CN115141373B - Preparation method of epoxy phthalonitrile/polysiloxane copolymer resin - Google Patents

Preparation method of epoxy phthalonitrile/polysiloxane copolymer resin Download PDF

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CN115141373B
CN115141373B CN202210930919.5A CN202210930919A CN115141373B CN 115141373 B CN115141373 B CN 115141373B CN 202210930919 A CN202210930919 A CN 202210930919A CN 115141373 B CN115141373 B CN 115141373B
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phthalonitrile
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epoxy
polysiloxane copolymer
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CN115141373A (en
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杨志洲
胡文涛
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Qilu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin, relating to the technical field of organic synthesis; the method has the advantages of simple process, convenient operation, controllable process, mild condition, good repeatability and low cost, is convenient to popularize and use, and the prepared epoxy phthalonitrile/polysiloxane copolymer resin material has fluidity at room temperature, low molding processing temperature, good high temperature resistance, thermal stability and thermal oxygen stability after complete curing, and has wide application prospect in the fields of high temperature resistant coatings, aerospace and the like.

Description

Preparation method of epoxy phthalonitrile/polysiloxane copolymer resin
Technical Field
The invention discloses a preparation method, which relates to the technical field of organic synthesis, in particular to a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin.
Background
The polysiloxane resin is a high molecular material with excellent performance, is a cross-linked semi-inorganic polymer containing an inorganic Si-O main chain and an organic side group, and has the dual characteristics of an organic material and an inorganic material. The method is widely applied to the fields of aerospace, building construction, national defense industry and the like. However, with the rapid development of the military industry, the aerospace industry and the like, the problem of high-temperature corrosion is increasingly remarkable, and the current polysiloxane resin protective coating cannot meet the current development requirement.
Phthalonitrile resin, also called phthalonitrile resin, is an excellent high-performance polymer. Originally developed by the united states navy laboratory. Is prepared by taking 4-nitrophthalonitrile as an initial raw material and a plurality of phenolic organic matters under the weak alkaline condition. The phthalonitrile monomer is solidified by opening a cyano triple bond to carry out bulk addition polymerization under the heating condition, and small molecule byproducts are not released in the whole process, so that the shrinkage rate is low. However, the inherent structural characteristics of monomer molecules lead to higher melting point and curing temperature of the monomers, longer curing time, narrower processing window due to the temperature difference between the melting temperature and the curing temperature, and the cured product has great brittleness, which severely limits the application range.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin, which combines phthalonitrile resin and polysiloxane resin, so that not only can the brittleness of the resin be improved, but also the carbon residue rate of the resin be increased, and the thermal stability of the resin be improved, but also the curing temperature can be reduced, the processing window is widened, and the application range is enlarged.
The specific scheme provided by the invention is as follows:
a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin comprises the following steps: hydrolyzing and condensing methyl or phenyl alkoxy silane and amino alkoxy silane to obtain polysiloxane,
adding epoxy phthalonitrile into a reaction system to react to obtain epoxy phthalonitrile/polysiloxane copolymer resin, wherein the epoxy phthalonitrile has a structure shown in the following I and/or II:
in the preparation method, the methyl or phenyl alkoxy silane is one or a mixture of a plurality of methyl triethoxy silane, dimethyl diethoxy silane, tetraethoxy silane, diphenyl diethoxy silane, diphenyl dimethoxy silane, methyl trimethoxy silane, phenyl triethoxy silane, phenyl trimethoxy silane and dimethyl dimethoxy silane.
3. The preparation method according to claim 1 or 2, characterized in that the aminoalkoxysilane is one or a mixture of several of gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyldimethoxysilane, gamma-aminopropyl trimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane.
Further, in the preparation method, the mole percentage of the methyl or phenyl alkoxy silane is 40-95%, and the mole percentage of the amino alkoxy silane is 5-60%.
Further, the epoxy phthalonitrile is used in an amount of 0.1 to 3 times the mole number of the aminoalkoxysilane in the preparation method.
In the preparation method, an organic solvent is added into the reaction system for dissolving reactants and products, wherein the organic solvent is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
Further, in the preparation method, the reaction temperature of the hydrolytic condensation is 45-100 ℃ and the reaction time is 4-24 hours.
Further, in the preparation method, the reaction temperature of the polysiloxane and the epoxy phthalonitrile is 50-120 ℃ and the reaction time is 6-48 hours.
