CN107573470B - Modified thermosetting phenolic resin and preparation method thereof - Google Patents
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Abstract
The invention relates to a 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester modified thermosetting phenolic resin and a preparation method thereof, wherein the phenolic resin is prepared by adding 2-20 parts by mass of an ammonia solution into reactants comprising 200-300 parts by mass of phenol, 200-300 parts by mass of a formaldehyde solution, 150-250 parts by mass of 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester, 10-50 parts by mass of o-phenylphenol and 10-50 parts by mass of o-cresol according to the mass part ratio.
Description
Technical Field
The invention relates to 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester modified thermosetting phenolic resin and a preparation method thereof, belonging to the technical field of resin matrix composite materials.
Background
The phenolic resin is widely applied to the fields of aviation, aerospace, construction, automobile industry and the like due to excellent heat-resistant stability, technological performance and flame retardant performance. However, the curing mechanism of the phenolic resin is dehydration condensation reaction between hydroxymethyl groups and between the hydroxymethyl groups and active hydrogen atoms on a benzene ring, so that a large amount of small molecular water is inevitably generated in the curing process of the phenolic resin, and the product is porous; in addition, the main structure is a mode of connecting phenol ring and methylene, so that the chemical structure of the phenolic resin is rigid, the steric hindrance is large, the reactive functional groups are limited, a cross-linked molecular structure with a larger size cannot be formed at the high-temperature curing stage of the resin, the upper limit of the mechanical property of the resin is reached, the cured phenolic resin is brittle and has poor mechanical property, and the mechanical property requirement of a high-temperature-resistant composite material product prepared by taking the phenolic resin as a matrix cannot be met.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin and a preparation method thereof.
The technical solution of the invention is as follows:
the modified thermosetting phenol-formaldehyde resin comprises 200-300 parts by mass of phenol, 200-300 parts by mass of a formaldehyde solution, 150-250 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl dicarboxylate, 10-50 parts by mass of o-phenylphenol, 10-50 parts by mass of o-cresol and 2-20 parts by mass of an ammonia water solution;
the preferable mode is as follows: the raw materials comprise 210-280 parts by mass of phenol, 210-280 parts by mass of formaldehyde solution, 160-240 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 15-45 parts by mass of o-phenylphenol, 15-45 parts by mass of o-cresol and 6-14 parts by mass of ammonia water solution;
further preferred is: the raw materials comprise 220-260 parts by mass of phenol, 220-260 parts by mass of formaldehyde solution, 180-220 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 20-40 parts by mass of o-phenylphenol, 20-40 parts by mass of o-cresol and 8-10 parts by mass of ammonia water solution;
the structural formula of the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester is as follows:
the concentration of the ammonia water is 25-28%.
A preparation method of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin comprises the following steps:
(1) dissolving phenol in a formaldehyde solution according to the mass part ratio, sequentially adding o-phenylphenol and o-cresol, adding ammonia water according to the mass part ratio of 1/2 after completely dissolving the o-phenylphenol and the o-cresol under the condition of stirring in a water bath at 40-45 ℃, slowly heating to 65-75 ℃, and carrying out constant temperature reaction;
(2) continuing heating the solution obtained in the step (1) to 85-95 ℃, adding the remaining ammonia water with the mass fraction ratio of 1/2, and carrying out constant temperature reaction;
(3) and (3) adding 4, 5-epoxycyclohexane-1, 2-diglycidyl diformate into the solution obtained in the step (2), stirring, and then stirring and dehydrating in a water bath at 85-95 ℃ under a vacuum condition to prepare the 4, 5-epoxycyclohexane-1, 2-diglycidyl diformate modified thermosetting phenolic resin.
