrile resin monomer and 2g (9.79mmol) of 1, 7-bis-hydroxymethyl-m-carborane are added into a four-neck flask, then 20g N-methyl pyrrolidone is added, the mixture is heated to 180 ℃, the mixture is mechanically stirred for 4 hours, the solution is poured into deionized water after the reaction is finished, the mixture is stirred for 30 minutes, and the precipitated precipitate is obtained through reduced pressure suction filtration. And drying the precipitate in an oven at 100 ℃ for 20 hours to obtain the biphenyl phthalonitrile resin prepolymer. The prepolymer has good solubility in ethyl acetate, acetone, tetrahydrofuran, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
Curing the prepolymer:
weighing the synthesized biphenyl phthalonitrile resin prepolymer in a ceramic crucible, and curing in a muffle furnace according to the following step heating program (the heating rate is 5 ℃/min): 240 ℃/2h +280 ℃/2h +300 ℃/2h +320 ℃/2h +350 ℃/4h, and obtaining the biphenyl phthalonitrile resin condensate after the muffle furnace is cooled to the room temperature.
FIG. 1 is a DSC spectrum of a phthalonitrile resin prepolymer in example 1. And carrying out DSC test at 50-400 ℃ at a heating rate of 10 ℃/min under nitrogen purging. An endothermic peak appears at 228 ℃, which is the melting point of the monomer, and obvious exothermic peaks appear at 266 ℃ and 317 ℃, which shows that the 1, 7-bis-hydroxymethyl-m-carborane has obvious catalytic effect on the curing of the phthalonitrile resin
FIG. 2 is a TGA spectrum of a cured product of the phthalonitrile resin prepolymer in example 1. The thermogravimetric analysis test was performed at a temperature rise rate of 10 ℃/min. Thermogravimetric analysis data were as follows: example 1 thermal decomposition temperatures (T) in Nitrogen and air atmospheresd5) 581 ℃ and 565 ℃ and 80.30% and 40.63% of carbon residue (1000 ℃) in a nitrogen atmosphere and an air atmosphere, respectively. The phthalonitrile pre-polymerized resin has excellent heat oxidation resistance and can be applied to the fields of aerospace, national defense and the like.
Example 2
Pre-polymerization of phthalonitrile resin:
15g (31.25mmol) of bisphenol A type phthalonitrile resin monomer and 1.5g (7.34mmol) of 1, 7-bis-hydroxymethyl-m-carborane are added into a four-neck flask, 25g N, N-dimethylformamide is added, the mixture is heated to 150 ℃, the mixture is mechanically stirred for 2 hours, and after the reaction is finished, the solution is poured into deionized water and stirred for 60 minutes, and the precipitated precipitate is obtained by decompression and suction filtration. And drying the precipitate in an oven at 100 ℃ for 20 hours to obtain the biphenyl phthalonitrile resin prepolymer. The prepolymer has good solubility in ethyl acetate, acetone, tetrahydrofuran, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
Curing the prepolymer:
weighing the synthesized bisphenol A type phthalonitrile resin prepolymer in a ceramic crucible, and curing in a muffle furnace according to the following step heating program (the heating rate is 5 ℃/min): 240 ℃/1h +280 ℃/2h +300 ℃/2h +320 ℃/2h +350 ℃/2h, and the biphenyl phthalonitrile resin condensate is obtained after the muffle furnace is cooled to the room temperature.
FIG. 3 is a TGA spectrum of a cured product of the phthalonitrile resin prepolymer in example 2. The thermogravimetric analysis test was carried out at a temperature rise rate of 10 ℃/min. Thermogravimetric analysis data were as follows: example 1 thermal decomposition temperatures (T) in Nitrogen and air atmospheresd5) The respective carbon residue rates were 448 ℃ and 491 ℃ and the carbon residue rates (1000 ℃) in a nitrogen atmosphere and an air atmosphere were 73.53% and 13.97%.