The invention also provides an epoxy phthalonitrile/polysiloxane copolymer resin, which is prepared according to the preparation method of the epoxy phthalonitrile/polysiloxane copolymer resin.
The invention also provides application of the epoxy phthalonitrile/polysiloxane copolymer resin.
The invention has the advantages that:
the invention provides a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin, which has the advantages of simple preparation process, convenient operation, controllable process, mild condition, good repeatability, low cost and convenient popularization and use, and the prepared epoxy phthalonitrile/polysiloxane copolymer resin material has fluidity at room temperature, low molding processing temperature, good high temperature resistance, thermal stability and thermal oxygen stability after complete solidification, and has wide application prospects in the fields of high temperature resistant coatings, aerospace and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of the method of the invention.
FIG. 2 is a schematic diagram showing the TGA test curve of an epoxyphthalonitrile/polysiloxane copolymer resin prepared from epoxyphthalonitrile of the molecular structural formula I under nitrogen atmosphere. As is evident from FIG. 2, the temperature at which the epoxy phthalonitrile/polysiloxane copolymer resin loses 5% weight is 420℃while the temperature at which the conventional silicone resin loses 5% weight is about 250 ℃. It is fully explained that the epoxy phthalonitrile/polysiloxane copolymer resin has much higher thermal stability than the common silicone resin.
FIG. 3 is a schematic representation of a TGA test curve of a prior art methylphenyl silicone resin under a nitrogen atmosphere. The curves of different proportions in the graph are all methylphenyl silicone resins, which shows that the methylphenyl silicone resins have strong mass loss peaks at 200-300 ℃.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a preparation method of epoxy phthalonitrile/polysiloxane copolymer resin, which is characterized in that methyl or phenyl alkoxy silane and amino alkoxy silane are hydrolyzed and condensed to obtain polysiloxane.
Adding epoxy phthalonitrile into a reaction system to react to obtain epoxy phthalonitrile/polysiloxane copolymer resin, wherein the epoxy phthalonitrile has a structure shown in the following I and/or II:
the reaction formula in which the epoxyphthalonitrile of the molecular structural formula I reacts with the polysiloxane can be referred to as follows:
the epoxy phthalonitrile in the reactants can also be:
wherein R is 1 ，R 2 At least one of which is 4- (hydroxyethoxy) -1, 2-phthalonitrile or 4- [4- (2-hydroxyethoxy) phenoxy]-1,2 phthalonitrile groups, if not H.
In the invention, phthalonitrile monomer is connected to polysiloxane chain segment through ring opening polymerization to form epoxy phthalonitrile/polysiloxane copolymer resin. the-Si-O-Si-in the copolymer resin chain segment increases flexibility, and the copolymer resin has lower melting point and is a light yellow liquid product with fluidity at room temperature, so that the copolymer resin is easy to be preliminarily cured and molded at room temperature, is obviously different from the phthalonitrile resin or the organic silicon resin which is known at present, can be further cured at high temperature, has better processing performance than other phthalonitrile resin and polysiloxane copolymer resin, widens the processing window, obviously improves the thermal oxygen stability, and further expands the application range of epoxy phthalonitrile/polysiloxane copolymer resin.
In a specific application, reference may be made to the following examples.
The specific implementation process of the embodiment 1 is as follows:
step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 75℃for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 406℃at 5% under a nitrogen atmosphere.
The specific implementation process of the embodiment 2 is as follows:
step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide were added to the single-necked flask, and the mixture was stirred at 55℃for 8 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 12 hours at 100 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 408℃at 5% under a nitrogen atmosphere.
Example 3
Step 1: 2.40g (0.01 mol) of phenyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide were added to a single-neck flask and stirred at 80℃for 5 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 10 hours at 120 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 419℃at 5% under a nitrogen atmosphere.
Example 4
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 50℃for 24 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 48 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 410℃at 5% under a nitrogen atmosphere.
Example 5
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 50℃for 18 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured at a weight loss temperature of 418℃at 5% under a nitrogen atmosphere.
Example 6
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of N, N-dimethylacetamide are added into a single-neck flask, and stirred at 100 ℃ for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured at a weight loss temperature of 401℃at 5% under a nitrogen atmosphere.