In the step (1), the constant-temperature reaction time is 1-3 h;
in the step (2), the constant-temperature reaction time is 1-3 h;
in the step (3), firstly stirring for 10-20 min, and then stirring and dehydrating for 0.5-1.5 h in a water bath at 85-95 ℃ under a vacuum condition.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention prepares 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin by an in-situ polymerization method, phenol, o-phenylphenol, o-cresol and formaldehyde are subjected to addition reaction under the catalysis of ammonia water to generate oligomers containing a large amount of hydroxymethyl, the hydroxymethyl on a phenol ring is continuously subjected to dehydration condensation reaction to achieve chain growth, after the chain growth reaches a certain degree, 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester is added, the phenol hydroxyl and an epoxy functional group are subjected to ring-opening reaction to introduce the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester into a main chain structure of the phenolic resin, the release of small molecular water in the curing process of the phenolic resin is reduced, and the epoxy resin is grafted with the 4, 5-epoxy cyclohexane-1, the flexible molecule with 2-diglycidyl diformate and multiple functionality solves the problem of porosity of the product to a certain extent, improves the mechanical property of the phenolic resin and improves the tensile modulus of the phenolic resin.
(2) The invention adopts an in-situ polymerization method to introduce the multifunctional flexible chain structure of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester into the skeleton structure of the phenolic resin, and is realized by the ring-opening reaction of epoxy active groups and phenolic hydroxyl groups, and the invention has the beneficial effects that the multifunctional flexible structure of the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester reduces the molecular steric hindrance to a certain extent, improves the molecular crosslinking degree, improves the mechanical properties of the phenolic resin, and improves the tensile modulus of the phenolic resin, for example.
(3) The 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin has a solid content of more than 75%, a 50 wt% phenolic resin methanol solution prepared according to the solid content has a rotational viscosity of 10-150 mPa · s and a tensile modulus of 3.96-5.22 GPa.
(4) The 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin prepared by the method has more excellent performance;
(5) the preparation method of the 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester modified thermosetting phenolic resin has the advantages of simple process, simple operation, low equipment requirement performance and easy popularization and application.
(6) The invention relates to a 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester modified thermosetting phenolic resin and a preparation method thereof, wherein the phenolic resin is prepared by adding 2-20 parts by mass of an ammonia solution into reactants comprising 200-300 parts by mass of phenol, 200-300 parts by mass of a formaldehyde solution, 150-250 parts by mass of 4, 5-epoxycyclohexane-1, 2-diformic acid diglycidyl ester, 10-50 parts by mass of o-phenylphenol and 10-50 parts by mass of o-cresol according to the mass part ratio.
(7) The preparation method reduces the release of small molecular water in the curing process of the phenolic resin, solves the problem of porosity of the product to a certain extent, improves the mechanical property of the phenolic resin and improves the tensile modulus of the phenolic resin.
(8) The invention can solve the problems of porosity, poor mechanical property and the like of a product taking phenolic resin as a matrix, and optimizes the curing reaction mechanism of the phenolic resin by reasonably designing the chemical structure of the phenolic resin, thereby reducing the defect holes of the product to a certain extent. Meanwhile, a multifunctional molecule with certain flexibility is introduced, so that the molecule is relatively violent in thermal motion and relatively has small steric hindrance in a high-temperature curing stage, the crosslinking degree of the resin is improved to a certain extent, and the excellent mechanical property of the resin can be ensured. The invention adopts 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester as a molecular chain modifier, and utilizes the phenolic hydroxyl of phenolic resin with a certain chain segment length to carry out ring-opening reaction with the epoxy functional group in the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, and the phenolic resin is grafted to the phenolic resin skeleton structure, and the curing mechanism of the phenolic resin modified by the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester is converted into the mechanism of the ring-opening curing and the dehydration condensation reaction synergistic curing of epoxy rings from the original dehydration condensation reaction which can generate a large amount of micromolecules, thereby reducing the release of the micromolecules, reducing the holes of products and simultaneously improving the mechanical property of the resin.
Drawings
FIG. 1 is a schematic diagram of the synthetic mechanism of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate modified thermosetting phenolic resin of the present invention;
FIG. 2 is a comparison graph of infrared spectra of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenol-formaldehyde resin and 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to the present invention, in which curve (a) is 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester and curve (b) is 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenol-formaldehyde resin.