Example 3
Pre-polymerization of phthalonitrile resin:
30g (68.49mmol) of biphenyl phthalonitrile resin monomer and 8g (39.16mmol) of 1, 7-bis-hydroxymethyl-m-carborane are added into a four-neck flask, then 40g N, N-dimethylacetamide is added, the mixture is heated to 165 ℃, the mixture is mechanically stirred for 6 hours, the solution is poured into deionized water after the reaction is finished, the mixture is stirred for 10 minutes, and the precipitated precipitate is obtained through reduced pressure suction filtration. And drying the precipitate in an oven at 100 ℃ for 5 hours to obtain the biphenyl phthalonitrile resin prepolymer. The prepolymer has good solubility in ethyl acetate, acetone, tetrahydrofuran, 1, 4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
Curing the prepolymer:
weighing the synthesized biphenyl phthalonitrile resin prepolymer in a ceramic crucible, and curing in a muffle furnace according to the following step heating program (the heating rate is 5 ℃/min): 240 ℃/2h +280 ℃/2h +300 ℃/4h +320 ℃/4h +350 ℃/6h, and obtaining the biphenyl phthalonitrile resin condensate after the muffle furnace is cooled to the room temperature.
FIG. 4 is a TGA spectrum of a cured product of a phthalonitrile resin prepolymer in example 3. The thermogravimetric analysis test was performed at a temperature rise rate of 10 ℃/min. Thermogravimetric analysis data were as follows: example 1 thermal decomposition temperatures (T) in Nitrogen and air atmospheresd5) The respective temperatures were 554 ℃ and 589 ℃, and the carbon residue ratios (1000 ℃) were 83.30% and 48.63% in a nitrogen atmosphere and an air atmosphere.
Claims (6)
1. A phthalonitrile resin prepolymer is characterized in that raw materials comprise phthalonitrile resin and 1, 7-bis-hydroxymethyl-m-carborane;
the mass parts of the raw material formula of the prepolymer system are 100 parts of phthalonitrile resin and 10-26.7 parts of 1, 7-bis-hydroxymethyl-m-carborane;
and the prepolymer is prepared by a method comprising the following steps:
dissolving 100 parts of phthalonitrile resin and 10-26.7 parts of 1, 7-bis-hydroxymethyl-m-carborane in an organic solvent in parts by weight, and performing prepolymerization reaction for 1-8 hours at 100-250 ℃;
pouring the reaction solution into water, stirring for 1-60 min, and completely separating out a precipitate; and (4) carrying out suction filtration, and drying the precipitate product at 80-150 ℃ for 1-50 h to obtain the phthalonitrile resin prepolymer.
2. The method for preparing a phthalonitrile resin prepolymer, according to claim 1, comprising the steps of:
dissolving 100 parts of phthalonitrile resin and 10-26.7 parts of 1, 7-hydroxymethyl-m-carborane in an organic solvent according to parts by weight, and carrying out prepolymerization reaction for 1-8 h at 100-250 ℃;
pouring the reaction solution into water, stirring for 1-60 min, and completely separating out a precipitate; and (4) carrying out suction filtration, and drying the precipitate product at 80-150 ℃ for 1-50 h to obtain the phthalonitrile resin prepolymer.
3. The method of claim 2, wherein the phthalonitrile resin is: bisphenol a-type phthalonitrile resin, bisphenol S-type phthalonitrile resin, bisphenol F-type phthalonitrile resin, biphenyl-type phthalonitrile resin, benzoxazine-type phthalonitrile resin, phenol-aldehyde-type phthalonitrile resin, nitrile ether-type phthalonitrile resin.
4. The method according to claim 2, wherein the organic solvent is one or more of 1, 4-dioxane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
5. The method of claim 2, wherein the prepolymerization temperature is 160 to 220 ℃.
6. The method of claim 2, wherein the prepolymerization time is 1 to 4 hours.
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| RU2201423C2 (en) * | 2000-12-26 | 2003-03-27 | Государственное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Polymeric binding agent and high-strength thermostable composition materials based on thereof |
| RU2225417C1 (en) * | 2002-11-11 | 2004-03-10 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" | Heterocyclic thermoreactive polymer |
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