Example 7
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 75℃for 6 hours;
step 2: 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile/polysiloxane copolymer resin is prepared, 1.46g (0.005 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred at 75 ℃ for 24 hours to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 413℃at 5% under a nitrogen atmosphere.
Example 8
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide are added to a single-neck flask, and the mixture is stirred at 90℃for 6 hours;
step 2: 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile/polysiloxane copolymer resin is prepared, 1.46g (0.005 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 12 hours at 100 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 410℃at 5% under a nitrogen atmosphere.
Example 9
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylacetamide were added to a single-necked flask, and the mixture was stirred at 100℃for 5 hours;
step 2: 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile/polysiloxane copolymer resin is prepared, 1.46g (0.005 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 12 hours at 100 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 415℃at 5% under a nitrogen atmosphere.
Example 10
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 80℃for 6 hours;
step 2: 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile/polysiloxane copolymer resin is prepared, 1.46g (0.005 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred at 75 ℃ for 24 hours to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 421℃at 5% under a nitrogen atmosphere.
Example 11
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 75℃for 6 hours;
step 2: epoxy phthalonitrile/polysiloxane copolymer resin preparation, adding 0.73g (0.0025 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile and 0.50g (0.0025 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile into a single-mouth bottle, and stirring at 75 ℃ for 36 hours to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 413℃at 5% under a nitrogen atmosphere.
Example 12
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.48g (0.0025 mol) of gamma-aminopropyl methyldiethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 75℃for 16 hours;
step 2: 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile/polysiloxane copolymer resin is prepared, 1.46g (0.005 mol) of 4- [4- (2-oxiranylmethoxy) phenoxy ] -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred at 75 ℃ for 24 hours to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 419℃at 5% under a nitrogen atmosphere.
Example 13
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.55g (0.0025 mol) of gamma-aminopropyl triethoxysilane, 0.72g (0.04 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 75℃for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 416℃at 5% under a nitrogen atmosphere.
Example 14
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.55g (0.0025 mol) of gamma-aminopropyl triethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide are added to a single-neck flask, and the mixture is stirred at 55℃for 8 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 12 hours at 100 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 403℃at 5% under a nitrogen atmosphere.
Example 15
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.55g (0.0025 mol) of gamma-aminopropyl triethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide were added to a single-necked flask and stirred at 80℃for 5 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 10 hours at 120 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 411℃at 5% under a nitrogen atmosphere.
Example 16
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.41g (0.0025 mol) of gamma-aminopropyl methyldimethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 50℃for 24 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 48 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 403℃at 5% under a nitrogen atmosphere.
Example 17
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.41g (0.0025 mol) of gamma-aminopropyl methyldimethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are placed in a single-necked flask, and the mixture is stirred at 50℃for 18 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 415℃at 5% under a nitrogen atmosphere.
Example 18
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.41g (0.0025 mol) of gamma-aminopropyl methyldimethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran are added to a single-necked flask, and the mixture is stirred at 100℃for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 409℃at 5% under a nitrogen atmosphere.
Example 19
Step 1: 1.36g (0.01 mol) of methyltrimethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.45g (0.0025 mol) of gamma-aminopropyl trimethoxysilane, 0.72g (0.04 mol) of water and 20ml of dimethyl sulfoxide are added into a single-neck flask, and stirred at 120 ℃ for 5 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 411℃at 5% under a nitrogen atmosphere.
Example 20
Step 1: 1.36g (0.01 mol) of methyltrimethoxysilane, 0.68g (0.0025 mol) of diphenyldiethoxysilane, 0.55g (0.0025 mol) of gamma-aminopropyl triethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide are added to a single-neck flask, and the mixture is stirred at 110℃for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 12 hours at 100 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 413℃at 5% under a nitrogen atmosphere.
Example 21
Step 1: 1.48g (0.01 mol) of dimethyldiethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.55g (0.0025 mol) of gamma-aminopropyl triethoxysilane, 0.72g (0.04 mol) of water and 20ml of N, N-dimethylformamide are added to a single-neck flask and stirred at 80 ℃ for 5 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 10 hours at 120 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured at a weight loss temperature of 418℃at 5% under a nitrogen atmosphere.
Example 22
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.52g (0.0025 mol) of 3- (2-aminoethylamino) propylmethyldimethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran were added to a single-necked flask, and the mixture was stirred at 50℃for 24 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 48 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 417℃at 5% under a nitrogen atmosphere.