Detailed Description
The thermosetting phenolic resin modified by 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate is prepared by adding 2-20 parts by mass of an ammonia water solution into 200-300 parts by mass of phenol, 200-300 parts by mass of a formaldehyde solution, 150-250 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 10-50 parts by mass of o-phenylphenol and 10-50 parts by mass of o-cresol.
The reactant comprises 210-280 parts by mass of phenol, 210-280 parts by mass of formaldehyde solution, 160-240 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 15-45 parts by mass of o-phenylphenol and 15-45 parts by mass of o-cresol, and is prepared by adding 6-14 parts by mass of ammonia water solution for catalysis;
the reactant comprises 220-260 parts by mass of phenol, 220-260 parts by mass of formaldehyde solution, 180-220 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 20-40 parts by mass of o-phenylphenol and 20-40 parts by mass of o-cresol, and is prepared by adding 8-10 parts by mass of ammonia water solution for catalysis.
The concentration of the ammonia water is 10-50%.
The preparation method of the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin comprises the following steps:
(1) dissolving phenol in a formaldehyde solution according to the mass part ratio, sequentially adding o-phenylphenol and o-cresol, adding ammonia water according to the mass part ratio of 1/2 after completely dissolving the o-phenylphenol and the o-cresol under the condition of stirring in a water bath at 40 ℃, slowly heating to 65-75 ℃, and carrying out constant temperature reaction;
(2) slowly heating the solution obtained in the step (1) from 65-75 ℃ to 85-95 ℃, adding the remaining ammonia water with the mass fraction ratio of 1/2, and carrying out constant-temperature reaction;
(3) adding 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring, and then stirring and dehydrating in a water bath at 85-95 ℃ under a vacuum condition to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin.
And (3) carrying out constant-temperature reaction for 1-3 h in the step (1).
And (3) carrying out constant-temperature reaction for 1-3 h in the step (2).
In the step (3), after stirring for 10-20 min, stirring and dehydrating for 0.5-1.5 h in water bath at 85-95 ℃ under a vacuum condition.
The invention is described in further detail below with reference to the following figures and specific examples:
the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin is prepared by adding 2-20 parts by mass of an ammonia water solution into 200-300 parts by mass of phenol, 200-300 parts by mass of a formaldehyde solution, 150-250 parts by mass of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 10-50 parts by mass of o-phenylphenol and 10-50 parts by mass of o-cresol.
The reactants are preferably: the catalyst is prepared by adding 6-14 parts by mass of ammonia water solution into 210-280 parts by mass of phenol, 210-280 parts by mass of formaldehyde solution, 160-240 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 15-45 parts by mass of o-phenylphenol and 15-45 parts by mass of o-cresol.
Further preferably: the catalyst is prepared by adding 220-260 parts by mass of phenol, 220-260 parts by mass of formaldehyde solution, 180-220 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 20-40 parts by mass of o-phenylphenol and 20-40 parts by mass of o-cresol into 8-10 parts by mass of ammonia water solution for catalysis.
Most preferably: the catalyst is prepared by adding 230-250 parts by mass of phenol, 230-250 parts by mass of formaldehyde solution, 190-200 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 25-35 parts by mass of o-phenylphenol and 25-35 parts by mass of o-cresol into 8.5-9.5 parts by mass of ammonia water solution for catalysis.
Wherein the concentration of the ammonia water is 25-28%.
The preparation method of the 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin comprises the following steps:
(1) dissolving 200-300 parts of phenol in 200-300 parts of formaldehyde solution according to the mass part ratio, sequentially adding 10-50 parts of o-phenylphenol and 10-50 parts of o-cresol, adding 1-7.5 parts of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 65-75 ℃, and reacting at constant temperature for 1-3 hours;
(2) slowly heating the solution obtained in the step (1) from 65-75 ℃ to 85-95 ℃, adding the rest 1-7.5 parts of ammonia water, and reacting at constant temperature for 1-3 h;
(3) adding 150-250 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 10-20 min, then stirring and dehydrating for 0.5-1.5 h in water bath at 85-95 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin.
FIG. 1 shows a schematic diagram of the synthesis mechanism of the thermosetting phenol-formaldehyde resin modified by diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate according to the present invention.
The 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin is a light yellow viscous liquid, the solid content is more than 75%, a 50 wt% phenolic resin methanol solution prepared according to the solid content has the rotational viscosity of 10-150 mPa & s, and the average value of the tensile modulus is 3.96-5.22 GPa (higher than that of the common phenolic aldehyde by 3-4 GPa).
Example 1
Dissolving 240 parts of phenol in 240 parts of formaldehyde solution according to the mass part ratio, sequentially adding 30 parts of o-phenylphenol and 30 parts of o-cresol, adding 4.5 parts of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 70 ℃, and reacting at constant temperature for 1.5 hours;
then slowly heating the obtained solution from 70 ℃ to 90 ℃, adding the rest 4.5 parts of ammonia water, and reacting for 2 hours at constant temperature;
then adding 200 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 20min, then stirring and dehydrating for 1h in a water bath at 90 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin. The ammonia concentration was 26%.
The 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin obtained in the embodiment is light yellow viscous liquid, and the solid content is 81%; the rotational viscosity of the phenol resin methanol solution prepared at 50 wt% based on the solid content was 96 mPas, and the tensile modulus of the cured thermosetting phenol resin was 5.22 GPa.
FIG. 2 shows the comparison of the IR spectra of the prepared diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate modified thermosetting phenol-formaldehyde resin and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate at 1735cm-1、910cm-1Near the characteristic absorption peak of the epoxy functional group, 1020cm-1、1180cm-1The absorption peak of ether bond generated after the reaction of phenolic hydroxyl and epoxy functional group is nearby, which proves that the flexible structure of 4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester is successfully introduced into the phenolic resin skeleton structure by the in-situ polymerization method, and other characteristic absorption peaks are shown in Table 1Shown in the figure:
TABLE 14 infrared spectroscopic analysis of 5, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenol-formaldehyde resins
Example 2
Dissolving 200 parts of phenol in 200 parts of formaldehyde solution according to the mass part ratio, sequentially adding 10 parts of o-phenylphenol and 10 parts of o-cresol, adding 1 part of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 65 ℃, and reacting at constant temperature for 1 hour;
then slowly heating the obtained solution from 65 ℃ to 85 ℃, adding the rest 1 part of ammonia water, and reacting for 1 hour at constant temperature;
adding 150 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 10min, then stirring and dehydrating for 0.5h in a water bath at 85 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin. The ammonia gas mass concentration in the ammonia water solution is 25 percent.
The 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin obtained in the example is light yellow viscous liquid, and the solid content is 75%; preparing a 50 wt% phenolic resin methanol solution with the rotary viscosity of 18mPa & s according to the solid content; the tensile modulus of the cured thermosetting phenol resin was 4.03 GPa.
Example 3
Dissolving 300 parts of phenol in 300 parts of formaldehyde solution according to the mass part ratio, sequentially adding 50 parts of o-phenylphenol and 50 parts of o-cresol, adding 7.5 parts of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 75 ℃, and reacting at constant temperature for 3 hours;
then slowly heating the obtained solution from 75 ℃ to 95 ℃, adding the rest 7.5 parts of ammonia water, and reacting for 3 hours at constant temperature;
adding 250 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 20min, then stirring and dehydrating for 1.5h in a water bath at 95 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin. The ammonia gas mass concentration in the ammonia water solution is 28 percent.
The 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin obtained in the embodiment is yellow extremely viscous liquid, is solid at normal temperature and has the solid content of 83%; preparing 50 wt% of phenolic resin methanol solution according to the solid content, wherein the rotary viscosity of the phenolic resin methanol solution is 120mPa & s; the tensile modulus of the cured thermosetting phenol resin was 4.87 GPa.