Example 23
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.61g (0.0025 mol) of diphenyldimethoxysilane, 0.56g (0.0025 mol) of 3- (2-aminoethylamino) propyltrimethoxysilane, 0.36g (0.02 mol) of water and 20ml of tetrahydrofuran were placed in a single-necked flask, and the mixture was stirred at 50℃for 18 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to spin evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 426℃at 5% under a nitrogen atmosphere.
Example 24
Step 1: 1.78g (0.01 mol) of methyltriethoxysilane, 0.37g (0.0025 mol) of dimethyldiethoxysilane, 0.66g (0.0025 mol) of 3- (2-aminoethylamino) propyltriethoxysilane, 0.36g (0.02 mol) of water and 20ml of dimethyl sulfoxide are added to a single-necked flask, and the mixture is stirred at 100℃for 6 hours;
step 2: 4- (2-oxiranylmethoxy) -phthalonitrile/polysiloxane copolymer resin is prepared, 1.00g (0.005 mol) of 4- (2-oxiranylmethoxy) -phthalonitrile is added into a single-mouth bottle, and the mixture is stirred for 24 hours at 75 ℃ to obtain copolymer resin solution;
step 3: and (3) product treatment: the resulting mixture was subjected to rotary evaporation to remove the solvent, to give a pale yellow viscous copolymer resin, which was cured, and which had a weight loss temperature of 421℃at 5% under a nitrogen atmosphere.
The epoxy phthalonitrile/polysiloxane copolymer resin obtained by the method has excellent comprehensive performance and has wide application prospect in the high-tech fields such as aerospace, electronic ships, automobile machinery and the like. The epoxy phthalonitrile/polysiloxane copolymer resin has high temperature resistance level, good dimensional stability, small high-temperature deformation, good bearing performance and remarkable weight reduction effect, solves the problem that the traditional metal scheme is too heavy in quality, solves the problem that the phenolic resin matrix composite scheme is insufficient in temperature resistance level and large in dimensional deformation at high temperature, and is suitable for preparing high-dimensional-precision high-temperature-resistant composite components.
Other reagents used in the invention are all reagents which can be purchased or prepared in the prior art and are not described repeatedly.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (9)

1. A process for preparing epoxy phthalonitrile/polysiloxane copolymer resin features that the hydrolytic condensation of methyl or phenyl alkoxy silane and amino alkoxy silane is carried out at 45-100 deg.C,
adding epoxy phthalonitrile into a reaction system for reaction at 50-120 ℃, wherein the dosage of the epoxy phthalonitrile is 0.1-3 times of the mole number of amino alkoxy silane, and the epoxy phthalonitrile/polysiloxane copolymer resin is obtained, and the epoxy phthalonitrile has a structure shown in the following I and/or II:
。
2. the preparation method according to claim 1, wherein the methyl or phenyl alkoxysilane is one or a mixture of methyl triethoxysilane, dimethyl diethoxysilane, diphenyl dimethoxysilane, methyl trimethoxysilane, phenyl triethoxysilane, phenyl trimethoxysilane, and dimethyl dimethoxysilane.
3. The preparation method according to claim 1 or 2, wherein the aminoalkoxysilane is one or more of gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyldimethoxysilane, gamma-aminopropyl trimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, and 3- (2-aminoethylamino) propyltrimethoxysilane.
4. The method according to claim 1, wherein the molar percentage of the methyl or phenyl alkoxysilane is 40% -95% and the molar percentage of the amino alkoxysilane is 5% -60%.
5. The preparation method according to claim 1, wherein an organic solvent is added to the reaction system for dissolving the reactants and the products, and the organic solvent is tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
6. The process according to claim 1, wherein the hydrolytic condensation is carried out for a reaction time of 4 to 24 hours.
7. The process according to claim 1, wherein the reaction time of the polysiloxane with epoxyphthalonitrile is from 6 to 48 hours.
8. An epoxyphthalonitrile/polysiloxane copolymer resin, characterized in that it is prepared by the method for preparing the epoxyphthalonitrile/polysiloxane copolymer resin according to any one of claims 1 to 7.
9. Use of an epoxyphthalonitrile/polysiloxane copolymer resin according to claim 8 in the field of high temperature coatings and aerospace applications.
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