Example 4
Dissolving 220 parts of phenol in 280 parts of formaldehyde solution according to the mass part ratio, sequentially adding 20 parts of o-phenylphenol and 20 parts of o-cresol, adding 6 parts of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 70 ℃, and reacting at constant temperature for 2.5 hours;
then slowly heating the obtained solution from 70 ℃ to 90 ℃, adding the rest 6 parts of ammonia water, and reacting for 1 hour at constant temperature;
adding 180 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 15min, then stirring and dehydrating for 1h in a water bath at 90 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin. The ammonia gas mass concentration in the ammonia water solution is 26 percent.
The 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin obtained in the embodiment is yellow viscous liquid, and the solid content is 78%; preparing a 50 wt% phenolic resin methanol solution with the rotational viscosity of 103 mPas according to the solid content; the tensile modulus of the cured thermosetting phenol resin was 4.51 GPa.
Example 5
Dissolving 280 parts of phenol in 220 parts of formaldehyde solution according to the mass part ratio, sequentially adding 40 parts of o-phenylphenol and 40 parts of o-cresol, adding 4 parts of ammonia water after the o-phenylphenol and the o-cresol are completely dissolved under the condition of stirring in a water bath at 40 ℃, slowly heating to 70 ℃, and reacting at constant temperature for 2.5 hours;
then slowly heating the obtained solution from 70 ℃ to 90 ℃, adding the rest 4 parts of ammonia water, and reacting for 1 hour at constant temperature;
adding 220 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, stirring for 15min, then stirring and dehydrating for 1h in a water bath at 90 ℃ under a vacuum condition, and cooling to room temperature to prepare the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin. The ammonia gas mass concentration in the ammonia water solution is 26 percent.
The 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin obtained in the embodiment is yellow viscous liquid, and the solid content is 79%; preparing a 50 wt% phenolic resin methanol solution with the rotational viscosity of 62mPa & s according to the solid content; the tensile modulus of the cured thermosetting phenol resin was 3.96 GPa.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.
Claims (2)
1. A4, 5-epoxy cyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin is characterized in that:
the modified thermosetting phenolic resin comprises 210-280 parts by mass of phenol, 210-280 parts by mass of a formaldehyde solution, 160-240 parts by mass of 4, 5-epoxycyclohexane-1, 2-diglycidyl phthalate, 15-45 parts by mass of o-phenylphenol, 15-45 parts by mass of o-cresol and 6-14 parts by mass of an ammonia water solution;
the concentration of the ammonia water is 25% -28%;
the preparation method of the 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester modified thermosetting phenolic resin comprises the following steps:
(1) dissolving phenol in a formaldehyde solution according to the mass part, sequentially adding o-phenylphenol and o-cresol, adding ammonia water with the mass fraction of 1/2 after completely dissolving the o-phenylphenol and the o-cresol under the condition of stirring in a water bath at 40-45 ℃, slowly heating to 65-75 ℃, and carrying out constant temperature reaction;
(2) continuously heating the solution obtained in the step (1) to 85-95 ℃, adding the remaining 1/2 mass percent ammonia water, and carrying out constant temperature reaction;
(3) adding 4, 5-epoxycyclohexane-1, 2-diglycidyl diformate into the solution obtained in the step (2), stirring, and then stirring and dehydrating in a water bath at 85-95 ℃ under a vacuum condition to prepare the 4, 5-epoxycyclohexane-1, 2-diglycidyl diformate modified thermosetting phenolic resin;
in the step (1), the constant-temperature reaction time is 1-3 h;
in the step (2), the constant-temperature reaction time is 1-3 h;
in the step (3), firstly, stirring for 10-20 min;
and (3) stirring and dehydrating for 0.5-1.5 h in water bath at 85-95 ℃ under a vacuum condition.
2. The thermosetting phenol-formaldehyde resin modified by diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate according to claim 1, wherein: the modified thermosetting phenolic resin comprises, by mass, 220-260 parts of phenol, 220-260 parts of a formaldehyde solution, 180-220 parts of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 20-40 parts of o-phenylphenol, 20-40 parts of o-cresol and 8-10 parts of an ammonia water solution.
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